KENYATTA UNIVERISTY

SCH 421
Reactor design
by
ISAAC MWANGI

https://meet.google.com/hwc-bbqs-koo
 Course outline

CUE FORMAT COURSE OUTLINES

Title of the course

SCH 421-Reactor design (35 credit hours)

Purpose of the course

The course covers the fundamentals of analysis and design of chemical reactors. The ideas and methods
covered in this course will equip the students with knowledge, principles, skills and techniques that are applied
in reactor design

Expected Learning Outcomes of the Course

This course aims to establish fundamental knowledge in the area of reaction kinetics for the students in
reactor design. Chemical reactions occur in different phases- gas phase, in solutions with different solvents,
between interfaces including gas-solid and liquid-solid, and other interfaces in solid and liquid states.
At the end of this course, students should be able to:
(i) Explain the chemical kinetics necessary for reactor design
(ii) Classify reactors and develop their design equations
(iii) Explain the effect of temperature, pressure and concentration on rates of reaction and their
respective influence on reactor design
(iv) Explain the working principals of different reactors
(v) Interpret kinetics data obtained from reactor and reaction mechanisms for application in reactor
design

Course Content
Rates plus its temperature and concentration dependence. Kinetic data interpretation. Types of reactors, such
as Batch, Continuous stirred tank, plug flow, single and multiple, plus recycle reactors. Reactor designs for
single and multiple solid catalyzed reactions as well as for series-parallel multiple reactions. Temperature and
pressure effects on yield. Rate and product distribution.

Mode of Delivery
This could include lectures- 2 hrs per week plus open session 2 hrs per month. This will include problem-based
learning, experiential learning, group-based learning, independent studies and e-learning.
Instructional Materials and/or Equipment
 Laboratory practicals
 Animated visual aids
Course Assessment
 Two continuous assessment tests (CATS) 20 marks
 Laboratory reports 10 marks
 Final examination 70 marks

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 Course outline

Core Reading Materials for the Course

 Required Text: J.B. Rawlings and J.G. Ekerdt, Chemical Reactor Analysis and Design Fundamentals,
Second edition Nob Hill Publishing, 2012.
 Fogler, HS, 2005, Elements of Chemical Reaction Engineering, 4th Edition, Prentice Hall
Schuler, ML & Kargi, F, 2002, Bioprocess Engineering, 2nd Edition, Prentice Hall.
 F2006: H.S. Fogler, "Elements of Chemical Reaction Engineering", Prentice-Hall, 4rd edition, 2006.
 F2011: H.S. Fogler, "Essentials of Chemical Reaction Engineering", Pearson Education, 1st edition, 2011.
 Smith, "Chemical Engineering Kinetics", McGraw-Hill (1981), 3rd edition.
 Levenspiel, "Chemical Reaction Engineering", 2nd edition, Wiley (1972). 3rd edition (1998).

 Other reference texts are listed on the course website and are generally available in the Library

COURSE CONTENT EXPECTED DURATION

Introduction to chemical reactors and reactor design Week 1 & 2

Conversion, Material balance and reactor sizing Week 3 & 4
Rate Laws and Stoichiometry Week 5
Cat 1 Week 6
Temperature dependent rate of reactions Week 7 & 8
Multiple Reactions-Selectivity and yield Week 9
Cat 2 Week 10

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 Introduction

1. Introduction

Lesson 1: Basic introduction of chemical reactors.

Chemical Reactor design is a field that studies the rates and mechanisms of chemical reactions
and the design of the reactors in which they take place.

Chemical reaction and chemical reactor

What is a chemical reaction?
A chemical reaction is a chemical process in which substances act mutually on each other to form products
different from the initial substances. Thus, substance changes into other different species forming products
with different chemical formula- thus different products. That process happens in a vessel if the desired
products have to be reclaimed.

A chemical reactor is a vessel in which a chemical process takes place resulting in the transformation of the
reactions to the desired products. It is designed to contain chemical reactions and has to be a complex device
in which heat transfer, mass transfer, diffusion and friction may occur. A reactor must then have provisions of
safety and controls. As all chemical reactions and process are centered in the reactor, the design becomes the
most important factor determining the overall process and economics thereof.

What is reactor design?

Design is a field of study that deals with the studies in the rates and mechanisms of chemical reactions
considering the reactions that take place in a given reactor.

Design here means the creation of a plan or convention for the construction of an object or a system
(blueprints,). In this case, it is the creation of an enclosure for efficient chemical reactions to give expected
products from specific reactants.

A chemical reactor is an enclosed volume in which a chemical reaction takes place being one of the classic unit
operations whose design intends to maximize the net present value for the given reaction. Thus it has distinct
boundaries.

The design of a reactor is not a routine matter but many alternatives are proposed for the process to provide
optimum results. A design may have low reactor cost, but the materials (product) leaving the unit may be such
that their treatment requires a much higher cost than alternative designs. Hence, the economics of the overall
process must be considered in the design process. Reactor design uses information, knowledge, and experience
from a variety of areas such as thermodynamics, chemical kinetics, fluid mechanics, heat transfer, mass
transfer, and economics.

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 Introduction

Chemical reaction engineering is the synthesis of all these factors with the aim of properly designing a
chemical reactor. To find what a reactor is able to do we need to know the kinetics, the contacting pattern and
the performance equation. We show this schematically in Figure (1).

Figure 1 A basic reactor

Regarding the functions of the reactor, there is an expression that relates the input to the output for various
kinetics and various contacting patterns which can be given as shown in equation 1.

Output  f[input, kinetics, contacting] (1)

This is called the performance equation. This equation is important because with this expression, one can
compare different designs and conditions to find out which gives the best, and then scale up to larger units.

