Material and Energy Balance for a Fermenter

BT2061: Biochemical Thermodynamics

M. Hamsa Priya

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What is a bioreactor or fermenter?

M. Hamsa Priya BT2061:Fermenter 2 / 22

What is a bioreactor or fermenter?
A reactor in which microbes (bacteria or yeast) act on an organic material
(substrate) to produce additional microbes (biomass) and other desired
and undesired products

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 Material Balance

Material Balance for a Fermenter

Can you write a material balance (mass or molar balance) equation

for biomass?

M. Hamsa Priya BT2061:Fermenter 3 / 22

 Material Balance

Material Balance for a Fermenter

Can you write a material balance (mass or molar balance) equation

for biomass?
What information is needed?

M. Hamsa Priya BT2061:Fermenter 3 / 22

 Material Balance

Material Balance for a Fermenter

Can you write a material balance (mass or molar balance) equation

for biomass?
What information is needed?
How to calculate the rate of generation of biomass?

M. Hamsa Priya BT2061:Fermenter 3 / 22

 Material Balance

Material Balance for a Fermenter

Can you write a material balance (mass or molar balance) equation

for biomass?
What information is needed?
How to calculate the rate of generation of biomass?
One needs to know the stoichiometric chemical equation for biomass
generation!

M. Hamsa Priya BT2061:Fermenter 3 / 22

 Material Balance

Material Balance for a Fermenter

Can you write a material balance (mass or molar balance) equation

for biomass?
What information is needed?
How to calculate the rate of generation of biomass?
One needs to know the stoichiometric chemical equation for biomass
generation!
What is the stoichiometric formula for glucose?

M. Hamsa Priya BT2061:Fermenter 3 / 22

 Material Balance

Material Balance for a Fermenter

Can you write a material balance (mass or molar balance) equation

for biomass?
What information is needed?
How to calculate the rate of generation of biomass?
One needs to know the stoichiometric chemical equation for biomass
generation!
What is the stoichiometric formula for glucose?
What is the stoichiometric formula for biomass?

M. Hamsa Priya BT2061:Fermenter 3 / 22

 Material Balance

Material Balance for a Fermenter

Can you write a material balance (mass or molar balance) equation

for biomass?
What information is needed?
How to calculate the rate of generation of biomass?
One needs to know the stoichiometric chemical equation for biomass
generation!
What is the stoichiometric formula for glucose?
What is the stoichiometric formula for biomass?
Chemical composition of substrate (mixed organic waste) and some
products are also not well defined
Material balance and other thermodynamic analysis of a fermenter is
thus complicated

M. Hamsa Priya BT2061:Fermenter 3 / 22

 Material Balance

Material Balance for a Fermenter

Roels average biomass expression: CH1.8 O0.5 N0.2

Due to complex chemical composition of biomass, some substrates
and products, mass balance for bioreactors are usually done for each
atomic element.
Each chemical species is represented on C-mole basis
For example, 1 mole of CH3 COOH is represented as CH2 O

M. Hamsa Priya BT2061:Fermenter 4 / 22

 Material Balance

Exercise Problem

Fermentation of carbon monoxide in aqueous solution using the

bacterium Methylotrophicum to produce acetic acid, butyric acid, and
additional cell is represented as

CO + xO2 +yN2 + zH2 O → 0.52CO2 + 0.21CH3 COOH+

0.006CH3 CH2 CH2 COOH + 0.036C − mole cells.

How many moles of oxygen, nitrogen, and water are consumed for
each mole of carbon monoxide consumed?
Note: Use Roels average biomass expression for cells.

M. Hamsa Priya BT2061:Fermenter 5 / 22

 Material Balance

Exercise Problem

Fermentation of carbon monoxide in aqueous solution using the

bacterium Methylotrophicum to produce acetic acid, butyric acid, and
additional cell is represented as

CO + xO2 +yN2 + zH2 O → 0.52CO2 + 0.21CH3 COOH+

0.006CH3 CH2 CH2 COOH + 0.036C − mole cells.

