Chemical Engineering

Design

2019

Thomas Rodgers
Contents

List of Figures iii

Nomenclature v

1 Material Balances 1
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2 Classification of Process Operations . . . . . . . . . . . . . . . . . . . . 3
1.3 Simple Continuous Process . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4 Reactive, Single Stage Processes . . . . . . . . . . . . . . . . . . . . . . 7
1.5 Processes with Recycle . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

2 Reactor Design 15
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2 Mole Balance for Reactors . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.3 Mole Balance Applied to Plug Flow Reactor . . . . . . . . . . . . . . . . 19

3 Energy Balances 25
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.2 Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.3 Energy balances on non-reacting systems . . . . . . . . . . . . . . . . . 31
3.4 Energy balances involving chemical reactions . . . . . . . . . . . . . . . 34

4 Conversion of Landfill Gas to Town’s Gas 39

4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.2 Process Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.3 Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

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List of Figures

1.1 Mass balance for a simple distillation column. . . . . . . . . . . . . . . . 5

1.2 Recycle stream for reactor . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.3 System boundaries for recycle . . . . . . . . . . . . . . . . . . . . . . . 11
1.4 Example reactor with recycle . . . . . . . . . . . . . . . . . . . . . . . . 12

2.1 Schematic representation of the design of a reactor volume. . . . . . . . . 19

2.2 Schematic representation of a PFR. . . . . . . . . . . . . . . . . . . . . . 20
2.3 Mole balance of component i in a differential segment of ∆V . . . . . . . 20
2.4 Molar flowrate of component A and B as a function of volume in a PFR. . 21

3.1 Enthalpy variation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

3.2 Simple continuous system . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.3 Heating water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.4 Heating water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

4.1 BFD for LFG to TG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

iii
iv
Nomenclature

Roman
C Concentration mol m−3
c Speed of light 3 × 108 m s−1
Cp Specific heat capacity J kg−1 ◦ C−1
E Energy J
G Generation mol s−1
h Specific enthalpy kJ kg−1
k Rate constant varies
ṁ Mass flow rate kg s−1
m Mass kg
Mw Molecular weight −
−3 −1
ṅ Molar flow rate mol m s
N Moles mol
P Pressure Pa
Q Energy J
−1 −1
R Ideal gas constant 8.314 J mol K
r Reaction rate mol s−1
T Temperature K
t Time s
−1
u Specific internal energy kJ kg
V Volume m3
3 −1
v Volumetric flow rate m s
X Conversion −
x Mole fraction (usually liquid phase) −
y Mole fraction (usually vapour phase) −
Greek
ν Stoichiometric coefficient −
ξ Extent of reaction mol

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Chapter 1
Material Balances

Contents
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2 Classification of Process Operations . . . . . . . . . . . . . . . . . . 3
1.3 Simple Continuous Process . . . . . . . . . . . . . . . . . . . . . . . 4
1.3.1 Step 1 - Drawing a Flowchart . . . . . . . . . . . . . . . . . . 4
1.3.2 Step 2 - Setting up the Balance Equations . . . . . . . . . . . . 4
1.4 Reactive, Single Stage Processes . . . . . . . . . . . . . . . . . . . . 7
1.5 Processes with Recycle . . . . . . . . . . . . . . . . . . . . . . . . . 11

1
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 1.1. INTRODUCTION

1.1 Introduction
A balance can be written for any conserved quantity (e.g. total mass, mass of a particular
species, energy, momentum etc.), and the general balance equation has five terms. The
balance equation must be set up for a particular system, the boundaries of which must be
defined.

Question
For example in 2017, 97,100 people moved into the Greater Manchester (the sys-
tem), 46,700 people moved out, 33,700 were born, and 26,200 died. What is the
change in the population of Greater Manchester? The annual change corresponds to
the increase in the population after one year and has units of persons per year.

Our system can be defined as the boundary of Greater Manchester which in 2018
contains 2,690,445 people. The change can be calculated as,
In − Out + Born − Died = Change
97, 100 − 46, 700 + 33, 700 − 26, 200 = 57, 900

In solving this problem we used the general balance equation,

General Balance Equation

Input − Output + Generation − Consumption = Accumulation

   
Enters Leaves      
 through   through  Produced Consumed Build-up
 system  −  system
    +  within  −  within  =  within 

system system system
boundaries boundaries
(1.1)

This is the only equation needed to solve material balance problems. In most cases we can
eliminate some of the terms in the equation. For example if we consider the case of a sys-
tem with no reaction we can eliminate the consumption and generation terms. If we also
assume the process is a steady state, i.e. no change, then there is no accumulation

1.2 Classification of Process Operations

In addition to the terms in the material balance, the way that we set up the material balance
will depend on how the process is operated:
Continuous Operation in which all materials enter and leave continuously throughout
the operating period. Therefore, we do not start with a given amount of material as
there is a continuous flow of feed. We use balance equations on the rates of flow of
material (e.g. rate of input etc.). This is called a differential balance.

c T.L. Rodgers 2019 3

CHAPTER 1. MATERIAL BALANCES

Batch Operation in which materials are put in at a certain time, the process takes place
for some time, and the materials are then removed. In this case, we will use balance
equations between two instants in time. We will thus be balancing the amount of
the accumulated quantity between the beginning and the end of the operation. This
is called an integral balance.
Semi-batch is all other combinations of continuous and batch operation, e.g. Semi-
continuous, Open batch, etc.
Steady State is when a process can be considered to be operating with no change in
variables (i.e. flowrates, compositions, temperatures, and pressures of all streams)
with time. Operations for which this is not true are classified as transient.

1.3 Material Balance for a Simple Continuous Process

Let us consider a process that is continuous and at steady state with no reaction. As stated
above the generation, consumption, and accumulation terms are therefore all zero. This
means that the balance equation, equation 1.1, can be simplified to:

Input = Output (1.2)

1.3.1 Step 1 - Drawing a Flowchart

The first step is to draw a flowchart of the process, with boxes or other symbols to indicate
process operations (reactors, mixers, distillation columns etc.), and lines with arrows to
indicate inputs and outputs. For example, let’s think about a distillation column, which
takes a feed of 2500 kg h−1 of 35 % ethanol and 65 % water. The distillation column
separates this feed into two streams, one of 85 % ethanol with 15 % water and one of 5 %
ethanol with 95 % water.
With this information the streams can be labelled with the amount or flow rate of each
component. To do this we must first choose a basis for the calculation. A basis of calcu-
lation is an amount or flow rate of a stream or component we decide we want to fix (see
Infobox 1). For this example, a sensible basis would be the total flow rate of the feed as
then we don’t need to scale anything. The system can be drawn as in Figure 1.1.

1.3.2 Step 2 - Setting up the Balance Equations

As the process is non-reactive we can set up balance equations simply as equation 1.2.
Balance equations can in principle be set up for each component as well as a total balance.
However, the total balance will be a sum of the component balances, so the number of
independent balances (i.e. the number of simultaneous equations) is equal to the number
of components involved (this is only true for a non-reactive system).
Before we can set up the material balance we must define the system. We do this simply
by drawing its boundaries on the flow diagram, the dashed boundary in Figure 1.1.

4 c T.L. Rodgers 2019

 1.3. SIMPLE CONTINUOUS PROCESS

D kg h−1
0.85 ethanol
0.15 water
2500 kg h−1
0.35 ethanol
0.65 water

B kg h−1
0.05 ethanol
0.95 water

Figure 1.1: Mass balance for a simple distillation column.

We only need to consider the flow of material across the system boundary, and we can
write differential material balances equations for the total mass, ethanol, and water,

Input = Output
Total mass: F = 2500 = D + B
Ethanol: 0.35F = 0.35(2500) = 0.85D + 0.05B
Water: 0.65F = 0.65(2500) = 0.15D + 0.95B

This gives us three equations, with only two unknowns to determine (D & B). However,
one of these equations is redundant. If we sum the last two equations, we obtain the first
equation, i.e. the sum of the mass fractions in each stream being unity. In general for
an operation involving N components, N independent material balance equations can be
obtained. Solving the two simultaneous equations allows calculation of D and B.

Total: 2500 = D + B
B = 2500 − D
Ethanol: 875 = 0.85D + 0.05B
= 0.85D + 0.05 (2500 − D)
= 0.8D + 125
750 = 0.8D

D = 937.5 kg h−1
B = 1562.5 kg h−1

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CHAPTER 1. MATERIAL BALANCES

Infobox 1: Scaling and Basis of Calculation.

Since a material balance can always be scaled, a material balance calculation can be
performed on the basis of any convenient stream amount or flow rate, and the results can
afterwards be converted to units on a time basis. Thus, the first step is always to choose
the basis of calculation. The choice of the basis of calculation is arbitrary; any choice
should lead to a correct solution. However, an appropriate choice may make the problem
simpler to solve.

This means that a balanced flowsheet, for which material balances for all compo-
nents are satisfied, can be scaled up or down. A balanced process can be scaled up or
down by increasing the amount or flow rate of all streams proportionately, while keeping
the composition of all streams constant.

For example: 1 kg of benzene is mixed with 1 kg of toluene to produce 2 kg of

mixture. The composition of the mixture is obviously 50 %w/w benzene and 50 %w/w
toluene.