Chemical reactors are therefore vessels designed to contain chemical reactions capable to maximize net
present value for the given reaction. The design ensures that reactions proceed with the highest efficiency
towards the desired output, giving the highest yield with the least cost to purchase and operate. Normal
operating expenses herein include energy input, energy removal, raw material costs and labour.

There are mainly two basic vessel types of chemical reactors

 A tank
 A pipe or tubular reactor (laminar flow reactor(LFR))

Both types can be used as continuous or batch reactors. Most reactors are run at steady-state, but can also be
operated in a transient state. When a reactor is first brought back into operation (after maintenance or out of
operation) it would be considered to be in a transient state, where key process variables change with time.

Both types of reactors can accommodate one or more solids (reagents, catalyst, or inert materials), but the
inputs and products are typically liquids and gases.

There are three main basic models used to estimate the most important process variables of different
chemical reactors:
 Batch Reactor
 Continuous Stirred-Tank Reactor (CSTR)
 Plug Flow Reactor (PFR)

In real life situations, reactors are modeled as a combination of these basic types. Key process variables or
parameters that are optimized include:-

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 Introduction

Residence time (τ) , Volume (V) , Temperature (T) , Pressure (P) , Concentrations of chemical species (C1, C2,
C3, ... Cn), Heat transfer coefficients (h, U)

All these parameters affect the rate of formation of products. Therefore chemical kinetics is the
study of chemical reaction rates and reaction mechanisms. Therefore, reactor design relies heavily
on chemical kinetics as the rate of production is the heart of producing almost all industrial
chemicals.

It is primarily knowledge of chemical kinetics and reactor design that classify and rate the chemical
engineer. The selection of a reaction system that operates in the safest and most efficient manner
is the key to the economic success or failure of a chemical plant.

Chemical reactions occurring in a reactor may be exothermic or endothermic. Therefore the reactor should be
thermostated to operate at the desired temperature.

A reactor particularly the tubular type can have channels or be packed with particles or pellets to enhance the
rate of reaction-catalyst. The reactants, in liquid or gas phase, are pumped through the catalyst bed.

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2. Modified and reactor characteristics

Lesson2: The section’s Objectives

At the end of this unit you should be able to;
(a) Describe the different types of ideal reactors
(b) Explain the Characteristics of each reactor
(c) Explain Conversion using the mass balance equation
(d) Calculate the rate of change of reactants
(e) Use ideas, concepts and skills acquired to develop array of reactors to solve
problems in real life situation.

2.1 Types of Reactors.

Ideal reactors normally refer to simplified models of reactors, in which various approximations are made.
These approximations allow us to describe the behaviour of the reactor using simple mathematical expressions.
There are three types of ideal reactors:
 The batch reactor
 The continuously stirred tank reactor (CSTR)
 Plug flow reactor (PFR) or Continuous tubular reactor (CTR).

2.1.1 Batch Reactor

This type of reactor is charged (filled) through the holes at the top; while reaction is carried out. Nothing else
is put in or taken out until the reaction is done. The tank easily heated or cooled by a heat jacket. Batch
reactors are usually used when a company wants to produce a range of products involving different reactants
and reactor conditions. They can then use the same equipment for these reactions. Examples of processes that
use batch reactors include the manufacture of colourants (dye, pigment) and margarine.

Figure 2 Simple batch reactors

Kinds of Usage Advantages Disadvantages

Phases Present
1. Gas phase 1. Small scale production 1. High conversion per unit volume 1. High operating cost
2.Liquid phase 2. Intermediate or one shot production for one pass 2. Product quality more variable
3.Liquid Solid 3. Testing new process that have not been 2. Flexibility of operation-same than with continuous operation
fully reactor can produce one product 3. Difficulty of large scale
4. .Manufacture of expensive products. one time and a different product production
5. Pharmaceutical,Fermentation the next
3. Easy to clean

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Characteristics

Semi-batch reactor
It operates much like batch reactors in that they take place in a single stirred tank with similar equipment.
However it is modified to allow reactant addition and/or product removal in time. A semi-batch reactor,
however, allows partial filling of reactants with the flexibility of adding more as time progresses. Semi-batch
reactors are used primarily for liquid-phase reactions, two-phase reactions in which a gas usually is bubbled
continuously through the liquid, and also for biological and polymerization reactions.

2.1.2. Continuous-Flow Reactors

2.1.2.1 Continuous-Stirred Tank Reactor CSTR

In a CSTR reactor there is a constant inflow of reactants in the feed stream and a constant outflow of
products in the exit stream. Except for the start-up and shut-down, the reactor is operated at a steady state
in which the reactor contents do not change with time.

Figure 3 A CSTR reactor

Characteristics

It runs at steady state, where the flow rate IN must equal the mass flow rate OUT, otherwise the tank will
overflow or go empty (transient state). The feed assumes a uniform composition throughout the reactor,
where the exit stream has the same composition as in the tank.
 The reaction rate is associated with the final (output) concentration.
 The reactor is equipped with an impeller to ensure a uniform and proper mixing.
 Dividing the volume of the tank by the average gives the volumetric flow rate through the tank and
hence gives the residence time, or the average amount of time a discrete quantity of reagent spends
inside the tank.

Kinds of Usage Advantages Disadvantages

Phases Present
1. Gas phase 1. When agitation is required 1. Continuous operation 1. Lowest conversion per unit volume, very
2.Liquid phase 2. Series configurations for 2. Good temperature control large reactors are necessary to obtain high
3.Liquid Solid different concentration streams 3. Easily adapts to two phase runs conversions
4. Simplicity of construction 2. By-passing and channeling possible with poor
5. Low operating (labor) cost agitation
6. Easy to clean

2.1.2.1.1 Some important aspects of the CSTR:

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This type of reactor is economically beneficial to operate several CSTRs in series as it can allow an operation
at a higher reagent concentration and therefore a higher reaction rate. In such cases, the sizes of the
reactors may be varied in order to minimize the total capital investment required to implement the process.

