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
 Overall Course Content

Heterogeneous reactions Non-ideality

Packed bed Catalysis & RTD &

Mass transfer
reactor - Catalytic non ideal
& reaction
PBR reactor reactor
 References
&
grading system

Assignments: 20%
Quizes : 20%
UTS : 30%
UAS : 30%

You can contact me at:

[email protected]
 Part 1. Packed Bed Reactor

Content Objectives

➢ Packed bed reactor (PBR) ➢ Understand the difference between PBR

➢ Design equation of PBR and batch/CSTR/PFR
➢ Review of concentration of gas with ➢ Able to formulate the design equation
variable volume for PBR
➢ Pressure drop in PBR ➢ Understand the effect of pressure drop
to reaction rate and conversion
➢ Able to calculate / design a simple PBR
taking into account the pressure drop
 Packed
Bed
Reactor
➢ Tubular reactor (PFR) packed with solid catalyst
particles
➢ Most often used to catalyze gas reactions
Packed Bed Reactor
 Packed Bed Reactor

Advantage Disadvantage

➢ For most reactions, gives highest ➢ Difficult to control T (as with PFR)
conversion per weight of catalyst ➢ Difficult to replace the catalyst
(compare to any catalytic reactor) ➢ Channeling of the gas flow results in
➢ Gases approximate plug flow (easier to ineffective use of parts of the reactor
model) bed
➢ Hot spots may form and may ruin
(damage) the catalyst
 Packed Bed Reactor
Hotspot and Channeling
 Packed Bed Reactor
Reaction occurs on the surface of the catalyst (solids)

(for the same type of catalyst) if catalyst mass >> → reactive surface area >>

Reaction rate is based on mass of solid catalyst (rather than reactor volume)

Hence, the unit of −𝑟𝐴′ is mol A reacted/time/mass of catalyst

What was the unit of −𝑟𝐴 in homogeneous reaction (CRE/TRK 1)?

Bulk catalyst density

In PBR, catalyst weight (W) is more important than reactor volume

 Packed Bed Reactor
Example: a heterogeneous reaction and corresponding rate law of the
hydrodemethylation of toluene (T) to form benzene (B) and methane (M) carried out over a solid catalys
 Exercise
𝑚𝑜𝑙
1. Determine the rate law if the dimension of 𝑘 = . The rate laws should be elementary as written
𝑘𝑔−𝑐𝑎𝑡.ℎ.(𝑎𝑡𝑚)2
for reactions that are either of the form A + B → C.

2. Give the units of 𝑘 for the gas-solid catalyzed irreversible reactions

If the rate law is
′
𝑘 𝑃𝐴 𝑃𝐵
−𝑟𝐴 =
1 + 𝐾𝐴 𝑃𝐴 + 𝐾𝐵 𝑃𝐵

3. Write the rate law for the following heterogeneous reaction assuming the reaction follows an elementary rate
law and gas phase reaction. Give the units of 𝑘.

A B + C.
 Design Equation of PBR
Analogous with that of PFR (tubular reactor)

Assumed no radial gradients (in C, T, or reaction rate)

Dividing by ΔW with limit of ΔW → 0 we get:

𝑑𝐹𝐴 𝑑𝑋
= 𝑟𝐴′ or 𝐹𝐴0
𝑑𝑊
= −𝑟𝐴′
𝑑𝑊
 Design Equation of PBR
𝑑𝑋 Integration of design equation as a function of X
𝐹𝐴0 = −𝑟𝐴′
𝑑𝑊 (conversion) depends on the form of CA=f(X)

If total volumetric flow rate remain constant:

𝐹𝐴 = 𝐹𝐴0 (1 − 𝑋)
 Example
A second-order reaction of 2A → B + C is taking place in a 20 m, 1½ -inch
schedule 40 pipe packed with catalyst.
The initial pressure is 10 atm, with entering volumetric flow rate of 7.15 m3/h.
Solid catalyst density in the pipe is 1923 kg/m3, void fraction (porosity, Φ) is
0.45, cross-sectional area on the pipe (Ac) is 0.0013 m .
2