1 kg C6 H6 2 kg
0.5 kg C6 H6 kg−1
1 kg C7 H8 0.5 kg C7 H8 kg−1

This is a balanced process as the material balances for both components are satisfied.
The process can be scaled up or down and by multiplying the amount or flow rate of each
stream by a constant factor, e.g. multiply by 300,

300 kg C6 H6 600 kg
0.5 kg C6 H6 kg−1
300 kg C7 H8 0.5 kg C7 H8 kg−1

One of the flowrates needs to be known per unit time in order to convert all other flows
to a time basis. For instance, if 500 kg of total feed is to be processed per hour, then the
flowrates can be converted to kg/hr with multiply by 250 hr−1 ,

250 kg hr−1 C6 H6 500 kg hr−1

0.5 kg C6 H6 kg−1
250 kg hr−1 C7 H8 0.5 kg C7 H8 kg−1

6 c T.L. Rodgers 2019

 1.4. REACTIVE, SINGLE STAGE PROCESSES

1.4 Material Balances for Reactive, Single Stage Processes

If reaction occurs, a balance for a species involved in any reaction(s) must include the
generation and/or consumption terms. Conservation of mass is one of the fundamental
laws of the universe, along with conservation of energy, except where nuclear reactions
are involved, in which case mass can be converted to energy via the equation,
E = mc2 (1.3)

Because c is such a large term, a very small amount of mass is converted into vast amounts
of energy - this is why nuclear energy is such an attractive prospect. But in most process
industries, except the nuclear industry, we don’t get nuclear reactions occurring, so we
can take it as fundamentally true that mass is conserved.
When tackling problems which involve reactions we must always perform our balance
with molar quantities and not masses. If data is provided in terms of mass (e.g. compo-
sition as %w/w), the first step is to convert compositions and flows to a molar basis. We
need to use molar quantities as these are balanced across reactions.
Balances can be written for species or for atomic elements. Atomic balances don’t have
generation or consumption as atomic species can’t be created or destroyed in chemical
reactions (see Infobox 2). Species balances must account for any consumption or gener-
ation associated with reactions. This can be achieved either using reaction stoichiometry
or considering an ’extent of reaction’. It is important to note that in a reaction the number
of moles does not have to be conserved.
Consider a simple reaction,
(−νA ) A + (−νB ) B → νC C + νD D

where νA , νB , νC , and νD are called stoichiometric coefficients. Note that stoichiometric

coefficients are negative for reactants and positive for products.

Question
Consider the reaction,

2NH3 + 1.5O2 → N2 + 3H2 O

What are the stoichiometric coefficients for the components in the reaction? Initially
4.8 moles of NH3 and 3.8 moles of O2 are present. Which is the limiting reactant?

The stoichiometric coefficients can be read from the equation, with the reactants
being negative and the products being positive,
νNH3 = −2, νO2 = −1.5, νN2 = 1, νH2 O = 3
The limiting reactant is the reactant that runs out first, i.e. would give the lowest
extent of reaction is completly consumed:
NNH3 ,0 4.8
ξ= = = 2.4
|νN H3 | 2

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CHAPTER 1. MATERIAL BALANCES

Infobox 2: Atomic Balances.

All balances on atomic species take the form input = output since atomic species
can neither be generated or consumed in chemical reactions. It is simplest to carry
out separate species balances for inert stream components (i.e. those not involved in
any reaction) and exclude these species from the atomic balances. The method is best
explained by considering an example.

A furnace, as shown below, burns a mixture of methane (CH4 ) and ethane (C2 H6 )
in air. The composition of the flue gas is measured on a dry basis (ignoring H2 O) and the
amount of water in the flue gas is measured. What is the fraction of methane in the feed
and the amount of air needed?

100 kmol
y mol CH4 mol−1 259.7 kmol H2 O
(1 − y) mol C2 H6 mol−1 Ng kmol flue gas(dry)
Furnace
0.8599 mol N2 mol(dry)−1
Na kmol air 0.1088 mol CO2 mol(dry)−1
0.79 mol N2 mol−1 0.0313 mol O2 mol(dry)−1
0.21 mol O2 mol−1

First set up material balances for all atomic elements involved in the reaction, and species
balances for any non-reacting inerts (N2 in this case). For this problem we set up material
balance equations for C, H, O and N2 . For the input of C into the system we have 1
kmol of C per kmol of CH4 and 2 kmol of C per kmol of C2 H6 . As atomic species are
conserved, there is no generation or consumption, and assuming the process is steady
state the balances become,
Input = Output
C: 1 × 100y + 2 × 100(1 − y) = 1 × 0.1088Ng
H: 4 × 100y + 6 × 100(1 − y) = 2 × 259.7
O: 2 × 0.21Na = 1 × 259.7 + 2 × 0.0313Ng + 2 × 0.1088Ng
N2 : 1 × 0.79Na = 1 × 0.8599Ng
This produces four balance equations,

200 − 100y = 0.1088Ng

600 − 200y = 519.4
0.42Na = 259.7 + 0.2802Ng
0.79Na = 0.8599Ng

The balance equation for H yields immediately the fraction of CH4 in the feed. Solving
the equations gives, y = 0.403, Ng = 1467.8 kmol, and Na = 1597.7 kmol.

Remember: We cannot use an overall balance equation to help solve the problem
as the total number of moles is not conserved in the reaction system.

Note that for atomic balances we do not have to consider what reactions occur or
the reaction stoichiometry.

8 c T.L. Rodgers 2019

 1.4. REACTIVE, SINGLE STAGE PROCESSES

NO2 ,0 3.8
ξ= = = 2.53
|νO2 | 1.5
Thus NH3 would run out first, so is the limiting reactant.

For a general reaction, for each reactant the ratio of the change in the number of moles
present, d Ni , to the stoichiometric coefficient, νi , for the reactant is the same in each
case, and this ratio is called the extent of reaction, ξ,

Extent of Reaction
d Ni Ni,0 − Ni
ξ= = (1.4)
νi νi

The extent of reaction can be used in material balance calculations, if the number of
moles of a species i present before the reaction is Ni,0 , then the number of moles after the
reaction can be found using,
Ni = Ni,0 + νi ξ (1.5)

This can also be written in terms of a molar flow as,

ṅi = ṅi,0 + νi ξ (1.6)

In many cases reactions will not proceed to completion, due to equilibrium limitatons or
reaction kinetics. The conversion is often used as an indication of how far a reaction has
proceeded. Conversion, Xi , is the fraction of a specified reactant which is consumed by
the reaction,

Conversion
d Ni ξνi
Xi = − =− (1.7)
Ni,0 Ni,0

For example, lets think about a reactor with the following reaction taking place,
2NH3 + 1.5O2 → N2 + 3H2 O

Suppose we initially have 10.0 moles of NH3 and 8.0 moles of O2 . If the conversion
of NH3 is 0.75, we can work out how many moles of each of the four species exit the
reactor.
The extent of the reaction can be calulated from the conversion using equation 1.7,
XNH3 nNH3 ,0 (0.75)(10.0)
ξ=− =− = 3.75
νNH3 (−2)

Thus using equation 1.1 where the accumulation is zero due to being at steady state,
produces,
Input + (Generation − Consumption) = Output
NH3 : 10.0 + (ξνNH3 = (3.75)(−2) = −7.50) = 2.50 mol
O2 : 8.0 + (ξνO2 = (3.75)(−1.5) = −5.625) = 2.375 mol
N2 : 0.0 + (ξνN2 = (3.75)(1) = 3.75) = 3.75 mol
H2 O: 0.0 + (ξνH2 O = (3.75)(3) = 11.25) = 11.25 mol

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CHAPTER 1. MATERIAL BALANCES

Question
A furnace, as shown below, burns a mixture of methane (CH4 ) and ethane (C2 H6 ) in
air. The composition of the flue gas is measured on a dry basis (ignoring H2 O) and
the amount of water in the flue gas is measured. Assuming complete combustion,
thus the reactions below, what is the fraction of methane in the feed and the amount
of air needed?
CH4 + 2O2 → CO2 + 2H2 O
C2 H6 + 3.5O2 → 2CO2 + 3H2 O

100 kmol
y mol CH4 mol−1 259.7 kmol H2 O
(1 − y) mol C2 H6 mol−1 Ng kmol flue gas(dry)
Furnace
0.8599 mol N2 mol(dry)−1
Na kmol air 0.1088 mol CO2 mol(dry)−1
0.79 mol N2 mol−1 0.0313 mol O2 mol(dry)−1
0.21 mol O2 mol−1

Input + (Generation − Consumption) = Output

CH4 : 100y + (−1)ξ1 = 0.0
C2 H6 : 100(1 − y) + (−1)ξ2 = 0.0
O2 : 0.21Na + (−2)ξ1 + (−3.5)ξ2 = 0.0313Ng
CO2 : 0.0 + (1)ξ1 + (2)ξ2 = 0.1088Ng
H2 O: 0.0 + (2)ξ1 + (3)ξ2 = 259.7
N2 : 0.79Na + 0.0 = 0.8599Ng

So we have six equations,

100y = ξ1
100(1 − y) = ξ2
0.21Na − 2ξ1 − 3.5ξ2 = 0.0313Ng
ξ1 + 2ξ2 = 0.1088Ng
2ξ1 + 3ξ2 = 259.7
0.79Na = 0.8599Ng

We can solve five of these simultaneous equations for the five unknowns y, ξ1 , ξ2 ,
Na , and Ng .
Giving y = 0.404, ξ1 = 40.4 kmol, ξ2 = 59.6 kmol, Na = 1597.1 kmol, and Ng =
1467.3 kmol.

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 1.5. PROCESSES WITH RECYCLE

1.5 Processes with Recycle

Many chemical processes involve a recycle stream, where unreacted material is separated
from products and returned to the reactor. In order to avoid the build up of inerts in the
recycle stream, a small flow rate purge stream is often removed from the recycle, as in
Figure 1.2.

Feed Reactor Separator Product

Recycle
Purge

Figure 1.2: Recycle stream for a reactor.

The presence of a recycle can complicate material balance calculations as the composition
of the reactor feed will depend on the composition of the reactor output. The solution of
this type of problem is the same as for any multistage process. We can define system
boundaries in a number of different ways, for example Figure 1.3.

Feed Reactor Separator Product

Recycle
Purge

Figure 1.3: Some example system boundaries for a recycle stream for a reactor.

