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INDUSTRIAL CHEMISTRY
I. Industrial Chemistry
By
Module 6
Module 7
Module 9
Unit I
Unit II
Hydrocarbons
Unit III
Alkyl halides
Unit IV
Amines
Unit I
Unit III
Unit I
Unit III
Heterocyclic compounds
Thermodynamics
Chemical principles of variable constituents
III. Time
This unit will require 120 hours
Unit I. Introduction to industrial chemistry and the chemical industry (15
hrs)
Unit
6.
Industrial
Organic
Chemistry
II
(Fermentation,
Ethanol,
IV. Materials
You will require the following tools and resources for completing the module:
Computer, CD-ROM, and e-library
V. Module Rationale
Industrial chemistry deals with commercial production of chemicals and related
products from natural raw materials and their derivatives. It enables humanity to
experience the benefits of chemistry when we apply it in the exploitation of
materials and energy. When we apply chemistry in the transformation of
materials and energy to make useable products, this results in growth and
improvement in areas such as food production, health and hygiene, shelter and
clothing. The economic growth of industrialized countries relies on the
manufacturing industry for finished products. The goal of studying industrial
chemistry at university is to try and bridge the gap between classical chemistry
and chemistry is applied in industry. The chemical industry is highly globalized
and produces thousands of chemicals from a wide variety of raw materials by
means of varied technologies for varied end uses. It is therefore important to
base the study of industrial chemistry on an understanding of the structure of the
industry and the unit operations and unit processes that make up the chemical
processes. On the basis of natural raw materials sources and the chemistry
VI. Overview
This module starts by defining industrial chemistry and then gives a view of the
chemical industry, its position in the general economy, and its classification in
terms of the chemical processes that characterize it. To enable the study of
selected chemical processes, unit operations and unit processes, especially
those that are relevant in later learning actvities, are then covered in Unit 2. With
this background, it will be easy to study industrial inorganic and organic chemical
industries. The study of extractive metallurgy in Unit 3 draws on the knowledge of
size reduction and separation unit operations learnt earlier, as well as chemical
conversions that take place during pyroprocessing. The extractive metallugy of
iron, copper and aluminium is included. In Unit 4, we focus our attention on some
basic inorganic industrial processes that synthesize products from a variety of
raw materials derived from the natural environment. They include manufacture of
chlorine and sodium hydroxide from brine, ammonia from methane and nitrogen,
sulphuric acid from sulphur, fertilizer and cement from mineral ores. The study of
organic industrial chemistry then starts with petroleum refining followed by the
manufacture of selected petrochemicals and polymers. The module closes with
3
the study of ethanol, pharmaceuticals, soaps and detergents. These are high
value-added products, some of which are produced through the fermentation
route.
6.1 Outline
Unit 1: Introduction to Industrial Chemistry (15 hours)
Flow diagrams
Froth flotation
Fractional distillation
Unit processes
Mineral ores
Ore dressing
Pyroprocessing
Refining
Ammonia
Sulphuric acid
Fertilizer
Cement
Petroleum processing
Petrochemicals
Polymers
Unit
6:
Organic
Chemical
Industries
II
Fermentation,
Ethanol,
Fermentation
Ethanol
Pharmaceuticals
General
Industrial
Chemistry
Industrial
Inorganic
Chemistry
5
Industrial
Organic
chemistry
Introduction
to industrial
chemistry and
chemical
industry
Unit
operations
and unit
processes
Extractive
metallurgy
Chlor-alkali,
ammonia,
sulphuric
acid, fertilizer,
cement
Petroleum,
petrochemical
s and
polymers
Fermentation,
ethanol,
pharmaceutical
s, soaps and
detergents
ii.
iii.
iv.
v.
Explain using flow diagrams and equations, how crude oil is refined, and
how some petrochemicals and polymers are synthesized.
vi.
b. Classify the chemical industry in terms of scale, raw materials, end use
and value addition
c. Distinguish between unit operations and unit processes
d. Describe chemical processes by means of flow diagrams
e. Carry out material balances for a simple process
Unit 2: Unit Operations and Unit Processes
At the end of this unit you should be able to:
a. List the various reasons for undertaking size reduction and enlargement
in the chemical industry
b. Describe the operation principles of some size reduction equipment and
size enlargement equipment
c. Explain how industrial materials can be separated on the basis of their
magnetic, electrostatic, hydrophobic and volatility differences respectively
d. Discuss various organic unit processes including polymerization,
alkylation, hydrolysis and their application in the chemical industry.
Unit 3: Inorganic Chemical Industries Part I: Extractive Metallurgy
At the end of this unit you should be able to:
a. Describe the various stages mineral ores go through in a typical mineral
ore dressing process.
b. Write equations to describe calcination and roasting
c. Explain what happens during smelting
d. Describe the extractive metallurgy of iron
e. Describe the extractive metallurgy of aluminium
f. Describe the extractive metallurgy of copper
Unit 4: Inorganic chemical Industries Part II: Chlor-alkali, Ammonia,
Sulphuric Acid, Fertilizer, Cement
At the end of this unit you should be able to
a. Describe using equations and diagrams, the electrolytic process for the
production of sodium hydroxide and chlorine using mercury, diaphram and
membrane cells
b. Explain how ammonia is manufactured from methane and air by the Haber
process
c. Describe the Contact process for the manufacture of sulphuric acid
d. Discuss the various types of fertlizers and the manufacture of phosphate
fertilizer
e. Describe using diagrams, equations and unit operations, for the
manufacture of Portland cement.
