Lesson 3.

Chemical Reactor Design

Javier R. Viguri

Department of Chemistry and Process & Resource Engineering

University of Cantabria
vigurij@unican.es
 Lesson 3.2
Chemical Reactor Design
INDEX

1.- Objectives and Introduction

2.- General procedure for reactor design
3.- Ideal and Real reactors
4.- Batch reactor overview
5.- Semibatch reactor overview
6.- CSTR (Continuous Stirred Tank Reactor)
7.- PFR (Plug Flow Reactor)

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OBJECTIVES

 Provide an overview and description of some basic ideas

about chemical reactors, indicating some important
aspects, and describing ideal reactors

 Provide a generalized overall procedure for reactor

design that applies to most reacting systems

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1.- Introduction: Examples of chemical reactors
 Have you ever seen a reactor ? What kind of reactor ?
 What reactions take place in that reactor?

 Do you think that your system IS A REACTOR ?

 Does your system MORE THAN ONE reactor ?
 That KIND OF IDEAL REACTOR looks like ?
 What are the INPUTS and OUTPUT of your reactor system ?

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1.- Introduction
 Reactor is the heart of a chemical process: Feeds  Products

 Usually designed as special items for a given project

- Many reactors are unique and proprietary (particularly in
catalytic reactions or multiphase flow reactions)
 We need to ensure achieving the desired YIELDS and
SELECTIVITY at FULL SCALE

 Design based on
Detailed modelling of the kinetics and hydrodynamics
vs.
Scale-up from a pilot plant reactor or previous designs (making
suitable allowance for heat & mass transfer, residence time,…)
 The final volume (V) is often determined by
Needs for mixing, segregation of heat transfer more that by
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residence time required for the reaction.
Here, the reactor is the core of an Industrial plant to manufacture poly
(methyl 2-methylpropenoate) (PMMA), a Speciality Polymer

Here, the proprietary reactor to manufacture ammonia from nitrogen and hydrogen

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2.- General procedure for reactor design
The reactor is a small
fraction of the process
fixed capital cost, but
the reactor
performance  very
significant impact on
capital and operating
costs of the process
(raw material, wastes,
recycle, separation
system needs, etc.)
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2.- General procedure for reactor design

1.- Collect required data

Heats of reaction Estimation by simulation models
Phase equilibrium constants (Aspen)
Diffusion coefficients Prediction using correlations
Heat and mass transfer coefficients
Reaction rate constants (k) Measured experimentally in an
iterative process (different conditions)

2.- Select reaction conditions

Critical Step. Will often govern the selection of reactor type (e.g.
conditions cause reagents and products in vapor phase  CSTR not
applicable)

3.- Determine materials of construction

Materials  F (T, P, compounds)
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2.- General procedure for reactor design
4.- Determine the rate limiting step and critical sizing parameters of
the reactor
The reaction rate (r) is usually limited by one of the following
fundamental processes which rate is the governing parameter in
reactor sizing (Experimental)
Intrinsic kinetics: Rate of the reaction itself (r)
Mass transfer rate: Particularly important in multiphase reactions and in
reactions that use porous heterogeneous catalysts
Heat transfer rate: Heating and cooling reactor is necessary and/or reaction in
a heat-transfer device (such as a heat exchanger or fired heater)
Feed Addition rate: If “starving” (muriendo de hambre) is necessary because
exothermic reaction, very rapid or requires a very low concentration of one of
the components for optimal yields.
Mixing rate: For very fast reactions can be the limiting step (the slowest) 
Local rates of reaction could exist 9
2.- General procedure for reactor design

The rate-limiting step can depend on the type of reactor that is selected
for the experimental program. Care must be used when scaling up data
to ensure that the same fundamental process will be rate-limiting in a
larger vessel.

Critical sizing parameter for the reactor  Table

These parameters allow the [Reactor Volume or Volume/Mass of

catalysts or contacting area for mass transfer] to be scaled up relative to
the mass or volumetric flow of reactor feed.