Figure 4 Flow sheet for the manufacture of nitrobenzene from benzene using a series of CSTR

2.1.3. Continuous Tubular Reactor CTR -Plug flow reactor (PFR)

2.13.1 Characteristics

This design consists of a long cylindrical tube or many short reactors operated at steady state. Concentration
changes with length down the reactor. The concentrations of the species involved vary along the profile and
this increases the reaction rate slows. It thus has a higher efficiency than a CSTR of the same volume. That
is, given the same space-time, a reaction will proceed to a higher percentage completion in a PFR than in a
CSTR.

The plug flow reactor model (PFR, also called continuous tubular reactor, CTR, or piston flow reactor) is a
model used to enable reactions in a continuous flow systems through a cylindrical geometry. This model is used
to predict the behavior of chemical reactors of such design, so that key reactor variables, such as the
dimensions of the reactor, can be estimated. A schematic representation of a PFR is shown in Figure 5.

Figure 5 Plug flow reactor (PFR)

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; and the amount of the reactants decrease as the
product increases with the distance along the flow.

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Figure 6 Concentration profile

The length needs to be chosen such that the desired conversion is achieved. The PFR is similar to the CSTR in
that it is operated under steady-state conditions except for the start-up and shut down of the reactor.
Considering a section along the flow profile, a slice of the reactor shown 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 conditions.

Figure 7 A section with a homogeneous composition

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 7. Thus the mole balance on the flux j can
be expressed as:-
In  Out  generation Accumulation
n j / V  n j / V  V  rj / .V  0
Again If rate is in concentration per time, multiplying it with volume will give the numbet of moles
This can be written as n j / V  n j / V  V  rj / .V
Thus n j / V  V  n j / V  rj / .V
Dividing by V gives
n j / V  n j / V  V rj .V
 r
V V j
Where r is the retained conentration
n dn dn
 r  j  rj  dn j  rj dV  j  dV
V dV rj

This implies that the reactor volume V1 necessary to reduce nA0 to nAt can be calculated from the differential
below.
dn dn dn
r  dV Upon integrating   dV    V  ln n
dV r r

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In order to model a PFR, a few assumptions need to be made. In contrast to the CSTR
or batch reactor, the PFR is not well-mixed as the conversion increases with the distance

Phases Usage Advantages Disadvantages

Primarily Gas 1. Large Scale 1. High Conversionper Unit Volume 1. Undesired thermal gradients may exist
Phase 2. Fast Reactions 2. Low operating(labor) cost) 2. Difficult temperature control
3. Homogeneous Reactions 3. Good heattransfer 3. Shutdown and cleaning may beexpensive
4. Heterogeneous Reactions 4. Hot spot occur for exothermic reaction
5. Continuous Production
6. High Temperature

With the help pf the Bernoulis equation developed as shown, the information provided below shows that the
surface area of a PFR affects the volume flowrate.

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According to Bernoulis’s principal, when the pressure is high in a tube, the velocity is low and the vice versa.
This is the same experience in a tubular reactor.

Activity-Derive the Bernoulli’s equation

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2. 2 Heterogeneous catalytic reactors

Heterogeneous catalytic reactors put emphasis on catalyst effectiveness factors and the heat and mass
transfer implications. Heterogeneous catalytic reactors are among the most commonly utilized reactors in the
chemical engineering industry. These are reactors that are derived from the PFR which include Catalytic
reactors (packed bed and Fluidized-bed Reactor reactors). They have insignificant motion of catalyst particles.

2. 2.1 Catalytic reactor

Catalytic reactors are often implemented as plug flow reactors because their analysis requires more
complicated treatment. The rate of a catalytic reaction is proportional to the amount of catalyst in contact
with the reagents, as well as the concentration of the reactants. There are both Homogeneous and
heterogeneous catalytic reactors.
Heterogeneous catalytic reactors with a solid phase catalyst and fluid phase reagents, its efficiency is
proportional to the exposed area, of diffusion of reagents into the reactor and products out, and efficacy of
mixing. This is because catalytic reaction pathways often occur in multiple steps with intermediates that are
chemically bound to the catalyst; and as the chemical binding to the catalyst is also a chemical reaction, it
affects the kinetics. Catalytic reactions often display so-called falsified kinetics, when the apparent kinetics
differs from the actual chemical kinetics due to physical transport effects.

The behavior of the catalyst is also a consideration. Particularly in high-temperature petrochemical processes,
catalysts are deactivated by processes such as sintering , coking, and poisoning.

2.3 Packed bed Reactor (fixed-bed, PBR)

A fixed bed reactor is cylindrical thus a tubular reactor filled with catalyst pellets. The reactants flowing
through the bed are converted into products. The catalyst may have multiple configuration including: one large
bed, several horizontal beds, several parallel packed tubes, multiple beds in their own shells. The various
configurations may be adapted depending on the need to maintain temperature control within the system. The
pellets may be spherical, cylindrical, or randomly shaped pellets. They range from 0.25 cm to 1.0 cm in
diameter. The flow of a fixed bed reactor is typically downward. The flow of a fixed bed reactor is typically
downward.

Phases Usage Advantages Disadvantages

1. Gas-Soli Heterogeneous Most reaction gives the highest 1. Difficulties with temperature control.
2. Liquid-Solid reaction conversion per weight of catalyst 2. Catalyst is usually troublesome to replace
3. Gas-Liquid -Solid of any catalytic reactor. 3. Channeling of the gas or liquid flow occurs, resulting in ineffective use
of part of the reactor bed

Figure 8 Packed bed Reactors

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2.4. Trickle-bed reactors (TBR)

A trickle-bed reactor (TBR) is a reactor that uses the downward movement of a liquid and the downward (co-
current) or upward (counter-current) movement of gas over a packed bed of catalyst particles. It is
considered to be the simplest reactor type for performing catalytic reactions where a gas and liquid (normally
both reagents) are present in the reactor and accordingly it is extensively used in processing plants. Typical
examples are liquid-phase hydrogenation, hydrodesulphurization, and hydrogenitrogenation in refineries. It is
also used oxidation of harmful chemical compounds in wastewater. The reactor finds use in the treatment of
waste water where the required biomass resides on the packed bed surface.