Usually problems of this type can be solved most efficiently using an overall balance along
with a combination of balances around the reactor, separator, mixing point and splitting
point.
The definition of conversion can often cause confusion for problems involving a recycle
stream.
Normally ‘conversion’ refers to the overall conversion i.e.
Reactant consumed in the process
XO = (1.8)
Reactant supplied in the feed

This may be different to the conversion across the reactor, which is sometimes called the
‘conversion per pass’ i.e.
Reactant consumed in reactor
XR = (1.9)
Reactant fed to reactor

Thus the overall conversion is the conversion between the feed and product and the con-
version per pass is the conversion between the inlet and the outlet of the reactor.
Consider a simple problem where a reactant A is fed to a process at a rate of 100 kmol h−1 .
The feed is mixed with a recycle stream and fed to a reactor where a product B is produced

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CHAPTER 1. MATERIAL BALANCES

by the reaction A → B, Figure 1.4. Most of the unreacted A is separated from the reactor
product stream and recycled. If the overall conversion is 90% and the conversion per pass
is 20%, determine the composition and flow rate of all streams, assuming that there is no
B in the recycle stream.
The overall conversion of the system is 0.9, which means that,
XA,O ṅA,1
ξO = −
νA
(0.9)(100)
ξO = − = 90 kmol h−1
(−1)

Therefore the outlet flow rate, ṅ4 is given by,

Output = Input + (Generation − Consumption)

ṅA,4 = ṅA,1 + νA ξO
ṅA,4 = (100) + (−1)(90) = 10 kmol A h−1
ṅB,4 = ṅB,1 + νB ξO
ṅB,4 = (0) + (1)(90) = 90 kmol B h−1

We know that there is no B in the recycle stream, so the amount of B in stream 4 is equal
to stream 3. Also, as there is no B in the recycle or the feed, the flowrate of B in stream 2
is also 0. Therefore we have,
1 2 3 4 5
−1
A kmol h 100 ? ? 10 ?
B kmol h−1 0 0 90 90 0
Now a balance around the reactor can be undertaken based upon the reactor conversion of
0.2,
XA,R ṅA,2
ξR = −
νA
0.2ṅA,2
ξR = − = 0.2ṅA,2
−1

Therefore the reactor outlet flow rate, ṅ3 is given by,

Output = Input + (Generation − Consumption)

ṅA,3 = ṅA,2 + νA ξR
ṅA,3 = ṅA,2 + (−1)(0.2ṅA,2 ) = 0.8ṅA,2 − − − − − − − 1
ṅB,3 = ṅB,2 + νB ξR
ṅB,3 = ṅB,2 + (1)(0.2ṅA,2 ) = ṅB,2 + 0.2ṅA,2 − − − − − − − 2

1 2 3 4
100 kmol A h−1 Reactor Separator

Figure 1.4: Example reactor with reactor and separator with recycle.

12 c T.L. Rodgers 2019

 1.5. PROCESSES WITH RECYCLE

From 2,

ṅB,3 = ṅB,2 + 0.2ṅA,2

ṅB,3 − ṅB,2
ṅA,2 =
0.2
(90) − (0)
ṅA,2 = = 450 kmol A h−1
0.2

and from 1,

ṅA,3 = 0.8ṅA,2
ṅA,3 = 0.8(450) = 360 kmol A h−1

A final balance on the separator allows calculation of the amount of A recycled in stream
5,

Input = Output
ṅA,3 = ṅA,4 + ṅA,5

ṅA,5 = ṅA,3 + ṅA,4

ṅA,5 = (360) + (10) = 350 kmol A h−1

Therefore we have,
1 2 3 4 5
A kmol h−1 100 450 360 10 350
B kmol h−1 0 0 90 90 0

c T.L. Rodgers 2019 13

14
Chapter 2
Reactor Design

Contents
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1.1 Definitions of Reaction Rate . . . . . . . . . . . . . . . . . . . 17
2.1.2 Reaction Equation or Rate Law . . . . . . . . . . . . . . . . . 17
2.1.3 Rate Equations in terms of Extent of Reaction . . . . . . . . . . 18
2.2 Mole Balance for Reactors . . . . . . . . . . . . . . . . . . . . . . . 18
2.3 Mole Balance Applied to Plug Flow Reactor . . . . . . . . . . . . . . 19

15
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 2.1. INTRODUCTION

2.1 Introduction
Before describing the reactors, we need to first discuss how to provide mathematical ex-
pressions for the rate at which reactions occur using rate laws.

2.1.1 Definitions of Reaction Rate

The reaction rate represents how fast a chemical component is converted into another by
a chemical reaction. More specifically, the reaction rate, ri , is the moles of i formed (or
appearing) per unit volume per unit time (moli m−3 s−1 ). The reaction rate is negative
when the moles of i are being consumed by the reaction (as occurs for reactants before
any product has been formed). The reaction rate is positive when the moles of i increase
with time due to the reaction (as occurs for products before any product has been formed).

Reaction Rate
The reaction rate can be positive or negative for any component of a reaction de-
pending on the direction of the equilibrium from the initial compositions.

2.1.2 Reaction Equation or Rate Law

A reaction equation is an algebraic equation that is solely a function of the properties of

the reacting materials and reaction conditions (e.g. species concentration, temperature,
pressure, or type of catalyst) at any point in the system.

Rate Law
The rate equation is independent of the type of reactor (e.g. batch or continuous
flow) in which the reaction is carried out.

A −−→ products
The reaction rate may be a linear function of concentration, i.e. −rA = kCA or may
be some other algebraic function of concentration, such as −rA = kCA2 or −rA =
(k1 CA ) / (1 + k2 CA ).
For a given reaction, the concentration dependence of the rate must be determined from
experimental observation. Typical examples of reaction rates are a first order reaction
given by,
− rA = kCA (2.1)

or a second order reaction,

− rA = kCA2 (2.2)

where k is called the rate constant, which varies with temperature. The order of the
reaction with respect to a component i corresponds to the exponent of concentration i
in the rate law. Note that the reaction rate, r, corresponds to a rate of formation. For

c T.L. Rodgers 2019 17

CHAPTER 2. REACTOR DESIGN

a reactant, the rate of formation is going to be negative as the reactant is consumed by

the reaction, hence the negative sign in Equations 2.1 and 2.2. Usually the order of the
reaction provides some insight into the molecular mechanism for the reaction. A first
order reaction corresponds to a uni-molecular process, whereas a second order reaction
corresponds to reaction controlled by collisions between molecules. These rules are only
strictly true when the reaction is an elementary step. Most reactions are combinations of
elementary steps, which can lead to more complicated rate laws. In addition, the rate law
can depend on the relative concentrations of the components. For instance, rate laws are
independent of the concentrations of components, which occur at a large excess relative
to another component (e.g. water).

2.1.3 Rate Equations in terms of Extent of Reaction

Consider the simple reaction A −−→ B, if this is first order, then the rate can be given by
equation 2.1,
− ri = kCi

where Ci is the concentration of i and can be related to the number of moles, Ni , by,

Ni = Ci V (2.3)

for a constant volume reactor, V , or, to the molar flow rate, ṅi , by

ṅi = Ci v (2.4)

for a constant volumetric flow rate, v, reactor. This means that for a constant volumetric
flow rate reactor with a first order reaction, we can write,
k
− ri = ṅi (2.5)
v

From equation 1.6, we know that the number of moles in terms of the extent of reaction
is,
ṅi = ṅi,0 + νi ξ

Substituting this into equation 2.5 gives,

k
− ri = (ṅi,0 + νi ξ) (2.6)
v

This can also be carried out for other reaction rate functions.

2.2 Mole Balance for Reactors

Ideal reactors normally refer to simplified models of reactors, in which various approxi-
mations are made. These approximations allow us to describe the behaviour of the reactor
using simple mathematical expressions.

18 c T.L. Rodgers 2019

 2.3. MOLE BALANCE APPLIED TO PLUG FLOW REACTOR

Reactor Mole Balance

The mole balance is used to determine either the time (for a batch reactor) or the re-
actor volume (for a flow reactor) required to convert a specified amount of reactants
into products.

The mole balance for a reactor can be written as equation 1.1,

Input − Output + (Generation − Consumption) = Accumulation
d Ni
ṅi,0 − ṅi + Gi =
dt

where ṅi is the molar flowrate of species i (with units of moles sec−1 ) and Ni is number
of moles of component i in the reactor. The above mole balance is performed over a
volume element in the reactor over which all the system variables (e.g. temperature,
concentration) are spatially uniform. In this case, the production rate in a reaction Gi
(mol s−1 ) over a given volume element, V , Figure 2.1, can be calculated from the rate of
formation of i, ri , by:
Gi = ri V (2.7)

Note that the production rate is negative when a reactant is being consumed.

ṅi,0 ṅi
V

Figure 2.1: Schematic representation of the design of a reactor volume.

2.3 Mole Balance Applied to Plug Flow Reactor

Plug flow reactors (PFR) are mainly used for gas phase reactions and may be packed with
catalyst. A schematic representation of a PFR is shown in Figure 2.2. The reactants are
continuously fed into a cylindrical tube, while the products are continuously withdrawn.
The reaction occurs as the stream flows through the reactor; the amount reacted increases
with the distance down the cylindrical tube. The length needs to be chosen such that the
desired conversion can be achieved. The PFR is operated under steady-state conditions
except for the start-up and shut down of the reactor. The analysis below is only given for
the steady state condition, which is used for sizing the reactor.
In order to model a PFR, a few assumptions need to be made. The PFR is not well-
mixed, as the conversion increases with the distance down the tube. However, a well-
mixed assumption is applied, in the radial direction only, that is, we assume that there
are no gradients of composition or temperature in the radial direction. Thus, a slice of the
reactor (i.e. ∆V in Figure 2.3 below) contains a homogeneous distribution of temperature
and composition. Having no radial variation also requires that the velocity distribution in
the PFR is flat, which is better approximated under turbulent flowing conditions1 . Lastly,
we assume that there is no axial mixing; this allows us to omit terms due to diffusion or
dispersion in the mole balance.
1
High velocity and low viscosity, e.g. a gas

c T.L. Rodgers 2019 19

CHAPTER 2. REACTOR DESIGN

Reactants Products

Figure 2.2: Schematic representation of a PFR.

ṅi,0 ṅi|V ṅi|V +∆V ṅi

∆V

V V + ∆V

Figure 2.3: Mole balance of component i in a differential segment of ∆V .

