Chemical Reactor Design-CHEM-E7135

The field that studies the rates and mechanisms of chemical

reactions and the design of the reactors in which they take place

Yongdan Li
Professor of Industrial Chemistry
Department of Chemical and
Metallurgical Engineering
School of Chemical Technology
Aalto University
Email: yongdan.li@aalto.fi
Kemistintie 1, E404
Course Timetable

8 Lectures, 3 Assignments and 1 Project are contained

Date/time Place Topic Lecturers
Mon 7th of Jan 10:15-12:00 Ke 5 D 311 Lecture 1: Introduction to the course and basic Yongdan Li
kinetics

Mon 21th of Jan 10:15-12:00 Ke 5 D 311 Lecture 2: Ideal reactor design Yongdan Li
Mon 28th of Jan 10:15-12:00 Ke 5 D 311 Lecture 3: Non-ideal flow patterns Yongdan Li
Mon 4th of Feb 10:15-12:00 Ke 5 D 311 Assignment 1: Lecture 1-2 Reetta Karinen/Tiia
Assign the project Viinikainen
Yingnan Zhao/Yongdan Li
Mon 11th of Feb 10:15-12:00 Ke 5 D 311 Lecture 4: Typical catalytic reactors Yongdan Li

Mon 25th of Feb 10:15-12:00 Ke 5 D 311 Assignment 2: Lecture 3-4 Reetta Karinen/Tiia
Viinikainen
Fri 1th of Mar 10:15-12:00 Ke 5 D 311 Lecture 5: Typical non-catalytic reactors Yongdan Li
Mon 4th of March 10:15-12:00 Ke 5 D 311 Lecture 6: Micro-structured reactors Yongdan Li
Fri 8th of March 10:15-12:00 Undetermined Feedback of project Yingnan Zhao/Yongdan Li
Mon 11th of March 10:15-12:00 Ke 5 D 311 Lecture 7: Biochemical reaction systems Yongdan Li
Fri 15th of March 10:15-12:00 Ke 5 D 311 Lecture 8: Reactors with ion transfer through Zhengze Pan/Yongdan LI
interfaces
Mon 18th of March 10:15-12:00 Ke 5 D 311 Assignment 3: Lecture 5-7 Reetta Karinen/Tiia
Viinikainen
Contact Information

 Professor Yongdan Li
– Office hours whenever office door is open, room E404
– yongdan.li@aalto.fi

 University lecturer Reetta Karinen

– Office hours whenever office door is open, room E406
– reetta.karinen@aalto.fi

 University teacher Tiia Viinikainen

– Office hours whenever office door is open, room E406
– tiia.viinikainen@aalto.fi

3
Text Book

Chemical
Reaction
Engineering
Third Edition

Octave Levenspiel
Department of Chemical Engineering
Oregon State University

Online version of the textbook available in Aalto University:

https://app.knovel.com/web/toc.v/cid:kpCREE0005/viewerTy
pe:toc/root_slug:viewerType%3Atoc/url_slug:root_slug%3Ac
hemical-reaction-engineering?kpromoter=federation

4
Assignments

A teacher will guide you to do assignments

A. Examples
B. Assignments

Solution

A. Several examples are demonstrated to teach you how to

calculate the related problems
B. Assignments should be completed by you with the help of
teachers

5
Project

Design a Non-catalytic Reactor for Olefins Production by Pyrolysis

Some related materials will be given in Mycourse

Submit a design report: Detailed requirements will be listed after the first
assignment
• Background
• Reactor selection
• Mass balance
• Heat balance
• Flow pattern
• Reactor volume
………

Attention: A feedback about your project should be given before the end of the lectures -
Show introduction and plan of the project

6
Handling

 MyCourses is used during the course

– mycourses.aalto.fi/
– General information and time table
– Lecture slides
– Exercises and assignments
– Project materials

 Submission of assignments and project in MyCourses

Content Given Accepted DL
First assignment Mon 04th of Feb Thu 14th of Feb
Second assignment Mon 25th of Feb Thu 07th of Mar
Third assignment Mon 18th of Mar Thu 28th of Mar
Project assignment Mon 04th of Feb Mon 01st of Apr
Feedback of project on Fri 8th of Mar, 10:15-12:00

7
Evaluation

Assignment - 20%

 Completed assignments are marked by teachers at the end

 Total number of exercises in the assignment is 10

Points distribution Number of exercises to

be completed
20 P (7.5-10]
15 p (5-7.5]
10 p (2.5-5]
5P [0.5-2.5]

Project - 80%

 Submitted design project report are evaluated by teachers according to

validity and logicality
8
Overview of Chemical Reactor Design

Typical chemical process

Chemical reaction engineering (or reactor design) is the engineering practice

concerned with the exploitation of chemical reactions on a commercial scale.
Its goal is the successful design and operation of chemical reactors.

