CIE4485

Wastewater Treatment
Prof.dr.ir. Jules van Lier

11. Anaerobic Treatment Fundamentals COD Balance

CT4485 Wastewater Treatment

Lecture 5a: Anaerobic Treatment Fundamentals
Prof.dr.ir. Jules van Lier
COD balance
13 December 2012

Delft
University of
Technology

Challenge the future

Learning objectives
What does COD actually means?
Making A COD balance over an anaerobic reactor
How to use the COD balance

IWA: Chapter 16
Metcalf & Eddy: Chapt.10
Anaerobic Wastewater Treatment

Anaerobic Conversion of Organic Matter

What happens with
the COD?

Organic Polymers
proteins carbohydrates lipids

Hydrolysis
Mono- and oligomers
amino acids, sugars, fatty acids
Acidogenesis
Volatile Fatty Acids
Lactate
Ethanol

Acetogenesis
Acetate

H2 / CO2

Methanogenesis
CH4 / CO2
Anaerobic Wastewater Treatment

What is Chemical Oxygen Demand (COD) ??

The theoretical COD calculation of organic compound

CnHaObNd
is based on a complete oxidation.
The amount of required O2 depends on the oxidation state of C:

CnHaObNd
Oxidation state:
(2b + 3d - a)/n

+a
-2b
-3d
Anaerobic Wastewater Treatment

Chemical Oxygen Demand (COD)

The number of electrons made free per atom C in the complete oxidation
of CnHaObNd amounts to:

4 (2b+3d-a)/n

(or 4n + a - 2b - 3d)

as +4 is the most oxidized form of C (CO2)

The required number of O2 molecules for the complete

oxidation is:
CnHaObNd + (4n+a-2b-3d) O2
n CO2 + (a-3d) H2O + d NH3
1 O2 accepts max. 4 electrons
Anaerobic Wastewater Treatment

Chemical Oxygen Demand (COD)

In the standardized COD test with bichromate as oxidizer (150C) almost
all organic compounds

CnHaObNd
are completely converted in CO2 and H2O
But: organic N stays reduced and is converted in NH3
(similar to organic O)
The required number of O2 molecules for the complete oxidation is
(no NOx produced, in contrast to BOD test):

CnHaObNd + (4n+a-2b-3d) O2
n CO2 + (a-3d) H2O + d NH3
Anaerobic Wastewater Treatment

That is Chemical Oxygen Demand (COD) !!

1 mol of organic matter demands:
(4n+a-2b-3d) moles O2 or 8(4n+a-2b-3d) g O2
Theoretical COD calculation:
CODt = 8(4n+a-2b-3d)/(12n+a+16b +14d)
mg COD/mg CnHaObNd

CnHaObNd + (4n+a-2b-3d) O2
n CO2 + (a-3d) H2O + d NH3
Anaerobic Wastewater Treatment

Anaerobic Wastewater Treatment

What is Total Organic Carbon (TOC) ??

Organic matter measured as CO2 after incineration
(corrections needed for inorganic carbon in waste sample)
TOCt = 12n / (12n + a + 16b + 14d) g TOC/gCnHaObNd

Anaerobic Wastewater Treatment

g COD and g TOC per g organic compound (no N)

Ratio COD / TOC: 8(4n+a-2b-3d)/(12n) = 8/3 + 2(a-2b-3d)/(3n)

4
2
7
6
3
2
3
1
2
0

g COD
(g CnHaOb)
0.18
0.35
0.75
1.07
1.07
1.07
1.22
2.38
1.29
3.08

g TOC
(g CnHaOb)
0.27
0.26
0.38
0.40
0.40
0.40
0.39
0.77
0.39
0.92

COD/TOC
ratio
0.67
1.33
2.00
2.67
2.67
2.67
3.11
3.11
3.33
3.33

1
2
0
0
1
1
0
0

2.21
3.43
3.43
3.43
2.09
1.50
3.73
4.00

0.62
0.75
0.86
0.86
0.52
0.38
0.80
0.75

3.56
3.83
4.00
4.00
4.00
4.00
4.67
5.33

Compound

Oxalic acid
Formic acid
Citric acid
Glucose
Lactic acid
Acetic acid
Glycerine
Phenol
Ethylene glycol
Benzene