Remember that the mole balance needs to be done over a volume element that has a
uniform distribution of temperature and composition. This corresponds to the volume
element shown in Figure 2.3. Consider the mole balance on i in a differential segment of
reactor volume ∆V . Applying the mole balance,

In − Out + (Generation − Consumption) = Accumulation

(2.8)
ṅi|V − ṅi|V +∆V + ri ∆V = 0

and rearranging for the rate of reaction gives,

ṅi|V +∆V − ṅi|V
= ri (2.9)
∆V

Now if we take the limit as ∆V → 0, then

d ṅi
= ri (2.10)
dV

From equation 1.6 we know that the number of moles in terms of the extent of reaction,
is given by,
ṅi = ṅi,0 + νi ξ

For a very small change in moles, |ṅi,0 − ṅi | → 0, we can write,

d ṅi
= νi (2.11)
dξ

Combining equations 2.10 and 2.11 gives,

dξ ri
= (2.12)
dV νi

20 c T.L. Rodgers 2019

 2.3. MOLE BALANCE APPLIED TO PLUG FLOW REACTOR

Integrating with limits of ξ = 0 when V = 0 (the inlet) and ξ = ξR when V = VR (the

outlet) gives, Z ξR Z ξR
dξ dξ
VR = νi = νi (2.13)
0 ri 0 ri

Consider the reaction A −−→ B as a first order reation, where we know that the rate can
be given by equation 2.6,
k
− ri = (ṅi,0 + νi ξ)
v
The reactor volume, VR , necessary to gain a desired extent of reaction, ξR , is therefore
given by substituting the above into equation 2.13,

νi v ξR
Z
dξ
VR = − (2.14)
k 0 (ṅi,0 + νi ξ)

Therefore, upon integration we find,

 ξR
νi v 1
VR = − ln (k (ṅi,0 + νi ξ))
k νi 0
 
v ṅi,0 + νi ξR
VR = − ln
k ṅi,0
 
v νi ξR
VR = − ln 1 + (2.15)
k ṅi,0

Figure 2.4 shows a plot of the molar flowrates for A and B as a function of the reactor
volume.

ṅA0

ṅA ṅB

V V
(a) (b)

Figure 2.4: Molar flowrate of component A and B as a function of volume in a PFR.

Note that in deriving Equation 2.15 we have assumed that the volumetric flowrate, v, of
the gas is independent of the position in the PFR. The conditions when v is a constant
can be deduced from considering the ideal gas law, v = ṅt RT /P (assuming that a gas
is being reacted in the PFR), where ṅt is the total molar flowrate. Thus, the temperature,
pressure, and total molar flowrate must be constants for v to be a constant. In the reaction

c T.L. Rodgers 2019 21

CHAPTER 2. REACTOR DESIGN

of A going to B, for each mole of A consumed, one mole of B is formed so that indeed the
total molar flowrate is a constant. However, if the number of moles reacted does not equal
the moles consumed, we would need to account for the change in v as a function of the
change in mole number along the reactor. In addition, if the reactor is not isothermal, we
would also have to consider how v depends on T . How T depends on position in reactor
would be determined from a differential energy balance.

Question
Substitute the second order rate equation −rA = kCA2 into Equation 2.13 and find
the answer for VR . Assume no change in the total number of moles.

Z ξR
dξ
VR = νi
0 ri
k 2 k
− ri = kCi2 = 2
ṅi = 2 (ṅi,0 + νi ξ)2
v v
ξR
νi v 2 ξR νi v 2
Z 
dξ 1
VR = − =
k 0 (ṅi,0 + νi ξ)2 k νi (ṅi,0 + νi ξ) 0
v2 v 2 ṅi,0 − ṅi,0 − νi ξR
 
1 1
VR = − =
k ṅi,0 + νi ξR ṅi,0 k ṅi,0 (ṅi,0 + νi ξR )
2
v νi ξR 1
VR = −  
k ṅi,0 ṅi,0 νi ξR
1+
ṅi,0

Question
Consider the liquid phase cis-trans isomerisation of 2-butene which can be written
symbolically as
A −−→ B.
The first order (−rA = kCA ) reaction is carried out in a tubular reactor in which the
volumetric flow rate, v, is constant, i.e. v = v0 .
Determine the reactor volume necessary to reduce the exiting concentration of A to
10 % of the entering concentration when the volumetric flow rate is 5 m3 min−1 and
the specific reaction rate constant, k, is 0.23 min−1 .

As the exit concentration of A is 10 % of the initial concentration, we know that the

conversion must be 90 % (100 − 10) or 0.9. From equation 1.7 we know that for A,
νA ξR
XA = −
nA,0
νA ξR
= −XA = −0.9
nA,0
The volume of a plug flow reactor for a first order reactor is given by equation 2.15,

22 c T.L. Rodgers 2019

 2.3. MOLE BALANCE APPLIED TO PLUG FLOW REACTOR

Infobox 3: Mole Balance Applied to Batch Reactors.

A batch reactor is a reactor in which reactants are mixed together and the reaction is al-
lowed to proceed for a given time in a closed vessel with no inlet or outlet flows, as below.
Provision for mixing, heating, or cooling of the reactants may be required. Batch reactors
are normally used for small-scale operations, testing new processes, the manufacture of
expensive products, and processes difficult to convert to continuous. The advantage is that
high conversions can be achieved due to leaving the reactants in reactor. The disadvan-
tages are high labour costs, variability of products (batch to batch), and they are difficult
to operate/automate for large-scale production.

NA moles of A

In order to model a batch reactor, we need to make the assumption that at any given time
the reactor is well-mixed so that the composition, temperature, and pressure are the same
everywhere in the reactor. When the reaction takes place in a liquid (or sometimes solids),
very often the reacting component occurs at a much lower concentration then the principal
component of the liquid (i.e. the solvent). In this case, a good approximation is that the
volume of the liquid and pressure in the reactor remain constant with time as there is only
a small change in the density of the liquid during the reaction.
From equations 2.7 and 2.7 we have the general balance,

Input − Output + (Generation − Consumption) = Accumulation

d Ni
ṅi,0 − ṅi + ri V
dt
As we have no input or output, ṅi,0 = ṅi = 0, therefore we can simplify the equation to
be,
d Ni dξ
ri V = = νi
dt dt
Integrating with limits ξ = 0 when t = 0 (i.e. the initial condition) and ξ = ξR when
t = tR (i.e. the reaction time), Z ξR
νi
tR = dξ
0 ri V
Now we need to substitute in a rate law for the reaction, for example equation 2.6,
k
−ri = (Ni,0 + νi ξ)
V
νi ξ R
Z
1
tR = − dξ
k 0 (Ni,0 + νi ξ)
 ξR
νi 1
tR = − ln (Ni,0 + νi ξ)
k νi
  0  
1 Ni,0 + νi ξR 1 νi ξR
tR = − ln = − ln 1 +
k Ni,0 k Ni,0

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CHAPTER 2. REACTOR DESIGN

 
v νA ξR
VR = − ln 1 +
k nA,0
(5)
VR = − ln (1 + (−0.9)) = 50 m3
(0.23)
This could be acheived with a cylindrical reactor with a diameter of 2 m and a length
of 15 m.

24 c T.L. Rodgers 2019

Chapter 3
Energy Balances

Contents
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.2 Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.2.1 Heat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.2.2 Enthalpy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.2.3 Specific heat capacity . . . . . . . . . . . . . . . . . . . . . . . 29
3.2.4 Phase Change . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.3 Energy balances on non-reacting systems . . . . . . . . . . . . . . . 31
3.4 Energy balances involving chemical reactions . . . . . . . . . . . . . 34

25
26
 3.1. INTRODUCTION

3.1 Introduction
Energy is expensive. Energy is also what makes things happen, the agent of change,
and therefore something that is needed in a process (processes bring about change and
therefore require energy). So energy is central in the process industries, but it is expensive.
We therefore need to make sure we are using energy appropriately, but that we are not
using too much.
Typical problems that a process engineer might be required to solve include:
• How much power is required to pump water from a storage vessel to a process unit?
(The answer determines the size of the pump.)
• How much heat is required to convert water at 30 ◦ C into steam at 180 ◦ C? How
much coal will this require each day?
• What is the total energy requirement for a process? How much will this energy
cost? How can the process be designed to minimise the total energy requirement by
maximising energy recovery?
These questions are answered by performing an energy balance, which accounts for all
the energy entering and leaving a system.

3.2 Energy
Before we consider energy balances, it is important that we remind ourselves very clearly
that energy has a variety of forms. If we overlook one of the forms of energy entering or
leaving the system, we will not calculate the energy balance correctly.
Forms of energy include:
Kinetic energy - energy arising from motion. This is important if the system is rapidly
moving, such as a bullet. Most processes are fairly stationary, so the kinetic energies
involved are negligible and can be ignored in the energy balance. But this might
not be true if, for example, a stream enters or leaves the system with high velocity,
such as a jet from a nozzle.
Potential energy - energy arising from being moved against gravity. Most processes
occur at or near the Earth’s surface, so potential energy is not a major consideration
in an energy balance. However, when liquids are pumped to several meters above
the ground, the energy requirement to pump them may be substantial, and certainly
is the energy that you would need to consider in sizing the pump motor.
Internal energy - the energy of molecular motion (translation, vibration, and rotation)
and of intermolecular attraction and repulsion. This is related to enthalpy, which
we will talk about later, and is usually obtained from tables.
Heat and work - in many ways these are the forms of energy most familiar to us. In
an important sense, heat and work are different from the other forms of energy
described above, in that they are energy in transit, i.e. energy being transferred
from one body to another. Possibly this is why they seem familiar to us. Looking
at a brick, it is not evident that it contains internal energy, but if you drop it on your
foot, the work it does on your foot is felt quite evidently.

c T.L. Rodgers 2019 27

CHAPTER 3. ENERGY BALANCES

It is the interchange of energy that causes changes and is therefore at the heart of pro-
cesses. So heat and work, which are forms of energy being interchanged between materi-
als, are therefore at the heart of energy balances.

3.2.1 Heat

Heat is the most familiar form of energy. We know that a stove feels hot and ice feels
cold. To describe this familiar phenomenon more carefully, what happens is that when
we touch a stove, heat flows from the stove to our hand, and it therefore feels hot (relative
to our hand). When we touch an ice cube, heat flows from our hand to the ice cube, and
it feels cold (relative to our hand). From these familiar notions we can formulate two
important ideas:
• Heat is a form of energy that flows, or as we often say, is transferred from one object
to another or between a system and its surroundings. Because of this heat flow, one
object loses some energy, and the other object gains this energy. When we hold an
ice cube, heat flows from our hand to the ice cube. So our hand loses some of its
energy content, as shown by the decrease in its temperature. Conversely, the energy
content of the ice cube increases, as shown by the fact that the ice cube melts (or
increases in temperature).
• In order for there to be a flow of heat, there must be a temperature difference or
gradient (heat, like water, will only flow “downhill” i.e. from hot to cold).
From these two ideas, we can define heat as “the form of energy which flows from one
object or system to another as the result of a temperature difference”. And it is one of
the laws of thermodynamics, and something that we know from our everyday experience,
that the direction of the flow is from hotter bodies to colder bodies.