Thermodynamics Chemical kinetics Fluid mechanics

Mass transfer Heat transfer Economics

9
Overview of Chemical Reactor Design

Performance equation
relates input to output

Input Output

Contacting pattern or how materials Kinetics or how fast things happen. If

flow through and contact each other in very fast, then equilibrium tells what
the reactor, how early or late they mix, will leave the reactor. If not so fast, then
their clumpiness or state of aggregation. the rate of chemical reaction, and maybe
By their very nature some materials are heat and mass transfer too, will
very clumpy, for instance, solids and determine what will happen.
noncoalescing liquid droplets.
Information needed to predict what a reactor can do

Output = f [input, kinetics, contacting] (1)

10
Overview of Chemical Reactor Design

Develop appropriate performance equations by reaction types

Classification of chemical reactions useful in reactor design

It depends on how we choose to treat them, and this in turn depends on which
description we think is more useful.

11
Overview of Chemical Reactor Design

Reaction rate is the key issue

If the rate of change in number of moles of component i due to reaction is

dNi/dt, the rate of reaction is defined as follows.

Based on unit volume of reacting fluid,

1 𝑑𝑁𝑖 𝑚𝑜𝑙𝑒 𝑖 𝑓𝑜𝑟𝑚𝑒𝑑 (2)

𝑟𝑖 = =
𝑉 𝑑𝑡 (𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑓𝑙𝑢𝑖𝑑)(𝑡𝑖𝑚𝑒)

Based on unit mass of solid in fluid-solid systems,

1 𝑑𝑁𝑖 𝑚𝑜𝑙𝑒 𝑖 𝑓𝑜𝑟𝑚𝑒𝑑

𝑟𝑖 ′ = = (3)
𝑊 𝑑𝑡 (𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑)(𝑡𝑖𝑚𝑒)

12
Overview of Chemical Reactor Design

Reaction rate is the key issue

Based on unit interfacial surface in two-fluid systems or
based on unit surface of solid in gas-solid systems,

′′
1 𝑑𝑁𝑖 𝑚𝑜𝑙𝑒 𝑖 𝑓𝑜𝑟𝑚𝑒𝑑
𝑟𝑖 = = (4)
𝑆 𝑑𝑡 (𝑠𝑢𝑟𝑓𝑎𝑐𝑒)(𝑡𝑖𝑚𝑒)

Based on unit volume of solid in gas-solid systems,

1 𝑑𝑁𝑖 𝑚𝑜𝑙𝑒 𝑖 𝑓𝑜𝑟𝑚𝑒𝑑

𝑟𝑖 ′′′ = = (5)
𝑉𝑠 𝑑𝑡 (𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑)(𝑡𝑖𝑚𝑒)

Based on unit volume of reactor, if different from the rate based on unit
volume of fluid,

1 𝑑𝑁𝑖 𝑚𝑜𝑙𝑒 𝑖 𝑓𝑜𝑟𝑚𝑒𝑑

𝑟𝑖 ′′′′ = = (6)
𝑉𝑟 𝑑𝑡 (𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑜𝑟)(𝑡𝑖𝑚𝑒)

13
Overview of Chemical Reactor Design

Relationship between these definitions:

Variables Affecting the Rate of Reaction

In homogeneous systems the temperature, pressure, and composition are

obvious variables.

Heat and mass transfer may play important roles in determining the rates
of heterogeneous reactions.

14
Overview of Chemical Reactor Design

Broad classification of reactor types

(a) The batch reactor. (b) The steady-state flow reactor. (c), (d), and (e) Various forms of the
semibatch reactor

15
Overview of Chemical Reactor Design

Broad classification of reactor types

Batch Ideal for small-scale experimental studies on reaction kinetics

or small amounts of material are to be treated industrially.
Ideal for industrial purposes when large quantity of materials
is to be processed and when the rate of reaction is fairly high
Steady-state flow
to extremely high. Good product quality control can be obtai-
ned (oil industry).
It offers good control of reaction speed because the reaction
proceeds as reactants are added. It was used from the calor-
Semibatch
imetric titrations in the laboratory to the large open hearth
furnaces for steel production.