.
Figure 9 Trickle-bed reactors

This reactor is often utilized in order to handle feeds with extremely high boiling points.

2.5. Moving bed reactors

A moving bed reactor has a fluid phase that passes up through a packed bed. Solid is fed into the
top of the reactor and moves down. It is removed at the bottom. Moving bed reactors require
special control valves to maintain close control of the solids. For this reason, moving bed reactors
are less frequently used than the above two reactors.

Figure 10 Moving bed reactor

2.6 Rotating bed reactors

A rotating bed reactor (RBR) holds a packed bed fixed within a basket with a central hole. When
the basket is spinning immersed in a fluid phase, the inertia forces created by the spinning motion
forces the fluid outwards, thereby creating a circulating flow through the rotating packed bed. The

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 Modified and reactor characteristics

rotating bed reactor is a rather new invention that shows high rates of mass transfer and good
fluid mixing. RBR type reactors have mostly been applied in biocatalysis reactions or decoloration
applications.

Figure 11 Rotating bed reactor

2.7 Fluidized bed reactors

This reactor is analogous to the CSTR in that its contents, heterogeneous reactor, are well mixed It
thussuspends small particles of catalyst by the upward motion of the fluid to be reacted. The fluid is typically
a gas with a flow rate high enough to mix the particles without carrying them out of the reactor. The particles
are much smaller than those for the above reactors. Typically on the scale of 10-300 microns. One key
advantage of using a fluidized bed reactor is the ability to achieve a highly uniform temperature in the
reactor.
Phases Usage Advantages Disadvantages

1. Gas-Solid 1. Heterogeneousreaction 1. Good mixing 1. Bed-fluid mechanics not well known

2. Liquid-Solid 2. Reactor can handle large amounts 2. Temperature is relatively 2. Severe agitation can result in catalyst destruction
3. Gas-Liquid & of feed and solids uniform throughout and dustformation
Solid 3. Catalyst can be 3. . Uncertain scale-up
continuously regenerated
with good the use of an
auxiliary loop
4. Good temperature control

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Figure 12 Fluidized-bed Reactors

2.8 Slurry reactors

A slurry reactor contains the catalyst in a powdered or granular form. This reactor is typically used when one
reactant is a gas and the other a liquid while the catalyst is a solid. The reactant gas is put through the liquid
and dissolved. It then diffuses onto the catalyst surface. Slurry reactors can use very fine particles and this
can lead to problems of separation of catalyst from the liquid. Trickle-bed reactors don't have this problem
and this is a big advantage of trickle-bed reactor. Unfortunately large particles in trickle bed means much
lower reaction rate. Overall, the trickle bed is simpler, the slurry reactors usually have a high reaction rate
and the fluidized bed is somewhat in-between.

2.9 Multiple reactors

This is a combination of reactors either as a way to increase performance or because of existent

infrastructure that needs to be used to optimize the economics of a project. Such a combination can be
treated as a single reactor where the output to one is the entrance to the other. Nevertheless, there are
some particularities of coupled reactors that this section addresses.

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 Modified and reactor characteristics

Figure 13 A sludge multi reactor wastewater treatment plant

The figure shows an advanced wastewater treatment and power reduction in a multiple-reactor activated
sludge process with automatic oxygen supply system.

2.10 Arrangement of Reactors

2.10.1 Reactors in Series:

This is the case where one reactor is fed to the next one as shown below

Figure 14 Reactors in Series

2.10.2 Reactors in Parallel

Identical reactors in parallel behave just like a single reactor. Only the through-put is multiplied by the
number of reactors. This is true for BRs, CSTRs and PFRs.

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 Modified and reactor characteristics

Figure 15 reactors in parallel

Given that rate of reaction of (rA) as a function of conversion, one can design any sequence of
reactors. This is because reaction rate equation which is a mathematical expression describes the
progress of a homogeneous reaction, thus how rapidly component “A” forms or disappears in a given
environment as a function of the conditions.
dN 1  dN 
Rate   In terms of concentration,Thiscan be expressedas Rate   
dt V  dt 

Thereforethe rate becomes a function of volume V and can be expressedas : -

1  dN 
Rate    = f (conditions within the region of volumeV)
V  dt 

This implies that in reactor design, the size, type of reactor and method of operation are best for a given job.
Because this may require that the conditions in the reactor vary with position or with time, this question can
only be answered by a proper integration of the rate equation for the operation.

This can pose difficulties because the temperature and composition of the reacting species may vary from
point to point within the reactor, depending on the endothermic or exothermic character of the reaction, the
rate of heat addition or removal from the system, and the flow pattern of fluid through the vessel. In effect,
then, many factors must be accounted for in predicting the performance of a reactor.

How best to treat these factors is the main problem of reactor design. An equipment in which homogeneous
reactions are effected can be one of three general types; the batch, the steady-state flow, and the unsteady-
state flow or semi-batch reactor. The last classification includes all reactors that do not fall into the first two
categories.