3.2.2 Enthalpy

We noted earlier the concept of Internal Energy, that is, the energy that a material pos-
sesses as a result of the motion and attractions and repulsions of its molecules. This
energy depends on the composition of the material and its state, which is determined by
it’s temperature and pressure. Related to the internal energy is the enthalpy, which is
defined as,
h = u + Pv (3.1)

where h is specific enthalpy (enthalpy per unit mass, units kJ kg−1 ), u is specific internal
energy (kJ kg−1 ), P is pressure (Pa), and v is specific volume (m3 kg−1 ).
The properties of enthalpy are as follows:
• For a given material, at constant pressure, the enthalpy depends only on the ma-
terial’s temperature and physical state. So, for example, water at 100 ◦ C has less
energy and less enthalpy than steam at 100 ◦ C.
• At constant temperature and physical state, the change of enthalpy with pressure is
negligible for gases, and very small for liquids and solids. This means that for liq-
uids, if you know the enthalpy at a given temperature and the corresponding vapour
pressure (the pressure at which the liquid would boil), then this is close enough for

28 c T.L. Rodgers 2019

 3.2. ENERGY

other pressures. Tables often give enthalpy data at a particular temperature and the
corresponding vapour pressure.
• The enthalpy of a substance at a specific set of conditions (T , P and physical state)
is independent of the route taken to reach those conditions. In addition enthalpy
is an extensive quantity, i.e. the total enthalpy of a component is just given by the
number of moles of that component times molar enthalpy h.

3.2.3 Specific heat capacity

When you heat up a material, its enthalpy increases as the temperature increases. The
amount of energy needed to raise the temperature of a material by 1 ◦ C varies. For water,
for example, it takes about 4200 J to raise the temperature of 1 kg by 1 ◦ C, while for air, it
takes only about 1000 J (less than a quarter) to achieve the same temperature rise.
The amount of energy required to heat up a kilogram of a material by 1 ◦ C is called its
specific heat capacity, Cp (“specific” refers to the fact that we are dealing with a kilogram
- if we were talking about the energy to heat up a mole of material, we would use the
molar heat capacity). The units of specific heat capacity are J kg−1 ◦ C−1 i.e. the amount
of energy in Joules to raise the temperature of 1 kg by 1 ◦ C.
The specific heat capacity is the slope of the graph of enthalpy against temperature (pro-
vided the material does not change its phase),

Specific Heat Capacity

dh
Cp = (3.2)
dT

The above equation can be integrated to calculate the amount of energy required to raise
the temperature of 1 kg (or 1 mol) of a pure substance from T1 to T2 .
Z T2
Q = ∆h = Cp d T (3.3)
T1

Note that this approach only works when there is no phase change during the heating
process. In order to evaluate the integral, we need to know how heat capacity depends
upon temperature.
Often, the specific heat capacity depends on the temperature, thus it is common to provide
it as a general expression, for example,

Cp = A + BT + CT 2 + DT 3 (3.4)

where A, B, C, and D are experimentally measured, empirical constants that depend on

the molecule type.

c T.L. Rodgers 2019 29

CHAPTER 3. ENERGY BALANCES

3.2.4 Phase Change

Water at atmospheric pressure boils when it reaches 100 ◦ C, to form steam at 100 ◦ C. Both
are at the same temperature, but steam contains more energy than water. To put it another
way, it takes energy to convert water into steam.
The amount of energy required to convert water into steam is called the latent heat of
vapourisation. Similarly, when steam gives up this energy and condenses into water, this
is called the latent heat of condensation. The magnitude of the energy change is the same
whether we are evaporating water or condensing steam. For water/steam at 100 ◦ C and
atmospheric pressure, the latent heat of vaporisation/condensation is 2257 kJ kg−1 . Com-
paring this with the enthalpy difference between water at 0 and 100 ◦ C of 419.2 kJ kg−1 ,
we can see that it takes a lot more energy to convert water into steam than it does to heat
water from 0 to 100 ◦ C.
Similarly, it takes energy to melt ice, and water turning to ice gives up energy. This is
called the latent energy of melting or fusion, and has a magnitude of 333.5 kJ kg−1 at
0 ◦ C.
Figure 3.1 below shows the change in enthalpy with temperature for water, as it changes
from ice to liquid water to steam, showing that the largest change arises due to the latent
heat of vaporisation.

3,000

Specific heat capacity / kJ kg−1 K−1

2,500 4
Enthalphy / kJ kg−1 (black)

2,000 ice water steam

3
Latent heat of
1,500 vapourisation/condensation
(grey)

1,000 2

500
1
0 Latent heat of
melting/fusion

−500 0
−40 −20 0 20 40 60 80 100 120 140
Temperature / ◦ C

Figure 3.1: Variation with temperature of enthalpy (black lines, left axis) and specific
heat capacity (grey lines, right axis) of ice, water, and steam at atmospheric pressure.

Question
Air at 25 ◦ C is able to “carry” a maximum of 0.0202 kg water per kg air (at which
point the air is considered saturated). Calculate the temperature drop of dry air that
would cause it to end up at 25 ◦ C and 10% saturated with water, and therefore the
initial temperature of the air.
Latent heat of vapourisation of water at 25 ◦ C is 2442 kJ kg−1 , and the specific heat

30 c T.L. Rodgers 2019

 3.3. ENERGY BALANCES ON NON-REACTING SYSTEMS

capacity of air can be taken as 1.005 kJ kg−1 K−1 .

Basis: 1 kg air The energy required to evaporate the water in 1 kg air at 25 ◦ C is,

hevap water = mw ∆ hvl = (1 × 0.0202 × 0.1)(2442) = 4.5 kJ

The energy released by cooling of 1 kg of air is,

hcooling = ma Cp ∆ T = (1)(1.005)∆ T = 1.005∆ T kJ

For the energy to balance the amount released by cooling the air has to equal that
gained by the evaporating water,

hevap water = hcooling

4.5 = = 1.005∆ T
T = 4.48 ◦ C

Initial air temperature = 25 + 4.48 = 29.5 ◦ C.

3.3 Energy balances on non-reacting systems

Conservation of energy is one of the fundamental laws of the universe, along with con-
servation of mass, except where nuclear reactions are involved, in which case mass can
be converted to energy via equation 1.3, as dicussed in Section 1.4.
But in most process industries, except the nuclear industry, we don’t get nuclear reac-
tions occurring, so we can take it as fundamentally true that both energy, and mass, are
conserved independently. This means that all the energy that enters a system must leave,
one way or another, or else must accumulate in the system, i.e. the same balance as in
equation 1.1,

In − Out + Generation − Consumption = Accumulation (3.5)

Just as with mass balances, this applies to overall plant balances, to individual unit op-
erations, and to small elements within equipment. Applying this law to conservation of
energy within process equipment results in sets of equations, either algebraic or differen-
tial, which describe the variation of temperature or heat flow within the equipment.
We must remember to include all forms of energy involved, and recognise that a particular
form of energy is not necessarily conserved, as energy can be transformed, e.g. from
mechanical work into heat.
For the continuous system in Figure 3.2, at steady state (i.e. no accumulation) where there
is no shaft work (i.e. no compressors or turbines), the energy balance, equation 3.5, can

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CHAPTER 3. ENERGY BALANCES

be written as,
       
Enthalpy Heat transfer Enthalpy Heat transfer
+ = +
of inputs to process of outputs from process
(3.6)
ṁin hin + Q̇in = ṁout hout + Q̇out

In this case the change in the kinetic and potential energy of the flowing stream have been
neglected, as they are likely small in comparison to the enthalpy and heat change.
Therefore to allow us to perform the energy balance, we need to establish equations for
the enthalpy of the various components flowing into and out of the system. The enthalpy
of any component in phase β at the given temperature and pressure needs to be calculated.
Usually a reference enthalpy is taken as the heat formation, ∆ hf , i.e. the enthalpy change
when one kg (or kmol) of a species is formed from its elements in its usual physical phase
α (i.e. vapour, liquid, or solid) at 25 ◦ C and 1 atm,

Component Enthalpy
Z Tp Z T
hβ (T ) = ∆ hf,α + Cp,α d T + ∆ hβα (Tp ) + Cp,β d T (3.7)
25 Tp

where Tp corresponds to the temperature of phase change from α to β.

For example, lets think about a system that is used to heat water, as in Figure 3.3. How
much energy does it take heat this water? The enthalpy of formation of water at 25 ◦ C is
−285.83 kJ mol−1 , the latent heat of vapourisation at 100 ◦ C is 40.68 kJ mol−1 , the mo-
lar heat capacity of water is 75.30 J mol−1 K−1 , and the molar heat capacity of steam is
36.50 J mol−1 K−1 .
To solve this problem we need to use equation 3.6, where we can calculate the values of
the enthalpy from equation 3.7.

hl (25) = ∆ hf,l (25)

= (−285.83) = −285.83 kJ mol−1

Q̇in kJ s−1

ṁin kg s−1 ṁout kg s−1

hin kJ kg−1 hout kJ kg−1

Q̇out kJ s−1

Figure 3.2: Energy balance for a simple continuous system.