2
1
6
6
3
2
3
6
2
6

2
2
8
12
6
4
8
6
6
6

Acetone
Palmitic acid
Cyclohexane
Ethylene
Ethanol
Methanol
Ethane
Methane

3
16
6
2
2
1
2
1

6
32
12
4
6
4
6
4

Anaerobic Wastewater Treatment 10

Anaerobic Wastewater Treatment 11

Calculating the Theoretical Methane Production

Theoretical methane production depends on:
- the biodegradability of the substrate
- the oxidation state of the organic compound
Oxidation state of
biodegradable compound:

CnHaObNd
Oxidation state:
+a
- 2b

2b + 3d - a
n

- 3d

Anaerobic Wastewater Treatment 12

Theoretical CH4 / CO2 production of

various organic compounds

COMPOSITION OF THE BIOGAS

100 CH4
0 CO
2

Methanol, Methylamine
Fats
Algae, Bacteria
Proteins

50

CH4
CO

Carbohydrates, Acetic acid

Citric acid

Formic acid, Carbon monoxide

Oxalic acid

0 CH4
100 CO
2

Urea

-4

-2

MEAN OXIDATION STATE OF CARBON

Anaerobic Wastewater Treatment 13

Methane Production from CnHaObNd

Basic principles:
- part of C will be completely reduced (CH4)
- the other part of the C will be completely oxidized (CO2)
- N and O stay completely reduced
- the average oxidation state of C stays the same

Anaerobic Wastewater Treatment 14

Methane Production from CnHaObNd

Assumption:
- fraction X of C goes to reduced CH4 (oxidation state C = -4)
- fraction (1-X) of C goes to oxidised CO2 (oxidation state C = +4)

Since the oxidation

state does not change:

-4X + 4(1-X) =

2b + 3d - a
n

x = (a - 2b - 3d)/8n + 4/8
Anaerobic Wastewater Treatment 15

Methane Production from CnHaObNd

so CnHaObNd is converted in:
n.x.CH4
n. (1-x).CO2
d NH3
substitution of x gives:
...

x = (a - 2b - 3d)/8n + 4/8
Anaerobic Wastewater Treatment 16

Methane Production from CnHaObNd

C n H a Ob N d

n X CH4 + n (1-X) CO2 + d NH3

(n/2 + a/8 b/4 3d/8) CH4

(n/2 a/8 + b/4 + 3d/8) CO2

Buswells formula

x = (a - 2b - 3d)/8n + 4/8
Anaerobic Wastewater Treatment 17

Buswells formula
Theoretical CH4-yield for a compound CnHaObNd follows from:
CnHaObNd + (n a/4 b/2 + 3d/4) H2O
(n/2 + a/8 b/4 3d/8) CH4 + (n/2 a/8 + b/4 + 3d/8) CO2 + d NH3
Actual methane production differs owing to:
- Limited biodegradability of compounds
- Part of organic matter is used for cell growth (bacterial yield)
- Possible presence of alternative electron acceptors
- High solubility of CO2 / HCO3- in the water fraction
(influences ratio CO2/CH4, not CH4 production)

Anaerobic Wastewater Treatment 18

Anaerobic Wastewater Treatment 19

COD consumed by alternative electron acceptors

Required COD to be calculated from complete reduction reaction
1. COD oxidation with sulphate

COD SO4 H 2 S CO2

8e S 6 S 2
2

2. COD oxidation with sulphite

3. COD oxidation with nitrate

Stochiometric calc.:

COD SO3 H 2 S CO2

6e S 4 S 2
COD 2 NO3 N 2 CO2
5e N 5 N 0

1 mol SO421g SO421 g SO321 g NO31 g NO3- -N

~2 mol O2
=> 0.67 g COD
=> 0.6 g COD
=> 0.65 g COD
=> 2.86 g COD
Anaerobic Wastewater Treatment 20

10

pH and the CO2 fraction in the biogas

CH3COOH CH3COO- + H+

1.0
0.9

At neutral pH:

0.8
0.7

CH3COO- + H2O
CH4 + HCO3-

Propionate

0.6

Butyrate
Acetate

0.5
0.4
0.3

At low pH:

0.2

CH3COOH CH4 + CO2

0.1
0

pH
Anaerobic Wastewater Treatment 21

Metabolism generated alkalinity from protein degradation:

decrease in biogas CO2
CnHaObNd + (n - a/4 - b/2 + 3d/4) H2O
(n/2 + a/8 - b/4 - 3d/8) CH4 + (n/2 - a/8 + b/4 + 3d/8) CO2 + d NH3

+
H2O OH- + H+

d NH4+
CO2 + H2O H2CO3 H+ + HCO3Anaerobic Wastewater Treatment 22

11

Theoretical CH4 / CO2 production of

various organic compounds
Actual production depends on
overall wastewater characteristics !

COMPOSITION OF THE BIOGAS

100 CH4
0 CO
2

Methanol, Methylamine
Fats
Algae, Bacteria
Proteins

50

CH4
CO

Carbohydrates, Acetic acid

Citric acid

Formic acid, Carbon monoxide

Oxalic acid

0 CH4
100 CO
2

Urea

-4

-2

MEAN OXIDATION STATE OF CARBON

Anaerobic Wastewater Treatment 23

Theoretical CH4 / CO2 production

based on COD/TOC ratio
120.00
+2

+4

CH4 in biogas (%)

100.00

C mean oxidation state

CH4
Ethane

80.00
60.00

-4

-2

Methanol, ethanol
Palmitic acid
Acetone

Benzene, ethylene glycol

Glycerine, phenol
Betaine (trimethyl glycine)
Acetate, glucose, lactic acid
Phenyl alanine
Insuline

40.00

Citric acid, Glycine

Formic acid

20.00

Oxalic acid

0.00 CO2
0.00

1.00

2.00

3.00

4.00

5.00

6.00

COD/TOC ratio

Expected CH4 %in biogas: 18.75 x COD/TOC

Anaerobic Wastewater Treatment 24

12

Anaerobic Wastewater Treatment 25

Conversion CH4 production - COD

The oxidation of CH4 requires 2 moles of O2:
CH4 + 2 O2 CO2 + 2H2O
x = (a - 2b - 3d)/8n + 4/8
Since the fraction X of the compound CnHaObNd that will go to CH4,
The COD of compound CnHaObNd is 2 fraction X mol O2/l or:
2 (n/2 + a/8 b/4 3d/8) mol O2/l
The overall oxidation state of organic compounds will not
change during anaerobic conversion:
A COD balance can be made: COD-in = COD-out
Anaerobic Wastewater Treatment 26

13

COD-Balance
COD gas

Anaerobic
reactor

COD influent

COD effluent

COD sludge
CODinfluent = CODeffluent + CODgas + CODsludge
Balance always fits !!!
Anaerobic Wastewater Treatment 27

Measurable COD fractions in various compartments

COD influent:

- COD soluble
- COD solids
- COD colloidal

COD effluent:

- COD soluble organic

- COD soluble inorganic (e.g. H2S)
- COD solids
- COD dissolved reduced gases

COD gas:

- COD CH4
- COD H2S
- COD H2

COD sludge:

- COD entrapped solids

- COD newly grown biomass
- COD entrapped
Anaerobic Wastewater Treatment 28

14

Working with the COD Balance

COD equivalents in produced gas:
1 mol CH4 = 2 mol O2
22.4 l (STP) CH4 = 64 g O2 or 64 g COD
1 l CH4 (STP) = 64/22.4 = 2.86 g COD
Or: 1 g COD = 0.35 l CH4 (STP)
COD equivalents in sludge:
1 g sludge - VSS = 1.42 g COD
(based on heterotrophic biomass:
C5H7O2N 113 g VSS per mol X)

Question: what is the biogas and sludge production in a UASB treating

sugar mill wastewater: - Q = 500 m3/day
- COD = 3.5 kg/m3
- Sludge Yield = 10%
- Efficiency = 90%
Anaerobic Wastewater Treatment 29

Set up COD Balance

Balance: 1750 - 175 -175 = 1400 kg COD/dag
= 1400/2.86 = 489,5 m3 CH4/dag

3.5 * 500
= 1750 kg COD/day

Anaerobic
reactor

90% efficiency
= 10% in effluent
= 175 kg COD/day

10% sludge Yield:

175 kg sludge COD/day
123 kg VSS/day

Anaerobic Wastewater Treatment 30

15

Anaerobic Wastewater Treatment 31

CH4/CO2 ratio
What kind of biogas composition do you expect?
(Consider sucrose as main component C12H22O11)
X = (a 2b 3d)/8n + 4/8 = (22-2*11-0)/(8*12) + 4/8 = 0.5
The composition is 50% CH4 and 50% CO2
Why CH4 content will be higher in practice?