TABLE 15.1

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2.- General procedure for reactor design
5. - Preliminary sizing, layout and costing of the reactor

Sizing Parameter  Reactor Volume, Catalyst volume +

Additional space for internal heat transfer devices, V-L
distribution, inert vapor space, support material (packed bed),
fluid distribution (fluidized bed)

Reactor is a  Pressure vessel (L and D), crystallizer (if reaction leads

to precipitation of a product) (L and D), Fired Heater or Heat Exchanger
(if endothermic reaction) (Area)

Capital Cost of Reactor (€) = F (sizing parameter as L and D, Area….)

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2.- General procedure for reactor design

6.- Estimate reactor performance

Chemical Companies use this approach to scale-up:

Small Pilot Plant  Demonstration Unit  Full Scale

using [Experimental Methods + Computer Modeling/Simulation]

7.- Optimization, only if unexpected components or results (S,Y) are

obtained (because the reactor cost is a relatively small fraction of the
plant total capital cost).

8.- Make an effective hand-off of the design  to deliver to the

Mechanical Engineering Designer and Design Team

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3.- Ideal and Real Chemical reactors
Ideal reactors

 The adjective IDEAL refers to the state of mixing in the reactor.

 It is assumed to be perfect in the case of ideal batch, continuous

stirred tank and plug flow reactors.

Easy to study (model) Easy heat transfer

Ideal Reactors (IR) vs.

Real Reactors (RR)

Know performance Real R =Σ (Ideal R)

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3.- Ideal and Real Chemical reactors

 How do you represent a BATCH

reactor?

Colorants and Margarine being

produced in a batch reactor.
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3.- Ideal and Real Chemical reactors

 How do you represent a

Continuous Stirred Tank
Reactor ?

A CSTR reactor, used to make

poly (ethylene)
By kind permission of Total.
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3.- Ideal and Real Chemical reactors

 How do you represent a PLUG

FLOW REACTOR?

Tubular reactors used as

bioreactors for the production of
algae to obtain biodiesel

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3.- Ideal and Real Chemical reactors

Ideal reactors and some real reactors that approximate the same flow pattern
and have performance close to that of ideal reactors
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3.- Ideal and Real Chemical reactors
Types of Ideal Reactors

dC A In general. i.e. in CSTR and PFR the d/dt =0, and them, dCA/dt= 0,
− rA ≠ −
dt but rA≠0 for design the reactor correctly

The expression of rA would be: − rA = − K ⋅ C A2 − rA = − K ⋅ C A − rA = − K ⋅ C AC B

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3.- Ideal and Real chemical reactors
Basic Mass Balances for the Ideal reactors are

In General: Accumulation in the reactor = [Flow IN - Flow OUT + REACTION ]

as a function of time
Number of moles If liquid phase or dC A
gas phase if bed V
of A in the reactor = − K ⋅ C A2 V
dN A reactor volume dt
Batch Reactor = ra V = − K ⋅ C A V remain constant  …and the reaction does
2
dt
not depend on the
volume of the reactor
dN A
CSTR
= 0 ; 0 = FA0 − FA + rAV
dt Molar flowrate
Molar flowrate out
enters the reactor
the reactor
dN A dN A
Semibatch Reactor ≠0 ; = FA0 − FA + rAV FA0 =0 or FA=0
dt dt
dFA Change of FA in function of
PFR = rA accumulative V=0 to V=Vt
dV
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4.- Batch reactor overview
Batch reactor is essentially a tank, almost always with a liquid

• Is a closed system with NOT adding NOR removing material

• Common at the laboratory scale, but are used extensively on
large scale  Greater number of products than any other
reactor
• Because usually liquid phase, means most cases is constant
density  that simplify the analysis

By assuming well mixed means the C and T are uniform though the reactor 
 NOT Gradient within the reactor  This simplifies energy balances
 But C, T change with the time as the reaction proceed

HEAT TRANSFER is very important for most

large scale reactors, because most reactions at large
scale are EXOTHERMIC

 A typical arrangement is the use of external jacket

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4.- Batch reactor overview
SCALE UP
An important aspect is the scale up from a small reactor in the laboratory to large
commercial scale, and how to do modelling. The tactic:
€1 + €2 > €3
Laboratory  €1  Pilot Plant  €2  Full-scale production
Know the k
and transport
Laboratory-bench-scale unit  €3 
limitations

 For scaling up in ISOTHERMAL conditions, the T not change with t, because

- Good heat transfer
- The action of a lot of solvent, very low heat of reaction

and them the isothermal scale-up is really directly, i.e.