16
Overview of Chemical Reactor Design
Batch Reactor
Flow Reactor

17
Example I: Ammonia Synthesis

Ammonia is the initial chemical material for a variety of industries. Ammonia synthesis
is therefore a very important process in chemical world.

N2 ＋ 3H2  2NH3

The reaction features

High temperature 470~520 oC

High pressure 20～35 MPa
Exothermic process

The requirements for reactors

The reactor must bear high temperature and high pressure

The heat generated by the reaction must be removed in time

18
Ammonia Synthesis

The core layer of the reactor

bare the high temperature

The reactor shell bare

the high pressure

The heat generated by the reaction

was removed by the cool N2 and H2,
and the feeding N2 and H2was
preheated

N2 and H2

NH3
19
Example II: Fluid Catalytic Cracking (FCC)

Heavier fractions are converted into naphtha and middle distillates

AlCl3 Acid-treated clay silica-alumina Zeolites

Earthly 20th century 1930 1940 1963-Nowadays

Catalyst
20% Zeolite Y
80% Matrix

The reaction features

 FCC is an endothermic process

 Coke deposits on the catalyst,
so the catalyst easily deactivates

20
Fluid Catalytic Cracking (FCC)

The catalyst
and coke

Coke was burned,

and the catalyst was
heated

The hot catalyst

21
Example III: Hydrocarbon Thermal Cracking

The raw material is heated to 750-900 oC for pyrolysis without catalyst

Raw Material Naphtha oil, but natural gas, refinery gas, light oil, diesel, heavy oil
etc. are also occasionally used
Products Ethylene, propylene, butadiene

The reaction features

 The reaction is strongly endothermic. Increasing the temperature is advantageous for

the formation of olefins

 The residence time of the feedstock in the reactor should be as short as possible. If
reaction reaches equilibrium, large amounts of hydrogen and carbon will be formed.

 Reducing the pressure helps to improve the ethylene balance composition and
inhibit the coking reaction

22
Hydrocarbon Thermal Cracking

Diameter 75 ~ 133 mm
length: 80~90 m
Wall temperature 1050 ~1100 oC

Flow rate 277 m/s

Residence time 0.09s
Outlet gas temperature 875 oC

Tubular reactor

The reactor is placed at the center of the furnace and the heat is adsorbed in the flame.

Using high temperature resistant alloy steel: HP-40 ( Ni-Cr alloy steel )

23
Hydrocarbon Thermal Cracking

At the later period of the reaction

 The volume of gas in the tube increases greatly. The pressure drop caused by small
diameter is obvious
 The conversion of the reaction becomes high, and the demand for heat is
moderated
 The coking is serious and the large diameter can reduce the risk of coke blockage

Variable diameter
(increase)
24
1. Kinetics of Chemical Reactions
Lecture 1.1 Basis of Kinetics

The Rate Equation

Suppose a single-phase reaction：
The most useful measure of reaction rate for reactant A is

The rates of reaction of all molecules are related by

Temperature

Experience shows that the rate of reaction is influenced by the composition and energy
of the material.
26
Lecture 1.1 Basis of Kinetics

The Rate Equation

Suppose a single-phase reaction：
The most useful measure of reaction rate for reactant A is

The rates of reaction of all molecules are related by

Temperature

Experience shows that the rate of reaction is influenced by the composition and energy
of the material.
27
Lecture 1.1 Basis of Kinetics

Single and Multiple Reactions

When a single stoichiometric equation and single rate equation are chosen
to represent the progress of the reaction, we have a single reaction.

When more than one stoichiometric equation is chosen to represent the

observed changes, then more than one kinetic expression is needed to
follow the changing composition of all the reaction components, and we
have multiple reactions.

Series reactions, more complicated,

Parallel reactions,

28
Lecture 1.1 Basis of Kinetics

Elementary and Nonelementary Reactions

aA + bB cC + dD

The rate-controlling
mechanism involves The number of collisions
The number of
the collision or is proportional to the
collisions of molecules
interaction of a A concentration of
A with B is proportional
molecules with b B reactants in the mixture
to the rate of reaction
molecules (T constant)

Such reactions are called elementary reactions.

Otherwise, the ones are called nonelementary reactions.

