Introduction to Reactor Design

Topics to be covered
Reactor & Types
Elements and Parameters important for reactor
design
General mole balance (GMB)
Application of GMB for specific reactor design
Chemical Reaction Engineering

Mechanisms of Reaction and

Rates of Reaction

Reaction Kinetics and Rate

Equations

Reactor Design and Selection

 A Chemical Reactor

In Reactor out

• Transforms Raw materials to Products

• Can be batchwise, semicontinuous or continuous
• Classification often based on the number of phases
– gas, liquid, solid, catalyst
• The process chemistry determines very much the reactor
selection
 Chemical Reactors
• An industrial chemical reactor is complex device in which heat transfer,
mass transfer, diffusion and friction may occur along with chemical reaction
with provisions of safety and controls.
• All chemical processes are centered in a chemical reactor. The design of a
chemical reactor Is the most important factor in determining the overall
process economics.
• These are vessels designed to contain chemical reactions.
• There are the two main basic vessel types, tank and pipe.
At the start of the design work , the following information is
presumably available:
Reaction Type
Need for catalyst
Phases involve
The mode of temperature and pressure control, and
Production capacity
• Single Displacement or Substitution Reaction
A + BC = AC + B
• Metathesis or Double Displacement Reaction
AB + CD = AD+ CB

In addition to the basic data, include

A heat and mass transfer characteristics (Endothermic,
Exothermic)
Physical, chemical and thermodynamic properties of
components taking part in the reaction.
CORROSION- erosion characteristics of any potential hazard
associated with reaction system.
 Reaction Rate (T, P, Conc., Catalyst)
 Introduction to Reactor Design
• Rate equation describes the progress of a homogeneous reaction. The rate
equation for a reacting component i is an intensive measure, and it tells how
rapidly component i forms or disappears in a given environment as a function of
the conditions there, or rA= f (conditions within the region of volume V).

• In reactor design we want to know what size and 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 as well as time, this question can only be
answered by a proper integration of the rate equation for the operation.
• This may pose difficulties because the
• Temperature and composition of the reacting fluid 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.
• The flow pattern of fluid through the vessel.
 Basic Reactor Design Elements
• Material Balances [Also called mass balance]
– Is an application of conservation of mass to the analysis of physical systems.
– The mass that enters a system must, by conservation of mass, either leave the
system or accumulate within the system .
Input = Output + Accumulation -------Non Reactive Systems
• Heat Transfer and Mass Transfer
-Is the phrase commonly used in engineering for physical processes that involve
molecular and convective transport of atoms and molecules within physical
system.
• -Transfer of mass from high concentration to low concentration.
• jacket,
• internal coils,
• external heat exchanger,
• cooling by vapor phase condensation
• fired heater.
 Basic Reactor Design Elements
• Reactor design usually involves the following:
– Knowledge of nature of reaction
• Catalytic or Non-Catalytic
• Homogeneous or Heterogeneous
• Reversible or Irreversible
– Selection of operating conditions
• Temperature, Pressure, Concentrations
• Type of catalyst (if applicable)
• Flow rates
– Selection of reactor type for a given application
– Estimation of reactor volume required to process given amount
(moles or molar rate) of raw material to desired amount of products
• How fast does the reaction occurs (reaction rates) dictates how
large the reactor volume will be
• Design of isothermal reactors involves solution of MOLE BALANCE
equation only
– In some cases, pressure drop must also be calculated
 Our approach to reactor design
• Operations of most reactors are relatively complex
– Temperature is not uniform and/or constant
– Multiple reactions can occur
– Flow patterns are complex
• To gain an insight into basic concepts relevant to reactor
design, we will, first, consider simplified and/or ideal reactor
systems.
• Let us first familiarize ourselves with some common
terminologies and notations that we will be using
throughout the reactor design and selection.
 Good Design
• Prediction of response of the reacting system
in changes to operating conditions
• Comparison of yields for alternative designs
• Economics for all alternatives
Where the composition within the reactor is uniform (independent of
position), the accounting may be made over the whole reactor.
Where the composition is not uniform, it must be made over a
differential element of volume and then integrated across the whole
reactor for the appropriate flow and concentration conditions.
 Reactor Design
• In real 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.
• Equipment in which homogeneous reactions are effected can be one of three
general types;
• Batch
• Steady-state flow
• Unsteady-state flow or semi-batch reactor.
The last classification includes all reactors that do not fall into the first two
categories. These types are shown in figure
 Common Reactor Types

