Bits, Pilani - K. K. Birla Goa Campus Kinetics & Reactor Design

BITS, PILANI – K. K.
BIRLA GOA CAMPUS
KINETICS & REACTOR DESIGN

Chapter 4
PROF. SRINIVAS KRISHNASWAMY

PROFESSOR
DEPARTMENT OF CHEMICAL ENGINEERING
BITS PILANI, K. K. BIRLA GOA CAMPUS
Time to put the Jigsaw together!!!
After this chapter you will be able to use the
information from the previous 3 chapters
together to arrive at a logical structure for design
of reactors
Mole Balance Rate Laws Stoichiometry
September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 2

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Isothermal reactor design
Heat Effects
Solve Reactor Engineering problems
Isothermal Design via reasoning and not memorizing!!!
Stoichiometry Just plugging formulas is risky
Rate Laws PART 1: Mole balances in terms of X
Mole Balance

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Algorithm for Isothermal Reactor
Design

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Algorithm for Isothermal Reactor
Design

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Elementary Gas Phase reactions in
various reactors (CSTR)
The elementary gas phase reaction takes

place in a CSTR at constant temperature
(500 K) and constant pressure (16.4 atm).
The feed is equal molar in A and B.

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Mole balance
Rate Law
Stoichiometry
DERIVE THE LAST

TWO

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V=1701 dm3

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various reactors (PFR)
Mole balance
Rate Law
Stoichiometry
Gas phase, isothermal (T = T0), no

pressure drop (P = P0), CAo= CBo ,
v=vo(1+eX)

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various reactors (PFR)
V=227 dm3
CAo=0.2, v=vo=25 dm3/s,

k=10 dm6/mol2 s, =-0.5,
X=0.9

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various reactors (Batch Reactor)
Mole balance
Rate Law
Stoichiometry

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various reactors (Batch Reactors)
CAo= 0.2, k =10 dm6/mol2 s t = 41 sec

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Practice makes perfect!!!
The liquid phase reaction
is carried out isothermally in a CSTR. Pure A

enters at a volumetric flow rate of 25 dm3/s and
at a concentration of 0.2 mol/dm3.
What CSTR volume is necessary to achieve a
90 % conversion when k = 10 dm3/(mol*s)?
(1125 dm3)
What is the space time? (45 secs)
CAMPUS
The hydrolysis of acetic anhydride is to be carried out at 25 °C.
The water and acetic anhydride are mixed immediately before
entering the reactor where the entering steam is 7.8 wt % acetic
anhydride (1M) and 92.2 wt % water (51.2M). The volumetric feed
rate of liquid in 0.0033 dm3/s.
Additional Information
k'=1.97x10-4 dm3/mol s @ 25°C with E = 12,000 cal/mol
(a) What conversion can be achieved in a 1 dm3 CSTR at 25°C?

(b) What conversion can be achieved in a 0.311 dm3 PFR?
(c) What time is required to achieve 80% conversion in a batch
reactor?
CAMPUS
Example: Determine Xe for a PFR with no pressure drop, P = P0
Given that the system is gas phase and isothermal, determine the
reactor volume when X = 0.8 Xe.
Reaction Additional Information

CA0 = 0.2 k = 2 dm3/mol-
mol/dm3 min
KC = 100 FA0 = 5 mol/min
dm3/mol

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 The following reaction takes place in a CSTR:
A B
Pure A is fed to the reactor under the following

FAo= 10 mol/min
conditions:
CAo = 2 mol/dm3 Rate Law: -rA = kCA
What is the
conversion in the
V= 500 dm3 CSTR?
and
k=0.1/min

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The following reaction takes place in a CSTR:
Pure A is fed to the reactor under the following conditions:

FAo = 10 mol/min Rate Law: -rA = kCA
CAo = 2 mol/dm3 The activation energy:
At T=350 K E=20 kcal/mol
V= ?
and
k=? X=0.75

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The zero order reaction
is carried out in a CSTR and in a PFR. For an

entering volumetric flowrate of 10 dm3/s at a
concentration of .5 mol/dm3, what is the space
time for each reactor to achieve 90% conversion.
Additional Information: kA = 0.01 mol/dm3.s

