A21283

EXAMINATION INFORMATION

Temperature: Degrees K = ºC +273.15

Values of the gas constant, R:

8.314 kJ kmol-1 K-1 or J mol-1 K-1, 0.08314 bar m3 kmol-1 K-1,
0.08206 atm m3 kmol-1 K-1

PART 1. BASIC EQUATIONS

(1) The Arrhenius Equation

− Ea

Rate constant, k = Ae RT
Ea is the activation energy of the reaction.

(2) Reactor Design Equations

t = reaction time
XA dX A
(a) Batch t = C A0 ∫ CA0 = initial concentration of A
0 ( − rA )
XA = fractional conversion of A

(− rA ) = reaction rate per unit volume of fluid (expressed as a kinetic equation)

(b) Plug Flow

Vr X A dX
(i) Homogeneous =∫ A
Vr = reactor volume
FA0 0 ( − rA )
FA0 = molar flow rate of A
W dX A XA
(ii) Heterogeneous =∫ W = catalyst loading
FA0 0 ( − rA∗ )

( − rA∗ ) = reaction rate per unit mass of catalyst

(c) Continuous Stirred Tank Reactor (CSTR)

Vr XA W XA
(i) Homogeneous = (ii) Heterogeneous =
FA0 ( − rA ) FA0 ( − rA∗ )

PART 2. CATALYTIC REACTOR DESIGN

Section 2.1. Calculations involving effectiveness factors and Thiele’s modulus

Due to poor diffusion in the catalyst pores the central parts of the catalyst pellets may
be largely ineffective (the reactant is used up before it gets there).

The intrinsic reaction rate is the rate which would occur if the temperature and
reactant concentration throughout each catalyst pellet were the same as at the
surface of the pellet.
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actual rate of reaction

The effectiveness factor (or “efficiency”), η =
intrinsic rate

Useful Equations
You should be able to use the following two equations, though a detailed derivation
would not be required in an examination.

Definition of Thiele’s modulus (for first order reaction in spherical pellets)

1/ 2 1/ 2
 k1   kσ S g ρ p 
φ S1 = R  V  and also φ S1 = R 
 DA ,eff   D A, eff 

R pellet radius kV1 intrinsic first order rate constant

DA, eff effective diffusivity of A in the kσ intrinsic first order rate constant
pellet per unit area of surface.

Sg surface area per unit mass ρp density of the pellet

Calculation of η from Thiele’s modulus (for first order reaction in spherical pellets)

 3   1   1  exp ( φS1 ) − exp ( −φS 1 )

η S 1 =     −    tanhφS 1 =
 φ S 1   tanh φ S 1   φ S 1   exp ( φS 1 ) + exp ( −φS1 )

Section 2.2. Reactor Sizing Calculations

The following results are important and you should be able to derive them (particularly
the ones shown with an asterisk, ∗) if required and/or use them.

Reaction rate per unit volume of catalyst bed ( − rABED )

∗ ( − rABED ) = (− rAV )(1 − ε b )

volume of space between pellets

where ε b = bed voidage =
total volume of bed

Calculation of catalyst bed volumes required to give a final conversion XAf of reactant
A under isothermal conditions
The methods used are based on integration of the differential mass balance equation.
dz  4F  1 dVb F0
∗ =  A20  BED
or ∗ = ABED .
dX A  πd  − rA dX A − rA

where z = axial distance from the bed inlet, XA = conversion of reactant A

d = bed diameter FA0 = molar flow of reactant A at the bed inlet.
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In some cases, numerical or graphical integration methods are required, though in

others an analytical solution is readily obtained. For example, if the reaction is
isothermal, irreversible and first order with intrinsic rate constant kV1 and volume
changes in the reaction are negligible.

∗ ( − rABED ) =ηk v1C A0 (1 − ε b ) (1 − X A )

where CA0 is the concentration of A in the feed.

Substitution in the differential mass balance equation and integration then gives:
 −ν 
∗ Vb =  1 0  ln 1 − X Af ( )
 ηkv (1− ε b ) 

where Vb is the bed volume, which gives the specified final conversion XAf and v0 is the
volumetric flow rate of the feed.

Catalytic reactions whose rate is controlled by reactant diffusion over the surface
boundary film. In this case the reaction rate per unit volume of bed is given by:
3
∗ ( )
− rABED =   kCAC AB (1− ε b )
R
where
(− rABED ) = rate of consumption of A per unit volume of bed ( = reaction rate)
R = effective radius of catalyst pellets
C AB = concentration of A in the bulk fluid adjacent to the pellets
εb = bed voidage
kCA = mass transfer coefficient for transport of A across the surface boundary film.

If volume changes during the reaction are negligible, CAB = CA0 (1 – XA), where CA0 is
the concentration of A in the feed stream and XA is the conversion of A. Substituting in
the differential mass balance equation and integrating gives:

 v0 R 
∗ Vb = −   ln(1− X Af )
 3kCA (1 − ε b ) 

where
Vb = bed volume which gives the specified final conversion of XAf of A
v0 = volumetric flow rate of feed.

END OF PAPER

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