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Chemical Reaction
Engineering 1
TEKNIK KIMIA – UNIVERSITAS PERTAMINA 2019

Catia Angli Curie, MS.

Agung Nugroho

Example of the CRE Algorithm

 Find CA and CB for X = 0.9, apply the algorithm to the above reaction
occurring in a Batch, CSTR, and PFR and find the its design parameter

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Example of the CRE Algorithm

Example of the CRE Algorithm

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Isothermal Reactor Design for Unsteady Processes

Contents Objectives
 Mole balance in terms of mole or ❑ Able to simplify species’s mole balances
molar flow rate as the basis equations for solving unsteady
 Unsteady reactor: process
 CSTR Start up ❑ Able to use polymath to solve the
 semibatch reactor obtained ODE(s) for semibatch process
 Exercises:
 semibatch
 time to reach steady state in a CSTR

Mole Balance in Terms of

mole/ molar flow rate

Sometimes, it is easier to have the Main differences

balance in terms of mole or molar flow
1. Mole balance in conversion – algorithm:
rate:
 Mole balance is written only for 1 species
 Membrane reactors
 Multiple reactions
2. Mole balance in molar flow rate – algorithm:
 Unsteady states
 Mole balance need to be written for every
species involved in the rate law
When there’s change in volumetric flow
 Need to relate the rate law of each species
rate, the preferred balance is in terms of
molar flow rate  Often need a solver to solve the equations

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Isothermal reactor design

algorithm for mole balance

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Example : Gas-Phase Reaction in a PFR—

Molar Flow Rates

 Nitrous oxide (NO) can be produced by the gas-phase second-order reaction.

2NOCl → 2NO+Cl2
 This reaction is to be carried out at 425°C and 1641 kPa (16.2 atm). Pure NOCl (226 mol/s) is to be
fed, and the reaction follows an elementary rate law. It is desired to produce NO in PFR with a
volume of 100 dm3.
(a) Plot the molar flow rates of each species as a function of volume reactor.
(b) What is the reactor volume necessary to achieve 85% conversion?

Mole balance:

Rate law:

𝑘2 𝐸 1 1
𝑙𝑛 = −
𝑘1 𝑅 𝑇1 𝑇2

𝐸 1 1
−
𝑘2 = 𝑘1 𝑒 𝑅𝑇1 𝑇2

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Polymath

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CSTR Start-up

Time to reach steady state on CSTR

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Unsteady-State Isothermal Reactor

Operation: CSTR Start-Up
CA0u0 u0CA
 Unsteady state: concentrations vary with time & accumulation is non-zero

 Goal: Determine the time necessary to reach steady-state operation

 General Mole Balance:

In - Out + Generation = Accumulation
𝑑𝑁𝐴 moles A in CSTR changes with time until
𝐹𝐴 0 − 𝐹𝐴 + 𝑟𝐴 𝑉 =
𝑑𝑡 steady state is reached
 Use concentration rather than conversion in the balance equation
𝑑𝑁𝐴 C A0u0 − C Au0 + rA V dNA  1  C A0
−
CA
+ rA =
dC A
𝐶𝐴 0 𝜐0 − 𝐶𝐴 𝑣0 + 𝑟𝐴 𝑉 = → =  
𝑑𝑡 V dt  V    dt
𝑉 Divide by V to convert dNA to dCA dC A
𝜏= C A0 − C A + rA = 
𝜐0 dt
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CSTR Start-Up: 1st Order Reaction

dC A We integrated this eq to find

C A0 − C A + rA =  𝑑𝐶𝐴 CA (t) while CSTR of 1st order
dt Combine 𝐶𝐴 0 − 𝐶𝐴 − 𝑘𝐶𝐴 𝜏 = 𝜏
𝑑𝑡 rxn is in unsteady-state:
−rA = kC A
𝐶𝐴 0
𝑑𝐶𝐴 1 𝐶𝐴 0 𝐶𝐴 𝑡 − 𝐶𝐴
𝑑𝐶𝐴 1 + 𝑘𝜏 1 + 𝑘𝜏 1 + 𝑘𝜏
→ = 1 + 𝑘𝜏 − 𝐶𝐴 →න =න 𝑑𝑡 → ln =0− 𝑡
𝑑𝑡 𝜏 1 + 𝑘𝜏 𝐶𝐴 0 𝜏 𝐶𝐴 0 𝜏
0 − 𝐶𝐴 0 −0
1 + 𝑘𝜏 1 + 𝑘𝜏