• Batch Reactor
• Semi-Batch Reactors
• Flow Reactor
– Continuous-Stirred Tank Reactor (CSTR)
– Plug Flow Reactor (PFR)
– Packed Bed Reactor (PBR)
• Other Reactor Types
– Fluidized Bed Reactor
– Trickle Bed Reactor
 Brief Introduction to Reactors

Let us briefly indicate the particular features and the main areas of
application of these reactor types.
 The batch reactor is simple, needs little supporting equipment, and is
therefore ideal for small-scale experimental studies on reaction kinetics.
Industrially it is used when relatively small amounts of material are to be
treated.
 The steady-state flow reactor is ideal for industrial purposes when large
quantities of material are to be processed and when the rate of reaction is
fairly high to extremely high. Supporting equipment needs are great;
however, extremely good product quality control can be obtained. As may
be expected, this is the reactor that is widely used in the oil industry.
 The semi-batch reactor is a flexible system but is more difficult to analyze
than the other reactor types. It offers good control of reaction speed
because the reaction proceeds as reactants are added.
External Heat Exchanger
Cooling by Vapor Phase Condensation
 Batch reactor
One in which feed material is treated as a
whole for a fixed period of time.

Key Characteristics
• unsteady-state operation (by definition)
• no spatial variation of concentration or temperature, i.e. lumped
parameter system (well-mixed)
• mainly used for small scale operation
• suitable for slow reactions
• mainly (not exclusively) used for liquid-phase reaction
• charge-in/clean-up times can be large
 Semi batch reactor

One or more reactant is in a batch modes, while co reactant is

fed and withdrawn continuously.
Batch Reactor
Semi-batch Reactor
 Stirred Tank Reactor or Continuous Stirred
Tank Reactors (CSTR’s)
Consist of a tank fitted with a mechanical agitator and a cooling
jacket or coils.
 One or more fluid reagents are introduced into a tank reactor.
At steady state, the flow rate in must be equal the mass flow
rate out.
All calculations performed with CSTR’s assume perfect mixing.
The reaction proceeds at the reaction rate associated with the
final (output) concentration.
 Economically beneficial to operate in series or in parallel.
Small CSTR’s operating in series would be equivalent to a PFR.
 Plug Flow Reactor (PFR)
One or more fluid reagents are pumped through a pipe or
tube.
All calculations performed with PFR’s assume no upstream
or downstream mixing.
Reagents may be introduced into the reactor’s inlet.
 Has a higher efficiency than a CSTR at the same value.
PFR’s or TFR’s are generally used for gaseous reactions but
are also suitable for some liquid-phase reactions.

Key Characteristics
• Steady-state operation
• Spatial variation in axial direction but not in radial direction + no temporal
variation, i.e. distributed system
• suitable for fast reaction mainly used for gas phase reaction
• temperature control may be difficult
• there are no moving parts
Schematic Diagram of Plug Flow Reactor
 Conversion (X)
• Quantification of how far a reaction has progressed

Moles of species " i" reacted

X
Moles of species " i" fed

• Batch Reactors

N IO  N I
X
N IO

• Continuous (or Flow) Reactors

FIO  FI
X 
FIO
 General Mole Balance
System
Volume,
V

Fj0 Gj Fj

 Molar Flow  Molar Flow   Molar Rate   Molar Rate 

 Rate of    Rate of   Generation    Accumulation
       
 Species j in   Species j out  of Species j  of Species j 
dN j
Fj 0  Fj  Gj 
dt
 mole   mole   mole   mole 
          
 time   time   time   time 
 General Mole Balance

If spatially uniform
G j  r jV

If NOT spatially uniform

 V1
V2
rj1
rj 2
G j1  rj1V1
G j 2  rj 2 V2



 General Mole Balance

W
G j   rjiVi
i1

Take limit
n
Gj   rji Vi   r dV
j
i1 lim V  0 n  
 General Mole Balance
System
Volume,
V

FA0 GA FA

General Mole Balance on System Volume V

In  Out  Generation  Accumulation

dN A
FA 0  FA   rA dV 
dt
 General Mole Balance Equation (GMBE)
General mole balance equation is the foundation of reactor design.

