Reaction Engineering

Preparing for the exam

Reetta Karinen
Tiia Viinikainen

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Reaction engineering
L1 Ex0 L10: Preparing for the exam
Catalysis
Ideal reactors L3
A Homogeneous catalysis L2 Ex1
Adsorption
L4 Ex2
Reaction mechanisms
.. . . .
.. . L5 Ex3
Deactivation

L6 Ex4
External diffusion L8
A, B
overall diffusion
L7
Mechanical strength L9 Internal diffusion Ex5

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Exam

• Three assignments needs to be accepted to

have the right to take the exam
• 4-5 questions in the exam
• Only material allowed in the exam is
handwritten collection of equations
– A4 sheet, on both sides
– Equations with their limitations, symbols with their
explanations and units
– Collection of equations needs to be returned in the exam
– Collection of equations may be worth of one additional
point (copied collections of equations are not worth the
point)

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Exam

• Dec 11 at 13-18
– No registration required for those who have
registered to the fall 2018 course

• Feb 20 at 9-14 Registration in Oodi required

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Catalytic reactors

=− ′

Batch reactor

Continuous stirred tank Packed bed reactor (PBR)

reactor (CSTR)
̇ = ̇
= − ′
− ′

Reactor volume V in design equations is replaced by the catalyst weight W

Reaction rate becomes –rA’ ,i.e. reaction rate per catalyst weight,
then the unit of the reaction rate becomes, for example, mol/(kgcat min)

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Adsorption isotherms

Langmuir Freundlich
⁄
= =
1+

Temkin Henry
= ln =

Fitting the experimental data to isotherms:

• Which are the parameters and which are the constants?
• Linearization of the isotherm into the form of y = kx + b
• Calculating the functions f(y) ja f(x) from the experimental data
• Plotting the calculated values, f(y) vs. f(x)
• Fitting a straight line to the values
• Solving the constants from the obtained equation

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Derivation of rate laws - Instructions

1. Select mechanism For elementary reaction

2. Make rate law for each step (steps 2A+B↔3C
are elementary) rate law is:
3. Assume rate-limiting step (RDS) -rA = r+ + r-
– For RDS, k is small -rA = k+CA2CB – k-CC3
– For others r/k ≈ 0
4. Solve surface concentrations
5. Write site balance and solve Cv
6. Substitute surface concentrations and
Cv into rate law Atlantic
7. Substitute Kp (if overall reaction is
irreversible) A B
8. Compare with data
9. Extract parameters
CV CA∙S CB∙S

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Question 1: Mechanism
Catalytic dehydration of methanol (ME)
to form dimethyl ether (DME):
2 ME → DME + H2O
100
90
80
Partial pressures (kPa)

70
60
N2
50
ME
40
H2O
30
DME
20
10
0
0 50 100 150 200 250 300
Time (s)

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 Deactivation of catalysts

Activity of catalyst at
time t
Activity

=
=0

First-order decay:
Time =
Any physical or chemical process that decreases Second-order decay:
the amount of active sites or their activity 1
→ Reaction rate decreases =
1+

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Question 2: Is deactivation taking place?

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External diffusion with reaction

Two limiting cases: CAb

1. Rapid reaction
→ reaction rate dependent only on
diffusion CAs
− ′′ ≈
2. Slow reaction
→ reaction rate dependent only on
rate of reaction
− ′′ ≈ ′′
When limiting factor is unknown
Useful equation for mass-transfer limited PBR
(valid for 1st order reaction) In steady state –rA’ = -rA’’
1 (reaction rate = mass transfer rate,
ln =
1− check units!!)

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Mass-transfer coefficient, kc

Mass-transfer coefficient, kc, is calculated using

Sherwood number:
ℎ= CAb

Correlations for Sherwood number, e.g.: CAs

a) Frössling correlation:
ℎ = 2 + 0.6
b) Colburn J factor:
. .
ℎ= and = . + .
c) Thoenes-Kramers correlation:
ℎ = 1.0 ′

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Question 3: External diffusion

20 % conversion is achieved in a gas phase reaction in a PBR. The

external mass transfer is limiting the reaction.
The reactor length is 0.4 m and the gaseous reactant is fed in at the rate
of 40 m/s with kinematic viscosity of 3.0∙10-4 m2/s. The diameter of
spherical catalyst particles is 0.8 cm.
To increase the conversion, temperature is typically increased. What else
you could do to increase the conversion? List three examples and support
your suggestions with calculations.

1
ln =
1−

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Internal diffusion

Internal effectiveness factor (h)

− ′
= CAb
− ′
–rA’ = actual reaction rate (measured)
CAs
–rAs’ = reaction rate, if CA = Cas . .. .CA
.
=
3
coth −1
.
R

Thiele modulus, nth order reaction, spherical particles:

′′
=

Weisz-Prater criteria (CWP):

− ′
= =

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Mass transfer and reaction in packed bed

Overall effectiveness factor W

(first-order reaction): CAb
Ω= CAs
1+ ′′ / . .. .CA
.
.
R
Useful equation for PBR (spherical
particles,
first-order reaction):
=1−

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Question 4: Internal diffusion

Dehydration of octanol to octene is carried out in a packed bed reactor with

spherical catalyst particles (diameter 0.2 cm). Pure octanol enters the reactor
at a superficial velocity of 4 m/s. The reaction is first order with respect to
octanol (k1’’ = 5∙10-6 m/s).

Calculate the length of bed necessary to achieve 88% conversion. The

reaction is internal diffusion-limited. (answer: 1.0 m)
Effective diffusivity for octanol: 3∙10-8 m2/s
Specific surface area: 150 m2/g
Density of catalyst particles: 2.8∙106 g/m3
Bed porosity: 0.65
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X = 1- e - ( Ωr b k '' S a L ) /U η= (f1 coth f1 - 1)
Ω=
1+ ′′ / f
1
2

k1'' ρc S a
f1 = R
De

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 …Question 4: Internal diffusion
Actual overall (observed) reaction rate
η=
reaction rate if whole particle exposed to the conditions of external surface cAs , Ts

Actual overall (observed) reaction rate

W=
reaction rate if whole particle exposed to the conditions of bulk cAb , Tb

- rA'' ,obs - rA'' ,obs

η= W= CAb
- r (cAs , Ts )
''
As - rAb
''
(cAb , Tb )
CAs
. .. C
Now external diffusion is not limiting and
. .. A
–rA(CAs, Ts) = –rA(CAb, Tb) R
Ø h=W

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