Chemical Reaction Engineering

Course Code: CHE 331

Course Cr. Hrs.: 4(3,1)
Course Instructor:
Dr. Muhammad Haris Hamayun
Assistant Professor,
Department of Chemical Engineering,
COMSATS University Islamabad, Lahore Campus.
Contact Email: mhhamayun@cuilahore.edu.pk
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 Course Contents

Kinetics of homogeneous reactions: rate of reaction, variables affecting the rate of

reaction, order of reaction, rate constant; searching for a mechanism of reaction,
activation energy and temperature dependency. Interpretation of batch reactor data for
single and multiple reactions. Integral method and differential method of analysis for
constant volume and variable volume batch reactors, search for a rate equation. Design
of homogeneous reactors, Batch, Mixed flow, Plug flow reactors, Comparison of single
reactor, multiple reactor systems in parallel/series. Temperature and pressure effects.
Adiabatic and non-adiabatic operations. Surface phenomenon and catalysis,
Heterogeneous reaction systems, rate equations for heterogeneous reactions, fluid
particle reactions, determination of rate controlling steps. Catalysis desorption
isotherms, kinetics of solid catalyzed reactions. Catalyst deactivation and regeneration.
Design of fluid-solid catalytic reactors.

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 Recommended Books

1) H. Scott Fogler, Elements of Chemical Reaction Engineering, 5th edition, Prentice

Hall, 2016.

2) Octave Levenspiel, Chemical Reaction Engineering, 3rd edition, Wiley India Pvt.
Limited, 2006.

3) Elsie Perkins, Chemical Reaction Engineering, WILLFORD Press, 2022.

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 CLOs and Mapping with PLOs

Understand • Describe the fundamentals of chemical reaction

(C2, PLO1) engineering.

Apply • Apply the fundamentals of chemical reaction

(C3, PLO1) engineering.

Analysis • Analyze the kinetic data using different methods of

(C4, PLO2) data analysis.

Design • Design isothermal and nonisothermal reactors (e.g.,

(C6, PLO3) Batch, CSTR, PFR, PBR etc.)

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 OBE in a Nutshell

◼ What do you want the students to have or able

to do? ◼ Knowledge, Skill, Affective

◼ How can you best help students achieve it?

◼ Student Centred Delivery

◼ How will you know what they have achieved it?

◼ Assessment

◼ How do you close the loop

◼ Plan, Do, Check, Act (PDCA)
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 Lecture # 16 (CLO # 1, 2, 3 and 4)

• Chapter # 5: Isothermal Design – Conversion

❖ Plug Flow Reactor

❖ Example # 5.3

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Always Remember the Algorithm!

Mole Balance Rate Law

Mole Balance

Stoichiometry Combine

Combine
Evaluate Evaluate

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Recap – Liquid Phase Reaction in PFR

Mole Balance

Combine
Evaluate

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Recap – Gas Phase Reaction in PFR

Mole Balance

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Example # 5.3: Design of PFR

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 Example # 5.3: Design of PFR

lbm
6
1y 1d 1h lb − mol
FB = 300 × 10 × × × ×
y 365 d 24 h 3600 s 28 lbm

lb − mol mol
FB = 0.340 = 154.4 (1 lb − mol ≅ 454 mol)
s s

FB = FA0 X
For 80% conversion

FB 0.340 lb − mol mol

FA0 = = = 0.425 = 193
X 0.8 s s
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 Solution
1) Mole Balance:
dX
FA0 = −rA
dV

For isothermal operation and no pressure drop, the equation is modified as:

X
dX
V = FA0 න
0 −rA

2) Rate Law: k = 0.072s−1 at 1000 K

Ea = 82 kcal/gmol
−rA = kCA

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 Solution
3) Stoichiometry:

For isothermal operation and no pressure drop, the equation is modified as:

𝑣 = 𝑣0 (1 + εX)

FA FA0 (1 − X) 1−X
CA = = = CA0
𝑣 𝑣0 (1 + εX) 1 + εX

FC FA0 X CA0 X
CC = = =
𝑣 𝑣0 (1 + εX) (1 + εX)

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 Solution
4) Combine:
X
dX
V = FA0 න
1−X
0 kCA0
1 + εX

X
1 + εX dX
V = FA0 න
0 kCA0 1 − X

FA0 X 1 + εX dX
V= න
CA0 0 k 1 − X

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 Solution
5) Evaluate:
FA0 X 1 + εX dX
V= න
kCA0 0 1−X