Unit 5: Organic Chemical Industries Part I: Petroleum, Petrochemicals and
Polymers
At the end of this unit you should be able to:
a. Discuss the occurrence and extraction of petroleum
b. Explain the purposes and application of fractional distillation, catalytic
cracking and catalytic reforming during petroleum processing
c. Describe using equations and flow diagrams, the manufacture of some
petrochemicals, namely, phthalic anhydride and adipic acid
d. Categorize plymerization reactions, polymers and polymer products
e. Describe the uses of various plastics
f. Explain how polyethylene and styrene butadiene rubber are manufactured
Unit 6: Organic Chemical Industries Part II: Fermentation, Ethanol,
Pharmaceuticals , Soaps and Detergents
At the end of this unit you should be able to:
a. Discuss factors that affect the viability of the fermentation route and those
that affect fermentation yield
b. Describe the process of manufacuring fermentation ethanol
c. Give a brief history of the pharmaceutical industry and the role played by
antibiotics
IX. Pre-assessment
Title of Preassessment: Industrail Chemistry Pre-assessment Test
9.1 Rationale
The purpose of this test is to assess your current chemistry knowledge that is a
prerequisite for successful learning of this module. To do this test, you will
require:
1. A calculator
2. A list of the elements with symbols, atomic numbers and atomic masses
3. Conversion tables for scientific units
QUESTIONS
1. Covert the following:
a) 140 oF to oC
b) 2 atm to kPa
c) 50 kcal to kJ
d) 0.3 kmoles sodium carbonate to Kg sodium carbonate
2. Calculate the % nitrogen in each of the following nitrogen fertilizers.
a) Ammonium nitrate
b) Ammonia
c) Diammonium phosphate
3. Which are the oxidizing agents in the redox reactions given below?
a) 4Fe + 3O2
2Fe2O3
b) Cl2 + 2NaBr
2NaCl + Br2
c) H2 + Cl2
2HCl
2ZnO(s) + 2SO2(g)
Horxn = -879kJ
C+D
9. (a) Write the equilibrium constant expression for the following reaction:
PCl5(g)
(b) What is the equilibrium constant for the reaction in (a) if equilibrium
concentrations in a 12 litre vessel are 0.21 moles PCl 5, 0.32 moles PCl3,
and 0.32 moles Cl2?
10. (a) Calculate the molar mass of the polyethylene molecule (CH 2-CH2)nwhere n = 10,000.
(b) How many litres of air (assuming 78% N 2, 22% O2 by volume) are
needed for the complete combustion of 1.0 litre of octane C 8H18 whose
density is 0.70g/ml. Assume density of air is 1.29g/l.
9.2. Answer key
Question
1.
a
b
c
d
2.
a
b
Answer
Marks
60oC
202.65kPa
209 kJ
31.8kg
1
1
1
1
35.00
82.35
1
1
10
c
3.
a
b
c
d
4.
5.
6.
7.
a
b
9.
10.
a.
b
10
a.
b.
TOTAL
40.6
O2
Cl2
F2
Cl2
99.59
CaCO3
CaO
CaO + H2O
Ca(OH)2
It has both acidic and
basic properties
1
1
1
1
3
1
1
1
4.51kJ
4.21M
The catalyst lowers the
activation energy, which
is the minimum energy
required to initiate a
chemical reaction
2
2
2
[PCl3][Cl2]/[PCl5]
K=0.04
1
2
280,000
4.11litres
1
3
30
X. Key Concepts
1. Alkylation is the introduction of an alkyl radical by substitution or addition
into an organic compound.
2. Antibiotics are chemical substances that can inhibit the growth of, and
even destroy, harmful microorganisms.
3. Catalytic cracking is the breaking up of complex hydrocarbons into
simpler molecules in order to increase the quality and quantity of lighter,
more desirable products and decrease the amount of residuals.
4. Catalytic reforming is a process used to convert low-octane naphthas
into high-octane compounds such as toluene, benzene, xylene, and other
11
12
13. Unit operations are the physical treatment steps employed in chemical
processes to transform raw materials and products into required forms.
14. Unit processes are the chemical transformations or conversions that are
performed in a process.
13
reference:
Extractive
metallurgy:
From
Wikipedia,
the
free
encyclopedia
http://en.wikipedia.org/Extractive_metallurgy
Abstract: This site gives definitions and brief discussions on the basic
technologies used in metal extraction. These include mineral processing
pyrometallurgy and hydrometallurgy. Extractive metallurgy of various metals can
be accessed from this site.
Rationale: The site and its links give a good overview of extractive metallurgy. It
supplements information given in Unit 3 on extractive metallurgy of copper,
aluminium and iron.
Reading # 4
Complete reference: Fertilizer: From Wikipedia, the free encyclopedia
http://en.wikipedia.org/Fertilizer
Description: Here you will find the history of the fertilizer industry, information on
macronutrients and micronutrients, nitrogen fertilizers and organic fertilizers.
Links to related topics are given.
Rationale: This reading will supplement what is provided in this module under
the subject of fertilizer.
cement.pdf
nitric acid and adipic acid.pdf
10J polyethylene.pdf
09E-SBRPolymerSummaryJuly16.pdf
antibiotics production.pdf
soaps and detergents.pdf
Abstract: The above files provide reading materials, which help you as
supplementary resource materials for this module.
Rationale: These resource materials give detailed explanations on theory,
manufacturing processes and other information on some of the products covered
in this module. These products include aluminium, ammonia, cement, adipic acid,
polyethylene, styrene butadiene rubber, antibiotics, soaps and detergents.
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16
Rationale: One article from this website covers the history, Bayer, Hall-Heroult
and alternative processes for aluminium production.
Useful Link # 5
Title: Cheresources
URL: http://www.cheresources.com
Screen capture
Description: Cheresources.com has been providing content and tools to
chemical engineers all over the world. The site has many free chemical
engineering resources as well as premium content and software for visitors to
choose from. Some of the free articles are targeted for students.