𝐶𝐴 1+𝑘𝜏
𝐶𝐴 0
→1− = 𝑒− 𝜏 𝑡
→ 1 − 𝑒 −𝑡
1+𝑘𝜏
= 𝐶𝐴 Start up equation
𝐶𝐴 0 𝜏
1 + 𝑘𝜏
1 + 𝑘𝜏

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CSTR Start-Up: 1st Order Reaction

𝐶𝐴 0 1+𝑘𝜏 C A0
→ 1 − 𝑒 −𝑡 𝜏 = 𝐶𝐴 → = C AS Steady state equation
1 + 𝑘𝜏 1 + k

At steady state t is large

Goal: combine start-up and SS eqs to estimate time In the unsteady state, when
to reach SS (ts) CA = 0.99CAS:
 C
 1 + k


(
→  A0  1 − e s (

− t 1+k )   C
 1
)
= 0.99  A 0 
+ k 



→ 1− e s(
− t 1+k ) 
= 0.99 → 0.01 = e s (
− t 1+k ) 
→ ln ( 0.01) = ln e s (
− t 1+k ) 
( )
1 + 𝑘𝜏 𝜏
→ −4.6 = −𝑡𝑠 → 𝑡𝑠 = 4.6
𝜏 1 + 𝑘𝜏 time to reach 99% of steady-state concentration in terms of k

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CSTR Start-Up: 1st Order Reaction


In the unsteady state, the time to reach CA = 0.99CAS is: t = 4.6
1 + k

When k is very small When k is very big 4.6

t = 4.6 ts =
(slow rxn), 1>>k: s (fast rxn), 1<<k k

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Example – time to reach steady state on CSTR

Ethylene glycol is produced through reaction:

Ethylene oxide + H2O → ethylene glycol
In a 197.325 ft3 CSTR. The reactor is to be operated isothermally with specific reaction rate constant
of 0.311 min-1. The reaction is following 1st order because water is present in excess, so the
concentration of water can be considered constant.
Total volumetric flow rate of the entering stream is 15.342 ft 3/min. Concentration of ethylene oxide
(A) in this stream is 0.5 lbmol/ft3. At steady state, the concentration of A at the exiting stream will be
0.1 lbmol/ft3. Determine the time needed to reach this steady state condition.

𝐶𝐴 0 1+𝑘𝜏 0.5 1+0.311 𝜏

→ 1 − 𝑒 −𝑡𝑠 𝜏 = 𝐶𝐴 → 1 − 𝑒 −𝑡𝑠 𝜏 = 0.1
1 + 𝑘𝜏 1 + 0.311 𝜏
ts = 23.5 min
𝑉
𝜏= = 12.86 𝑚𝑖𝑛
𝜐0

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Semibatch Reactor

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Motivation to use Semi-Batch Reactor :

Better Selectivity in

To enhance selectivity of desired product over side product

k
A + B ⎯⎯⎯
P →P rP = kpCA 2CB Desired product P
2
→ S rS = k SCA CB
kS
A + B ⎯⎯⎯ Undesired side product S
Instantaneous selectivity, SP/S, is the ratio of the relative rates*:
r k C 2C k C
SP/S = P = P A B = P A
rS k S C A CB2 k S CB

Higher concentrations of A favor formation of the desired product P

Higher concentrations of B favor formation of the undesired side product S
To maximize the formation of the desired product: Slowly feed B into the reactor containing A
Commonly used in bioreactors, when the enzyme is inhibited by excess substrate

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Semibatch reactors (unsteady reactor)

A+B→C+D
2 basic types of semibatch reactors:
 B is slowly fed to a reactor containing A  A & B are charged simultaneously, while C is
withdrawn continuously

Also called:
Reactive distillation

Is chosen when: It will:

 The reaction is extremely exothermic, or  Shifts reaction to the right
 If side reaction happens with high  Concentrate the remaining reactant → rate of
concentration of B (to control selectivity) reaction increases

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Mole Balance of Semibatch Reactor

 We’ll set up mole balance for type 1 (to control selectivity)

reactor is being filled
 If we have a reaction of : A + B → C
→ V changes with time,
Mole balance of A:

we’ll make the equation as a concentration term

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Mole Balance of Semibatch Reactor

 We’ll do mole balance for type 1 (to control selectivity)

reactor is being filled
 If we have a reaction of : A + B → C
→ V changes with time,
Mole balance of A:

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Mole Balance of Semibatch Reactor

 We can obtain the relation for dV/dt from overall mass balance:

For system with constant density:

𝑑𝑉
𝑣0 = and 𝑉 = 𝑉0 + 𝑣0 𝑡
𝑑𝑡

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Mole Balance of Semibatch Reactor