Rate of INPUT – Rate of OUTPUT + Rate of GENERATION = Rate of ACCUMULATION

dN A
FAO - FA + GA =
dt
FA

FAO
Control Volume = V

GA = (rate of formation of A) · V
= (rA)·V
 Batch Reactor Mole Balance

Batch

dN A
FA 0  FA   rA dV 
dt
FA 0  FA  0

Well Mixed  r dV
A  rAV

dN A
 rAV
dt
 Batch Reactor Mole Balance
dN A
Integrating dt 
rAV

when t = 0 NA=NA0
t = t NA=NA

NA
dN A
t 
N A0
 rAV

Time necessary to reduce number of moles of A from N A0

to NA.
 Batch Reactor Mole Balance

NA
dN A
t 
N A0
 rAV

NA

t
 CSTR Mole Balance

CSTR

dN A
FA 0  FA   rA dV 
dt

dN A
Steady State 0
 dt
 CSTR Mole Balance

Well Mixed  r dV  r V
A A

FA 0  FA  rAV  0

FA 0  FA
 V
rA
CSTR volume necessary to reduce the molar flow rate
from FA0 to FA.
 Plug Flow Reactor Mole Balance

V

FA FA


V V  V
 

 In  Out  Generation 
at V  at V  V   in V 0
     
FA V  FA V  V  rA V 0
 Plug Flow Reactor Mole Balance
Rearrange and take limit as ΔV 0

FA V V  FA V
lim  rA
V  0 V
dFA
 rA
dV

This is the volume necessary to reduce the entering molar
flow rate (mol/s) from FA0 to the exit molar flow rate of F A.

 Space time and Space velocity
Just as the reaction time t is the natural performance measure for a batch
reactor,
so are the space-time and space-velocity the proper performance measures of
flow reactors.

Thus, a space-velocity of 5 hr-l means that five reactor volumes of feed at

specified conditions are being fed into the reactor per hour. A space-time of 2
min means that every 2 min one reactor volume of feed at specified conditions
is being treated by the reactor.
It may be more convenient to measure the volumetric feed rate at some standard
state, especially when the reactor is to operate at a number of temperatures. If, for
example, the material is gaseous when fed to the reactor at high temperature but is
liquid at the standard state, care must be taken to specify precisely what state has
been chosen. The relation between the space-velocity and space-time for actual
feed conditions (unprimed symbols) and at standard conditions (designated by
primes) is given by
One liter per minute of liquid containing A and B (CA0 = 0.10 mol/liter, CBo =
0.01 mol/liter) flow into a mixed reactor of volume V = 1 liter. The materials
react in a complex manner for which the stoichiometry is unknown. The outlet
stream from the reactor contains A, B, and C (CAf = 0.02 mol/liter, CBf = 0.03
mol/iter, Ccf = 0.04 mol/liter). Find the rate of reaction of A, B, and C for the
conditions within the reactor.
 Plug Flow Reactor PFR

No radial gradients – only

axial
Steady state
PFR
 Packed Bed Reactor (PBR)

FA0 FA

Key Characteristics
• Similar to PFR. Can be thought of as PFR packed with solid particles, which are almost
always catalysts.
• Steady-state operation
• Mainly used for gas phase catalytic reaction although examples for liquid-phase
reaction are also known.
• temperature control may be difficult
• There are no moving parts
• Pressure drop across the packed bed is an important consideration
Staged Adiabatic Packed Bed Reactors
PERFORMANCE EQUATIONS FOR REACTORS
CONTAINING POROUS CATALYST PARTICLES
 Packed Bed Reactor Mole Balance

