CHEMICAL REACTION ENGINEERING

UNIT 1

CHE 3006 SAHLU BAKER

Introduction
2

Chemical reaction engineering is at the heart of virtually every chemical process. It separates the chemical engineer from other engineers (Fogler) Initiated and evolved primarily to accomplish the task of describing how to choose, size, and determine the optimal operating conditions for a reactor Knowledge and experience in thermodynamics, chemical kinetics, fluid mechanics, heat and mass transfer, and economics CRE is the synthesis of all these factors with the aim of properly designing and understanding the chemical reactor (J. Wood at Bham Univ).
CRE UNIT 1

Chemical Thermodynamics /Chemical Kinetics

3

y The two questions that must be answered for a

chemically reacting system are:

 

(1) what changes are expected to occur and (2) how fast will they occur

y the constraints placed on a reacting system by

thermodynamics should always be identified first

  

Enthalpy Fugacity Activity

CRE UNIT 1

Chemical Identity

The identity of a chemical species is determined by the kind, number, and configuration of that species atoms A chemical species is said to have reacted when it has lost its chemical identity. Three basic ways are:
1. Decomposition 2. Combination

3. Isomerization

Classification of Reaction type

5

y Two types: Homogeneous and Heterogeneous  A reaction is homogeneous if it takes place in one phase alone  A reaction is heterogeneous if it requires the presence of at least two phases to proceed

CRE UNIT 1

Reaction Rate
y The reaction rate is the rate at which a species

looses its chemical identity per unit volume. y The rate of a reaction (mol/dm3/s) can be expressed as either the rate of Disappearance: -rA or as the rate of Formation (Generation): rA

Reaction Rate

Consider the isomerization A B

rA = the rate of formation of species A per unit volume -rA = the rate of a disappearance of species A per unit volume rB = the rate of formation of species B per unit volume

Reaction Rate
y EXAMPLE: A B
If Species B is being formed at a rate of 0.2 moles per decimeter cubed per second rB = 0.2 mole/dm3/s Then A is disappearing at the same rate: -rA= 0.2 mole/dm3/s The rate of formation (generation of A) is rA= -0.2 mole/dm3/s

Reaction Rate
y For a catalytic reaction, we refer to -rA',

which is the rate of disappearance of species A on a per mass of catalyst basis. (mol/gcat/s) NOTE: dCA/dt is not the rate of reaction

Reaction Rate
y Consider species j: y rj is the rate of formation of species j per unit

volume [e.g. mol/dm3/s] y rj is a function of concentration, temperature, pressure, and the type of catalyst (if any) y rj is independent of the type of reaction system (batch, plug flow, etc.)
y rj is an algebraic equation, not a

differential equation -rA = k(T)CA

General Mole Balance

FA0= Entering molar flow rate of A (mol/time) FA= Exiting molar flow rate of A (mol/time) GA= Rate of generation(formation) of A (mol/time) V = Volume (vol e.g. m3) rA= rate of generation(formation) of A (mole/timevol) NA= number of moles of A inside the system Volume V (mols)

Ideal Reactor Types-Batch

y It has neither inflow nor outflow of reactants or

products which the reaction is being carried out. y Perfectly mixed y No variation in the rate of reaction throughout the reactor volume

BATCH

Batch Reactor
y All reactants are supplied to the reactor at the outset. The

y y y y y

reactor is sealed and the reaction is performed. No addition of reactants or removal of products during the reaction. Vessel is kept perfectly mixed. This means that there will be uniform concentrations. Composition changes with time. The temperature will also be uniform throughout the reactor - however, it may change with time. Generally used for small scale processes, e.g. Fine chemical and pharmaceutical manufacturing. Low capital cost. But high labour costs. Multipurpose, therefore allowing variable product specification.

Batch Reactor Mole Balance

Typical Laboratory Glass Batch Reactor

Typical Laboratory High Pressure Batch Reactor (Autoclave)

Typical Commercial Batch Reactor

Ideal Reactor Types-CSTR

y Normally run at steady state. y Quite well mixed y Generally modelled as having no spatial variations

in cencentration, temperature, or reaction rate throughout the vessel

CONTINUOUS STIRRED TANK REACTOR (CSTR) BACKMIX REACTOR

Backmixed, Well mixed or CSTR

FA0 (CA0)

Usually employed for liquid phase reactions.

FA (CA)

CA Vr, g Vr, l CA

CA

Use for gas phase usually in laboratory for kinetic studies.

Assumption: occurs. Perfect mixing

Schematic representation of a CSTR

Characteristics
y Perfect mixing: the properties of the reaction mixture are

uniform in all parts of the vessel and identical to the properties of the reaction mixture in the exit stream (i.e. CA,
outlet

= CA, tank)

y The inlet stream instantaneously mixes with the bulk of the

reactor volume. y A CSTR reactor is assumed to reach steady state. Therefore reaction rate is the same at every point, and time independent. y What reactor volume, Vr , do we take?
  

Vr refers to the volume of reactor contents. Gas phase: Vr = reactor volume = volume contents Liquid phase: Vr = volume contents

CSTR Mole Balance

Cutaway view of a Pfaudler CSTR/ Batch Reactor

Ideal Reactor Types-PFR

y Normally operated at steady state y No radial variation in concentration y Referred to as a plug-flow reactor y The reactants are continuously consumed as they

flow down the length of the reactor.

PLUG FLOW REACTOR (PFR), TUBULAR REACTOR

PFR, Tubular reactor

y There is a steady movement of materials along

the length of the reactor. No attempt to induce mixing of fluid element, hence at steady state:
At a given position, for any cross-section there is no pressure, temperature or composition change in the radial direction.  No diffusion from one fluid element to another.  All fluid element have same residence time.


Used for either gas phase or liquid phase reactions.

25

y The plug flow assumptions tend to hold when there is good radial

mixing (achieved at high flow rates Re >104) and when axial mixing may be neglected (when the length divided by the diameter of the reactor > 50 (approx.)) reaction must be noted in case the number of moles change during the reaction. e.g. A p B + C

y In the case of a gas phase reaction, the pressure history of the

y As the reaction progresses the number of moles increases. Therefore

at constant pressure, fluid velocity must increase as conversion increases.

CRE UNIT 1

Plug Flow Reactor Mole Balance

PFR:

The integral form is:

V!

dF A FA 0 r A
FA

This is the volume necessary to reduce the entering molar flow rate (mol/s) from FA0 to the exit molar flow rate of FA.

PBR, Tubular reactor

27

y Tubular reactor packed

with solids usually catalyst y Heterogeneous system y Similar to PFR no radial gradients in conc, temp or reaction time y Mass of solid determine rate of product formation

CRE UNIT 1

Packed Bed Reactor Mole Balance

PBR

FA0  FA  d rAdW dNA dt

The integral form to find the catalyst weight is:

dFA F A 0 rA d
FA

Selection of Reactors
y Batch

small scale production of expensive products (e.g. pharmacy) high labor costs per batch difficult for large-scale production when intense agitation is required relatively easy to maintain good temperature control the conversion of reactant per volume of reactor is the smallest of the flow reactors - very large reactors are necessary to obtain high conversions relatively easy to maintain usually produces the highest conversion per reactor volumn (weight of catalyst if it is a packed-bed catalyze gas reaction) of any of the flow reactors difficult to control temperature within the reactor hot spots can occur

y CSTR : most homogeneous liquid-phase flow reactors

y PFR : most homogeneous gas-phase flow reactors