Rationale: This is a useful link to search for detailed information on chemical
process technology for such products as ammonia, sulphuric acid and others
covered in this module. Some of the articles are from refereed journals.
Useful Link # 6
Title: The Contact Process
URL: http://uk.encarta.msn.com/media_761566936/Sulphuric_Acid.html
Screen capture
Description: This page describes the Contact Process for the manufacture of
sulphuric acid
Rationale: The article explain the reasons for the conditions used in the process.
It looks at the effect of proportions, temperature, pressure and catalyst on the
composition of the equilibrium mixture, the rate of the reaction and the
economics of the process.
Useful link # 7
Title: Chemical Intelligence
URL: http://www.icis.com/chemical/intelligence.aspx
Screen capture
17
18
deals
with
Useful Link # 10
Title: Soap and Detergent Association
URL: http://www.cleaning101.com/cleaning/chemistry/soapchem2.com
Screen capture
Description: This site is for Soap and Detergent Association who represent
manufacturers of household, industrial and institutional cleaning products;
producers and suppliers of associated raw materials and finished packaging.
Rationale: One of the article in this website is on the manufacturing processes
for soaps and detergents. It includes the history of soap, soap making, chemistry,
ingredients and manufacturing processes. The explanations which are in
laymans language are supplemented with interesting graphic illustrations. This
will greatly aid you in the study of this topic in Unit 6.
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processes, flow diagrams, material and energy balances. The various readings
given supplement the material presented in this module. At the end of the unit,
there are exercises you are required to do to test your understanding of the unit.
List of relevant readings
1. Chang R. (1991). Chemistry, 4th Edition, McGraw-Hill Inc. New York.
2. Chang R. and Tikkanen W. (1988). The Top Fifty Industrial Chemicals.
3. Price R.F. and Regester M.M. (2000), WEFA Industrial Monitor, 20002001, John Wiley & Sons Inc., New York.
List of relevant resources
Computer with internet facility to access links and relevant copywrite free
resources
http://commons.wikimedia.org/wiki/Category:Process_flow_diagrams
http://www.icis.com/intelligence.aspx
The first website exclusively deals with process flow diagrams, other
technical diagrams and photographs of industrial equipment and plants.
The site can increase your understanding and appreciation on how process
descriptions are presented in the form of diagrams.
The second website enables you to see how chemicals are categorized for
trade and technical purposes.
20
emerging
disciplines
such
as
biotechnology,
microelectronics,
21
Manufacturing
Agriculture
Energy
Transport
Communication
Education
Tourism
Building and construction
Trade
Finance
etc
1.2.1. Classification of the Manufacturing Industry
The manufacturing industry is the area of focus in the study of this module.
Manufacturing produces manufactured goods. This makes it distinct from other
sectors like agriculture which also produce goods. In manufacturing, materials
are transformed into other more valuable materials.
We define manufacturing industry as follows:
Manufacturing industry is a compartment of industry or economy which is
concerned with the production or making of goods out of raw materials by
means of a system of organized labour.
Manufacturing industry can be classified into two major categories namely,
heavy and light industry.
Light industries are easier to relocate than heavy industries and require
less capital investment to build.
22
23
organic
industries
produce
specialty
chemicals
which
include
24
petroleum refining, metallurgy and in many other processes. The top ranking of
oxygen is to do with its use in the steel industry.
Ethylene and propylene are usually among the top ten BOC. They are used in
the production of many organic chemicals including polymers.
BIC and BOC are referred to as commodity or industrial chemicals.
Commodity chemicals are therefore defined as low-valued products produced in
large quantities mostly in continuous processes. They are of technical or general
purpose grade.
1.3.1.2. Specialty Chemicals:
High-value adding involves the production of small quantities of chemical
products for specific end uses. Such products are called specialty chemicals.
These are high value-added products produced in low volumes and sold on the
basis of a specific function.
In this category are the so-called performance chemicals which are high value
products produced in low volumes and used in extremely low quantities. They
are judged by performance and efficiency. Enzymes and dyes are performance
chemicals. Other examples of specialty chemicals include medicinal chemicals,
agrochemicals, pigments, flavour and fragrances, personal care products,
surfactants and adhesives.
Specialty chemicals are mainly used in the form of formulations. Purity is of vital
importance in their formulation. This calls for organic synthesis of highly valued
pure chemicals known as fine chemicals
1.3.1.3.Fine Chemicals:
At times you will find that the raw materials for your product need to be very pure
for the product to function as desired. Research chemicals are in this category as
also are pharmaceutical ingredients. Such purified or refined chemicals are
called fine chemicals. By definition they are high value-added pure organic
chemical substances produced in relatively low volumes and sold on the basis of
exact specifications of purity rather than functional characteristics.
The global market share for each type is roughly as follows:
25
Commodities
80%
Specialties
18%
Fine
2%
26
27
Acylation
Alcoholysis
Alkylation
Amination
Ammonolysis
Aromatization
Calcinations
Carboxylation
Causitization
Combustion
Condensation
Dehydration
Dehydrogenation
Decomposition
Electrolysis
Esterification
Fermentation
Hydrogenation
Hydrolysis
Ion Exchange
Isomerization
Neutralization
Oxidation
Pyrolysis
put the raw materials in a form in which they can be reacted chemically
put the product in a form which is suitable for the market
In Table1.2, some common unit operations are given.
Table 1.2 Examples of unit operations
Agitation
Atomization
Centrifuging
Classification
Crushing
Decanting
Dispersion
Distillation
Evaporation
Filtration
Flotation
Gas absorption
Heat transfer
Humidification
Mixing
Pumping
Settling
Size reduction
28
one substance to another; drying, size reduction, distillation and evaporation are
performed.