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Zero order reaction in CSTR / PFR
Mole balance
Rate Law
Stoichiometry
Zero order
reaction in CSTR
PFR: DIY / PFR

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Final Problem
The following reaction follows an
elementary rate law
Initially 77% N2, 15% O2, 8% inerts are fed to a

batch reactor where 80% of the equilibrium
conversion (Xe = 0.02) is reached in 151 s. What
is the specific reaction rate constant k1?
Additional Information

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Scale up of liquid phase Batch
reactor data
 Helps meet moving from lab scale (microplant)

to real time reactors
 Analysis of batch scale data helps evaluate k
 Once k is known full scale batch reactor can be

designed

CAMPUS
Understanding Batch reactor times
Reaction time First order k Second order

tr (sec-1) kCAo (sec-1)
Hours 10-4 10-3

Minutes 10-2 10-1
Seconds 1 10
Milliseconds 1000 10,000
t = t f + te + t r + t c
For 1st Order
(1.5 – 3), (0.2 – 2.0),
t = (1/k) ln (X / 1- X )
varies, (0.5 – 1.0)
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Slight Shift in approach!
GETTING TOUGH

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Pressure Drop in Reactors
 In liquid phase reactions, the concentration of

reactants is insignificantly affected by large changes in
total pressure (TP)
 Effect of pressure can be neglected
 Important in gas phase reactions
Include P
Neglect P

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Pressure Drop in Reactors
 Gas phase reactions occur in PFR or PBR
OBJECTIVE: Find ratio P/Po as a function of volume V

or catalyst weight W to account for pressure drop
*** Differential form of the mole balance or design

equation is used

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Pressure Drop in PBR (STEP 1)
(dX/dW) = F1(X, P)
Consider a second order irreversible gas phase reaction
that occurs isothermally in a PBR

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(dP/dW) = F2(X, P)
Need to find (P/P0) as a function of W (or V if you have a
PFR)
Ergun Equation
= Porosity = void fraction = volume of void / total volume
G = u = superficial mass velocity (kg / m2.s)
U = Superficial velocity = volumetric flow / superficial area (m/s)

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(dP/dW) = F2(X, P)
From Continuity
Equation
dP / dz = o (Po/P) (T/To)(FT/Fto)
z is not our interest, W is!!!

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Get P in terms of W and not z!
CATALYST WEIGHT A
Bulk density is
mass of catalyst
per unit volume of
reactor bed

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Get P in terms of W and not z!
More suited for multiple reactions or for

pressure drop in membrane reactors
For single reactions use Ergun equation

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Single Reactions

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Pressure Drop in PBR (FINALLY!)
WHEW!!!!
FINALLY WE HAVE
SOMETHING
TWO COUPLED FIRST

ORDER DIFFERENTIAL
EQUATIONS SOLVED
ANALYTICALLY OR BY
COMPUTER

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ANALYTICAL SOLUTION
Never use this form when   0 or for

non-isothermal reactions
y = P / Po = [1 – (2oz / Po)]1/2 P = f(z)

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Where does this end?
We can now solve for X given W, or for W given X

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What does all this imply?

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Calculating pressure drop
(TB problem)
Plot the pressure drop in a 60 ft length of 1 and

1/2” Schedule 40 pipe packed with catalyst
pellets ¼” in diameter. There is a 104.4 lbm/hr of
gas flowing through the bed. The temperature is
constant along the length of the pipe at 260 oC.
The void fraction is 45 %and properties of gas
are the same of air at this temperature. The
enetering pressure is 10 atm
y = P / Po = [1 – (2oz / Po)]

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Calculating pressure drop
(Let us try this)
The elementary isomerization A --> B is carried out

at 20 atm in a fluidized CSTR containing
100 kg of catalyst where 50% conversion is achieved
It is proposed to replace the CSTR
with a packed bed reactor. The
entering pressure was 20 atm
and the exit pressure was found
to be 10 atm.

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What would be the conversion if No
pressure drop?
What information can you obtain from the CSTR?

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What would be the conversion in the
PBR with pressure drop?
NOTE X = 0.54
How do you calculate the pressure drop parameter?