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SELF-TEST QUESTIONS
(i) Given that the rate constant for a reaction in a batch reactor is 2.80x10-3 mol-1 dm3 s-1 calculate how long it will take for the material to
change by 30% its initial content
(ii) Calculate the flow rate in a 10.0 liters CSTR for a material to reduce to half its initial concentration when the rate constant is 1.38 x10-2
mol-1 dm3 s
(iii) Determine the rate constant for 80% conversion of a liquid material flowing through a 5.0 liters PFR without a catalyst at a rate of
5 mol/min

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 Features and areas of application of reactor types and mass balances

3.0 Features and areas of application of reactor types

Lesson 3: The section’s Objectives

At the end of this unit you should be able to;

(a) Derive rate equations for the different reactors
(b) Write expressions for all the species involved in the reaction
(c) Relate the chemical reaction timescale to the transport phenomena rate occurring in a
system

3.1 Material balance

Material balances express the constraint of conservation of mass, as applied to a process in ideal reactors.
Ideal reactors normally refer to simplified models of reactors, in which various approximations of material (in
and out) are made. These approximations allow us to describe the behaviour of the reactor using simple
mathematical expressions. In this section we study three types of ideal reactors: the batch reactor, the
continuously stirred tank reactor (CSTR), and the plug flow reactor (PFR). We show how to apply a mole
balance to each of them, which forms the basis for the reactor design.

The batch reactor is simple, needs little supporting equipment, therefore ideal for small-scale experimental
studies on reaction kinetics. In the industry, it is used when relatively small amounts of material are to be
treated.

The starting point for all design is the material balance expressed for any reactant (or product). This is the
material balance equation is as expressed bellow.
In  Out  generation Accumulation
n j / V  n j / V  V  rj / .V  0
Again If rate is in concentration per time, multiplying it with volume will give the numbet of moles
This can be written as n j / V  n j / V  V  rj / .V
Thus n j / V  V  n j / V  rj / .V
Dividing by V gives
n j / V  n j / V  V rj .V
 r
V V j
Where r is the retained conentration
n dn dn
 r  j  rj  dn j  rj dV  j  dV
V dV rj

This is the material balance equation can be re-written as a shown below:-

 Rate of reactants flow   Rate of reactants loss   Rate of accumulation of 
 Rate of flow into       
    out of element    due to chemical rx wthin the    reactants in the 
 the element of volume       
 of volume   element of volume   element of volume 
This information can be presented as shown in figure 15 below.
 Features and areas of application of reactor types and mass balances

Figure 16 Mass balance for an element of volume of the reactor.

3.2 Mole Balance for Batch reactors

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

IN - OUT  GENERATION  ACCUMULATI ON

 Rate of reactants flow   Rate of reactants loss/gaine d   Rate of accumulation of 
 Rate of flow into       
    out of element    due to chemical rx wthin the    reactants in the 
 the element of volume     element of volume   element of volume 
 of volume     
dN j
n j0 - nj  Gj 
dt
Where nj is the molar flow rate of species j (with units of moles sec-1) and Nj is number of moles of component
j in the reactor. The above mole balance is performed about 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 Gj over a given volume element, V , can be calculated from the rate of formation of j, rj , by:
G j  rjV
moles moles
rate   x volume
time time x volume

Batch reactors are normally used for small-scale operation, testing new processes, the manufacture of
expensive products, and processes difficult to convert to continuous. They have an advantage in that high
conversions can be achieved due to leaving the reactants in reactor. The disadvantages are high labour costs,
variability of products (batch to batch), and they are difficult to automate for large-scale production.

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 than the principal component of the liquid (the dispersing phase -
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.

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 Features and areas of application of reactor types and mass balances

If the reaction generates moles (product), the pressure in the reactor will increase, whereas if moles are
consumed, the pressure in the reactor will decrease. Because we assume that the batch reactor is well mixed
(remember the mole balance must be made over a volume element which is spatially uniform with respect to
composition and temperature) we can apply the mole balance over the entire volume of the reactor. There is no
inflow or outflow in a batch reactor, so nj0 = njt = 0.

From the rate expression

rA  KC A First order
rA  KC 2
A Second order

Rearranging first order and second order equations where r is the rate
From the rate equation, the total number of moles of the material converted will be rate multiplied by volume

The total number of moles of the material converted will be rate multiplied by volume
rAV  VKC A First order
VrA  VKC A2 Second order
dCAt
rA   kCA0 First order
dt
If rate is in concentration per time, multiplying it with volume will give the numbet of moles
N  dC N 
rAV  VkC A  k  A V  V  k  A V
 V  dt  V 
dC
V  kN A Thus VdC At  kN A 0 dt  But VdC At  dN At  VdC At  kN A 0 dt
dt
dN At dN At
Therefore dN At  kN A 0 dt   kdt   dt Upon integration
N A0 kN A 0
1 1 1
 dt  k  N A0
dN A  t 
k
ln N A  with limits

The equation predicts the mole time trajectrory at constant volume

For a reaction A→B, The mole tome trajectory will be as shown below.

Figure 17 Mole time trajectory

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 Features and areas of application of reactor types and mass balances

N A0 dN
Given that t 
rV  dCA  t   At
rAV
 with limits

Substitute for a second order if the rate equationis rA = kCA2 and find the answer for time (t)

3.3 Mole Balance Applied to CSTR

In a CSTR reactor there is a constant inflow of reactants in the feed stream and a constant outflow of
products in the exit stream. Except for the start-up and shut-down, the reactor is operated at a steady state
in which the reactor contents do not change with time.

Figure 18 CSTR reactor

The figure shows a typical CSTR showing the flow of the reacting material “A”. Here v is the volumetric flow
rate and the subscript 0 denotes a property of the feed stream (this contrasts with the batch reactor where
subscript 0 corresponds to a property at time zero i.e. t= 0).