By studying systematically these unit operations, which cut across industry and
process lines, the treatment of all processes is unified and simplified.
1.5. Flow Diagrams
A picture says more than a thousand words
Some chemical processes are quite simple; others such as oil refineries and
petrochemical plants can be very complex. The process description of some
processes could take a lot of text and time to read and still not yield 100%
comprehension. Errors resulting from misunderstanding processes can be
extremely costly.
To simplify process description, flow diagrams also known as flow sheets are
used. A flow diagram is a road map of the process, which gives a great deal
of information in a small space. Chemical engineers use it to show the
sequence of equipment and unit operations in the overall process to simplify the
visualization of the manufacturing procedures and to indicate the quantities of
material and energy transferred.
A flow diagram is not a scale drawing but it:
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30
31
32
2. The calculations obtained in 1 form the basis for energy balances through
the application of the law of conservation of energy.
3. We are able to make technical and economic evaluation of the process
and process units from the knowledge of material and energy
consumption and product yield obtained.
4. We can quantitatively know the environmental emissions of the process.
In mass balance calculations, we begin with two assumptions
You may write balances on total mass, total moles, mass of a compound, moles
of an atomic species, moles of a compound, mass of a species, etc.
1.6.2. Material Balance Equations
We might be tempted to think that in a process,
INPUT =OUTPUT
In practice, some material may accumulate in the process or in some particular
process units. For example, in a batch process, some material may remain
adhered to the walls of containers. In the dehydration of ethane to ethylene,
possible chemical reactions are as follows:
C2H6 (g)
C2H4(g)
C2H6 (g)
2C(s) +3H2(g)
C2H4(g)
2C(s) +2H2(g)
33
mass balance equation takes care of all these aspects. The following is a general
mass balance equation.
Accumulation within the system = Flow In through the system boundaries
- Flow Out through the system boundaries
+ generation within the system
- Consumption within the system
Simply put:
Accumulation =Flow in Flow out + Production Consumption
The system is any process or portion of a process chosen for analysis. A system
is said to be "open" if material flows across the system boundary during the
interval of time being studied; "closed" if there are no flows in or out.
Accumulation is usually the rate of change of holdup of material within the
system. If material is increasing, accumulation is positive; if it is decreasing, it is
negative. If the system does not change with time, it is said to be at steady state,
and the net accumulation will be zero.
The generation and consumption of material are the consequences of chemical
reactions. If there is no chemical reaction, the production and consumption terms
are typically zero.
1.6.3. Mass balance calculation procedure
The general procedure for carrying out mass balance calculations is as follows:
1. Make a block diagram (flow sheet) over the process
2. Put numbers on all the streams
3. List down all the components that participate in the process.
4. Find the components that are in each stream and list them adjacent to the
stream in the block diagram
5. Decide on an appropriate basis for the calculations e.g. 100kg raw
material A, 100kg/hr A, 1 ton of product, 100 moles reactant B etc.
34
F3
F4
35
F2 WC2
WA1, WB1 F1
F3 WA3, WC3
F4 WA4, WB4, WC4
WA1 is 50%
WC2 is 100%
WC3 is 25%
36
(F1 + F2 + F3) F4
F1 + F2 + F3
F2 = 0.4X(100/1) = 40kg
F3 = 1.5X(100/1) =150kg
Therefore F4 =
=
100 + 40 + 150
290kg
162.5 290WA4
162.5/290
0.56
WA4
50 290WB4
50/290
0.17
77.5 290WC4
77.5/290
0.27
WB4
AccumulationC =
WC4
37
Component
Kg/hr
Kg
s
A
50
2
3
B
C
A
50
40
112.5
100
100
50
100
75
100
100
C
A
37.5
162.5
150
25
56
100
50
77.5
50
17
290
27
100
Formative Evaluation
1. Distinguish between industrial and classical chemistry
2. What factors are used to classify an industry as heavy or light?
3. Define specialty chemicals
4. Explain how the lithosphere is an important source of natural raw materials for
the chemical industry
5. What is the difference between unit operations and unit processes?
6. What information would you expect to find in a block diagram for a chemical
process?
7. Discuss the use of symbols in process flow diagrams
8. What assumptions are made at the initial stages of carrying out material
balance for a chemical process?
9. Write the general mass balance equation
10. Producer gas has the following composition by volume:
Density, kg/m3
38
CO
28.0
1.2501
CO2
3.5
1.9768
O2
0.5
1.4289
N2
68.0
1.2507
2CO2
The oxygen is from the air whose volumetric composition is assumed to be 80%
N2 and 20% O2. The oxygen fed from the air and the producer gas is 20% in
excess of the amount required for complete combustion. The combustion is 98%
complete.
Carry out total material balance for this process based on 100kg of gas burned.
39
various
organic
unit
processes
including
polymerization,
operations
and
unit
processes.
Unit
operations
involve
physical
The Learning
40
2.
3.
4.
5.
6.
7.
41
42
generally used to grind material 6mm and finer, down to a particle size of 20 to
75 microns.
43
44
Lubricating characteristics
Particle size
Abrasiveness
45
46
47
48
49
Separation is carried out either dry using belt lifting magnets or wet using drum
magnetic separators. This technology is applied in mineral ore processing, as we
shall see in Unit 4.
The method used for dry particles is illustrated schematically in Fig 2.9.
50
51
The
collector molecule adsorbs on to the solid surface via the polar (charged) group.