32 c T.L. Rodgers 2019

 3.3. ENERGY BALANCES ON NON-REACTING SYSTEMS

Q̇in kW

100 mol water s−1 100 mol steam s−1

25 ◦ C 125 ◦ C

Figure 3.3: Example water heater calculation system.

hv (125) = ∆ hf,l (25) + Cp,l (100 − 25) + ∆ hvl (100) + Cp,v (125 − 100)
= (−285.83) + (75.30/1000)(100 − 25) + (40.68) + (36.50/1000)(125 − 100)
= − 238.59 kJ mol−1

Thus

ṁin hin + Q̇in = ṁout hout + Q̇out

(100)(−285.83) + Q̇in = (100)(−238.59) + (0)
Q̇in = (−23, 859) − (−28, 583) = 4, 724 kW

Question
A heater heats water as in the figure below and turns it into steam. What is the
temperature of the exiting steam?
The enthalpy of formation of water at 25 ◦ C is −285.83 kJ mol−1 , the latent heat
of vapourisation at 100 ◦ C is 40.68 kJ mol−1 , the molar heat capacity of water is
75.30 J mol−1 K−1 , and the molar heat capacity of steam is 36.50 J mol−1 K−1 .
5000 kW

100 mol water s−1 100 mol steam s−1

25 ◦ C T ◦C

hl (25) = ∆ hf,l (25)

= (−285.83) = −285.83 kJ mol−1

hv (125) = ∆ hf,l (25) + Cp,l (100 − 25) + ∆ hvl (100) + Cp,v (T − 100)
= (−285.83) + (75.30/1000)(100 − 25) + (40.68) + (36.50/1000)(T − 100)
= − 243.15 + 0.0365T kJ mol−1

c T.L. Rodgers 2019 33

CHAPTER 3. ENERGY BALANCES

Thus

ṁin hin + Q̇in = ṁout hout + Q̇out

(100)(−285.83) + (5000) = (100)(−243.15 + 0.0365T ) + (0)
3.65T = 732.25
T = 200.62 ◦ C

3.4 Energy balances involving chemical reactions

When chemical reaction occurs we must account for the enthalpy change associated with
the reaction. The general approach for this is to use the standard heat of formation for
each component as we did when there was no reaction.
Let us take the example of methane at 25 ◦ C being supplied to a furnace, Figure 3.4, where
it is burned in air supplied at 250 ◦ C, as in,

CH4 + 2O2 → CO2 + 2H2 O

The reaction goes to completion with simultaneous heat transfer within the furnace from
the product gases. The gases then leave at 1000 ◦ C. Determine the amount of heat trans-
ferred per kmol of methane.
The standard heats of formation (25 ◦ C and 1 atm) are,
CH4(g) = −74, 900 kJ kmol−1
CO2(g) = −393, 800 kJ kmol−1
H2 O(l) = −286, 000 kJ kmol−1
Elements in standard form = 0 kJ kmol−1
the molar heat capacities are,
O2,25→250 = 29.58 kJ kmol−1 K−1
O2,25→1000 = 33.29 kJ kmol−1 K−1
N2,25→250 = 29.58 kJ kmol−1 K−1
N2,25→1000 = 31.35 kJ kmol−1 K−1
H2 O,25→1000 = 38.66 kJ kmol−1 K−1
CO2,25→1000 = 49.85 kJ kmol−1 K−1

1 kmol CH4
25 ◦ C x kmol H2 O
y kmol CO2
10 kmol air Furnace z kmol O2
250◦ C n kmol N2
0.79 mol N2 mol−1
0.21 mol O2 mol−1

Figure 3.4: Example water heater calculation system.

34 c T.L. Rodgers 2019

 3.4. ENERGY BALANCES INVOLVING CHEMICAL REACTIONS

and the latent heat of vaporisation of water at 25 ◦ C = 44, 000 kJ kmol−1 .

Firstly a mass balance must be undertaken for the system, as in equation 1.1 where the
accumulation is zero due to being at steady state, and the extent of reaction, ξ is equal to
the number of moles of CH4 into the furnace, as the reaction goes to completion,
Input + (Generation − Consumption) = Output
CH4 : 1 + (ξνCH4 = (1)(−1) = −1) = 0 mol
O2 : 0.21 × 10 + (ξνO2 = (1)(−2) = −2) = 0.1 mol
N2 : 0.79 × 10 + (ξνN2 = (1)(0) = 0) = 7.9 mol
H2 O: 0.0 + (ξνH2 O = (1)(2) = 2) = 2 mol
CO2 : 0.0 + (ξνCO2 = (1)(1) = 1) = 1 mol

Now the mass balance has been completed, we can undertake the energy balance. The
enthalpy in is,
N ∆ hf (25) + N Cp (T − 25) = Total
CH4 (25): (1)(−74, 900) + 0 = −74, 900 kJ
O2 (250): (0.21 × 10)(0) + (0.21 × 10)(29.58)(250 − 25) = 13, 977 kJ
N2 (250): (0.79 × 10)(0) + (0.79 × 10)(29.58)(250 − 25) = 52, 578 kJ
Total: = −8, 345 kJ

The enthalpy out is,

N ∆ hf (25) + N ∆ hvl (25) + N Cp (T − 25) = Total
O2 (1000): (0.1)(0) + 0 + (0.1)(33.29)(1000 − 25) = 3, 246 kJ
N2 (1000): (7.9)(0) + 0 + (7.9)(31.35)(1000 − 25) = 241, 473 kJ
H2 O(1000): (2)(−286, 000) + (2)(44, 000) + (2)(38.66)(1000 − 25) = −408, 613 kJ
CO2 (1000): (1)(−393, 800) + 0 + (1)(49.85)(1000 − 25) = −345, 196 kJ
Total: = −509, 090 kJ

Thus the total energy balance for the system is,

Nin hin + Qin = Nout hout + Qout
(−8, 345) + (0) = (−509, 090) + Qout
Qout = (−8, 345) − (−500, 745) = kJ

Thus 500, 000 kJ is released by the furnace for every kmol of CH4 burned.

Question
The first stage of sulfuric acid production is the adiabatic (no energy added/lost)
combustion of liquid sulfur with 100% excess air. This produces sulfur dioxide gas
at a high temperature. The sulfur dioxide is then reacted with more air to form
sulfur trioxide in the contact process; this is then further reacted with water to form
sulfuric acid. What is the temperature of the sulfur dioxide gas after the combustion
(adiabatic means no heat given or lost from the system)?
S(l) SO2
120 ◦ C O2
100% excess air N2
25 ◦ C T ◦C

Enthalpy of fusion (melting) for sulfur, ∆ hls,S (120 ◦ C) = 2000 kJ kmol−1

c T.L. Rodgers 2019 35

CHAPTER 3. ENERGY BALANCES

Standard heat of formation of SO2 , ∆ hf,SO2 = −297, 000 kJ kmol−1

Molar heat capacities:
S(s) = 26.0 kJ kmol−1 ◦ C−1
SO2(g) = 51.0 kJ kmol−1 ◦ C−1
O2(g) = 33.3 kJ kmol−1 ◦ C−1
N2(g) = 31.5 kJ kmol−1 ◦ C−1

Firstly a mass balance must be undertaken for the system, as in equation 1.1 where
the accumulation is zero due to being at steady state, and the extent of reaction, ξ is
equal to the number of moles of S in, as the reaction goes to completion. Also as
the air is 100% excess, this means that the amount of O2 in is twice what is needed,
i.e. 2ξ. The amount of N2 is therefore related to the O2 0.79/0.21 times.
Let us take a basis of 1 kmol s−1 of S.
Input + (Generation − Consumption) = Output
S: 1 + (ξνS = (1)(−1) = −1) = 0 kmol s−1
SO2 : 0 + (ξνSO2 = (1)(1) = 1) = 1 kmol s−1
O2 : 2 + (ξνO2 = (1)(−1) = −1) = 1 kmol s−1
N2 : 7.52 + (ξνN2 = (1)(0) = 0) = 7.52 kmol s−1

Now the mass balance has been completed, we can undertake the energy balance.
The enthalpy in is,

ṅ∆ hf (25) + ṅ∆ hβ,α (T ) + ṅCp (T − 25) = Total

S(120): (1)(0) + (1)(2000) + (1)(26.0)(120 − 25) = 4, 470 kW
O2 (25): (2)(0) + 0 + 0 = 0 kW
N2 (25): (7.52)(0) + 0 + 0 = 0 kW
Total: = 4, 470 kW

The enthalpy out is,

ṅ∆ hf (25) + ṅ∆ hvl (25) + ṅCp (T − 25) = Total
SO2 (T): (1)(−297, 000) + 0 + (1)(51.0)(T − 25) = 51(T − 25) − 297, 000 kW
O2 (T): (1)(0) + 0 + (1)(33.3)(T − 25) = 33.3(T − 25) kW
N2 (T): (7.52)(0) + 0 + (7.52)(31.5)(T − 25) = 237(T − 25) kW
Total: = 321.3(T − 25) − 297, 000 kW

Thus the total energy balance for the system is,

ṅin hin + Q̇in = ṅout hout + Q̇out

(4, 470) + (0) = (321.3(T − 25) − 297, 000) + (0)
321.3(T − 25) = 301, 470
321.3T = 309, 502.5
T = 963.3 ◦ C

36 c T.L. Rodgers 2019

 3.4. ENERGY BALANCES INVOLVING CHEMICAL REACTIONS

Infobox 4: Solving energy balances by heat of reaction.

An alternative approach to solving energy balances is to use the standard heat of reaction.
The standard heat of reaction is defined as the amount of heat removed for a process
when the extent of reaction is 1 mole and the reactants and products enter and leave
the process at 25 ◦ C and in their usual state (i.e. the state at that temperature and pressure).

