DQO: Balance de masa

Curso Internacional:

Diseo, operacin y mantenimiento

de reactores anaerobios de flujo ascendente
Mrida, Mxico, 10-13 noviembre 2008

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

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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
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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 O)

The required number of O2 molecules for the complete

oxidation is (no NOx produced):
CnHaObNd + (4n+a-2b-3d) O2
n CO2 + (a-3d) H2O + d NH3
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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

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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

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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

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

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

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

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

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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

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COMPOSITION OF THE BIOGAS

Theoretical CH4/CO2 production of various organic compounds

100 CH4
0 CO2
Methanol, Methylamine
Fats
Algae, Bacteria
Proteins

50

CH4
CO2

Carbohydrates, Acetic acid

Citric acid

Formic acid, Carbon monoxide

Oxalic acid

0 CH4
100 CO2

Urea

-4

-2

MEAN OXIDATION STATE OF CARBON

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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

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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

state does not change:

-4X + 4(1-X) =

2b + 3d - a
n

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

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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
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Methane production from CnHaObNd

CnHaObNd

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
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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

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COD consumed by alternative electron acceptors

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

COD + SO4
8e + S

6+

H 2 S + CO2

S 2
2

2. COD oxidation with sulphite

3. COD oxidation with nitrate

Stochiometric calc.:

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COD + SO3 H 2 S + CO2

6e + S

4+

S 2

COD + 2 NO3 N 2 + CO2

5e + N 5+ N 0

1 mol SO42~2 mol O2

1g SO42=> 0.67 g COD
1 g SO32=> 0.6 g COD
1 g NO3N
=> 20/7 g COD = 2.86 g COD
(1 g NO3 => 0.65 g COD)
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Ratio of unionised VFA to total VFA as a function of pH

1.0

+
CH
CH33COOH
COOH
CH
CH33COO
COO-++HH+

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
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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+ + HCO3Lettinga Associates Foundation

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Theoretical CH4/CO2 production of various organic compounds

COMPOSITION OF THE BIOGAS

Actual production depends on

overall wastewater characteristics !
100 CH4
0 CO2
Methanol, Methylamine
Fats
Algae, Bacteria
Proteins

50

CH4
CO2

Carbohydrates, Acetic acid

Citric acid

Formic acid, Carbon monoxide

Oxalic acid

0 CH4
100 CO2

Urea

-4

-2

MEAN OXIDATION STATE OF CARBON

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g COD and g TOC per g organic compound

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

Methane
1
4
0
Ethane
2
6
0
Methanol
1
4
1
Ethanol
2
6
1
Cyclohexane
6
12
0
Ethylene
2
4
0
Palmitic acid
16
32
2
Acetone
3
6
1
Ethylene glycol
2
6
2
Benzene
6
6
0
Betaine*
5
11
2
Glycerine
3
8
3
Phenol
6
6
1
Lysine
6
14
2
Phenyl alanine
9
11
2
Insuline
254
377
75
Glucose
6
12
6
Lacitc acid
3
6
3
Acetic acid
2
4
2
Citric acid
6
8
7
Glycine
2
5
2
Formic acid
1
2
2
Oxalic acid
2
2
4
Carbondioxide
1 Foundation
0
2
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0
0
0
0
0
0
0
0
0
0
1
0
0
2
1
65
0
0
0
0
1
0
0
0

g COD / g
CnHaObNd
4.00
3.73
1.50
2.09
3.43
3.43
3.43
2.21
1.29
3.08
1.64*
1.22
2.38
1.53
1.94
1.45
1.07
1.07
1.07
0.75
0.64
0.35
0.18
0.00

g TOC / g COD/ TOC

CnHaObNd
0.75
5.33
0.80
4.67
0.38
4.00
0.52
4.00
0.86
4.00
0.86
4.00
0.75
3.83
0.62
3.56
0.39
3.33
0.92
3.33
0.51
3.20
0.39
3.11
0.77
3.11
0.49
3.11
0.65
2.96
0.53
2.72
0.40
2.67
0.40
2.67
0.40
2.67
0.38
2.00
0.32
2.00
0.26
1.33
0.27
0.67
0.27
0.00

C-ox.
state
-4.00
-3.00
-2.00
-2.00
-2.00
-2.00
-1.75
-1.33
-1.00
-1.00
-0.80
-0.67
-0.67
-0.67
-0.44
-0.08
0.00
0.00
0.00
1.00
1.00
2.00
3.00
4.00

CH4 %
100
87.5
75
75
75
75
72
67
62.5
62.5
60
58
58
58
56
51
50
50
50
37.5
37.5
25
12.5
0

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Theoretical CH4/CO2 production based on COD/TOC ratio

120.00
+2

+4

CH4 in biogas (%)

100.00
80.00
60.00

-4

-2

C mean oxidation state

CH4
Ethane

Methanol, ethanol
Palmitic acid
Benzene, ethylene glycol
Acetone
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

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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
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COD-Balance
COD gas

COD influent

Anaerobic
reactor

COD effluent

COD sludge
CODinfluent = CODeffluent + CODgas + CODsludge
Balance always fits !!!
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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

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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)

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%
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