Mass interaction law

For an elementary reaction: -rA = k CAa CBb

29
Lecture 1.1 Basis of Kinetics

Representation of an Elementary Reaction

any measure equiva-
lent to concentration

the order unchanged, but k different

However,
I
AMBIGUITY:
correct -r expression?
k1 refers to ?

II 1) write the stoichiometric

equation followed by the
complete rate expression.
2) give the units of the rate
constant

30
Lecture 1.1 Basis of Kinetics

Representation of a Nonelementary Reaction

Stoichiometry: Rate:

Develop a multistep reaction model to explain the kinetics

Br2 → 2Br ·
Br · and H ·
Br · + H2 → HBr + H · unobserved intermediates
H · + Br2 → HBr + Br ·

Suggested by chemistry of the materials

Determined by experiments

31
Lecture 1.1 Basis of Kinetics

Molecularity and Order of Reaction

Must be integer
 The molecularity of an elementary reaction (must be an elementary reaction)
is the number of molecules taking part in the reaction.
 This has been found to have the values of one, two, or occasionally three.

ath order with respect to A bth order with respect to B nth order overall

k: rate constant, (time)-1(concentration)1-n

 For non-elementary reaction: a, b, . . . , d are not necessarily related to the
stoichiometric coefficients.

 We call the powers to which the concentrations are raised the order of the Reaction.

A fractional value
is allowable
32
Lecture 1.1 Basis of Kinetics

Kinetic Model Development

 Type 1

A B: A X X B

For unseen and unmeasured intermediate X

Pseudo-steady-state approximation
-rX = 0

 Type 2

A+B C: A+B X X C

X C is rate-determining step
Quasi-equilibrium approximation
k1
A+B X K=k1/k2=[X]/([A][B])
k2
33
Lecture 1.1 Basis of Kinetics

Kinetic Model Example

(8)

(9)

(10) (11)

Type 1, steady-state
approximation

d[X]/dt ≈ 0 (12) (13)

Michaelis-Menten
(14)
type

34
Lecture 1.1 Basis of Kinetics

Temperature Dependency from Arrhenius' Law

Activation energy
Arrhenius’ Law J/mol

Frequency factor

Same concentration

Actually,
Mask pre-
sensitive
exponential term
Collision and transition
state theories

35
Lecture 1.1 Basis of Kinetics

Activation Energy and Temperature Dependency

1, Reactions with high activation

energies are very temperature-
sensitive.

2, Reactions are much more

temperature-sensitive in low
temperature range than in a
high temperature range.

Fig 1.1 Sketch showing temperature dependency of the reaction rate

36
Lecture 1.2 Constant-Volume Batch Reactor

Constant-Volume Constant-density
Constant-Volume
of reaction mixture reaction system

Most liquid-phase reactions and all gas-phase

reactions occurring in a constant-volume bomb

(15) (16)

For gas reactions with ri is to follow the change

changing numbers of moles in total pressure π

37
Lecture 1.2 Constant-Volume Batch Reactor

The Conversion
XA: the conversion of A

(17)

(18)

 Irreversible Unimolecular-Type First-Order Reactions

(19)

Suppose the first-order rate equation,

(20)

38
Lecture 1.2 Constant-Volume Batch Reactor

Separating and integrating,

(21)

In terms of conversion ( Eqs. 17 and 18) and the rate equation Eq. 20,

Rearranging and integrating,

21 or 22

(22)

Fig 1.2 Test for the first-order rate equation

39
Lecture 1.2 Constant-Volume Batch Reactor

 Irreversible Bimolecular-Type Second-Order Reactions

(23)

Note: The reacted amounts of A and B at any time t are equal, i.e., CA0XA= CB0XB,

Let M = CB0/CA0 be the initial molar ratio of reactants,

After separation and integration it becomes

40
Lecture 1.2 Constant-Volume Batch Reactor

After breakdown into partial fractions, integration, and rearrangement, the final result in
a number of different forms is

CA0  CB0

(24)

Fig 1.3 Test for the bimolecular mechanism A + B → R with CA0 ≠ CB0

41
Lecture 1.2 Constant-Volume Batch Reactor

Reactants are introduced in their stoichiometric ratio

go back to the original diff-

erential rate expression

For a second-order reaction with equal initial CA0 and CB0 or for the reaction

the defining second-order differential equation becomes

(25)

On integration it yields

(26)

42
Lecture 1.2 Constant-Volume Batch Reactor

Rate Equations of nth Order reaction

When the mechanism of reaction is not known

(27)