This reaction is known as chemisorption. The hydrocarbon chain is facing the
aqueous phase. This is shown in Fig.2.10.
from the wetted solid surface by air. In addition to the use of collectors to change
the surface property of the particles, other chemicals may be added to further
modify either the particles to be floated, or the particles that are to remain in the
suspension. Such chemical substances are called modifiers.
2.1.3.2.2 Flotation cell
The flotation cell is shown in Fig. 2.11. The material is ground in water to a
maximum 250m. It is introduced into the flotation cell. A frothing agent is added
to create a generous supply of fine bubbles when air is sparged. Examples of
frothers include pine oil and methyl amyl alcohol. The collector and other
additives are added. Hydrophobic particles are collected at the air-bubble
interface. The bubbles with attached mineral particles rise to the surface where
the material is removed. Particles that are readily wetted by water (hydrophilic)
tend to remain in the water suspension.
53
54
Fig 2.13. An
For distillation to take place in a distillation column, both vapour and liquid flowing
up and down respectively must be brought into intimate contact. This is done by
packing the column with inert solids, or installing plates at regular intervals
throughout the column height. Small distillation columns are normally packed
while large distillation columns are plated.
In plated columns, we need to provide for both vapour path and liquid paths at
each plate. The plates are perforated and the vapour passes through the
perforations. The liquid flows through pipes known as downcomers next to the
colum wall.
In Fig 2.13, the components of a continuous distillation column are shown.
55
56
Purpose
Separation of solids on the
basis of the difference
in
electrical
of
conductivity
components
Separation of
Sedimentation
solids
from
Application
Mineral ore dressing
extraction
or
leaching
forces
Separation of solid particles
Sugar manufacture
Spray drying
Liquid
liquid
or
solvent
extration
in which it is soluble.
A liquid containing a dissolved
Production
milk,
the
inorganic salts
solvent
yielding
of
synthetic
pigments,
resins
and
powdered product
Separation of a liquid solute
naphthenic
and
aromatic
soluble
Removal of a component from
in a liquid
Not give cyclic products by intramolecular ring closure because this will
terminate polymerisation.
H2O + -(NH-(CH2)6-NH-CO-(CH2)4)-
58
59
growing chain ends to find each other. The two unpaired electrons then join to
form a pair, and a new chemical bond joining their respective chains. This is
called coupling. Coupling is one of two main types of termination reaction.
Another way in which the unpaired electrons can shut down polymerization is
called disproportionation. In disproportionation, the unpaired electron of one
chain finds an electron in the carbon-hydrogen bond of the next carbon atom
forming a double bond at the end of the polymer chain.
Sometimes, the unpaired electron at the end of a growing chain pairs with an
electron from a carbon-hydrogen bond along the backbone of another polymer
chain. This starts a new chain growing out of the middle of the main chain. This is
called chain transfer to polymer, and the result is a branched polymer. It is
especially a problem with polyethylene, so much that linear non-branched
polyethylene cannot be made by free radical polymerization.
Polymerisation products are numerous with many uses and include phenolic
resins, alkyl resins, polyamides, polyesters, elastic foams, silicon polymers,
isocyanate polymers, epoxy resins, adhesives, coatings, polyethylene, vinyl
polymers and acrylic polymers (for paint industry) to mention but a few.
2.2.1.3. Emulsion polymerization
Emulsion polymerization is a type of free radical polymerization that usually starts
with an emulsion consisting of water, monomer and surfactant. The most
common type of emulsion polymerization is an oil-in-water emulsion, in which
droplets of monomer (the oil) are emulsified (with surfactants) in a continuous
water phase. Water-soluble polymers, such as certain polyvinyl alcohols or
hydroxyethyl celluloses, can also be used to act as emulsifiers/stabilizers.
Emulsion polymerization is used to manufacture several commercially important
polymers. Many of these polymers are used as solid materials and must be
isolated from the aqueous dispersion after polymerization. In other cases, the
dispersion itself is the end product. A dispersion resulting from emulsion
polymerization is often called a latex (especially if derived from a synthetic
rubber) or an emulsion (even though "emulsion" strictly speaking refers to a
dispersion of a liquid in water). These emulsions find applications in adhesives,
60
paints, paper and textile coatings. Because they are not solvent-based, they are
eco-friendly.
Advantages of emulsion polymerization include:
The final product can be used as is and does not generally need to be
altered or processed.
The total surface area of the micelles is much greater than the total
surface area of the fewer, larger monomer droplets; therefore the initiator
typically reacts in the micelle and not the monomer droplet.
61
More monomer from the droplets diffuses to the growing particle, where
more initiators will eventually react.
62
2)
3)
4)
5)
Metals
6)
Methyl and primary halides are most suitable for alkylation reactions. In principle
both of the hydrogens can be replaced with alkyl groups:
This can be utilized to form a cyclic system by using a dihalide as shown below:
63
2.2.3. HYDROLYSIS
In the hydrolysis of either organic or inorganic compounds, water and another
compound undergo double decomposition to form two products. The hydrogen
from the water goes to one product while the hydroxyl goes to the other product
as illustrated in the following equation:
XY +H2O
HY + XOH
Inversion of sugar
These reactions can be carried out with water alone. However, there are agents
that accelerate or catalyse the hydrolysis. These include:
Alkalis
Acids
Enzymes
64
Brief description
A chemical process
involves
that
Industrial applications
Intermediates in manufacture of phenol,
of
introduction
detergent,
compounds.
an
organic
molecule.
sulphonating
agents
polystyrene,
naphthalene
The
include
Hydrogenation
Production
an ionisable hydrogen of an
esters
acid.
A
chemical
of
with
the
molecular
another
reaction
hydrogen
substance
in
presence of a catalyst.
of
hydrogenation
synthetic
of
fibres
like
carbohydrates
to
others.