PBR

dN A
FA W   FA W  W   rA W 
dt
Steady State dN A
0
dt
FA W  W  FA W
lim  rA
W  0 W
 Packed Bed Reactor Mole Balance

Rearrange:
dFA
 rA
dW

The integral form to find the catalyst weight is:

 FA
dFA
W 
FA 0
rA

PBR catalyst weight necessary to reduce the entering

molar flow rate FA0 to molar flow rate FA.
 Solid catalyzed reactions
• Reactant gas can be made to contact solid
catalyst in many ways, and each has its
specific advantages and disadvantages.
• These may be divided into two broad types,
• Fixed bed reactors
• Fluidized-bed reactors.
 Reactor Mole Balance Summary
Reactor Differential Algebraic Integral

NA NA
dN A
Batch dN A
 rAV t 
dt rV
N A0 A

t
CSTR FA 0  FA
V
rA
FA
FA
dFA dFA
F drA
PFR
 rA V
dV  A0

V
Common Types of Catalytic Plant Reactors

1.Fixed-bed Reactors
a. Packed beds of pellet or monoliths
b. Multi-tubular reactors with cooling
c. Slow-moving pellet beds
d. Three-phase trickle bed reactors

2.Fluid-bed and Slurry Reactors

i. Slurry
ii. Bubble Column
iii. Fluidized bed reactors
 Characteristics of Plant-Scale Fixed Bed Reactors
Advantages Disadvantages
1. Ideal plug (or mixed) flow 1. Poor heat transfer in a large fixed bed.
2. Simple analysis a. Temp. control and measurement difficult
3. Low cost, low maintenance b. Thermal catalyst degradation
4. Little loss or attrition c. Non uniform rates.
5. Greater variation in operating conditions and contact 2. Non uniform flow patterns e.g. channeling
times is possible 3. Swelling of the catalyst; deformation of the reactor
6. Usually a high ratio of catalyst to reactants 4. Regeneration or replacement of the catalyst is
long residence time complete reaction difficult - shut down is required.
7 Little wear on catalyst and equipment 5. Plugging, high pressure drop for small beads or
8. Only practical, economical reactor at very high pellets - ∆P is very expensive.
pressures 6. Pore diffusional problems intrude in large pellets

Overcoming the Disadvantages

1. Monolithic supports overcome disadvantages 2, 5 & 6
2. Temperature control problems are overcome with:
a. Recycle
b. Internal and external heat exchanges
c. Staged reactors
d. Cold shot cooling
e. Multiple tray reactor - fluid redistributed & cooled between stages.
Catalyst is easily removed - varied from tray to tray.
f. Use of diluents
g. Temperature self regulation with competing reactions, one endo and one exothermic.
h. Temp control by selectivity and temporarily poisoning the catalyst
Fixed-bed reactors: characteristics, advantages, limitations

Advantages:
• Flexible- large variation in operating conditions and contact times
is possible
• Efficient- long residence time enables a near complete reaction
• Generally low-cost, low-maintenance reactors

Disadvantages:
• Poor heat transfer with poor temperature control
• Difficulty in regenerating or replacing spent catalyst
 a.. Reactants Inlet

Liquid Or
Feed Gaseous
Bath

Reactor Reactor
Inert balls Tube Tube

Catalyst
Gas Or
Liquid
Flow

Outlet
Product

Product b.
I II III IV

1 2 3 4
Figure Commercial fixed-bed, Fresh feed

adiabatic catalytic reactor.

