Anaerobic Wastewater Treatment

3 – Basic Calculations
Prof.Dr.ir. Jules B. van Lier
16-19 July 2012

Learning Objectives

1. What is COD
2. Meaning of COD/TOC ratio
3. Assessing COD mass balance
4. Predicting biogas and CH4 productions based on influent
characteristics
5. Basic calculations on reactor dimensioning
6. Basic calculations on reactor performance

COD Mass Balance 2

1
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:
+a
(2b + 3d - a)/n -2b
-3d
COD Mass Balance 3

What is 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 + ¼ (4n+a-2b-3d) O2 
n CO2 + ½(a-3d) H2O + d NH3
1 O2 accepts max. 4 electrons

COD Mass Balance 4

2
Chemical Oxygen Demand (COD)
In the standardized COD test with bichromate as oxidizer (150°C) almost
all organic compounds

CnHaObNd

are completely converted in CO2 and H2O

But: organic N stays reduced and is converted in NH3

(similar to ‘O’)

The required number of O2 molecules for the complete

oxidation is (no NOx produced):

CnHaObNd + ¼ (4n+a-2b-3d) O2 
n CO2 + ½(a-3d) H2O + d NH3
COD Mass Balance 5

Chemical Oxygen Demand (COD)

1 “mol” of organic matter demands:

¼ (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 + ¼ (4n+a-2b-3d) O2 
n CO2 + ½(a-3d) H2O + d NH3

COD Mass Balance 6

3
 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

COD Mass Balance 7

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)

Compound n a b g COD g TOC COD/TOC
(g CnHaOb) (g CnHaOb) ratio
Oxalic acid 2 2 4 0.18 0.27 0.67
Formic acid 1 2 2 0.35 0.26 1.33
Citric acid 6 8 7 0.75 0.38 2.00
Glucose 6 12 6 1.07 0.40 2.67
Lactic acid 3 6 3 1.07 0.40 2.67
Acetic acid 2 4 2 1.07 0.40 2.67
Glycerine 3 8 3 1.22 0.39 3.11
Phenol 6 6 1 2.38 0.77 3.11
Ethylene glycol 2 6 2 1.29 0.39 3.33
Benzene 6 6 0 3.08 0.92 3.33
Acetone 3 6 1 2.21 0.62 3.56
Palmitic acid 16 32 2 3.43 0.75 3.83
Cyclohexane 6 12 0 3.43 0.86 4.00
Ethylene 2 4 0 3.43 0.86 4.00
Ethanol 2 6 1 2.09 0.52 4.00
Methanol 1 4 1 1.50 0.38 4.00
Ethane 2 6 0 3.73 0.80 4.67
Methane 1 4 0 4.00 0.75 5.33

COD Mass Balance 8

4
 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 + 3d - a
- 2b
n
- 3d

COD Mass Balance 9

Theoretical CH4/CO2 production of various

organic compounds

100 CH4
0 CO
COMPOSITION OF THE BIOGAS

2
Methanol, Methylamine

Fats

Algae, Bacteria
Proteins
CH4 Carbohydrates, Acetic acid
50
CO
Citric acid
2

Formic acid, Carbon monoxide

Oxalic acid

Urea
0 CH4
100 CO
-4 -2 0 2 4
2

MEAN OXIDATION STATE OF CARBON

COD Mass Balance 10

5
 Methane production from CnHaObNd

Methane Production from CnHaObNd

Basic principles:

- part of C will be completely oxidized

- the other part of the C will be completely reduced
- N and O stay completely reduced
- the average oxidation state of C stays the same

COD Mass Balance 11

Methane production from CnHaObNd

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

Since the oxidation 2b + 3d - a

-4X + 4(1-X) =
state does not change: n

x = (a - 2b - 3d)/8n + 4/8

COD Mass Balance 12

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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

COD Mass Balance 13

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

Buswell’s formula

x = (a - 2b - 3d)/8n + 4/8

COD Mass Balance 14

7
 Buswell’s 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

COD Mass Balance 15

COD ‘consumed’ by alternative electron acceptors

Required COD to be calculated from complete reduction reaction
1. COD oxidation with sulphate COD  SO 2  H S  CO
4 2 2

8e  S 6  S 2
2
2. COD oxidation with sulphite COD  SO3  H 2 S  CO2
6e  S 4   S 2 

COD  2 NO3  N 2  CO2

3. COD oxidation with nitrate
5e  N 5  N 0
Stochiometric calc.: 1 mol SO42- ~2 mol O2
1g SO42- => 0.67 g COD
1 g SO32- => 0.6 g COD
1 g NO3—N => 20/7 g COD = 2.86 g COD
(1 g NO3 => 0.65 g COD)
COD Mass Balance 16

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Ratio of unionised VFA to total VFA as a
function of pH
CH3COOH  CH3COO- + H+
1.0
0.9
0.8 At neutral pH:
0.7
Propionate CH3COO- + H2O
0.6
Butyrate  CH4 + HCO3-
0.5 Acetate
0.4
0.3 At low pH:
0.2
CH3COOH  CH4 + CO2
0.1

