Design of a Chemical Process:

General and Chemical

Considerations
CHEM 409-02

Industrially Important Chemicals

19 of the top 50 production chemicals (by
tonnage) are inorganic
These can be manufactured from common
raw starting materials

Industrially Important Chemicals

Industrial Gases
Production tonnage (2002):
Nitrogen (#2 at 35 billion kg in 2002)
Oxygen (#3 at 28 billion kg in 2002)
Isolated from air by exploiting "phase
change (Lecture 409-01)

Industrially Important Chemicals

What are some general (non-chemistry)

considerations that apply to setting up a
new manufacturing process ?

General Considerations

Cost
Market forces
Availability of starting materials
Safety
Environmental concerns
Transport & Storage
Location
Regulations
Chemistry
Required purity of product(s)

What are some chemistry concepts

that should be considered when
designing a process ?
E.g. for the reaction:

A+B C
reactants

desired
product

D
co-product

General Chemistry Considerations

Is it a viable reaction ?
Ease of product isolation (and purification)
Kinetics and Thermodynamics
Pressure and Temperature
Phase and Phase Change
Products (relative reactivity and waste ?)

A+B C+D

Reaction Thermodynamics
Application of LeChateliers principle to
design industrial processes
The chemical equilibrium of a reaction
ultimately dictates its efficiency
This chemical equilibrium can be altered in
the desired direction by controlling the
reaction conditions

Write the equilibrium (mass action)

expression for the general chemical
reaction:
aA + bB

cC

http://www.youtube.com/watch?v=54RZE73QMDU

dD

Heterogeneous Equilibria:
Refers to equilibria where the reactants or
products are in different phases
Pure solids and liquids do NOT have
variable concentrations
Gases and solutions can have variable
concentrations

Industrially Important Chemicals

Lime Kiln

Modern Lime Kiln:

http://www.youtube.com/watch?v=GU4KNV1hRiQ

For Interest: Historical Lime Kiln in three parts:

http://www.youtube.com/watch?v=IJpZsvYygF8
http://www.youtube.com/watch?v=wXQS105fAwY
http://www.youtube.com/watch?v=aIOYmX4tA9k
Also Google calcining

Reaction Kinetics
How fast does a reaction occur ?

For the conversion of ozone to oxygen

2 O3 3 O2
the rate of ozone consumption was
measured as 2.5 x 10-5 mol L-1 s-1
What is the rate of O2 production ?
What is the difference between average rate
and instantaneous rate ?

Reaction Kinetics
For a proposed reaction mechanism there
can be one step that is much slower that
all the others, this is known as the rate
determining step

Catalysis
A catalyst is a substance that increases
the rate of reaction, but is neither created
or destroyed in the process
Homogeneous catalysts are in the same
phase as the reacting substances
Heterogeneous catalysts are in a different
phase as the reacting substances

Most Produced Chemicals List

Inorganic Nitrogen-Containing Compounds
Ammonia (#6)
Nitric Acid (#18)
Ammonium Nitrate (#15)
Ammonium Sulfate (#31)

All these start from nitrogen gas

Manufacture of Important Inorganic

Nitrogen Compounds

Synthesis of Ammonia
At the end of 19th century there was a
concern about the ability of humankind to
feed its growing population (~1.8 billion
people)
Developments in chemistry allowed for
large-scale manufacture of ammonia for
use in the production of fertilizers

Synthesis of Ammonia
A critical milestone in the development of
catalytic synthesis of ammonia was the
demonstration of Fritz Haber and
coworkers in 1909 that ammonia could be
produced at significant rates (2 kg/day)
using an osmium catalyst at 175 atm
Osmium is the best catalyst for the
reaction but it is very expensive - iron
catalyst is more commonly used

Synthesis of Ammonia
Currently, there are around 600 large
scale plants worldwide with a capacity of
500 to 1500 tons per day
85% of ammonia is used for nitrogen
fertilizers; urea is the most important
accounting for 40% of ammonia usage
Other industrial uses include the
production of nitric acid, amines, nitriles,
nylon and organic nitrogen compounds

RSC YouTube
https://www.youtube.com/watch?v=wiwl4eoHbig

Ammonia Production

Ammonia Production
Haber-Bosch industrial process
first used at BASF company (Germany)

Synthesis of Ammonia
N2 + 3H2 2NH3 H = -92.4 kJ mol-1

How can Le Chateliers principle be

applied (in theory) to the above reaction
in order to maximize the product side of
the equilibrium ?

Schematic

Boiling Points:
NH3 = -33 C
N2 = -196 C
H2 = -253 C

Jess (p.187)

What are the typical reaction conditions

for the Haber-Bosch Process ?
Why are these conditions a compromise ?
How is this compromise dealt with in
practical terms ?
What effect does the catalyst have on the
equilibrium ?

Thermodynamics
1,000 bar = 987 atm = 100,000 kPa

Temperature
Remember Kinetics !!!!!
Lower temperature = slower reaction
A manufacturer is trying to produce as much
product as possible per day
Not economically viable to achieve an
equilibrium mixture which contains a very high
proportion of ammonia if it takes several years !

Ammonia Production

High temperatures are needed to overcome the

chemical inertness of N2 gas (kinetics)
Compromise temperature: 450C
Compromise Pressure: 250 atmospheres (
kPa)

What are the typical reaction conditions

for the Haber-Bosch Process ?
Why are these conditions a compromise ?
How is this compromise dealt with in
practical terms ?
What effect does the catalyst have on the
equilibrium ?

General Mechanism of Ammonia

Synthesis
Both reactants are
dissociatively
adsorbed on the
catalyst surface
before reaction
The dissociative
adsorption of N2 is the
rate determining step

General Mechanism of Ammonia

Synthesis

Sketch a schematic diagram of the

Haber-Bosch process

See also:
http://www.youtube.com/watch?v=c4BmmcuXMu8
http://www.youtube.com/watch?v=ZGZqa6iAR7o

Schematic of Conditions
The yield of ammonia per pass ranges between
20 and 30%
Unconverted synthesis gas leave the reactor
together with
ammonia