On separation and integration it yields

(28)

Trial-and-error solution select a value for n and calculate k. The value of n which minimizes
the variation in k is the desired value of n

n>1 the reaction never goes to completion

Curious features
the reactant concentration will fall to zero and
n<1
then become negative

43
Lecture 1.2 Constant-Volume Batch Reactor

Zero-Order Reactions high concentration

concentration independent
(29)
radiation intensity,
available surface

Integrating and noting that CA can never become negative

(30)

30

30

Fig 1.4 Test for a zero-order reaction

44
Lecture 1.2 Constant-Volume Batch Reactor

Overall Order of Irreversible Reactions from the Half-Life t1/2

If CB0/CA0 = β/α…, at any time CB/CA = β/α…

(31)

Integrating for n ≠ 1 gives

Half-Life t1/2 (Time needed for CA /CA0 =1/2) is

32a

(32a)

45
Lecture 1.2 Constant-Volume Batch Reactor

Irreversible Reactions in Parallel

(33)

(34)

(35)

Eq. 33, which is of simple first order, is integrated to give

(36)

dividing Eq. 34 by Eq. 35 we obtain the following

(37)

46
Lecture 1.2 Constant-Volume Batch Reactor

36
37

Fig 1.6 Plotting for Eqs. 36, 37 Fig 1.7 Concentration-time curves for Parallel reactions

47
Lecture 1.2 Constant-Volume Batch Reactor

Irreversible Reactions in Series

First consider consecutive unimolecular type first-order reactions

(38)

(39)

(40)

Start with a concentration CA0 of A, no R or S present. Integrate Eq. 38,

(41)

Substitute CA in Eq. 39

(42) (43)

48
Lecture 1.2 Constant-Volume Batch Reactor

Because there is no change in total number of moles,

(44)

In general, for any number of reactions in series it is the slowest

step that has the greatest influence on the overall reaction rate

Differentiate Eq. 43 and set dCR/dt = 0, CR, max occurs

(45) (46)

49
Lecture 1.2 Constant-Volume Batch Reactor

41

44
Evaluate k1 and k2

46 43

45

Fig 1.8 Typical concentration-time curves for consecutive first-order reactions

50
Lecture 1.2 Constant-Volume Batch Reactor

First-Order Reversible Reactions

Irreversible reactions can be considered as reversible ones with large equilibrium constants.

equilibrium constant (47)

Starting with M = CR0/CA0

(48)

Now at equilibrium dCA/dt = 0, Hence

(49) and (50)

Combining the above three equations (48, 49, 50)

(51)

51
Lecture 1.2 Constant-Volume Batch Reactor

Reversible i

(51) 51

special case CAe=0 or

XAe=1 or
KC= ∞

Irreversible ii

(21) (22)
21-22

Fig 1.9 Test for the unimolecular type reversible (i) and irreversible (ii) reactions

52
Lecture 1.2 Constant-Volume Batch Reactor

Second-Order Reversible Reactions

For the bimolecular-type second-order reactions

(52a) (52c)

(52b) (52d)

When CA0=CB0 and CR0=CS0=0

53

(53)

Fig 1.10 Test for the reversible bimolecular reactions

53
Lecture 1.3 Varying-Volume Batch Reactor

The progress of the reaction is followed

by noting the movement of the bead with
time

Fig 1.11 A varying-volume batch reactor

Isothermal constant Volume is linearly related

pressure operations to the conversion (54)

(55)
Fractional change in volume of the system between no
conversion and complete conversion of reactant A

pure A 50% A
Example
50% Ar

54
Lecture 1.3 Varying-Volume Batch Reactor

Noting that (56)

On combining with Eq. 54

(57)

(isothermal varying-volume systems)

In general

Replace V (Eq. 54) and NA (Eq. 56)

(58)

in terms of volume (Eq. 54)

(59)

55
Lecture 1.3 Varying-Volume Batch Reactor

 Zero-Order Reactions

(60)

 First-Order Reactions

Replace XA by V from Eq. 54 and integrate it gives

(61)

 Second-Order Reactions
or

(62)

56
Chemical Reactor Design
The field that studies the rates and mechanisms of chemical
reactions and the design of the reactors in which they take place

Yongdan Li
Professor of Industrial Chemistry
Department of Chemical and
Metallurgical Engineering
School of Chemical Technology
Aalto University
Email: yongdan.li@aalto.fi
Kemistintie 1, E404