0
4 5 6 7 8 9

pH

COD Mass Balance 17

Metabolism generated alkalinity

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+ + HCO3-

COD Mass Balance 18

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 Theoretical CH4/CO2 production of various
organic compounds
Actual production depends on
100 CH4
overall wastewater characteristics !
0 CO2
COMPOSITION OF THE BIOGAS

Methanol, Methylamine

Fats

Algae, Bacteria
Proteins
CH4 Carbohydrates, Acetic acid
50
CO2
Citric acid

Formic acid, Carbon monoxide

Oxalic acid

Urea
0 CH4
100 CO2
-4 -2 0 2 4

MEAN OXIDATION STATE OF CARBON

COD Mass Balance 19

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)

Compound n a b g COD g TOC COD/TOC
(g CnHaOb) (g CnHaOb) ratio
Oxalic acid 2 2 4 0.18 0.27 0.67
Formic acid 1 2 2 0.35 0.26 1.33
Citric acid 6 8 7 0.75 0.38 2.00
Glucose 6 12 6 1.07 0.40 2.67
Lactic acid 3 6 3 1.07 0.40 2.67
Acetic acid 2 4 2 1.07 0.40 2.67
Glycerine 3 8 3 1.22 0.39 3.11
Phenol 6 6 1 2.38 0.77 3.11
Ethylene glycol 2 6 2 1.29 0.39 3.33
Benzene 6 6 0 3.08 0.92 3.33
Acetone 3 6 1 2.21 0.62 3.56
Palmitic acid 16 32 2 3.43 0.75 3.83
Cyclohexane 6 12 0 3.43 0.86 4.00
Ethylene 2 4 0 3.43 0.86 4.00
Ethanol 2 6 1 2.09 0.52 4.00
Methanol 1 4 1 1.50 0.38 4.00
Ethane 2 6 0 3.73 0.80 4.67
Methane 1 4 0 4.00 0.75 5.33

COD Mass Balance 20

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Theoretical CH4/CO2 production based on
COD/TOC ratio
120.00
+4 +2 0 -2 -4
100.00 “C” mean oxidation state CH4
CH4 in biogas (%)

Ethane
80.00
Methanol, ethanol
Palmitic acid
Benzene, ethylene glycol Acetone
60.00 Glycerine, phenol Betaine (trimethyl glycine)
Acetate, glucose, lactic acid Phenyl alanine
Insuline
40.00
Citric acid, Glycine

20.00 Formic acid

Expected CH4 % = 18.75 x COD/TOC
Oxalic acid (Provided no organic S compounds present)
0.00 CO2
0.00 1.00 2.00 3.00 4.00 5.00 6.00
COD/TOC ratio

COD Mass Balance 21

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 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

COD Mass Balance 22

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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)

COD Mass Balance 23

COD-Balance
COD gas

Anaerobic
COD influent COD effluent
reactor

COD sludge

CODinfluent = CODeffluent + CODgas + CODsludge

Balance always fits !!!

COD Mass Balance 24

12
 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

COD Mass Balance 25

Cálculos básicos
Conversiones útiles

 DQO del metano

CH4 + 2 O2  CO2 + 2 H20

16 g CH4 se oxidan con 64 g O2

1 g CH4  4 g O2

“1 g de metano tiene una DQO de 4 g”

COD Mass Balance 26

26

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Cálculos básicos
Conversiones útiles

 DQO del ácido acético/acetato

CH3COOH + 2O2  2CO2 + 2H20

se oxidan con
60 g AcH  64 g O2
1 g AcH (1 g Ac)  1.067 g O2

“1 g de ácido acético (acetato) tiene una

DQO de 1.067 g”

COD Mass Balance 27

Cálculos básicos
Conversiones útiles

 Producción de biogás

CH3COOH  CH4 + CO2

producen

64 g COD-AcH  16 g CH4 (1 mol)  22.4 L CH4 (STP)

1 g COD-AcH  0.350 L (STP)

“1 kg de DQO convertida produce 350 L de metano en CNPT”

COD Mass Balance 28

Lettinga Associates Foundation 28

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Cálculos básicos
Conversiones útiles
 Volumen de gas a DQO
Temperatura (°K) = 303
Temperatura normal (°K) = 273
Presión (atm) = 1
Volumen molar de un gas (L) = 22.4
Masa molar CH4 (g/mol) = 16
DQO de 1 mol CH4 (g DQO) = 64
Factor (g DQO-CH4/mL CH4 condiciones reales) = 0.00257
Factor (kg DQO-CH4/m3 CH4 condiciones reales) = 2.57

= 273/303*1*16/(22.4*1000)*64/16 = 0.00257 g DQO-CH4 CNPT/mL

COD Mass Balance 29

Lettinga Associates Foundation 29

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% COD Mass Balance 30

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