The first step in designing a CSTR is to determine the volume required to achieve a given conversion using a
mole balance. In order to do this, we need to make the well-mixed assumption used for the batch reactor. Thus
we assume that the composition and temperature in the reactor are uniformly distributed and we can then
apply the mole balance about the entire reactor volume. Furthermore, under the well-mixed assumption, the
exit stream is at the same composition and temperature as the contents inside the reactor. At steady state,
the reactor contents do not change with time.

dN j
Thereforeit is a steady state where 0
dt
Plugging the mole balance gives

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 Features and areas of application of reactor types and mass balances

n j0  n j
Plugging mole balance gives where : - In  Out  generation 0 Then n j 0  n j  rjV  0  V 
 rj
Volume
According to molar rates,n j  C j v Where v is the volumetric flowrate given as
time
v0C A0  vCAt v0C A0  vCAt
Substituting n j with vand V j We get V  But rj  kC ATherefore V 
 rj kC At
 
 
vC A0  C At  v C A0  C At  v  C A0
When vo  v then V  V  x V  - 1
kC k C k C 
 
At At  At 

Example problem
v0C A0  vCAt
Given that V  Substitute the second order rate equation..rA  kCA2
 rj
v0C A0  vCAt
and find expression for the volumeV Hint V 
kCAt2
3.4 Mole balance applied to plug flow reactor (PFR)

PFRs are mainly used for gas phase reactions and may be packed with catalyst. A schematic representation of a
PFR is shown below.

Figure 19 Plug flow reactor

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 similar to the CSTR in that it is operated under steady-state conditions except for the start-up and shut
down of the reactor.

In order to model a PFR, a few assumptions need to be made. Unlike the CSTR or batch reactor, the PFR is not
well-mixed as the conversion increases with the distance along the tube.

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 Features and areas of application of reactor types and mass balances

However, it is assumed that there are no gradients of composition or temperature in the radial direction.
Thus, it is done at a condition to enable an accurate calculation of the size of the reactor. Thus a
slice of the reactor ΔV contains a homogeneous distribution of composition. Having no radial variation also
requires that the velocity distribution in the PFR is flat, which is better approximated under turbulent flowing
conditions. Lastly, we also assume that there is no axial mixing, this allows us to omit terms due to diffusion or
dispersion in the mole balance.

Figure 7-repeated

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 the Figure 7. Thus the mole balance on the flux j
can be expressed as:-
In  Out  generation Accumulation
n j / V  n j / V  V  rj / .V  0
Again If rate is in concentration per time, multiplying it with volume will give the numbet of moles
This can be written as n j / V  n j / V  V  rj / .V
Thus n j / V  V  n j / V  rj / .V
Dividing by V gives
n j / V  n j / V  V rj .V
 r
V V j
Where r is the retained conentration
n dn dn
 r  j  rj  dn j  rj dV  j  dV
V dV rj
This implies that the reactor volume V necessary to reduce nA0 to nAt can be calculated from the differential
below.

Figure 6 -repeated

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 Features and areas of application of reactor types and mass balances

The graph shows that the molar flow rate of component A and B as a function of volume in a PFR as previously
indicated.

dn dn
From the above equation, r  dV when the first order kinetics is applied,where rA  kCA
dV r
d C A  dC 
and nA  C A Therefore, dV   A  dCA
kCA kCA kCA
Uponint egration
dn  
 dV   r   kCA dCA  V  k ln C
When the reactants are gaseous, the conditions Vt is constant can be deduced using the gas equation.
ni RT
PV  ni RT  V 
P

Thus, the temperature, pressure, and total molar flow rate must be constants for V to be a constant. In the
reaction of A going to B, for each mole of A consumed, one mole of B is formed so that indeed the total molar
flow rate is a constant.

In the event that the number of moles are not equal the moles consumed, there is need to account for the
change in V as a function of the change in mole number along the reactor.

Example problem

dn 2
Given that  dV    Substitute r for the second order rate equation ..r  kC
A A
r

Also, 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. This behaviour should be
contrasted to what happens in a gas phase reaction in a batch reactor. In this case, the volume of the reactor
is a constant so that the pressure changes when the reaction either generates or consumes moles.

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 Features and areas of application of reactor types and mass balances

Summary
The key design equationshave been derived for each type of ideal reactor using the assumptions
involved in the ideal reactor definitions. Additionally,the expressions have been derived to determine
the time or volume required to achieve a reactant concentration for 1st - order reactions.
dN A
Batch t  
rAV
n j0  n j
CSTR V  
rj
dnA
PFR V  
rA
* *Substitute the second order rate equation..rA  kCA2

Activity-Discuss the questions below within your group

SELF-TEST QUESTIONS
Material A was introduced in a batch reactor and it was found out that 50% of the A was
converted to the product after 50 minutes.
i) If the reaction was first-order kinetics, how much more time is required to have 86.5%
conversion?
ii) How long could the same product be realized if the reaction was second order?

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 Conversion and reactor sizing

4.0 Conversion and reactor sizing

Conversion describes how much of a reactant has reacted and how much of a desired product was
formed in relation to the undesired product(s). Conversion can be defined for (semi-) batch and
continuous reactors and as instantaneous and overall conversion.

Lesson 4: Objectives
At the end of this unit you should be able to;
(a) Determine the limiting reactant
(b) Calculate the time dependent convers ions
(c) Explain the difference in the conversion between different reaction orders
(d) Use Design Equations for Flow Reactors to calculate the size of a reactor

The concept of conversion is useful as it provides a direct measure of the extent of reaction. Furthermore,
when only one reaction is occurring in the reactor, all molar flow rates can be expressed in terms of the
conversion, which makes solving the design equation easier.

Consider the reaction:

aA+ bB  cC + dD
Where the lower-case letters are the stoichiometric coefficients and upper-case letters the chemical species.

Take species “A” as the basis of calculation therefore, divide through by the coefficient of “A”to get the
ration o of the content of reacting species.

