Introduction to Reactor Technology – Ojumu TV (PhD)

Reactor Technology 4

TV Ojumu (PhD)
2.25 Science Building
[email protected]

Department of Chemical Engineering TV Ojumu (PhD)

Introduction to Reactor Technology – Ojumu TV (PhD)

Topics Tasks
The Energy Balance
Non Isothermal
Applications of the Energy Balance
Reactions
Nonisothermal Continuous-Flow Reactors
Reactors with heat exchange
Define concepts associated with Catalysis and
understand the properties of Catalysis
Catalysis and Understand the steps involved in Catalytic
Catalytic Reactions
Reactors Synthesize Rate Laws, mechanisms, and rate
limiting steps.
Design of Reactors for gas-solid reactions

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Introduction to Reactor Technology – Ojumu TV (PhD)
Schedule

8 Steady-state non-isothermal reactor design – energy balance, heat

capacities, heat of reaction
9 Steady-state non-isothermal reactor design – non-isothermal
continuous-flow reactors, adiabatic reactors
10 Catalysis and catalytic reactors – catalysts, steps in catalytic
reactions
11 Catalysis and catalytic reactors – synthesis of rate law, mechanism,
and rate-limiting step
12 Catalysis and catalytic reactors – design of reactor for gas-solid
reactions
13 Catalysis and catalytic reactors – heterogeneous data analysis for
reactor design

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Introduction to Reactor Technology – Ojumu TV (PhD)

Non-isothermal Reactor Design

TV Ojumu (PhD)
2.25 Science Building
[email protected]

Department of Chemical Engineering TV Ojumu (PhD)

Introduction to Reactor Technology – Ojumu TV (PhD) Outline
Motivation for energy balance and how it can
be used to solve reactor design problems.
Development of energy balance and its
application to different reactor systems with a
view to relating temperature and conversion/
reaction rate.
Application of energy balance to design
adiabatic reactors.
Application of energy balance to reactors with
heat exchange.

Department of Chemical Engineering TV Ojumu (PhD)

Introduction to Reactor Technology – Ojumu TV (PhD) Motivation
Most reactions are not carried out
isothermally, therefore heat effects in
chemical reactors are important.
The basic design equations, rate laws &
stoichiometry were derived and used
previously for isothermal reactor design.
For nonisothermal condition, the designs are
evaluated as the temperature vary along the
length of PFR for example or when heat is
removed from CSTR.

Department of Chemical Engineering TV Ojumu (PhD)

 Information required for the design
of nonisothermal reactor
Introduction to Reactor Technology – Ojumu TV (PhD)

Calculate the reactor volume necessary for 70%

conversion.
The reaction is exothermic and the reactor (PFR) is
operated adiabatically. As a result, the temperature
will increase with conversion down the length of the
reactor.
dX −rA
For a PFR = Stoichiometry
dV FA0

Rate law −rA = kC A

Department of Chemical Engineering TV Ojumu (PhD)

 This eqn cannot be integrated directly
because k is not a constant, it is a
Introduction to Reactor Technology – Ojumu TV (PhD)

function of T

In order to solve this equation, we need to develop another

relationship between X & T or V & T
!
The energy balance provide this relationship

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Department of Chemical Engineering TV Ojumu (PhD)
 Energy Balance
First Law of Thermodynamics
Introduction to Reactor Technology – Ojumu TV (PhD)

For a closed system, no mass crosses the boundaries, The

change in total energy of the system, dE, is equal to the
heat flow to the system, dQ, minus the work done by the
system on the surroundings, dW
For a closed system

For open system - continuous-flow reactors: some of the

energy exchange is as a result of mass flow across the
system boundaries.
The energy balance for a single species entering and
leaving such system becomes:

For a open system

Department of Chemical Engineering TV Ojumu (PhD)

Introduction to Reactor Technology – Ojumu TV (PhD) Energy Balance for open system

(1)

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Introduction to Reactor Technology – Ojumu TV (PhD) Evaluating the work term
The work term in equation need
to be separated into “flow work”
and “other”.

Check that the unit of flow work term is Joules/s (watts).

Combine the above equation with eq. 1, we have

In chemical reactors, other forms of energy are negligible compared to

internal energy

Department of Chemical Engineering TV Ojumu (PhD)

Introduction to Reactor Technology – Ojumu TV (PhD)

Recall that we are trying to relate temperature,

conversion and rate of reaction in other to solve
reaction engineering problems with heat effects. The
above eqn. is the starting point to develop this
relationship.