How many moles of oxygen, nitrogen, and water are consumed for
each mole of carbon monoxide consumed?
Note: Use Roels average biomass expression for cells.
Write C-balance; O-balance; N-balance and H-balance

M. Hamsa Priya BT2061:Fermenter 5 / 22

 Material Balance

Exercise Problem

Fermentation of carbon monoxide in aqueous solution using the

bacterium Methylotrophicum to produce acetic acid, butyric acid, and
additional cell is represented as

CO + xO2 +yN2 + zH2 O → 0.52CO2 + 0.21CH3 COOH+

0.006CH3 CH2 CH2 COOH + 0.036C − mole cells.

How many moles of oxygen, nitrogen, and water are consumed for
each mole of carbon monoxide consumed?
Note: Use Roels average biomass expression for cells.
Write C-balance; O-balance; N-balance and H-balance
CO+0.0068O2 + 0.0036N2 + 0.4764H2 O →
0.52CO2 + 0.21CH3 COOH+
0.006CH3 CH2 CH2 COOH + 0.036C − mole cells.

M. Hamsa Priya BT2061:Fermenter 5 / 22

 Material Balance

Yield Factors

Stoichiometric equation for the reaction in a bioreactor is usually

written for 1 mole of substrate, say CO in the example
The stoichiometric coefficients are defined as yield factors
Yield factor for biomass produced per mole of substrate consumed,
YB/S is defined as

Number of C − moles of biomass produced

YB/S =
Number of C − moles of substrate consumed
In the example problem, YB/S = 0.036

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 Material Balance

Yield Factors

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 Material Balance

Yield Factors

For fermentation of carbon monoxide problem, the stoichiometric

equation in terms of yield factors is

CO+YO2 /S O2 + YN2 /S N2 + YW/S H2 O →

YC/S CO2 + YCH2 O/S CH3 COOH+
YCH2 O0.5 /S CH3 CH2 CH2 COOH + YB/S C − mole cells.

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 Material Balance

Steady State Mass Balance Equations

M. Hamsa Priya BT2061:Fermenter 9 / 22

 Material Balance

Steady State Mass Balance Equations

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 Material Balance

Steady State Mass Balance Equations

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 Material Balance

Steady State Mass Balance Equations

Carbon Balance:
0 = (ṄS )1 +(ṄN )1 ·CN −(ṄS )3 −(ṄN )3 ·CN −(ṄB )3 −(ṄP )3 ·CP −(ṄC )4
Simplified expression:
1 + YN/S · CN = YB/S + YP/S · CP + YC/S

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 Material Balance

Steady State Mass Balance Equations

Hydrogen Balance:

HS + YN/S · HN + YW/S · 2 = YB/S · HB + YP/S · HP

Nitrogen Balance:

NS + YN/S · NN = YB/S · NB + YP/S · NP

Oxygen Balance:

OS + YN/S · ON + 2 · YO2 /S + YW/S = 2 · YC/S + YB/S · OB + YP/S · OP

Use of yield factors, simplifies the balance equation

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 Material Balance

Energy balance for a Fermenter

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 Material Balance

Energy balance for a Fermenter

General Energy Balance Equation:

dU X dV
= Ṅk Hk + Q̇ + Ẇs − P
dt dt
k

Under steady state condition

0; s.s 0; s.s
dU
7 X dV

 = Ṅk Hk + Q̇ + Ẇs − P
dt k
dt

Hk refers to molar enthalpy for stream k, each stream is a mixture of

multiple chemical compounds
For mixtures, molar enthalpy of a stream is written as a linear
combination of partial molar properties of the constituents species

M. Hamsa Priya BT2061:Fermenter 15 / 22

 Material Balance

Energy balance for a Fermenter

Assumptions to solve energy balance equation for a fermenter
Partial molar enthalpies can be replaced by pure-component enthalpies,
as the effect of solution non-idealities on the enthalpy is small
compared with the very much larger heats of reactions
Temperature of the streams entering and leaving the fermenter are the
same
Unless the solution is very viscous, the energy input from stirring is
small compared with the heat of reaction
With these assumptions, the energy balance for the fermenter can be
written as
h i h i
0 = (ṄS )1 − (ṄS )3 HS + (ṄN )1 − (ṄN )3 HN − (ṄB )3 HB +
h i h i
(ṄW )1 − (ṄW )3 HW + (ṄO2 )2 − (ṄO2 )4 HO2 − (ṄP )3 HP +
h i
(ṄN2 )2 − (ṄN2 )4 HN2 − (ṄCO2 )4 HCO2 + Q̇