Recycle gas

Figure Commercial fixed-bed reactor designs for controlling

temperature: (a) multi-tubular heat-exchange reactor, (b) series of
fixed-bed, adiabatic reactors with interstage heating or cooling.
 CATALYST DEACTIVATION DIAGRAM

Pd Sites

Al2O3

A
Fresh Catalyst (high dispersion; high surface area)

Pore cintering
Cintered Pd

Al2O3 -Al2O3

B C
Old Catalyst Old catalyst
Low dispersion (low activity) Low surface area (low activity)
Characteristics of Plant-Scale Fluidized and Slurry Bed Reactors

Advantages Disadvantages
1. Frequent regeneration of the catalyst 1. Fluidized beds are complicated systems
possible. involving multiple reactors, heat exchangers,
2. Rapid mixing of solids in fluid beds means extensive valving and piping to provide
uniform gas composition. continuous system.
3. Isothermal operation and efficient 2. Extensive investment. Maintenance is high.
temperature control is practical. 3. Fluid flow is complex in fluidized and slurry
4. Small-diameter particles in fluid minimize bubble columns - less than ideal contacting.
pore diffusional resistance. Product distribution is changed - less
intermediate formed in a series reaction.
5. Improved thermal efficiency because of
high heat transfer rates. 4. Only a small variation in residence time
possible. Low residence times. Conversion
6. In the case of highly exothermic, liquid may be limited.
phase reactions, slurry reactors are less
complex and less expensive than heat- 5. Attrition & loss of Catalyst.
exchange-tubular systems.
a. Deentrained b.
vapor Continuous
phase Product
Product

Hydro- Spent
clone catalyst

Fresh
catalyst Dispersed
phase
Feed

Figure Liquid-phase slurry reactors: (a) forced-circulation, slurry-bed

reactor, (b) bubble-column, slurry-bed reactor.
 rotor
H2 from reservoir
(consumption measured)
P to heat source

pressure
vessel

shaft heater

liquid

product
withdrawal reactants + H 2

suspended products
catalyst
particles H2

Figure: Batch-slurry reactor for hydrogenation of specialty chemicals.

 Fundamentals
• Chemical reactor is the heart of the plant
Basic aim is to produce a specified product at a given rate from
unknown reactants.
How to proceed:
1- The type of reactor and its method of operation
2- The physical condition of reactants at inlet
What is desired:
1- Reactor Size: Volume and important dimensions
2-Composition and physical conditions of product
3- Temperature inside the reactor and H.T methodology
4- Operating pressure and any pressure drop occurring at inlet
or outlet of reaction mixture
The existence of any by product must be known
 Reactor Classification and type selection
Homogenous Reactors:
Only one phase is involved: gas or liquid
When more phases are involved the mixing is very important
Heterogeneous Reactors:
Two or more phases are involved.
Normally solids if present then are in catalyst form.
A heterogeneous reactor may involve a heterogeneous reaction
or a homogeneous reaction.

Heterogeneous reactors show greater variety of configuration

and contacting patterns than homogenous reactors.
 Types of Reactors
Batch Reactor (BR, STR)
The reactants are initially charged into the vessel and are well
mixed and left to react for a certain period of time. The
resultant mixture is then discharged. This is an unsteady
operation where the composition changes with time but is
uniform throughout the reactor at a specific time.
 Continuous Reactors
Continuous stirred tank reactor (CSTR, MFR, BMFR)
– An agitator is introduced to disperse the reactants thoroughly into
the reaction mixture immediately they enter the reactor.
– Product is continuously drawn out and that’s why known for
perfect mixing.
– Compositions at outlet and inside reactor are same.
– Best suitable for liquid phase reactions
Plug Flow Reactor: (PFR)
– These are tubular reactors generally but not necessarily.
– Often called piston flow, slug flow, ideal tubular flow or unmixed
flow reactors.
– The residence time for all the elements is same: Must be
– Sometimes used for liquid phase reactions but best suited for gas
phase reactions.
 Semi-Batch Reactors
– Aim of their invention is to get benefit of any thing by changing
the contacting pattern.
– One of the reactants may not be charged at once but slowly.
When required:
To react a gas with a liquid
To control a highly exothermic reaction
To improve the product yield in suitable circumstances
 Heat of Reaction and Reactor Type
• When heat of Reaction is too small then can be neglected
• But if it is high then this is major influencing factor
• The temperature of the system can rise or fall depending
upon the reaction type: Exothermic or Endothermic
• A relation must be there among enthalpy, heat transferred,
and temperature change of the system (Energy balance)