Anaerobic Wastewater Treatment 32

16

Dimensioning
What should be the size of the UASB reactor to treat the water?
Use the following equations and assumptions:
- reactor volume: Vr=CQi/Rv
- Volumetric loading rate Rv=10 kg COD/m3/day
- Minimum hydraulic retention time min = 8 h = Vr/Qi

reactor volume: Vr=CQi/Rv = 3.5*500/10 = 175 m3

Minimum hydraulic retention time min = 8 h

= 175/500 = 0,35 days = 8.4 hrs > min
so Vr is 175 m3

Anaerobic Wastewater Treatment 33

Anaerobic Wastewater Treatment 34

17

Factors that affect the applicability of

anaerobic treatment

Composition and fluctuations of organic compounds (SS,

biodegradability)
Waste water strength + fluctuations
Temperature + fluctuations
Availability of nutrients (N, P, micro-nutrients)
Buffer capacity / pH
Presence of alternative electron acceptors (SO4--, NO3-, etc.)
Risk of formation of inorganic precipitates
Risk of formation of scum layers and/or flotation layers
Presence of toxic compounds
Odor problems
Anaerobic Wastewater Treatment 35

Factors that affect the applicability of

anaerobic treatment

Composition and fluctuations of organic compounds (SS,

biodegradability)
Waste water strength + fluctuations
Temperature + fluctuations
Availability of nutrients (N, P, micro-nutrients)
Buffer capacity / pH

Presence of alternative electron acceptors (SO4--, NO3-, etc.)

Risk of formation of inorganic precipitates

Risk of formation of scum layers and/or flotation layers
Presence of toxic compounds
Odor problems
Anaerobic Wastewater Treatment 36

18

Impact of SO42- on the COD Balance

The same effluent also contains 0.2 kg SO42-/m3.
What will be the biogas production under these conditions?

COD SO4

H 2 S CO2

8e S 6 S 2

1 mol SO42- ~ 2 mol O2

2 mol of COD (64 g)

Per g SO42-, 0.67 g COD will be oxidized:

0.2 kg/m3 * 500 m3/day = 100 kg SO42- / day and thus
67 kg COD consumption
This gives 1400-67=1333 kg CH4-COD/day produced = 466 m3 CH4/day
(and 22,4 m3 of H2S if solubility is 0.015 g/L)
Anaerobic Wastewater Treatment 37

Factors that affect the applicability of

anaerobic treatment

Composition and fluctuations of organic compounds (SS,

biodegradability)
Waste water strength + fluctuations
Temperature + fluctuations
Availability of nutrients (N, P, micro-nutrients)

Buffer capacity / pH

Presence of alternative electron acceptors (SO4--, NO3-, etc.)

Risk of formation of inorganic precipitates
Risk of formation of scum layers and/or flotation layers
Presence of toxic compounds
Odor problems
Anaerobic Wastewater Treatment 38

19

Effects of pH on anaerobic digestion

Direct

effect on enzyme activity

(charge / tertiary structure of proteins)

Indirect

affecting toxicity of various compounds (H2S, NH3, VFA)

affecting the availability of nutrients

(e.g. by affecting the solubility)

affecting the availability of substrates (e.g. at pH<6.1, milk

proteins coagulate which makes them less available)

affecting the availability of CO2

(very low pCO2 at pH>8.0.)
Anaerobic Wastewater Treatment 39

pH range methane digestion

Hydrolysis
Acidogenesis
Acetogenesis
Methanogenesis
acetate
hydrogen
4

Anaerobic Wastewater Treatment 40

20

Buffer systems
Buffering capacity: capacity of solution to resist pH changes (e.g. added
H+ will be neutralised by buffer system)
N.B.:term for buffering capacity with respect to acids: alkalinity,
Especially brought by bicarbonate

Buffer system is usually brought by: mixture of weak acid and its conjugate
base. The optimum pH of a buffer depends on the pKa/pKb value of the
acid/base applied

Anaerobic Wastewater Treatment 41

Buffers in AWWT
Useful buffers are active in the neutral pH range (6 8).