 From mole balance of A, we’ve had:

𝑑𝐶𝐴
𝑟𝐴 𝑉 = 𝑉 + 𝐶𝐴 𝑣0 :V
𝑑𝑡
𝑑𝐶𝐴 𝑣0
= 𝑟𝐴 − 𝐶𝐴
𝑑𝑡 𝑉

Do the mole balance for B & C

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Differential equation for Semibatch reactor

Rate Law −𝑟𝐴 = 𝑘𝐶𝐴 𝐶𝐵

Can be solved
𝑉 = 𝑉0 + 𝑣0 𝑡 using ODE solver
software such as
𝑑𝐶𝐴 𝑣0 Polymath or
= 𝑟𝐴 − 𝐶𝐴
Mole Balance 𝑑𝑡 𝑉 MATLAB
𝑑𝐶𝐵 𝑣0 𝐶𝐵0 − 𝐶𝐵
= 𝑟𝐵 +
𝑑𝑡 𝑉
𝑑𝐶𝐶 𝑣0 𝐶𝐶
= 𝑟𝐶 −
𝑑𝑡 𝑉

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Example

The production of methyl bromide is an irreversible liquid-phase reaction that follows an

elementary rate law. The reaction

Is carried out isothermally in a semibatch reactor. An aqueaous solution of methyl amine

(B) at a concentration of 0.025 mol/L is to be fed at a volumetric rate of 0.05 L/s to an
aqueous solution of bromine cyanide (A) contained in a glass-lined reactor. The initial
volume of liquid in the reactor is to be 5 L with a bromine-cyanide concentration of 0.05
mol/L. The specific reaction rate constant is 2.2 L/s.mol.
a. Plot the concentration of bromine cyanide (A), methyl amine (B), methyl bromide (C),
cyanamide (D), and the rate of reaction as a function of time (use 0 – 500 as the time
range)
b. What is the time needed to reach 95% conversion of bromine cyanide (A)?

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ODE for Semibatch reactor

𝐴+𝐵 →𝐶+𝐷
Rate Law −𝑟𝐴 = 𝑘𝐶𝐴 𝐶𝐵 −𝑟𝐴 = −𝑟𝐵 = 𝑟𝐶 = 𝑟𝐷

𝑉 = 𝑉0 + 𝑣0 𝑡
𝐶𝐵0 = 0.025 𝑚𝑜𝑙/𝐿 𝑑𝐶𝐴 𝑣0
= 𝑟𝐴 − 𝐶𝐴
𝑣0 = 0.05 𝐿/𝑠 𝑑𝑡 𝑉
Mole Balance Can be solved
𝑉0 = 5𝐿 𝑑𝐶𝐵 𝑣0 𝐶𝐵0 − 𝐶𝐵 using ODE solver
= 𝑟𝐵 +
𝐶𝐴0 = 0.05 𝑚𝑜𝑙/𝐿 𝑑𝑡 𝑉 software such as
𝐿 𝑑𝐶𝐶 𝑣0 𝐶𝐶 Polymath or
𝑘 = 2.2 = 𝑟𝐶 − MATLAB
𝑠. 𝑚𝑜𝑙 𝑑𝑡 𝑉
𝑑𝐶𝐷 𝑣0 𝐶𝐷
= 𝑟𝐷 −
𝑑𝑡 𝑉
a. Plot 𝐶𝐴 , 𝐶𝐵 , 𝐶𝐶 , 𝐶𝐷 and −𝑟𝐴 as function of time (t=0-500s)

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Polymath

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The graph from the exercise

0.06 0.003

0.05 0.0025

0.04 0.002
Concentration

Cb
-rA

0.03 0.0015
Cd
Cc
0.02 0.001
Ca

0.01 0.0005

0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Time Time

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Homework

The production of ethylene glycol from ethylene chlorohydrin and sodium

bicarbonate
CH2OHCH2Cl + NaHCO3 → (CH2OH)2 + NaCl + CO2
Is carried out in a semibatch reactor. A 1.5 M solution of ethylene chlorohydrin is
fed at a rate 0.1 mole/min to 1500 L of a 0.75 M solution of sodium bicarbonate.
The reaction is elementary and carried out isothermally at 30oC where the specific
reaction rate is 5.1 L/mol/h. Higher temperatures produce unwanted side
reactions. The reactor can hold a maximum of 2500 L of liquid. Assume constant
density.
Plot the concentration of reactants and products, conversion, reaction rate, and
moles of glycol formed as a function of time

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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.

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