Chlorinated compounds are used in the
(chlorination,
bromination and
organic compound
ethylene
iodination)
Nitration
chlorohydrin
(freon),
DDT,
chlorides, etc.
Industrial solvents, dyestuffs, explosives,
an
organic
compound.
Formative Evaluation
65
alkylation
(ii)
hydrolysis
(iii)
sulphonation
(iv)
nitration
66
Computer with internet facility to access links and relevant copywrite free
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67
http://www.mine-engineer.com
http://electrochem.cwru.ed/encycl
The first site has useful informationon on various unit operations used in the
chemical industry. Photographs and other illustrations are given. The second site
has information on aluminium production.
3.1. Mineral ores
An ore is a mineral deposit which can be profitably exploited. It may contain three
groups of minerals namely:
a) valuable minerals of the metal which is being sought
b) compounds of associated metals which may be of secondary value
c) gangue minerals of minimum value.
Almost all metals are derived from mineral ores. There are also ores that contain
non-metals such as sulphur. Generally, the valuable mineral in an ore may be
found in the form of native metal, oxides, oxy-salts, sulphides or arsenides.
During mining, large open pits are excavated by breaking the ore using
explosives. Ores as mined may be in large lumps and therefore, some size
reduction is done at the mine. The ore is shoveled into trucks and transported to
the factory. If the mineral ore is found in waterbeds, mining is carried out by
dredging. For example, sand is dredged from river beds.
3.2. Ore dressing
Before the ores are subjected to the main chemical treatment steps, they are pretreated by a series of relatively cheap processes, mainly physical rather than
chemical in nature. These processes constitute what is known as ore dressing.
They are meant to effect the concentration of the valuable minerals and to render
the enriched material into the most suitable physical condition for subsequent
operations. Ore dressing may include:
68
If the ores are rich in the valuable mineral, above processes may not add value.
Such ores can be ground, sized and blended with other ores in order to provide a
homogeneous feed to say, a blast furnace or reaction bed.
3.2.1. Size Reduction
Size reduction may be carried out by first crushing the ore down to 7mm
maximum followed by grinding to smaller sizes. Jaw crushers can be used deep
in the mine to prepare the ore for transportation to the surface e.g. using bucket
elevators.
3.2.2. Sizing
Screens are used to separate particles according to size and may not affect the
concentrations of the ore minerals. Particles are separated into oversize and
undersize.
3.2.3. Sorting
The particles may be sorted by classification, flotation or magnetic methods.
Classifiers
These are devices that separate particles according to their different rates of
travel under gravity through a fluid medium such as water. Particles of different
densities, sizes and shapes have different falling velocities. Classifiers include
rake classifiers and jigs.
3.2.4. Flotation
Flotation uses difference in surface properties of the individual minerals. It is
readily applied to very fine concentrates and can distinguish ore mineral from
gangue, and also, one ore mineral from another.
3.2.5. Magnetic Separation
Ferromagnetic magnetite or iron minerals which can be chemically altered to
produce magnetite may be sorted out using a magnetic separator as described in
Unit 2.
69
70
After sorting and leaching, it is necessary to separate the solid and liquid phases.
Coarse solids may be freed from most of their moisture by draining. Slurries with
particles which can settle may be separated from the bulk of the liquid by settling
and subsequent decantation. These dewatering methods may reduce moisture
content to 50%. The moisture content may be reduced further by filtration and
drying. If the valuable ore is in the filtrate, it can be recovered by evaporation
followed by drying.
3.2.8. Agglomeration
When a particle size of an ore or concentrate is too small for use in a later stage
of treatment e.g. in a blast furnace, it must be reformed into lumps of appropriate
size and strength. This is done by any of the following methods:
pelletizing
briqueting
sintering
Briqueting
This is a mechanical process of agglomeration in which the materials, after
mixing with water and necessary bonding agents are pressed or extruded into
brick or block form. These blocks are then dried and hardened by heating. Use of
hydraulic cement allows hardening to be carried out cold. Briqueting is not
popular in mineral ore agglomeration.
Sintering
Sintering involves diffusion of material between particles. It is applied to the
consolidation of metallic and ceramic powder compacts which are heated to
temperatures approaching their melting points to allow diffusion to take place at
the points of contact of particles so that they grow together to form a rigid entity.
The process can be envisaged as a net migration of vacancies into the solid at
the highly curved energy surfaces near points of contact and again at low energy
areas away from contact points
Sintering may be accompanied by a chemical reaction.
3.3. Extraction Processes
71
So far we have been dealing with unit operations that prepare the ore for
chemical reactions used to extract the valuable metal from the ore. Now we want
to look at extraction and refining of the metal.
3.3.1. Calcination
This is the thermal treatment of an ore to effect its decomposition and the
elimination of a volatile product, usually carbon dioxide or water. The following
are calcinations reactions
CaCO3
CaO +
CO2
T = 10000C
MgCO3
MgO +
CO2
T = 4170C
MnCO3
MnO +
CO2
T = 3770C
FeCO3
FeO
CO2
T = 4000C
Calcination may be carried out in rotating kilns using countercurrent flow for
efficient heat transfer.
3.3.2. Roasting
Roasting involves chemical changes other than decomposition, usually with
furnace atmosphere. A roast may effect calcinations and drying as shown below.
2CuS +
O2
Cu2S +
SO2
(calcination)
Cu2S +
O2
2Cu
SO2
(roasting)
3.3.3. Smelting
This is essentially a smelting process in which the components of the charge in
the molten state separate into two or more layers which may be slag, matte,
speiss or metal
speiss:
elements
72
Smelting of metal involves reduction, usually by carbon or coal or coke and may
be performed in a blast furnace or an electric furnace.
