Chemical Reaction

Engineering 2
CRE-2
Te k n i k K i m i a U n i v e r s i t a s P e r t a m i n a
Agung Nugroho
Catia Angli Curie
2020
Part 2. Catalysis and Catalytic Reactors

Content Objectives
➢ Rate Limiting Step
➢ Able to make the reaction rate equation
➢ Adsorption limited
based on the rate limiting step
➢ Surface reaction limited
➢ Able to analyze experimental data, decide
➢ Desorption limited
the rate limiting step
➢ Analyzing experimental data
➢ Able to estimate the reaction rate
➢ Evaluation of the rate-law parameters
constants
➢ Reactor design for process limited by
➢ Able to design reactor for process limited
adsorption/surface reaction/desorption
by adsorption/surface reaction/desorption
➢ Packed bed reactor
➢ Fluidized bed reactor
Mechanism involving Inert
Disproportionation reaction of Cumene to Benzene and Propylene
The rate law for the case of no inerts adsorbing on the surface is:

If we were to have an adsorbing inert in the feed, the inert would not participate in the
reaction but would occupy active sites (chemisorption) on the catalyst surface:
Concentration of inert
adsorbed on the surface

Because the adsorption of the

inertis at equilibrium, the
concentration of sites occupied by
the inert is
 Determining Reaction Mechanism &
Rate-Limiting Step >75% of all
Select a mechanism heterogeneous
(specific mechanisms (eg. molecular / dissociative reactions that
adsorption, etc)) are not
diffusion-limited
Assume a rate limiting step are surface-
Check from surface-reaction-limited reaction limited
If still does not
agree with data Find the expression for 𝑪𝒊∙𝑺
Use other steps that are not rate-limiting to
eliminate ‘coverage-dependent terms’
Write a site balance

Derive the rate law & Compare with data

If the does not agree with
data
Determining Reaction Mechanism & Rate-Limiting Step
• Caution!
• The fact that the postulated rate-limiting step fit the data well does not
necessarily means that the mechanism is absolutely correct
Spectroscopic measurements are needed to confirm the mechanism absolutely
• But, if the proposed rate law can correlate the data very well, we can use it to
design the reactor

Temperature Dependence of the Rate Law

 The specific reaction rate, k, usually ↑ exponentially with T
 However, as adsorption is exothermic, if T↑, adsorption equilibrium constant ↓
 What’s next?
4 operations that chemical engineers need to be able to do:
• Deduce rate law
• Find mechanism Consistent with the experimental data
• Evaluate rate-law parameters
• Design (eg. PBR, CSTR)
 Exercise
Hydrogen & toluene (gas phase
reaction) are reacted over a solid
mineral catalyst containing
clipnotilolite (a crystalline silica-
alumina) to form methane & benzene

𝐶6 𝐻5 𝐶𝐻3 + 𝐻2 ⟶ 𝐶6 𝐻6 + 𝐶𝐻4

We wish to design a packed-bed

reactor and a fluidized CSTR to process
a feed consisting of 30% toluene, 45%
hydrogen, and 25% inert (the inert is
not adsorbed). Toluene is fed at a rate
of 50 mol/min at a temperature of
640oC and a pressure of 40 atm (4052
kPa).
Exercise • Only toluene is adsorbed
(molecular adsorption)
1.Propose the reaction mechanism • Eley-Rideal surface reaction (the
2.Determine the rate law based on the methane product is not sorbed)
differential reactor data and based on • Desorption of benzene
mechanism
3.Evaluate the rate-law parameter
4.Develop design equation to design the 𝑻+𝑺 ⇌ 𝑻∙𝑺
desired reactor
𝑯𝟐 + 𝑻 ∙ 𝑺 → 𝑴 + 𝑩 ∙ 𝑺
𝑩∙𝑺 ⇌𝑩+𝑺
Exercise
Select a mechanism
(specific mechanisms (eg. molecular / dissociative
adsorption, etc))

Assume a rate limiting step

Check from surface-reaction-limited

Find the expression for 𝑪𝒊∙𝑺

Use other steps that are not rate-limiting to eliminate
‘coverage-dependent terms’
Write a site balance

Derive the rate law & Compare with data

 Exercise
How does the rate
change by changing Pi?
 Exercise
How does the rate
change by changing Pi?
Exercise
If the reaction is surface-reaction-limited, we’ve had:

Does it match?
→Yes
This shows that the reaction is irreversible
or Kp is >>

So the rate of reaction become:

 Evaluation of Rate Law Parameter
• We may re-arrange the rate equation to linearize it
• Use non-linear regression (refer to Stat-Prob & Numerical method classes)
• Using linearized equation (from the exercise):
 Evaluation of Rate Law Parameter
(Using Linear regression Multivariable)
with
𝑦 = 𝑏0 + 𝑏1 𝑥1 + 𝑏2 𝑥2
= 560
= 8397.75
𝑃𝑇 𝑃𝐻 𝑃𝑀 𝑃𝐵
−𝑟𝑇′ 𝑦 𝑥1 𝑦 𝑥2 𝑦 2
𝑥1 2
𝑥2 𝑥1 𝑥2 = 1.12859
𝑥2 𝑥1 = 55.21987
71 1 1 1 0 0.0141 0.0000 0.0141 0 1 0
71.3 1 1 4 0 0.0140 0.0000 0.0140 0 1 0 = -546
41.6 1 1 0 1 0.0240 0.0240 0.0240 1 1 1
19.7 1 1 0 4 0.0508 0.2030 0.0508 16 1 4 where
42 1 1 1 1 0.0238 0.0238 0.0238 1 1 1 = 0.008997
17.1 1 1 0 5 0.0585 0.2924 0.0585 25 1 5
71.8 1 1 0 0 0.0139 0.0000 0.0139 0 1 0
142 1 2 0 0 0.0141 0.0000 0.0141 0 1 0
= 0.007161
284 1 4 0 0 0.0141 0.0000 0.0141 0 1 0
47 0.5 1 0 0 0.0106 0.0000 0.0053 0 0.25 0 = 0.007119
71.3 1 1 0 0 0.0140 0.0000 0.0140 0 1 0
117 5 1 0 0 0.0427 0.0000 0.2137 0 25 0
127 10 1 0 0 0.0787 0.0000 0.7874 0 100 0 𝑘 = 140.469 𝑥 10−10 𝑚𝑜𝑙
ൗ𝑔𝑐𝑎𝑡. 𝑠. 𝑎𝑡𝑚2
131 15 1 0 0 0.1145 0.0000 1.7176 0 225 0
133 20 1 0 0 0.1504 0.0000 3.0075 0 400 0
41.8 1 1 1 1 0.0239 0.0239 0.0239 1 1 1
𝐾𝐵 = 1.2638
෍ 61.5 12 0.662237 0.567215 5.996716 44 761.25 12 𝐾𝑇 = 1.0058
 Evaluation of Rate Law Parameter (Using SSE in excel)
𝑦 = 𝑏0 + 𝑏1 𝑥1 + 𝑏2 𝑥2

−𝑟𝑇′ 𝑃𝑇 𝑃𝐻 𝑃𝑀 𝑃𝐵 PH*PT/minrt calc Square error

71 1 1 1 0 0.01408 0.01429 4.29E-08 𝑏0 = 0.007133
71.3 1 1 4 0 0.01403 0.01429 7.10E-08
41.6 1 1 0 1 0.02404 0.02328 5.68E-07 𝑏1 = 0.008993
19.7 1 1 0 4 0.05076 0.05026 2.48E-07
42 1 1 1 1 0.02381 0.02328 2.76E-07 𝑏2 = 0.007159
17.1 1 1 0 5 0.05848 0.05926 6.03E-07
71.8 1 1 0 0 0.01393 0.01429 1.33E-07
142 1 2 0 0 0.01408 0.01429 4.29E-08
284 1 4 0 0 0.01408 0.01429 4.29E-08
47 0.5 1 0 0 0.01064 0.01071 5.46E-09 𝑘 = 140.2016 𝑥 10−10 𝑚𝑜𝑙ൗ𝑔𝑐𝑎𝑡.𝑠.𝑎𝑡𝑚2
71.3 1 1 0 0 0.01403 0.01429 7.10E-08
117 5 1 0 0 0.04274 0.04293 3.74E-08 𝐾𝐵 = 1.2608
127 10 1 0 0 0.07874 0.07872 2.57E-10
131 15 1 0 0 0.11450 0.11452 2.59E-10 𝐾𝑇 = 1.0037
133 20 1 0 0 0.15038 0.15032 3.63E-09
41.8 1 1 1 1 0.02392 0.02328 4.08E-07
SSE 2.55E-06
Evaluation of Rate Law Parameter (Using Polymath)
Exercise 𝐶6 𝐻5 𝐶𝐻3 + 𝐻2 ⟶ 𝐶6 𝐻6 + 𝐶𝐻4
For the reaction of toluene to form benzene & methane, we wish to design a packed-bed
reactor to process a feed consisting of 30% toluene, 45% hydrogen, and 25% inert (the inert is
not adsorbed). Toluene is fed at a rate of 50 mol/min at a temperature of 640oC and a
pressure of 40 atm (4052 kPa). Hydrogen is used in excess to help prevent coking. The
pressure drop parameter, α, is 9.8 x 10 kg . Determine the catalyst weight (in kg) in PBR to
-5 -1

achieve 60% conversion.

