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
6
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
8
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
9
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
10
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
11
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
13
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
14
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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