Consider a simple reaction,

(−νA ) A + (−νB ) B → νC C + νD D

As the products of a reaction must be made up of the same elements as the reactants, we
can determine the standard heat of any reaction from the standard heats of formation of
the reactants and products,
X
∆ h0R = νA ∆ hf,A + νB ∆ hf,B + νC ∆ hf,C + νD ∆ hf,D = νi ∆ hf,i
i

The enthalpy for the reaction at the actual temperature can then be calculated by summing
the three parts,
i enthalpy change to take the reactants from their initial temperature and state (gas,
liquid, or solid) to 25 ◦ C and their usual state,
X X
∆ H1 = mi Cp,i,β (25 − Tin ) + mi ∆ hαβ,i,25
i i

ii heat of reaction term given by multiplying the extent of reaction by standard heat
of reaction X
∆ H2 = ξr ∆ h0R,r
r

iii enthalpy change in taking the products from 25 ◦ C and their usual state to their final
temperature and final state.
X X
∆ H3 = mi Cp,i,β (Tout − 25) + mi ∆ hβα,i,25
i i

so that the total enthalpy is given by,

∆ HR = ∆ H1 + ∆ H2 + ∆ H3

c T.L. Rodgers 2019 37

38
Chapter 4
Conversion of Landfill Gas to Town’s
Gas

Contents
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.2 Process Description . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.2.1 Pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.2.2 Reformer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4.2.3 Shift Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4.2.4 Post-Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4.3 Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

39
40
 4.1. INTRODUCTION

4.1 Introduction
Landfill gas (LFG) is produced by anaerobic decomposition of general waste and con-
tains mainly Methane and Carbon Dioxide. The LFG may also contain other components,
which tend to be the factors that cause the gas to be un-useful in its untreated form. These
other components can include inerts, such as Nitrogen, potential poisons and toxins, such
as Hydrogen Sulphide and Mercury, or compounds that hinder the treatment of the gas,
such as Oxygen and Vanadium. The treatment of LFG is often complex as the concen-
tration and type of these contaminants vary with not only the landfill site, but also with
time in one particular landfill. One of the uses of LFG is the conversion to Town’s Gas
(TG).
TG tends to contain Methane and Hydrogen along with some other inert components,
such as Nitrogen and Carbon Dioxide. The important parameters for TG are the calorific
value and the flame speed. These will determine the correct amount of energy that can be
received from burning the Towns Gas, so that it can be lit and kept burning.
Product gas Property Range Normal Value
H2 46.3 − 50.3 mol% (dry) 49.0 mol% (dry)
CH4 28.2 − 30.7 mol% (dry) 28.5 mol% (dry)
CO2 + N2 18.8 − 21.0 mol% (dry) 19.5 mol% (dry)
CO 3.0 mol% (dry) maximum 3.0 mol% (dry)
H2 S 0 − 3.5 ppmv 0 ppmv
−3
THT Odorant 16.0 − 24.0 mg Nm 20.0 mg Nm−3
−3
Calorific Value 17.10 − 17.44 MJ m 17.27 MJ m−3
Specific Gravity 0.50 − 0.54 0.52
−3
Wobbe Index 23.2 − 24.8 MJ m 24.0 MJ m−3
−1
Flame Speed 33.0 − 37.0 ft s 35.0 ft s−1
Pressure 7 barg
Temperature 10 − 40 ◦ C 25 ◦ C
Dew Point 0 ◦ C at 7 barg

4.2 Process Description

The general process for turning LFG into TG can be seen as a block flow diagram as
Figure 4.1. Data for some of the streams is known, which is given as Table 4.1.

4.2.1 Pre-treatment

The LFG is firstly pre-treated, this involves removing the trace amounts of impurities,
such as:
• organosulphur, organochlorine and organofluorine – reacted with hydrogen over a
cobalt molybdate catalyst to hydrogen sulphide
• hydrogen sulphide – removed by reaction with Zinc Oxide or the Claus process
• hydrogen chloride and hydrogen fluoride – adsorbed with Na2 O
• mercury – adsorbed with sulphur doped activated carbon

c T.L. Rodgers 2019 41

CHAPTER 4. CONVERSION OF LANDFILL GAS TO TOWN’S GAS

• oxygen – burned with small amounts of added hydrogen

• vanadium, lead, and arsenic – adsorbed onto the cobalt molybdate catalyst
The treated LFG is also pressurised using a series of compressors up to the process pres-
sure of 2835 kPa, this pressurisation also causes the treated LFG to heat up to 660 K.

4.2.2 Reformer

After the pre-treatment the LFG is sent to the reformer. Steam reforming is the process
by which methane can be reacted with water to produce carbon monoxide and hydrogen.
This is usually carried out by contacting a mixture of methane and steam at high tem-
perature, with an activated Nickel Oxide catalyst. This process was conducted under a
pressure of up to 4000 kPa and at temperatures up to close to 1225 K. The main steam
reforming reaction is,
CH4 + H2 O −
)−
−*
− CO + 3 H2
This reaction is highly endothermic and requires an external source of heat and an initial
source of steam. This is generally carried out by preheating the steam – Methane mixture
in heat exchangers or fired heaters to around 1000 K and then heated during the reaction
over the nickel catalyst in tubes with a fired furnace. Some of the LFG is diverted to be
burned in this furnace, in this case it is 18.8 % of stream 3.
Methane is only partially converted to Hydrogen determined by the equilibrium of reac-
tion, which is in turn determined by the steam:methane ratio, pressure, temperature, etc.
In this case steam (1000 K and 2785 kPa) is added at 2.2 times the flow rate of methane
into the reformer.
In this case as we are producing TG we don’t need to convert all the methane to hydrogen.
Steam reformers have the ability to work at high conversion, therefore it is more econom-
ical to only send part of the LFG to the reformer and bypass some of the methane rich
LFG. The fraction of LFG sent to the reformer is x.
If carbon monoxide is also present in the feed, or as it is produced in the reformer, a
secondary reaction can take place in which this is too converted to carbon dioxide and
hydrogen, as,
CO + H2 O −
)−
−*
− CO2 + H2
Depending on the exact temperature, this reaction may proceed in reverse.

Table 4.1: Known stream compositions and flow rates for Figure 4.1.

Stream
Value
1 2 3 4 5 6 7
CH4 0.4994 0.4999 0.4999 0.0285
Mole Fraction

CO2 0.3520 0.3523 0.3523 0.1858

CO 0.0000 0.0000 0.0000
H2 O 0.1477 0.1478 0.1478 0.3052 0.1741
H2 0.0000 0.0000 0.0000
Impurities 0.0009 0.0000 0.0000
Total / mol hr−1 1000000 999100 999100 896618 1402163 1032254

42 c T.L. Rodgers 2019

c T.L. Rodgers 2019
Impurities
Steam Air
1000 K 298 K
333 K 660 K 1000 K
135 kPa Pre-treatment 2835 kPa 2785 kPa
LFG 1 2 3 1250 K
HX 1 Reformer Flue Gas
4
2585 kPa 1150 K
Water
HX 2 2635 kPa

Shift Reactor Water Removal

5 6 Water
550 K 617 K 373 K
2535 kPa 2385 kPa 2335 kPa
373 K
2335 kPa

Town’s Gas 7 CO2

373 K CO2 Removal 373 K
1000 kPa 1000 kPa

Figure 4.1: Block flow diagram for the conversion of land fill gas to town’s gas.

43
4.2. PROCESS DESCRIPTION
CHAPTER 4. CONVERSION OF LANDFILL GAS TO TOWN’S GAS

4.2.3 Shift Reactor

After the reformer there can be a large amount of carbon monoxide present. This needs
to be removed, which can be undertaken using the shift reaction,
CO + H2 O −
)−
−*
− CO2 + H2
This is usually carried out by contacting a mixture of carbon monoxide and steam in a
two step process, the first at high temperature and the second at a reduced temperature.
The first phase of this process is generally carried out at around 600 K. This process
is carried out with an iron oxide catalyst, and can be used to reduce carbon monoxide
concentrations to around 1-2 %. The second phase of this process is generally carried
out at around 470 K and uses a copper based catalyst and can further reduce the carbon
monoxide concentration to around 0.1-0.2 %. In this case this second process will not
be needed as we only need to reduce the concentration of carbon monoxide to around
3 %.
As the temperature of the shift reactor is much lower than the temperature at the exit of
the reformer heat needs to be removed from the process stream. This can be cooled using
a heat exchanger with cooling water; however, the some of this heat can be used to heat up
the entrance stream to the reformer. This is called process integration and saves energy,
in this case we save the heat energy needed to heat the stream to the reformer and save
the cooling water needed to cool part of the ext stream.

4.2.4 Post-Treatment

Before the TG can be used, some of the water and carbon dioxide needs to be removed to
match the specification. As we do not need perfectly dry gas, this means that the method
of cooling the gas and using a gas-liquid separator is perfectly adequate. The amount of
water separated on cooling is dependent on the vapour pressure of the water,poH2 O , at that
temperature, T , and the gas pressure, P . The mole fraction of water, y, in the gas phase
is given by,
poH2 O
yH2 O = (4.1)
P
If we know the mole fraction of water in the gas at the initial temperature and the frac-
tion at the final temperature we can calculate the amount of water removed. The vapour
pressure of water, in Pa, can be calculated by using, where T is in K,
 
o 7258.2 −6 2
pH2 O = exp 73.649 − − 7.3037 ln T + 4.1653 × 10 T (4.2)
T

Carbon dioxide can be removed from the process gas in a number of positions within the
process. The best position to do this will be after the reforming and shift reactions have
taken place, as these produce carbon dioxide. A number of methods are avalible to remove
carbon dioxide from the gas stream, for example adsorption or membranes; however, for
this case the exact method is not important. These separation methods are however not
perfect and often have a low separation, espeacilly if the separated gas is kept pure. In
this case we only need a low separation to acheive the product specification.

44 c T.L. Rodgers 2019

 4.3. DESIGN

4.3 Design
During the process some data about the stream flow rates and compositions are collected,
given in Table 4.1. Using this data the compositions of all the streams can be calculated
for the process.
1. What is the extent of the 2 reactions in the reformer and the reaction in the shift
reactor?
2. What is the temperature of the stream between HX 1 and HX 2?
3. What is the final specification of the TG, does it meet what is needed?
Some useful data can be seen in Table 4.2.

Taking a mass balance over stream 3 to stream 6 we can calulate the flow rates of all the
streams including the extent of the reactions, see table A.
Comparing the expesssions from Table A with the known values from Table 4.1, we can
write 5 equations,
1012061x − ξ1 − ξ2
H2 O Stream 4: 0.3052 = –1
1703398x + 2ξ1
1012061x − ξ1 − ξ2 − ξ3
H2 O Stream 5: 0.1741 = –2
1703398x + 2ξ1
405513x − ξ1
CH4 Stream 4: 0.0285 = –3
1703398x + 2ξ1
Total Stream 4: 896618 = 1703398x + 2ξ1 –4
Total Stream 6: 1402163 = 811269 + 892129x + 2ξ1 –5

Equation 4 can be substituted into 1 and 2 so that,

1012061x − ξ1 − ξ2
0.3052 =
896618
273647.8 = 1012061x − ξ1 − ξ2
1012061x − ξ1 − ξ2 − ξ3
0.1741 =
896618
156101.2 = 1012061x − ξ1 − ξ2 − ξ3

Table 4.2: Vapour phase properties of key components. *liquid water enthalpy of forma-
tion is −285.83 kJ mol−1 and the enthalpy of vapourisation is 44 kJ mol−1 .