In the blast furnace, coke is burned into CO 2 which reacts further with the carbon
to form CO. The ascending gases pre-heat the solid charge descending the stack
and reduce metal oxides to metal. This then is a process of drying followed by
calcination and roasting. The metal melts and the slag forms gangue and flux.
Where fusion or reduction temperature is above 1500 0C, electric melting is most
appropriately applied.
3.3.4. Refining
Electrolysis may be used for metal extraction and metal refining. In fire refining,
extracted metals are brought into liquid state and their composition finally
adjusted. In some case, this may be simple smelting to allow cathodically
entrained hydrogen to escape by diffusion. In other cases, impurities may react
to form compounds which are insoluble in the molten state.
Converters are used for oxidizing impurities out of blast furnace iron in steelmaking and for oxidation of sulphur from copper and nickel matte. Distillation
may also be applied in metal purification.
e. Alloy or special steels which besides carbon contain one or more metals
such as Ni, Cr, W, V, Mo, Mn.
3.4.2. Raw materials
The main raw materials for the manufacture of iron and steel are iron ore and
limestone or dolomite as flux. Coking coal is used as fuel. The fuel serves two
purposes: to heat the furnace and to produce CO which acts as the reducing
agent. To make special steels other materials such as nickel, chromium, cobalt
are added.
Iron ore deposits are found in India, China, Brazil, Canada, Germany and United
States of America. The ores include red haematite (Fe 2O3), the less inferior
brown hydrated haematite also known as limonite (2Fe 2O3.3H2O), the magnetic
magnetite (Fe3O4) which is black in colour and pyrites (FeS 2). The haematite is
easily reduced. Magnetite contains about 72% pure metal and it is reduced with
some difficulty.
3.4.3. Removal of impurities in iron ore
The presence of impurities in the iron ore not only reduce the iron content in the
ore but also increase production costs especially with regard to consumption of
flux and fuel.
If limonite is used, it is first dried before use. When the ore contains large
amounts of impurities, appropriate ore dressing operations are carried out on it.
When the ore is obtained in small particles, it is sintered into lumps.
The main impurities in iron ore are silica and alumina. Silica and alumina in the
presence of limestone makes the ore self-fusing with less production costs. At
high temperatures of the blast furnace, the flux reacts with alumina and silica to
form a complex of calcium-magnesium aluminium silicate known as slag.
Sulphur and phosphorus are also found in iron ores as impurities in the form of
sulphides (FeS), sulphates (CaSO4) and phosphates (Ca3(PO4)2 or Fe3(PO4)2).
Both sulphur and phosphorus, which can also come from the fuel used, are not
desired in iron and steel manufacture. Normally steel should not contain more
than 0.05% sulphur and 0.05% phosphorus. Sulphur can be removed in the blast
furnace slag. Phosphorus cannot be removed in the slag but passes through to
74
the pig iron where it is combined with steel in the convertor. As a result, the ores
are sometimes classified as acid or basic ores according to the amount of
phosphorus present. Acid ores contain less than 0.05% phosphorus while basic
ores has more than 0.05%.
A small amount of manganese is generally present in iron ores. Manganese is
advantageous for steel production because it reduces the effect of sulphur by
forming manganese sulphide (MnS). Sometimes, if manganese is absent from
the ores, it is added.
3.4.4. Fuel
Coke is the fuel used to melt the ore and also to reduce the iron ore to metallic
iron. Coke is produced at the bottom of the blast furnace by carbonization of coal
i.e. burning of coal in the absence of oxygen to remove volatile matter. Good
quality coke has about 80% carbon and 20% ash. It is hard to prevent the
formation of CO and its high porosity provides large surface area for the chemical
reactions. It is consumed at the rate of one ton per ton of pig iron.
3.4.5. Manufacture of Pig Iron
Pig iron is a direct product of smelting iron ore with fluxes and fuel in a tall blast
furnace. The oxygen is introduced at the top of the furnace, blown or blasted
through bronze or copper nozzles over the furnace materials in a number of
symmetrically placed tubes, called tuyeres. The air blast is preheated to a
temperature of about 7000C and pressure of 2.5kg/cm 2 using the hot exhaust
gases leaving the furnace at the top. Preheating greatly increases the economy
of steel production.
The molten iron and slag collect at the bottom of the furnace while the gases
escape from the top. The slag layer floats over the heavier iron and is periodically
collected as dross and stored as waste material that can be used for cement
manufacture or for making floor tiles
The pig iron is tapped and is either used to produce cast iron, stored in pigs of
sand bags or is taken for steel production. To make cast iron, the molten metal is
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poured into moulds of desired size and shape. The metal gets cooled and
solidifies taking the desired shape.
CO2 + 2 Fe3O4
Fe3O4 + CO
3FeO + CO2
3FeO + 3CO
3Fe + 3CO2
Fuel reactions
C + O2
CO2
CO2 + C
2CO
CaO + CO2
CaSiO3
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2Fe + SiO2
2FeO + Si
2Mn + SiO2
MnO + Si
MnO2 + 2C
Mn + 2CO
FeS + CaO + C
CaS + Fe + CO
FeS + Mn
Fe + MnS
Ca3(PO4)2 + 3SiO2 + 5C
3CaSiO3 + 2P + CO.
Most of the sulphur passes into the slag as CaS and MnS and only a small
portion remains in the metal as FeS and MnS.
Ore dressing may involve washing the ore, size classification and leaching.
3.5.1. Chemical treatment of bauxite
At this stage bauxite is crushed and ground to the correct particle size for
efficient extraction of the alumina through digestion with hot sodium hydroxide
solution which dissolves the aluminium hydroxide, forming a solution of sodium
aluminate.