H 2CO3 / HCO3 / CO3

pKa = 6.3

pKa = 10.3

H 2 PO4 / HPO4

pKa = 7.2

pH = pKa + log (A-/ HA)

NaAc / HAc
pKa = 4.8

NH4 / NH3
pKa = 9.3

H2 S / HS
pKa = 7.1

Anaerobic Wastewater Treatment 42

21

Bicarbonate alkalinity
Bicarbonate is generated in the digestion process itself (metabolism
generated alkalinity)

CH3COO- Na+ CH4 + HCO3If a solution of 5 g NaAc is digested the produced alkalinity is 5/82 = 60
mmol or 60 meq HCO3-.

Anaerobic Wastewater Treatment 43

Metabolism Generated Alkalinity

(digestion of protein)
C3H7O2N 2H2O CH4 2CO2 NH3

C3H7O2N 2H2O CH4 CO2 HCO3 NH4

(pH = 7)

Assume wastewater contains 2 g/l proteins (~C3H7O2N)

MW= 89 g
1 mole C3H7O2N => 1 mole NH4+-N
2/89 mole =>2/89 mole NH4+-N, or 22 mmole or 22 meq NH4+-N
This will bind 22 meq HCO3Anaerobic Wastewater Treatment 44

22

HENRYS LAW

CO2 (g)
CCO2(l) = H .
PCO2

CO2 (l)
+
H2O

CO3- + 2
H+

H2CO3

HCO3- +
H+
Anaerobic Wastewater Treatment 45

PREDICTING THE pH

Ka

[H ] [HCO3 ]
[H2CO3*]

[H2CO3*]

[H2CO3*] KH PCO2

[H ]

[H ] [HCO3 ]
KH PCO2
Ka

KH PCO2 Ka

[HCO3 ]

Where; KH=(H*R*T)-1= henrys constant (M atm-1)

H=henrys factor =[CO2]g/[H2CO3]aq=1.2
R=0.082057 atm deg-1M-1
T= degrees Kelvin (C+273)
PCO2= partial pressure CO2 atm= (%CO2)/100
Ka= dissociation constant H2CO3=10-6.3
[HCO3 -]=bicarbonate alkalinity (M)=[ALK]-[VFA]
Anaerobic Wastewater Treatment 46

23

[ HCO3 ]

K H PCO2 Ka
[H ]

Anaerobic Wastewater Treatment 47

Factors that affect the applicability of

anaerobic treatment

Composition and fluctuations of organic compounds (SS,

biodegradability)
Waste water strength + fluctuations

Temperature + fluctuations

Availability of nutrients (N, P, micro-nutrients)

Buffer capacity / pH
Presence of alternative electron acceptors (SO4--, NO3-, etc.)
Risk of formation of inorganic precipitates
Risk of formation of scum layers and/or flotation layers
Presence of toxic compounds
Odor problems
Anaerobic Wastewater Treatment 48

24

Temperature
Affects metabolic activity of bacteria
Affects transfer and solubility of gases
Affects settleability of biological solids
Reaction decreases with decreasing temperature (Arrhenius)
Final degradation extent is proportional to temperature

Anaerobic Wastewater Treatment 49

Bacterial Classification on Growth

Temperature
I
II
III

psychrophilic
mesophilic
thermophilic

<20C
20-40 C
>45C

(arbitrary borders)

Anaerobic Wastewater Treatment 50

25

Digestion rate at mesophilic temperatures

Anaerobic Wastewater Treatment 51

Differences in growth rate mesophiles thermophiles

Anaerobic Wastewater Treatment 52

26

Temperature effects on immobilized sludge systems

- Maximum activity determined by

mass transfer limitation
- Under optimum conditions only outer
layer is active
- Decrease in temperature affects
bacterial conversion rate but
granule activity is not affected
35C
30C
25C

S
d
Anaerobic Wastewater Treatment 53

Anaerobic Wastewater Treatment 54

27