A→ B − rA = − k ⋅ C A
1
t R = ln
1
Relationship between tR and x
k = Cte. k 1− x

and C vs. time is independent of the size of the reactor

C A = C A e − kt 21
0
4.- Batch reactor overiew
 For scaling up in ADIABATIC reactor (not heat removal nor added) the C vs.
time is independent of the size of the reactor too.

 Between these 2 extremes heat transfer systems, as we make the reactor larger
(as the volume increases)  Surface area for heat transfer does not increase faster

Example: Cylindrical reactor (D, h)

Scale-up magnitude Lab. Scale V and A x 10 Lab. Scale V and A increase
formula
Reactor Volume 1 hΠD2/4 103 V increase ten cubic
Heat Transfer Area 1 hΠD 102 A increase ten square
 The ability to transfer heat, changes automatically
 As the T=Function of t, the T increase much more in large scale reactors

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4.- Batch reactor overview
 In which cases would you use the batch reactor instead of a continuous system?
(in spite of all advantages of the continuous system !!!)

………..scale production (drugs, dyes…) NEW

SMALL
……….process or …..…process
UNTRIED
……….price materials CONTAMINATION
……….reaction terms LONG
……….fouling RAPID
……….of products (some fermentations) HIGH

SMALL scale production (drugs, dyes…)

NEW process or UNTRIED process
HIGH price materials
LONG reaction terms
RAPID fouling
CONTAMINATION of products (some fermentations)
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5.- Semi-Batch reactor overview

We add A (FAo ≠0, FA=0) OR remove A (FA ≠0, FA0=0).

The accumulation of number of moles A in reactor in t is:

dN A dN A
≠0 ; = FA0 − FA + rAV
dt dt

- The V is changing, and it can be defined as dV/dt = V0 (volumetric flowrate)

- In Semibatch reactor accumulation exist (dNA/dt ≠0) but in CSTR (dNA/dt =0)

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5.- Semi-Batch reactor overview
APPLICATION OF SEMIBATCH REACTOR

- Adding a cold reactant to prevent runaway reactions

- Adding reactive A to B in order to maintain very low
concentration of A in reactor and increase the selectivity
to the desired product C A+B  C (Desired reaction)
2A + B  D (Side reaction)

Adding H2 (g)
Removing the continuously
product in gas because its
phase concentration in the
liquid phase is low

Chemical Vapor Deposition (CVD) in the

semiconductor industry to produce films,
high-purity high-performance solid materials
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6.- CSTR (Continuous Stirred Tank Reactor)

If, V or Density = Cte.  FA = v CA

Where v is the volumetric flow

We define space time or hydraulic residence time, τ = V/vo

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7.- Plug-Flow Reactor (PFR) overview

The plug of material

moves on from
V=0 (t=0, x=0, CA0) to
V (t, xAf, CAf) in a plug
profile

dFA
0 = FA − ( FA + dFA ) + rA dV = rA
dV
as
xA =
FA − FA
0 [ ]
dFA = d FA0 (1 − x A ) = − FA0 dx A FA0 dx A = rA dV
FAo
FA = v CA
which integrated is

τ = V/vo , = V .CA0 /F A0
v is the volumetric flow τ is the spatial time
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7.- Plug-Flow Reactor (PFR) overview
WHY do you USE PFR?

- Large Quantities
- Continuous
- Easy maintenance (not moving parts)
- Usually contains catalysts

CONCERNS
- Poor Mixing  Use of static mixers

- Hot Spots  Smaller D to increase the heat

transfer rate and shell (heat transfer fluid) and
tube (catalyst) reactor
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