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Plot the conversion as a function of particle
diameter assume everything else is
unchanged.
As the particle diameter decreases, the pressure drop increases, so

the concentration decreases as does the reaction rate.
Consequently when the reaction rate is small the conversion will be
small. As the particle size increases the pressure drop decreases
and conversion increases. As the particle size increases the
pressure drop decreases and the concentration increases.
however, for large particles, it takes a long time for the reactants
to diffuse in and out of the catalyst particle.

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Practice (DIY)
What is the conversion of the PFR?
W = 500kg X=?
k = 0.1111 dm3 s-1 kg
FA0 = 10 mol/s
CA0 = 1 mol/dm3
0.96

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Practice (DIY)
FA0 = 10 mol/s
CA0 = 0.1 mol/dm3
X1 = 0.8
W2 = W1 W1 = ?
T = 350 K T = 325 K ; E = 2500 cal
X = 0.66
X2 =?

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Solution
X = 0.66
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DESIGN ON REACTORS

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Damkohler’s number
It is important to know what values of

Damkohler number, Da give high and low
conversion in continuous flow reactors.
Equation for the 1st order liquid phase reaction in

a CSTR can also be written in the Terms of
Damkohler number
CSTR in series
A first order reaction with no change
in the volumetric flow rate is to be
carried out in two CSTRs placed in
series:
CSTR’s in parallel
We now consider the

case in which equal
sized reactors are
placed in parallel rather
then in
series, and the feed is
distributed equally
among each of the
reactors

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Determine the PFR volume required to produce 300 miliion pounds
of ethylene a year cracking a feed stream of pure ethane. The
reactions is irreversible and follows a elementary rate law. We want
to achieve 80% conversion of ethane operating the reactor
isothermally at 1100 K at a pressure of 6 atm
Solution:
Objective Assessment of Chapter
 Describe the CRE algorithm that allows the reader to solve
chemical reaction engineering problems through logic rather
than memorization
 Size batch reactors, semi-batch reactors, CSTRs, PFRs, PBRs,

membrane reactors, and micro-reactors for isothermal operation
given the rate law and feed conditions
 Account for the effects of pressure drop on conversion in

packed bed tubular reactors
If you look upwards and see the stars, stop admiring

them. Start thinking as to whether you have lost your
roof!!!

CAMPUS

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BITS, PILANI – K. K.

BIRLA GOA CAMPUS

KINETICS & REACTOR DESIGN

PROF. SRINIVAS KRISHNASWAMY

Mole Balance Rate Laws Stoichiometry

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 2

Stoichiometry Just plugging formulas is risky

Rate Laws PART 1: Mole balances in terms of X

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 3

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 4

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 5

The elementary gas phase reaction takes

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 6

DERIVE THE LAST

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 7

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 8

Gas phase, isothermal (T = T0), no

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 9

CAo=0.2, v=vo=25 dm3/s,

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 10

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 11

CAo= 0.2, k =10 dm6/mol2 s t = 41 sec

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 12

is carried out isothermally in a CSTR. Pure A

k'=1.97x10-4 dm3/mol s @ 25°C with E = 12,000 cal/mol

(a) What conversion can be achieved in a 1 dm3 CSTR at 25°C?

Reaction Additional Information

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 15

Pure A is fed to the reactor under the following

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 16

Pure A is fed to the reactor under the following conditions:

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 17

is carried out in a CSTR and in a PFR. For an

Additional Information: kA = 0.01 mol/dm3.s

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 18

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 19

Initially 77% N2, 15% O2, 8% inerts are fed to a

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 20

 Helps meet moving from lab scale (microplant)

 Analysis of batch scale data helps evaluate k

 Once k is known full scale batch reactor can be

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 21

Reaction time First order k Second order

Hours 10-4 10-3

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 23

 In liquid phase reactions, the concentration of

 Effect of pressure can be neglected

 Important in gas phase reactions

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 24

 Gas phase reactions occur in PFR or PBR

OBJECTIVE: Find ratio P/Po as a function of volume V

*** Differential form of the mole balance or design

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 25

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 26

= Porosity = void fraction = volume of void / total volume

G = u = superficial mass velocity (kg / m2.s)

U = Superficial velocity = volumetric flow / superficial area (m/s)

September 22, 2019 BITS, PILANI – K. K. BIRLA GOA 27

z is not our interest, W is!!!