Use Appendix A.1 to carry out the integration:

FA0 1
V= 1 + ε ln − εX
kCA0 1−X

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 Solution
6) Parametric Evaluation:
P0
CA0 = yA0 CT0 = yA0
RT0

6 atm
CA0 = (1)
ft3. atm
0.73 o × 1980 oR
lb − mol. R

lb − mol mol
CA0 = 0.00415 3
= 0.066
ft dm3

ε = yA0 δ = 1 1 + 1 − 1 = 1
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 Solution
6) Parametric Evaluation:

The rate constant k is given at 1000 K, and we need to calculate k at reaction conditions,
which is 1100 K. (This expression was derived in Chapter-3).

E 1 1 E T2 − T1
k T2 = k T1 exp − = k T1 exp
R T1 T2 R T1 T2

82,000 cal/mol 1100K − 1000K

k T2 = 0.072 exp
1.987 cal/(mol. K) (1000K)(1100 K)

k T2 = 3.07 s−1
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 Solution
6) Parametric Evaluation:

FA0 1
V= 1 + ε ln − εX
kCA0 1−X
Substituting the values:
lb − mol
0.425 1
V= s 1 + 1 ln −X
−1 lb − mol 1−X
3.07 s 0.00415
ft3

1
V = 33.36 2 ln −X
1−X
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 Solution
6) Parametric Evaluation:
1
V = 33.36 2 ln −X
1−X
For 80% conversion,

1
V = 33.36 2 ln − 0.8
1 − 0.8

V = 80.7ft 3 = 2280 dm3 = 2.28 m3

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 Solution
6) Parametric Evaluation:

• Use a bank of 2-inch schedule 80 pipes in parallel that are 40 feet in length.
• For schedule 80 pipe, the cross-sectional area, AC, is 0.0205 ft2. The number of pipes
necessary is

80.7 ft 3
n=
0.0205 ft 2 40 ft

n = 98.4

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Solution

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 Lecture # 17 (CLO # 1, 2)

• Chapter # 5: Isothermal Reactor Design – Conversion

• Pressure Drop in Reactors

• Pressure Drop in Pipes

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 Liquid v/s Gas Phase Reactions

• For Liquid Phase Reactions: the concentration of reactants is insignificantly affected by

even relatively large changes in the total pressure. Consequently, we can totally ignore the
effect of pressure drop on the rate of reaction when sizing liquid-phase chemical reactors.

• For Gas Phase Reactions: the concentration of the reacting species is proportional to the
total pressure; therefore, proper accounting for the effects of pressure drop on the
reaction system can be a key factor in the success or failure of the reactor operation. This
fact is especially true in microreactors packed with solid catalyst. Here, the channels are so
small that pressure drop can limit the throughput and conversion for gas-phase reactions.

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 Pressure Drop and Rate Law
Recall our Previous Equation (From Chapter # 4): ε = 𝑦𝐴0 𝛿

θi + 𝑣i X P T0 Fi0
Ci = CA0 θi =
1 + εX P0 T FA0

b
𝑣i = Stoichiometric Coefficient (𝑣a = −1, 𝑣b = − )
a

Tasks:
- Determine the ratio pressure (P/P0) as a function of the PFR reactor volume, V, or the PBR
catalyst weight, W, to account for pressure drop.
- We then can combine the concentration, rate law, and design equation.
- However, whenever accounting for the effects of pressure drop, the differential form of the mole
balance (design equation) must be used.
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 CRE Algorithm – Steps # 1 & 2
Assume a 2nd order Reaction:
2A → B + C

1) Mole Balance:

dX
FA0 = −rA′
dW

2) Rate Law:

−rA′ = kCA2

* Units of −rA′ are moles/g-cat.min.

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 CRE Algorithm – Steps # 3 & 4
3) Stoichiometry:

FA FA0 (1 − X) 1−X P T0
CA = = = CA0
𝑣 P0 T 1 + εX P0 T
𝑣0 1 + εX
P T0

4) Combine:
2
1−X P T0
−rA′ = k CA0
1 + εX P0 T

2 2
dX 1−X P
For isothermal operation: FA0 = k CA0
dW 1 + εX P0
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 CRE Algorithm – Step # 5
5) Evaluate:
2 2
dX 1−X P
FA0 = k CA0
dW 1 + εX P0

2 2
dX kCA0 1−X P
= ❖ FA0 = 𝑣0 CA0
dW 𝑣0 1 + εX P0

dX
= F1 (X, P)
dW
Next Task:
Relate the pressure drop to the catalyst weight in order to determine the conversion as a function of
catalyst weight (i.e., catalyst mass).
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 Flow Through a Packed Bed
• Most gas-phase reactions are catalyzed by passing the reactant through a packed bed of
catalyst particles.