Department of Chemical Engineering TV Ojumu (PhD)

 Obtaining heat of reaction from molar flow rates

Energy balance for steady

Introduction to Reactor Technology – Ojumu TV (PhD)

state non iso thermal system

To write in terms of heat of reaction, consider

Expanding the summation terms, and

and substituting for F for species i with stoichiometric

coefficient vi i.e

Department of Chemical Engineering TV Ojumu (PhD)

 The steady state energy balance in terms of heat of reaction
Introduction to Reactor Technology – Ojumu TV (PhD)

is given as:

Expanding the enthalpy term as a function of temperature.

Department of Chemical Engineering TV Ojumu (PhD)

Introduction to Reactor Technology – Ojumu TV (PhD)

Energy balance equation in terms of constant heat capacities

Energy balance equation for the case of highly temperature

sensitive heat capacities

Department of Chemical Engineering TV Ojumu (PhD)

Introduction to Reactor Technology – Ojumu TV (PhD)

Example 2 - Heat of reaction

Calculate the heat of reaction for the

synthesis of ammonia from hydrogen
and nitrogen at 150oC in kcal/mol of N2
and also in kJ/mol of H2 reacted

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 Analysis and sizing of adiabatic reactors
Lets consider a system with the special set of condition of no
Introduction to Reactor Technology – Ojumu TV (PhD)

shaft work and adiabatic operation.

Recall that conversion was obtained from the energy

balance and not the mole balance equation. The above
equation gives explicit relationship between X & T needed
to be used in conjunction with the mole balance to solve
non isothermal reaction engineering problems.

Department of Chemical Engineering TV Ojumu (PhD)

 Adiabatic tubular reactor
The energy balance eqn. is arranged such that T=T(X)
Introduction to Reactor Technology – Ojumu TV (PhD)

The above eqn is coupled with performance eqn. for tubular

reactor to obtain temperature, conversion and concentration
profiles along the length of the reactor.

Software packages such as Polymath and MATLAB can be

used these equations.

Department of Chemical Engineering TV Ojumu (PhD)

Introduction to Reactor Technology – Ojumu TV (PhD) Liquid phase isomerization of n-butane

Additional Information

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Introduction to Reactor Technology – Ojumu TV (PhD)

Mole balance Rate Law

eqn.

rate constant EIUM constant as

as a function a function of T
of T

Stoichiometry (Liquid
phase reaction, v=vo)

Rate law expressed as a function of

Kc, CA0 and X

Recalling the steady state energy balance equation

For Adiabatic and No work condition, and

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 The steady state energy balance equation becomes
Introduction to Reactor Technology – Ojumu TV (PhD)

An expression relating T with X

i.e.

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 Introduction to Reactor Technology – Ojumu TV (PhD)

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 Using Polymath to solve non-isothermal
problems
Introduction to Reactor Technology – Ojumu TV (PhD)

d(X)/d(V) = -ra/Fa0 #
Ca0 = 9.3 #
Fa0 = .9*163 #
T = 330+43.3*X #
Kc = 3.03*exp(-830.3*((T-333)/(T*333))) #
k = 31.1*exp(7906*(T-360)/(T*360)) #
Xe = Kc/(1+Kc) #
ra = -k*Ca0*(1-(1+1/Kc)*X) #
rate = -ra #
V(0)=0
X(0)=0
V(f)=3.3

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 Introduction to Reactor Technology – Ojumu TV (PhD) Tubular reactor with heat exchange

.....1
Heat flow to the reactor
ctor
a is heat exchange area per unit volume

substitute Q into Equation 1, divide by deltaV and determine the limit as deltaV
tends to zero
.....2
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 Expanding Equation 2 (using product rule)
Introduction to Reactor Technology – Ojumu TV (PhD)

.....3
But from mole balance of species i over a PFR
and by differentiating enthalpy wrt V

substituting into Eq 3, we have

re-arranging Eq 4, we have

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 Introduction to Reactor Technology – Ojumu TV (PhD)

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Introduction to Reactor Technology – Ojumu TV (PhD)

A variety of numerical methods can be used to solve the

coupled differential equations

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Department of Chemical Engineering TV Ojumu (PhD)
Introduction to Reactor Technology – Ojumu TV (PhD)

Dependence of specific rate and equilibrium constants on temperature

Rate is zero at equilibrium, therefore:

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 But from energy balance equation
Introduction to Reactor Technology – Ojumu TV (PhD)

with heat exchange:

-6900kJ/kmol

Polymath program can be used to plot the profiles of X, Xe, T and -rA in the
reactor.

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Department of Chemical Engineering TV Ojumu (PhD)
 Introduction to Reactor Technology – Ojumu TV (PhD)

Department of Chemical Engineering

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 Introduction to Reactor Technology – Ojumu TV (PhD)

Department of Chemical Engineering

TV Ojumu (PhD)
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