Before designing, check for:

1- What is the heat of reaction?
2- Acceptable range of temperature?
 Different reactor configurations based on Temperature(Modes of
Operation)

Adiabatic Reactors

• Very easy to design

• Temperature drop or rise remains within acceptable range
• The properties of the product are not affected by such rise or
fall in temperature
Reactors with Heat Transfer
• This arrangement is used when isothermal operation is
desired
• The temperature can be controlled through internal coils,
external jackets or external heat exchanger
The factors which influence the H.T. are:
1-H.T. coefficient
2- Jacket Pressure
3- Jacket Pressure drop
4- Reactor pressure
5- Cleanliness
6- Cost
Reactor with Internal Coils
Jacketed Reactor and its types
Reactor with heat exchanger
 Choice of Process Conditions
Two main principles are involved:
1- Chemical Equilibrium
2- Chemical Kinetics
If equilibrium contact is very large, then reaction is said to be
irreversible. But there lies a max. extent of that reaction upto
which it can proceed (Chem. Equil.).
How to proceed: Find the applicable temperature range of
reaction and then investigate Kc under that temperature range.

From recommended literature it is found that:

 For Constant Density systems

For gas-phase reactions

 Approach to Reactor Selection
1. Identify number of phases present at reaction
conditions (thermodynamics)
– Single – Homogeneous system
– Multiple – Heterogeneous systems
2. Identify stoichiometry, number of reactions, energy requirements (e.g.
adiabiatic temperature rise/fall)
3. Identify mechanism (if possible) and plausible reaction pathways and active
intermediates
4. Decide on the purpose of reactor selection
 Evaluation of kinetic data
 Data for scale-up
 Commercial design
 Chemical Reaction Engineering Basics

 Molecular Level
– Mechanisms and kinetic rates
 Eddy (Particle) Level
– Micromixing & kinetics
– Intra phase diffusional effects (Thiele modulus, effectiveness factor)
– Inter phase transport effects

 Reactor Level
– Ideal flow patterns (CSTR, PFR)
– Non-ideal flow patterns between phases
– Contacting patterns
– Mixing
 For Homogeneous Systems:
 Identify the magnitude of heat transfer requirement
 Assess the effect of ideal flow patterns on volumetric
productivity and selectivity
 Select the best ideal flow pattern (batch, semi-batch, continuous
flow stirred tank reactor – CSTR, plug flow reactor – PFR)
 Optimize your objective function (related to profit) using as
manipulative variables:

- Feed reactant concentrations and their ratio

- Feed temperature
- Reactor temperature or temperature profile
 Approach the ideal by practical design as much as possible.

Keep things simple whenever possible!

 HOMOGENEOUS SYSTEMS
(Optimizing Volumetric Productivity)
Batch Reactor
t  0, C A  C A0  Moles of A  C VX
   A0 A
t  t , C A  C A 0 1  X A   reacted per unit time  t  ts
C A0
dC A
t s  shut down time t 
CA
  RA 
 reaction t ime

Continuous Flow Stirred Tank Reactor (CSTR)

FA0 FA = FA0(1-XA)
 Moles of A 
CA0    FA0 X A    RA  V
 reacted per unit time 
T = const.

Plug Flow Reactor (PFR)

FA0 

Moles of A
reacted per unit time

 
  FA0 X A   RA V
 
CA0 FA = FA0(1-XA)
X
1 A dX A
 V /[ 
X A 0  RA
]
S5
Volumetric Productivity for Product P then is
Fp  moles of P produced per unit time 
V  reactor vo lume 
 Fp   p
For CSTR
       RA 
V  CSTR  a 

 Fp


 
 p

    RA 
 p a
For PFR X
V  PFR  a  1 A dX A
X A 0  R A

where  p ais
 the ratio of stoichiometric coefficients
The ratio of volumetric productivities in the two systems

F V 
p  R 
PFR
 A
F V 
p CSTR
  RA 
Is the ratio of average reaction rate in a PFR and the reaction rate at exit conditions
of the CSTR
S6
proceeds at 649OC with the first-order rate