• The equation used most often to calculate pressure drop in a packed porous bed is the
Ergun equation:

dP −G 1 − φ 150 1 − φ μ
= + 1.75G
dz ρg c Dp φ3 Dp TURBULENT
LAMINAR

• In calculating the pressure drop using the Ergun equation, the only parameter that varies
with pressure is the gas density.
• We are now going to calculate the pressure drop through a packed-bed reactor.
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 Flow Through a Packed Bed
• Because the PBR is operated at steady state, the mass flow rate at any point down the
reactor, m (kg/s), is equal to the entering mass flow rate, m0 (i.e., equation of continuity)

mሶ = mሶ 0
dP −G 1 − φ 150 1 − φ μ
= + 1.75G
ρ𝑣 = ρ0 𝑣0 dz ρg c Dp φ3 Dp TURBULENT
LAMINAR

P0 T FT
𝑣 = 𝑣0
P T0 FT0
dP −G 1−φ 150 1 − φ μ P0 T FT
= + 1.75 G
𝑣0 P T0 FT0 dz ρ0 g c Dp φ3 Dp P T0 FT0
ρ = ρ0 = ρ0 β0
𝑣 P0 T FT

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 Flow Through a Packed Bed
Simplification: dP P0 T FT
= −β0
dz P T0 FT0

G 1−φ 150 1 − φ μ
Units: kPa/m, β0 = + 1.75 G
atm/ft ρ0 g c Dp φ3 Dp

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 Flow Through a Packed Bed

• For tubular packed-bed reactors, we are more interested in catalyst weight rather than the
distance z down the reactor. The catalyst weight up to a distance of z down the reactor is

W = (1 − φ)Ac z × ρc

Weight of Volume of Density of

Catalyst Solids solid catalyst

Bulk Density: ρb = ρc × (1 − φ)

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 Flow Through a Packed Bed

dP −β0 P0 T FT
=
dW (1 − φ)Ac ρc P T0 FT0

Simplification: We will use when multiple

dP −α P0 T FT reactions are occurring or
= when there is pressure drop
dW 2 P/P0 T0 FT0
in a membrane reactor.

dp −α T FT
= ❖ p = P/P0
dW 2 p T0 FT0

Units: kg-1 or 2β0

α=
lbm-1 (1 − φ)Ac ρc P0 32
 Flow Through a Packed Bed

• For single reactions in packed-bed reactors, it is more convenient to express the Ergun
equation in terms of the conversion X.

FT
= 1 + εX
FT0

FA0
ε = yA0 δ = δ
FT0 When ε < 0, the pressure drop ΔP will be less
(i.e., higher pressure) than that for ε = 0
dp −α T
= (1 + εX)
dW 2 p T0
When ε > 0, the pressure drop ΔP will be more
(i.e., lower pressure) than that for ε = 0
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 Summary – Flow Through a Packed Bed

• So, we have derived two equations!!

2 2
dX kCA0 1−X P dp −α T
= = (1 + εX)
dW 𝑣0 1 + εX P0 dW 2 p T0

dX dp
= F1 (X, p) = F2 (X, p)
dW dW

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 Analytical Solution

• For ε = 0, or if we neglect (εX) w.r.t. 1 (1>>>εX), the analytical solution can be

obtained for isothermal operation (T = T0).
Integrating with p= 1 (P= P0) at W0 yields
dp −α T
= (1 + εX)
dW 2 p T0 p2 = (1 − αW)
dp −α
= P
dW 2 p p= = (1 − αW)
P0
2pdp
= −α
dW
P 2β0 z
p= = (1 − )
dp2 P0 P0
= −α
dW 35
 Pressure Drop in Pipes
• Normally, the pressure drop for gases flowing through pipes without packing can be
neglected.
• For flow in pipes, the pressure drop along the length of the pipe can be approximated by

1/2
p = 1 − αp V

4fG2
αp =
Ac ρ0 P0 D

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