In this case, A is the limiting reactant thus chosen for the basis of calculations
b c d
A+ B C+ D
a a a
Every quantity is now ‘per mole of A’

The questions that arise are;-

 How can we quantify how far the reaction proceeds to the right?
 How many moles of C (or D) are formed for every mole of A consumed?
To answer these questions it is convenient to use a parameter, conversion. Conversion of A is defined as: -

No of moles of A reacted
XA 
No of moles of A fed
NOTE
Conversion
 For irreversible reactions, at the start X = 0 and at the end X = 1, in cases where all of A is consumed
(note that A will only be totally consumed if it is the limiting reactant in an irreversible reaction)
 For reversible reactions, the maximum conversion possible is controlled by the equilibrium constant;
the maximum value is termed the equilibrium conversion Xe
 Conversion and reactor sizing

Watch video on the link to enable you understand the basis of conversion and the limiting reactant.
https://www.youtube.com/watch?v=iUzEtjHzPoo

4.1 Conversion in Batch Reactors

This section will show the calculation of reactor volume and the time to achieve a given conversion in batch
systems.

All molar flow rates should be written in terms of the conversion of “A” and concentrations of components in
the reactor before the reaction has started.
 Moles of A reacted   Moles of A fed   Moles of A reacted 
    
 consumed     Moles of A fed 
N A0 x 
X fraction 
The number of moles of A that remain in the reactor after time, t, NAt is

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 Conversion and reactor sizing

 Moles of A initially fed 

 Moles of A in reactor    Moles of A consumed 
   in the reactor at time t0    
 at time t     by the reactor at time t0 
 
NA  N A0 - N A0 X
NA  N A0 - N A0 X  N A0 1 - X 
N A  N A0 - N A0 X  N A  N A0  - N A0 X Therefore N A 0  N A  N A0 X
N A0  N A
The equationcan thus be rearanged as X 
N A0
dN A
N  N A 0  N A Therefore dX 
N A0
Since this is the batch reactor,we invilvethe volume to get the concentration.
N  NA C  CA dCA
From X  A 0 we get X  A 0  dX 
N A0 C A0 C A0
Borrowing from N A0 - N A0 X  N A0 1 - X 

 [ N A0 1 - X  ] 
dN A d dN A0 dX dX
We can write - N A0   N A0 At time zero
dt dt dt dt dt

N
Knowing that Volume x concentration  Moles,then volumeV 
C
dN A
then rate r  can be expressedinterms of V and C as shown
dt
dN A dCA dN A
r V   rAV
dt dt dt
dN A
It is also clear that N A 0  N A  dN A ThereforeMole fraction dX   N A0 dX  dN A
N A0
dX dN A dX dX
If N A0 dX  dN A Then N A0   rAV From this equation,we get N A0  rAV  N A0  dt 
dt dt dt rAV
dX
Upon int egration, t  N A0  This is a form of the design equation
rAV
In order to perform the integration, the rate of formation and the volume need to be expressed as
a function of the conversion. As mentioned previously, often the volume is a constant for a batch
reactor. Considering the first-order rate law, where we showed that:-

dX dX
Since rAV  kN Acan be substituted in the design equation t  N A0  to read t  N A0 
rAV kN A
dX
But N A  N A0 1 - X  Then t  N A0 
dX
t  
dX 1
1 - X 
k 1 - X  k 

kN A0 1 - X 

ln1 - X 
1
Upon integration, t 
k

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 Conversion and reactor sizing

This provides a relationship between the time for the reaction needs to reach the specified conversion, X. The
only assumptions that have been used in deriving that equation for the reaction of A to B is that the reactor is
isothermal.

4.2 Conversion in Flow Reactors

For a flow reactor, the total rate at which species A is reacting within the entire system is nA0X-Where nA0 is
the number of moles at time zero and X is the fraction.

 Moles of " A" initially fed at time t0   Moles of " A" reacted 

nA0 X  X 
 time   Moles of " A" initially fed at time t0 
Moles of " A" reacted
From Mathematics , this gives
time
Molar feed rate of A to the system minus the rate of reaction in the system equals molar
flow rate leaving:

 Molar flow rate at which " A" is   Molar flow rate at which   Molar flow rate at which 
      
 fed to the system   " A" is consumed   " A" leaves 
n A0  n A0 X  nA
NA  N A0 - N A0 X  N A0 1 - X 
n A  n A0 - n A0 X  n A  n A0 1  X 

The rate of reaction is known in terms of concentration variables. The molar flow rates are converted to
concentrations using the volumetric flow rates. The inlet flow rate is thus given by:-
nA0  C A0 v0
For gases, the concentration CA0 can be calculated using the gas equation:-.
PA0 P A0
PV  nRT  PV  nA0 RT Thus C A0  
RT RT
Where pA0 is the partial pressure of “A” in the inlet, P0 is the inlet pressure, and γA0 is the inlet mole fraction

4.2. 1 CSTR Design Equations for Conversion Derivatization of the Dahmkohler number’

The Damköhler numbers are dimensionless numbers used in chemical engineering to relate the chemical
reaction timescale to the transport phenomena rate occurring in a system. It is named after German chemist
Gerhard Damköhler. The Karlovitz number is related to the Damköhler number by Da = 1/Ka.

nA0  nA
The design equation for CSTR is given by V When the mole fraction “X” is involved, this can be
 rA
nA0 X
presented as:- V 
 rA
This is based on the concentration divided by the rate n dn n  nA
n  CV  and V   dV   A0
C dC  rA

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 Conversion and reactor sizing

nA0 X
When rate in the form of concentration is involved then, V .
kCA
C A0v0 X V
But nA0  C A0v0 Therefore V  Where v0 is flow rate Therefore,  which is a measure of
kCA v0
C A0 X
time. This implies that 
kCA
This is the time necessary to process one volume of reactor fluid at the entrance conditions. This mean
residence time provides a measure of how long the fluid is in the reactor, which controls the conversion. The
larger the residence time”  ”, the greater the conversion.