Design
equations

Rate law

Stoichiometry 𝐹𝑖 Θ𝑖 + 𝜈𝑖 𝑋 𝑃 𝑇0
𝑃𝑖 = 𝐶𝑖 𝑅𝑇 where 𝐶𝑖 = = 𝐶𝐴0
𝑣 1 + 𝛿𝑦𝐴0 𝑋 𝑃0 𝑇
And for 𝛿=0:

Combine 𝐶𝑖 = 𝐶𝐴0 Θ𝑖 + 𝜈𝑖 𝑋
𝑃 𝑇0
𝑃0 𝑇
 𝑃 𝑇0
𝑃𝑇 = 𝐶𝑇 𝑅𝑇 𝐶𝑇 = 𝐶𝑇0 Θ 𝑇 + 𝜈𝑇 𝑋 −10 𝑚𝑜𝑙
𝑃0 𝑇 𝑘 = 140.469 𝑥 10 ൗ𝑔𝑐𝑎𝑡. 𝑠. 𝑎𝑡𝑚2
𝑃𝑇 = 𝑃𝑇0 1 − 𝑋 𝑝
𝑘 = 8.4281 𝑥 10−4 𝑚𝑜𝑙ൗ
𝑃𝐻2 = 𝑃𝑇0 Θ𝐻2 − 𝑋 𝑝 𝑘𝑔𝑐𝑎𝑡. 𝑚𝑖𝑛. 𝑎𝑡𝑚2

𝑃𝐵 = 𝑃𝑇0 𝑋 𝑝 𝐾𝐵 = 1.2638
𝑘𝑃𝐻2 𝑃𝑇 𝐾𝑇 = 1.0058
−𝑟𝑇 ′ =
1 + 𝐾𝐵 𝑃𝐵 + 𝐾𝑇 𝑃𝑇
𝑃𝑇0 = 12 𝑎𝑡𝑚

𝑑𝑋 −𝑟𝑇 ′ 𝐹𝑇0 = 50 𝑚𝑜𝑙/𝑚𝑖𝑛

= 𝑝 = 1 − 𝛼𝑊 1/2
𝑑𝑊 𝐹𝑇0 𝛼 = 9.8 𝑥 10−5 𝑘𝑔−1
𝑑𝑋 1 𝑘 𝑃𝑇0 1 − 𝑋 𝑝 𝑃𝑇0 Θ𝐻2 − 𝑋 𝑝
=
𝑑𝑊 𝐹𝑇0 1 + 𝐾𝐵 𝑃𝑇0 𝑋 𝑝 + 𝐾𝑇 𝑃𝑇0 1 − 𝑋 𝑝

2
𝑑𝑋 1 𝑘𝑃𝑇0 1 − 𝛼𝑊 1 − 𝑋 1.5 − 𝑋
=
𝑑𝑊 𝐹𝑇0 1 + 𝐾𝐵 𝑃𝑇0 𝑋 1 − 𝛼𝑊 1/2 + 𝐾𝑇 𝑃𝑇0 1 − 𝑋 1 − 𝛼𝑊 1/2

𝑑𝑊 1 + 𝐾𝐵 𝑃𝑇0 𝑋 1 − 𝛼𝑊 1/2 + 𝐾𝑇 𝑃𝑇0 1 − 𝑋 1 − 𝛼𝑊 1/2

= 𝐹𝑇0 2
𝑑𝑋 𝑘𝑃𝑇0 1 − 𝛼𝑊 1 − 𝑋 1.5 − 𝑋
𝑑𝑊 1 + 𝐾𝐵 𝑃𝑇0 𝑋 1 − 𝛼𝑊 1/2 + 𝐾𝑇 𝑃𝑇0 1 − 𝑋 1 − 𝛼𝑊 1/2
= 𝐹𝑇0 2
𝑑𝑋 𝑘𝑃𝑇0 1 − 𝛼𝑊 1 − 𝑋 1.5 − 𝑋

𝑑𝑊 1 + 15.1656 𝑋 1 − 9.8 𝑥 10−5 𝑊 1/2 + 12.0696 1 − 𝑋 1 − 9.8 𝑥 10−5 𝑊 1/2

=
𝑑𝑋 0.002427 1 − 9.8 𝑥 10−5 𝑊 1 − 𝑋 1.5 − 𝑋

• If we have (ODE):
• We can approximate the solution of such ODE using Runge Kutta 4 order method:
th
 Solution (Using RK4)
• Using 2 step (h=0.3) we can get:
• Step 1:
k1 k2 k3 k4
• X1=0.3 → 3589.623 5002.692 5062.737 7486.316 W1 = 1560.34 kg
• X2=0.6 → 7505.66 12157.51 12815.04 25673.42 W2 = 5716.55 kg