Find the conversion of the reaction, if the entering concentration of A is 0.1

kmol/m3, the specific reaction rate (k) is 12 m6/kmol.kg-cat.h, and the
pressure drop is ignored. Assume isothermal operation.
 Example
Solution
𝑑𝑋
𝐹𝐴0 = 𝑘 (𝐶𝐴0 (1 − 𝑋) )2
Design 𝑑𝐹𝐴 𝑑𝑊
= 𝑟𝐴′
equations 𝑑𝑊 E
𝐹𝐴0 𝑑𝑋 v 𝑋 12 (0.1) 𝜋
−𝑟𝐴 ′ = 𝑘𝐶𝐴 2 2 (1 − 𝑋)2 = 𝑑𝑊 a = (1.61𝑥0.0254)2 20 (1923)(1 − 0.45)
Rate law 𝑘 𝐶𝐴0 (1 − 𝑋) 7.15 4
l
C 𝑋
𝑑𝑋 𝑘 𝐶𝐴0 2 𝑊 u
o න = a X = 0.82
Stoichiometry 𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋) (1 − 𝑋) 2 𝐹
m 0 𝐴0
t
b e
𝐹𝐴0 = 𝐶𝐴0 .𝑣0 i 𝑋 𝑘𝐶𝐴0 𝜋 2
= 𝐷 𝐿 𝜌𝑐 (1 − ∅)
n (1 − 𝑋) 𝑣0 4
e
Catalyst 𝑊 = 𝑉 𝜌𝑏
= 𝐴𝑐 𝐿 𝜌𝑐 (1 − ∅)
𝜋 2
= 𝐷 𝐿 𝜌𝑐 (1 − ∅)
4
 Design Equation of PBR
Can the volumetric flow rate change?

Yes, it will change if:

Different stoichiometric number between reactant & product

N2 + 3 H2 ⇄ 2 NH3
There is pressure drop

P change → volumetric flow rate change! → concentration change

Recall concentration of i at system with variable flow rate (CRE1/TRK1)

𝐹𝑖 Θ𝑖 + 𝜈𝑖 𝑋 𝑃 𝑇0
𝐶𝑖 = = 𝐶𝐴0
𝑣 1 + 𝛿𝑦𝐴0 𝑋 𝑃0 𝑇
 Review of :
Concentration in continuous reactor as f(X) in system with variable
volumetric flow rate
To get Fi (stoichiometric table):
𝑏 𝑐 𝑑
A +𝑎 B → C + D
𝑎 𝑎
Initial FA0 FB0 FC0 FD0
𝑏 c
FA0 X
d
Reacted - FA0 X - FA0 X 𝑎
FA0 X
𝑎 𝑎
𝑏 c
FC0 + FA0 X
d
Remaining FA0 - FA0 X FB0 - FA0 X 𝑎
FD0 + FA0 X
𝑎 𝑎
c d 𝑏
Total Ftotal0 + ( + - - 1) FA0 X = FT0 + 𝛿. FA0 X
𝑎 𝑎 𝑎

𝑃0 𝑇 𝐹𝑇 𝑍
To get 𝑣 (simple EoS relation): 𝑣 = 𝑣0
𝑃 𝑇0 𝐹𝑇0 𝑍0

𝐹𝑖 𝐹𝐴 𝐹𝐴0 (1 − 𝑋) (1 − 𝑋) 𝑃 𝑇0
𝐶𝑖 = 𝐶𝐴 = = = 𝐶𝐴0
𝑣 𝑣 𝑃0 𝑇 1 + 𝛿𝑦𝐴0 𝑋 𝑃0 𝑇
𝑣0 1 + 𝛿𝑦𝐴0 𝑋
𝑃 𝑇0
 Review of :
Concentration in continuous reactor as f(X) in system with variable
volumetric flow rate
To get Fi (stoichiometric table):
𝑏 𝑐 𝑑
A +𝑎 B → C + D
𝑎 𝑎
Initial FA0 FB0 FC0 FD0
𝑏 c
FA0.X
d
Reacted - FA0.X - FA0.X 𝑎
FA0. X
𝑎 𝑎
𝑏 c
FC0 + FA0.X
d
Remaining FA0 - FA0.X FB0 - FA0.X 𝑎
F D0 + F A0. X
𝑎 𝑎
c d 𝑏
Total Ftotal 0 + ( + - - 1) FA0.X = FT0 + 𝛿. FA0.X
𝑎 𝑎 𝑎
𝑃0 𝑇 𝐹𝑇 𝑃0 𝑇
To get 𝑣 (simple EoS relation): 𝑣 = 𝑣0 = 1 + 𝛿𝑦𝐴0 𝑋
𝑃 𝑇0 𝐹𝑇0 𝑃 𝑇0
𝐹𝑖0 𝐹𝐴0
where Θ𝑖 = 𝑦𝐴0 =
𝐹𝐴0 𝐹𝑇0
𝐹𝑖 Θ𝑖 + 𝜈𝑖 𝑋 𝑃 𝑇0
The general form: 𝐶𝑖 = = 𝐶𝐴0
𝑣 1 + 𝛿𝑦𝐴0 𝑋 𝑃0 𝑇 𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 𝑜𝑓 𝑖
𝜈𝑖 =
Volumetric flow rate 𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 𝑜𝑓 𝐴
 Pressure Drop in a PBR
Ergun equation:

Dominant for laminar flow Dominant for turbulent flow

In isothermal operation, the only variable that varies with pressure is 𝜌

 Pressure Drop in a PBR
Ergun equation:

At steady state operation of PBR → mass flow rate is constant

𝑃0 𝑇 𝐹𝑇 𝑃 𝑇0 𝐹𝑇𝑜
Since 𝑣 = 𝑣0 Hence, 𝜌 = 𝜌𝑜
𝑃 𝑇0 𝐹𝑇0 𝑃0 𝑇 𝐹𝑇

The Ergun equation become:

 Pressure Drop in a PBR

Or in shorter form:

𝑑𝑃 𝑑𝑃
If we need to express the pressure drop as a function of catalyst weight (mass) ⇒
𝑑𝑧 𝑑𝑊
 Pressure Drop in a PBR

To simplify the form of dP/dW, taking

The dP/dW equation become

Let

The general pressure drop relation for single/multiple reactions

 Pressure Drop in a PBR

𝐹𝑇 𝐹𝑇𝑜 1 + 𝛿𝑦𝐴0 𝑋
If we’re dealing with single reaction: = = 1 + 𝛿𝑦𝐴0 𝑋
𝐹𝑇𝑜 𝐹𝑇𝑜
The dP/dW equation become 𝑑𝑝 𝛼 𝑇
=− 1 + 𝛿𝑦𝐴0 𝑋
𝑑𝑊 2𝑝 𝑇𝑜

when 𝛿 is negative, the pressure drop ΔP < that when 𝛿=0, and vice versa

In actual, we’ll then need to solve these equations simultaneously:

2 2
𝑑𝑋 𝑘 (1 − 𝑋) 𝑃 𝑇𝑜 𝑘 (1 − 𝑋) 𝑇𝑜 𝑑𝑝 𝛼 𝑇
= 𝐶𝐴0 = 𝐶𝐴0 𝑝 and =− 1 + 𝛿𝑦𝐴0 𝑋
𝑑𝑊 𝐹𝐴0 1 + 𝛿𝑦𝐴0 𝑋 𝑃0 𝑇 𝐹𝐴0 1 + 𝛿𝑦𝐴0 𝑋 𝑇 𝑑𝑊 2𝑝 𝑇𝑜
 Pressure Drop in a PBR
However, in the case when 𝛿=0 or when 𝛿𝑦𝐴0 𝑋 <<<1 and isothermal

𝑑𝑝 𝛼 𝑇 𝑑𝑝 𝛼
=− 1 + 𝛿𝑦𝐴0 𝑋 =−
𝑑𝑊 2𝑝 𝑇𝑜 𝑑𝑊 2𝑝

2𝑝 𝑑𝑝 𝑑𝑝2
Rearranging: = −𝛼 or = −𝛼
𝑑𝑊 𝑑𝑊

Integrating with p=1 (P=Po) at W=0

𝑃
𝑝2 = (1 − 𝛼𝑊) or 𝑝= = (1 − 𝛼𝑊)1/2
𝑃𝑜

In terms of length (no catalyst mass):

𝑊 = (1 − ∅)𝐴𝑐 𝑧𝜌𝑐 &
 Example
A second-order reaction of 2A → B + C is taking place in a 20 m, 1½ -inch schedule 40
pipe packed with catalyst.
The initial pressure is 10 atm, with entering volumetric flow rate of 7.15 m3/h.
Solid catalyst density in the pipe is 1923 kg/m3, void fraction (porosity, Φ) is 0.45, cross-
sectional area on the pipe (Ac) is 0.0013 m2. Find the conversion of the reaction, if the
entering concentration of A is 0.1 kmol/m3 and the specific reaction rate (k) is 12
m6/kmol.kg-cat.h, considering pressure drop with pressure-drop parameter 𝜷𝒐 = 25.8
kPa/m. Assume isothermal operation.
 References
Fogler, H. S. 2009. “Elements of Chemical Reaction Engineering”, 4th Ed. Prentice-Hall.

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

Thanks! Any questions?