We Know that nA  nA0 1  X  Then C A  C A0 1  X 

Plugging CA in terms of CA0 in the residence time, we get

  k (1  X   X
C A0 X C A0 X X
   
kCA kCA0 (1  X ) k (1  X )
 k (1  X   X  X  k  kX WhenkX is added on both sides,
We get X  kX  k  X 1  k   kX
k
Therefore, X 
1  k 
The equation provides a rapid way for estimating the conversion in terms of the product ” k ”, which is known
as the reaction ‘Dahmkohler number’. Values of the Damkohler number that equal to 0.1 give conversions of
about 10 %, whereas values equal to 10 give conversions of close to 90%.

Calculate the Dahmkohler number’ by substitution the first order kinetic equation with the second order
kinetics.

4.2.1 PFR Design Equations for Conversion

dnA
Starting from the PFR design equation  rA This has been derived from
dV

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 Conversion and reactor sizing

In  Out  generation Accumulation

n j / V  n j / V  V  rj / V  0
This can be written as n j / V  n j / V  V   rj / V
Thus n j / V  V  n j / V  rj / V
Dividing by V gives
n j / V  n j / V  V n
 rj  r
V V
Where r is the retained conentration
n dn j
r  rj
V dV

The molar flow rate of “A” at a given position in a PFR is given by nA  nA0 1  X 
where X corresponds to the conversion as a function of position in the PFR. The latter relation can be derived
by doing a mole balance about the entry to the PFR and any position in the PFR. Upon differentiation, we have
dnA  nA0 dX This has been derived from nA  nA0 1  X  . X being a fraction and 1  X  is the
variation of X.

dnA dn (1  X ) d (nA0  nA0 X ) nA0 dX

Thus  rA  A0  
dV dV dV dV
Upon Substituting this result into the design equation gives
dX dX
rA  nA0 which can be written as dV  nA0
dV rA
The integral form of the design equation is obtained by separating variables and doing the volume integration
from 0 to V in which case the conversion goes from 0 to X:Thus:-
dX dX
From dV  nA0 Upon int ergration,V  nA0 
rA rA
and C A  C A0 1  X When plugged in the equationabove V  nA0 
dX
r  kCA we get
rA
dX dX n dX
V  n A0   V  n A0   V  A0  1  X  Upon integration
kCA kCA0 1  X  kCA0

ln1  X  But we know that A0  v0 Then V  0 ln1  X 

n A0 n v
V
kCA0 C A0 k

then  ln1  X 
V 1
from residencetime "  " 
v0 k

Self -assessment
Calculate the residence time by substituting the first order kinetic equation with the second order kinetics

Page 8 of 37
 Conversion and reactor sizing

4.2.1 Application of the Design Equations for Flow Reactors. SIZING THE REACTOR

This section aims is to use the experimentally derived knowledge of the rate of reaction, “rA”, as a function of
conversion, X, to size CSTRs and PFRs

4.2.1 Design Equations for CSTR and PFR and the Levenspiel Plot
nA0 X dX
CSTR: V  PFR: V  nA0 
rA rA

From both equations, it shows that volume in both cases depend on the reciprocal of rate of reaction “r A”

A Table is provided here below that shows some real data for an isothermal reaction with conditions of T =
500 K, P = 8:2 atm, and nA0 = 0:4 mol s-1 for the purpose of sizing the reactor. In order to size a reactor from
nA0
experimental rate data, we first need to plot (m3) as a function of X (this plot is called a Levenspiel plot)
rA

Table 1 Real conversion data for isothermal reaction

X r(mole m-3s -1)

1 n
A0
(m3s mole-1) (m3)
rA rA

0 0.45 2.22 0.89

0.1 0.37 2.7 1.08
0.2 0.3 3.33 1.33
0.4 0.195 5.13 2.05
0.6 0.113 8.85 3.54
0.7 0.079 12.7 5.06
0.8 0.05 20 8

Figure 20 Levenspiel plot of the data

Figure 19 shows the Levenspiel plot for the data given in Table 1

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 Conversion and reactor sizing

4.2.2 CSTR calculation of volume

Then the flow rate can be used to calculate the volume, V , of a CSTR to give 80% conversion? From the data
1
above when X = 0:8, = 20 m3 s mol-1. If we substitute these values into the
rA

n A0 X
CSTR design equation CSTR: V  then we can determine the volume:
rA
n A0 X
CSTR: V   8 (m3 ) x0.8  6.4m3
rA
The volume at the mole fraction is equal to the area of a rectangle of height (8m3) and base (X = 0:8) on the
Levenspiel plot as shown

Figure 21 Volume obtained from the Levenspiel plot of CSTR

dX
Using the PFR design equation PFR: V  nA0  the volume from the same data the volume will be
rA
equal to the area under the curve.

Figure 22 Volume obtained from the Levenspiel plot of PFR

The design equation for the PFR contains an integral, thus the required volume can therefore be determined
from the area under the curve.

The findings based on each of the respective equation reveals that CSTR volume required is greater than the
PFR volume for the same conversion and reaction conditions.

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 Conversion and reactor sizing

Why is this?
The concentration in the CSTR everywhere is equal to the exit concentration, so that the reaction rate is
proportional to the exit concentration over the entire volume of the CSTR. In a PFR, the concentration of the
reactant A gradually decreases along the reactor until it reaches a minimum value given by the exit
concentration. As a consequence, the concentration of A in the PFR is always greater than that in the CSTR
when the same exit conversion is achieved. Because the rate is proportional to the concentration of A, the rate
is also greater everywhere in the PFR versus in the CSTR.

4.2.3 Reactors in Series

Putting CSTRs in series reduces the volume required. An infinite number in series is equivalent to a PFR.
Putting PFRs in series is equivalent of a longer PFR, see figure below.

Figure 23 Schematic representation of multiple-in series (a) CSTR volumes and (b) PFR volumes

Page 11 of 37