Component ∆ Hf kJ mol−1 Cp kJ mol−1 K−1

CH4 −74.6 0.0432
CO2 −393.5 0.044
CO −110.5 0.028
H2 O −241.8* 0.108
H2 0 0.029
N2 0 0.028
O2 0 0.032
Impurities −37.4 0.0741

c T.L. Rodgers 2019 45

 c T.L. Rodgers 2019
Table A.
CHAPTER 4. CONVERSION OF LANDFILL GAS TO TOWN’S GAS

Stream 3 Stream 3 = Furnace + Process = Reformer + Bypass

CH4 : 0.4999 499400 = 93887 + 405513 = 405513x + 405513(1 − x)
CO2 : 0.3523 352000 = 66176 + 285824 = 285824x + 285824(1 − x)
CO: 0 0 = 0 + 0 = 0 + 0
H2 O: 0.1478 147700 = 27768 + 119932 = 119932x + 119932(1 − x)
H2 : 0 0 = 0 + 0 = 0 + 0
Total: 999100 999100 = 187831 + 811269 = 811269x + 811269(1 − x)
Reformer Shift Remix
Input + (G − C) = Stream 4 + (G − C) = Stream 5 + Bypass = Stream 6
CH4 : 405513x + −ξ 1 = 405513x − ξ1 + 0 = 405513x − ξ1 + 405513(1 − x) = 405513 − ξ1
CO2 : 285824x + ξ2 = 285824x + ξ2 + ξ3 = 285824x + ξ2 + ξ3 + 285824(1 − x) = 285824 + ξ2 + ξ3
CO: 0 + ξ1 − ξ2 = ξ1 − ξ2 + −ξ3 = ξ1 − ξ2 − ξ3 + 0 = ξ1 − ξ2 − ξ3
H2 O: 1012061x + −ξ − ξ = 1012061x − ξ1 − ξ2
1 2 + −ξ 3 = 1012061x − ξ1 − ξ2 − ξ3 + 119932(1 − x) = 119932 + 892129x − ξ1 − ξ2 − ξ3
H2 : 0 + 3ξ1 + ξ2 = 3ξ1 + ξ2 + ξ3 = 3ξ1 + ξ2 + ξ3 + 0 = 3ξ1 + ξ2 + ξ3
Total: 1703398x + 2ξ1 = 1703398x + 2ξ1 + 0 = 1703398x + 2ξ1 + 811269(1 − x) = 811269 + 892129x + 2ξ1

46
 4.3. DESIGN

Subtracting these equations gives,

273648 − 156101 = (1012061x − ξ1 − ξ2 ) − (1012061x − ξ1 − ξ2 − ξ3 )

ξ3 = 117547 mol hr−1

Subtracting equation 5 from 4 gives,

896618 − 1402163 = (1703398x + 2ξ1 ) − (811269 + 892129x + 2ξ1 )

−505545 = − 811269 + 811269x
x = 0.377

Substituting equation 4 and x into equation 3 gives,

405513(0.377) − ξ1
0.0285 =
896618
25554 = 152878 − ξ1
ξ1 = 127324 mol hr−1

Therefore substituting the values of ξ1 , ξ3 , and x into equation 1 gives,

ξ2 = −19632 mol hr−1

This means that the flow rates in the streams are approximately (values will vary slightly
due to rounding):
Stream 3 Stream R Stream 4 Stream 5 Stream 6
CH4 499, 450 152, 849 25, 554 25, 554 278, 369
CO2 351, 983 107, 720 88, 048 205, 595 383, 686
CO 0 0 146, 956 29, 409 29, 409
H2 O 147, 667 381, 385 273, 648 156, 101 230, 829
H2 0 0 362, 323 479, 870 479, 870
Total 999, 100 641, 954 896, 618 896, 618 1, 402, 163
To calculate the temperature of the stream between HX1 and HX2 (Stream X) an energy
balance must be undertaken over HX1. From Figure 4.1 we can see that Stream 2 and 4
enter HX1 while Stream 3 and X exit HX1.
We therefore need the total enthaly for each of these streams:
Stream 2

ṅ ×( ∆ hf (298) + Cp (T − 298) ) = Total

CH4 : 499450 ×( −74.6 + (0.0432)(660 − 298) ) = −29448 MJ hr−1
CO2 : 351983 ×( −393.5 + (0.0440)(660 − 298) ) = −132899 MJ hr−1
CO: 0 ×( −110.5 + (0.0280)(660 − 298) ) = 0 MJ hr−1
H2 O: 147667 ×( −241.8 + (0.1080)(660 − 298) ) = −29933 MJ hr−1
H2 : 0 ×( 0 + (0.0290)(660 − 298) ) = 0 MJ hr−1
Total: = −192280 MJ hr−1

c T.L. Rodgers 2019 47

CHAPTER 4. CONVERSION OF LANDFILL GAS TO TOWN’S GAS

Stream 3
ṅ ×( ∆ hf (298) + Cp (T − 298) ) = Total
CH4 : 499450 ×( −74.6 + (0.0432)(660 − 298) ) = −22112 MJ hr−1
CO2 : 351983 ×( −393.5 + (0.0440)(660 − 298) ) = −127633 MJ hr−1
CO: 0 ×( −110.5 + (0.0280)(660 − 298) ) = 0 MJ hr−1
H2 O: 147667 ×( −241.8 + (0.1080)(660 − 298) ) = −24510 MJ hr−1
H2 : 0 ×( 0 + (0.0290)(660 − 298) ) = 0 MJ hr−1
Total: = −174256 MJ hr−1

Stream 4
ṅ ×( ∆ hf (298) + Cp (T − 298) ) = Total
CH4 : 25554 ×( −74.6 + (0.0432)(660 − 298) ) = −966 MJ hr−1
CO2 : 88048 ×( −393.5 + (0.0440)(660 − 298) ) = −31346 MJ hr−1
CO: 146956 ×( −110.5 + (0.0280)(660 − 298) ) = −12733 MJ hr−1
H2 O: 273648 ×( −241.8 + (0.1080)(660 − 298) ) = −40988 MJ hr−1
H2 : 362323 ×( 0 + (0.0290)(660 − 298) ) = 8952 MJ hr−1
Total: = −77080 MJ hr−1

Stream X
ṅ ×( ∆ hf (298) + Cp (T − 298) ) = Total
CH4 : 25554 ×( −74.6 + (0.0432)(T − 298) ) = −1906 + 1.10(T − 298) MJ hr−1
CO2 : 88048 ×( −393.5 + (0.0440)(T − 298) ) = −34647 + 3.874(T − 298) MJ hr−1
CO: 146956 ×( −110.5 + (0.0280)(T − 298) ) = −16239 + 4.115(T − 298) MJ hr−1
H2 O: 273648 ×( −241.8 + (0.1080)(T − 298) ) = −66168 + 29.554(T − 298) MJ hr−1
H2 : 362323 ×( 0 + (0.0290)(T − 298) ) = 0 + 10.507(T − 298) MJ hr−1
Total: = −133608 + 49.154T MJ hr−1

This then means that the total energy balance is:

Q̇in = Q̇out
hStream 2 + hStream 4 = hStream 3 + hStream X
(−192280) + (−77080) = (−174256) + (−133608 + 49.154T )
49.154T = 38504
T = 783 K

The next stage of the process is the water removal, to do this the temperature of the stream
is reduced by cooling. In this case the temperature is reduced to 373 K. This reduction in
temperature causes some of the water vapour to condense into liquid water. The fraction
of water remaining as vapour is governed by equation 4.1 with the vapour pressure given
by equation 4.2.
 
o 7258.2 −6 2
pH2 O = exp 73.649 − − 7.3037 ln 373 + 4.1653 × 10 373 = 100.7 kPa
373

Thus,
100.7
y H2 O = = 0.0431
2335

48 c T.L. Rodgers 2019

 4.3. DESIGN

The fraction of vapour that is not water (i.e. the other components) is therefore 1 −
0.0431 = 0.9569. This means that,

0.9569ṅTotal = ṅCH4 + ṅCO2 + ṅCO + ṅH2

0.9569ṅTotal = 278, 369 + 383, 686 + 29, 409 + 479, 870
ṅTotal = 1, 224, 092 mol hr−1

Therefore the flowrate of water vapour remaining is,

ṅH2 O = 0.0431ṅTotal = 0.0431 × 1, 224, 092 = 52, 758 mol hr−1

The rest of the water leaves as liquid water. The composition of the stream entering the
CO2 Removal is,
Flow rate / mol hr−1 Composition
CH4 278, 369 0.2274
CO2 383, 686 0.3134
CO 29, 409 0.0240
H2 O 52, 758 0.0431
H2 479, 870 0.3920
Total 1, 224, 092 1.0000
From Table 4.1 we know that after the CO2 removal the fraction of CO2 is 0.1858, there-
fore,

(1 − 0.1858) ṅTotal = ṅCH4 + ṅCO + ṅH2 O + ṅH2

0.9569ṅTotal = 278, 369 + 29, 409 + 52, 758 + 479, 870
ṅTotal = 1, 032, 254 mol hr−1

Therefore the flowrate of CO2 remaining is,

ṅCO2 = 0.1858ṅTotal = 0.1858 × 1, 032, 254 = 191, 848 mol hr−1

The summary of the streams can therefore be seen as,

c T.L. Rodgers 2019 49

 c T.L. Rodgers 2019
CHAPTER 4. CONVERSION OF LANDFILL GAS TO TOWN’S GAS

Stream
Value
1 2 3 R 4 5 6 7 Dry Product
CH4 0.4994 0.4999 0.4999 0.2381 0.0285 0.0285 0.1985 0.2696 0.2841
Mole Fraction

CO2 0.352 0.3523 0.3523 0.1678 0.0982 0.2293 0.2736 0.1858 0.1958
CO 0 0 0 0 0.1639 0.0328 0.021 0.0285 0.03
H2 O 0.1477 0.1478 0.1478 0.5941 0.3052 0.1741 0.1646 0.0511 0
H2 0 0 0 0 0.4041 0.5352 0.3422 0.4648 0.4898
Impurities 0.0009 0 0 0 0 0 0 0 0
Total / mol hr−1 1000000 999100 999100 641954 896618 896618 1402163 1032254 979506
T/K 333 660 1000 1000 1150 617 767 373 -
P / kPa 135 2835 2785 2785 2635 2385 2385 1000 -

50
 4.3. DESIGN

c T.L. Rodgers 2019 51