M. Hamsa Priya BT2061:Fermenter 16 / 22

 Material Balance

Energy balance for a Fermenter

Recollecting the concept of yield factor, the energy balance equation

can be simplified as

HS + YN/S HN + YO2 /S HO2 + YW/S HW + YN2 /S HN2 + YQ/S

= YB/S HB + YP/S HP + YCO2 /S HCO2

where,
Q̇
YQ/S =
(ṄS )1 − (ṄS )3
Note the enthalpies of oxygen, nitrogen, carbon dioxide and water are
on a per-mole basis, while that of the substrate, the product, and the
biomass are on a per C-mole basis.

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 Material Balance

Molar Enthalpy and the Heat of Combustion

Enthalpy of formation data may not be available, especially for the

biochemical species that are not completely defined
Enthalpies can be obtained from heat of combustion
Consider an example of obtaining enthalpy of benzene from
combustion reaction
Combustion Process:

C6 H6 + 7.5O2 → 6CO2 + 3H2 O

Energy Balance for the process is

0 = HC6 H6 + 7.5HO2 − 6HCO2 − 3HH2 O + Q

where, Q = −∆c HC6 H6 (Negative sign because heat of combustion is

usually reported as a positive number)
M. Hamsa Priya BT2061:Fermenter 18 / 22
 Material Balance

Molar Enthalpy and the Heat of Combustion

Note that when using heats of combustion, the reference states are
nitrogen as molecular nitrogen, hydrogen as water, carbon as carbon
dioxide, oxygen as molecular oxygen, and other elements that are
present in their oxidized states e.g., SO2
In this case,
HO2 = 0; HCO2 = 0; HH2 O = 0; HC6 H6 = ∆c HC6 H6

M. Hamsa Priya BT2061:Fermenter 19 / 22

 Material Balance

Molar Enthalpy and the Heat of Combustion

Note that when using heats of combustion, the reference states are
nitrogen as molecular nitrogen, hydrogen as water, carbon as carbon
dioxide, oxygen as molecular oxygen, and other elements that are
present in their oxidized states e.g., SO2
In this case,
HO2 = 0; HCO2 = 0; HH2 O = 0; HC6 H6 = ∆c HC6 H6

How to get heat of combustion for incompletely defined biomass?

M. Hamsa Priya BT2061:Fermenter 19 / 22

 Material Balance

Molar Enthalpy and the Heat of Combustion

Note that when using heats of combustion, the reference states are
nitrogen as molecular nitrogen, hydrogen as water, carbon as carbon
dioxide, oxygen as molecular oxygen, and other elements that are
present in their oxidized states e.g., SO2
In this case,
HO2 = 0; HCO2 = 0; HH2 O = 0; HC6 H6 = ∆c HC6 H6

How to get heat of combustion for incompletely defined biomass?

Hence, the concept of generalized degree of reduction
4Ci + Hi − 2Oi
ξi =
Ci
This tell number of electrons available for transfer to oxygen on
combustion of the compound
M. Hamsa Priya BT2061:Fermenter 19 / 22
 Material Balance

Generalized Degree of Reduction

Generalized degree of reduction for biomass composition CHai Obi Nci

Nitrogen Source Degree of reduction
NH3 4 + ai − 2bi − 3ci
HNO3 4 + ai − 2bi + 5ci
N2 4 + ai − 2bi
Glutamate (C5 H9 NO4 ) 4 + ai − 2bi − 21ci

Actually, degree of reduction is a purely calculatory convention

It has a priori little to do with the valencies of carbon, oxygen,
hydrogen and nitrogen in biomass, but is rather based on the choice
of a convenient linear combination of elemental balances, resulting in
the disappearance of the flows of carbon dioxide, water and the
nitrogen source for the final balance equation

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 Material Balance

Generalized Degree of Reduction

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 Material Balance

Heat of combustion using Generalized Degree of Reduction

General rule of thumb:

kJ
∆c H = 110.9 ξ
C − mole
kJ
∆c G = 112 ξ
C − mole

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