• Using 12 step (h=0.05) we can get:

• Step 12: k1 k2 k3 k4
• X12=0.6 → 26589.71 32013.66 32656.49 41702.74 W12 = 5702.303 kg
 Solution (Using MATLAB)
function TRK2_ex1_matlab
clear;clc;
Xspan = [0 0.6];
W0 = [0]; alpha = 0.000098;
[X,W]=ode45(@ODEfunTRK,Xspan,W0);
p = (1 - (alpha * W)).^0.5;
[X,W,p]
plot(W,X,W,p)
end

function dWdX= ODEfunTRK(X,W);

k = 0.00084281;
KB = 1.2638; KT = 1.0058;
PTo = 12; FTo = 50;
alpha = 0.000098;
p = (1 - (alpha * W)) ^ 0.5;
PB = PTo * X * p;
PT = PTo * (1 - X) * p;
Ph2 = PTo * (1.5 - X) * p;
minRT = k * Ph2 * PT / (1 + KB * PB + KT * PT);
dWdX = FTo / minRT;
end
Solution (Using Polymath)
 Exercises

(a)
(b)

(c)

(d) (c)
Solution

PBu increase → rate slightly increase

Solution

PMEK increase → has little or no

effect on rate
 Solution

PH2 increase → has little or no

effect on rate

MEK and H2 is not adsorbed or 𝑘 𝑃𝐵𝑢

Propose −𝑟𝐵𝑢 ′ =
weakly adsorbed on the surface. 1 + 𝐾𝐵𝑢 𝑃𝐵𝑢
 Solution
𝑘 𝑃𝐵𝑢
−𝑟𝐵𝑢 ′ =
1 + 𝐾𝐵𝑢 𝑃𝐵𝑢

Propose

𝑘 𝑃𝐵𝑢
−𝑟𝐵𝑢 ′ = 2
1 + 𝐾𝐵𝑢 𝑃𝐵𝑢

Value of k and KBu can be calculated using non-linear regression

 Solution: Mechanism
𝑩𝒖 + 𝑺 ⇌ 𝑩𝒖 ∙ 𝑺 Adsorption

𝑩𝒖 ∙ 𝑺 + S → 𝑴𝑬𝑲. 𝑺 + 𝑯𝟐 ∙ 𝑺 Surface Reaction

𝑴𝑬𝑲 ∙ 𝑺 ⇌ 𝑴𝑬𝑲 + 𝑺 Desorption
𝑯𝟐 ∙ 𝑺 ⇌ 𝑯 𝟐 + 𝑺 Desorption
 Fluidized Bed Reactor
• Analogue with CSTR → The content is well mixed

→ Even temperature distribution

• Modelling fluidized bed with CSTR is only an approximation (more complex model
is needed for precise calculation)
• Characteristic of fluidized bed reactor:

Advantages Disadvantages
→ Can handle large amount of feed & solids →Expensive reactor & expensive
→ Easy catalyst replacement/regeneration catalyst regeneration equipment
Fluidized Bed Reactor
Exercise 𝐶6 𝐻5 𝐶𝐻3 + 𝐻2 ⟶ 𝐶6 𝐻6 + 𝐶𝐻4
For the reaction of toluene to form benzene & methane, we wish to design a packed-bed
reactor to process a feed consisting of 30% toluene, 45% hydrogen, and 25% inert (the inert
is not adsorbed). Toluene is fed at a rate of 50 mol/min at a temperature of 640oC and a
pressure of 40 atm (4052 kPa). Hydrogen is used in excess to help prevent coking. Determine
the catalyst weight (in kg) in a fluidized CSTR (fluidized bed) with a bulk density of 400 kg/m3
to achieve 60% conversion.

Design
equations
𝑘𝑃𝐻2 𝑃𝑇
Rate law −𝑟𝑇 ′ =
1 + 𝐾𝐵 𝑃𝐵 + 𝐾𝑇 𝑃𝑇
At X = 0.6 W = 10249.6 kg

Stoichiometry 𝑃𝑇 = 𝑃𝑇0 1 − 𝑋
𝑃𝐻2 = 𝑃𝑇0 Θ𝐻2 − 𝑋
Combine
𝑃𝐵 = 𝑃𝑇0 𝑋
 References
Fogler, H. S. 2009. “Elements of Chemical Reaction Engineering”, 5th Ed. Prentice-Hall.

Levenspiel, O. 1999. “Chemical Reaction Engineering”, 3rd Ed. John Wiley & Sons.

Thanks! Any questions?