2NaOH + Al 2O3
The residual impurities (oxides of silicon, iron, titanium and aluminium i.e. SiO 2,
Fe2O3, TiO2, Al2O3). These insoluble impurities are called red mud which
together with fine solid impurities, are separated from the sodium aluminate
solution by washing and thickening. The solution is then seeded with aluminium
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2Al(OH)3 + 2NaOH
Al 2O3 + 3H2O
78
79
The anode butts are sent back to the anode plant to be ground and mixed into
new anode paste to be pressed and baked.
The molten aluminium is periodically tapped under vacuum from the furnace into
a crucible and cast into ingots.
3.6. EXTRACTIVE METALLURGY OF COPPER
Copper is mostly extracted from ores containing copper sulphides, copper oxides
or copper carbonates. Copper ores are generally poor and contain between 1.5
and 5% copper. Therefore, commercial extraction of copper involves several
dressing operations before the smelting stage.
The extraction of copper from its sulphide ores is done by eliminating the
gangue, iron, sulphur and minor impurities by the following steps yielding the
shown % copper after each step:
% copper
Concentration
15-25
Roasting
30-45
Smelting
Matte conversion
98
Fire refining
99.5
Electrolytic conversion
99.9
3.6.1. Concentrating
The purpose of concentration step is to separate the copper mineral from the
gangue. The ore is first crushed and finely ground. It is made into a slurry with
water and then fed into a froth flotation cell. The ore particles are lifted up by air
bubbles while the gangue remain in the cell. The froth containing the ore is
thickened and filtered.The pulp is dried to about 6% moisture.
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3.6.2. Roasting
The objective of roasting is to remove excess sulphur. Thus, if the ore does not
contain excess sulphur, roasting may be omitted and the ore directly smelted.
Roasting is carried out in a multiple hearth furnace or in a fluidized bed.
The dry pulp is fed into the roaster at 600 to 700 oC. The burning of the sulphide
ores supplies the heat to maintain the temperature at which roasting takes place.
The reactions at the roaster are as follows.
2As2S3 + 9O2
2As2O3 + 6SO2
2Sb2S3 + 9O2
2Sb2O3 + 6SO2
Fe2S3
2FeS + S
S + O2
SO2
2FeS + 3O2
2SO2 + 2FeO
4FeO + O2
2Fe2O3
The arsenic and antimony are volatiles and and leave with sulphur dioxide.
3.6.3. Matte smelting
At this stage the concentrate is smelted in a furnace to produce a mixture of
copper and iron, called matte.
Smelting is carried out at about 1350 oC. The rasted ore is in powder form and
cannot therefore be smelted conveniently in a blast furnace. It is done in a long
reverberatory furnace heated by coal dust. The following are the reactions that
take place in the furnace:
2FeS + 3O2
2FeO + 2SO2
FeO + SiO2
FeSiO3
Cu2O + FeS
Cu2S + FeO
CuO + FeS
CuS + FeO
2CuS
3Fe2O3 + FeS
Cu2S + S
7FeO + SO2
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Cu2S and part of the FeS form the matte. The silicates and oxides of iron are
slagged. The gangue is absorbed by the slag and removed.
3.6.4. Blister copper production
The object of the converter operation is to convert matte into molten blister
copper containing 96 to 98% copper and remove the iron rich slag
The operation is carried out in two stages each of which has a distinctive flame
colour. In the first stage, air is blown through the matte untill all the slag is formed
i.e. the total elimination of the FeS. Silica is used to react with the oxide. The slag
is removed by tilting the converter. Air is again blown through the matte and the
Cu2S is converted to Cu. The following are the reactions in the converter:
Slag formation stage:
Blister copper formation
2FeS + 3O2
2FeO + 2SO2
2FeO + 2SiO2
2FeSiO3
2Cu2S + 3O2
2Cu2O + 2SO2
2Cu2O + Cu2S
6Cu + SO2
Formative Evaluation
1. What unit operations are generally carried out during mineral ore dressing?
2. Describe how an electrostatic separator works
3. Explain what sintering is.
4. Distinguish using equations, the difference between calcination and roasting.
5. How are silica and alumina removed from iron ore?
6. Describe how pig iron is manufactured in a blast furnace.
7. Describe the process of extracting alumina from bauxite.
8. Draw a schematic diagram of a Hall-Heroult electrolytic cell for aluminium
manufacture and explain how it works.
9. With respect to extractive metallurgy of copper, write equations for reactions
that take place during
a. roasting
b. matte smelting.
10. Why is it necessary to fire and electrolytically refine copper?
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84
Computer with internet facility to access links and relevant copywrite free
resources
85
86
2Cl ( aq ) Cl 2( g ) 2e
At cathode
2 Na ( aq ) 2e Hg 2 Na / Hg
Overall: 2 NaCl ( aq ) 2 NaHg Cl 2 ( g )
The amalgam (a mercury-sodium alloy) is taken to a different vessel for
decomposition according to the equation:
87
ii.
They easily become congested with use (shown by high voltage drop) and
therefore must be replaced regularly.
iii.
Diaphragms permit flow of brine from anode to cathode and this reduces
greatly on side reactions like formation of sodium hypochlorite.
iv.
Diaphragm cells with metal cathodes like titanium coated with rare earth
oxides, rarely develop congested diaphragms and do not require regular
replacement. This reduces on operating costs.
88
v.
vi.
Diaphragm cell technology is still in use, but the use of asbestos in the cells is
causing new plants to turn to the newer ion-exchange or membrane technology.
4.1.6. Membrane Cells
Improved designs of membrane cells and cheaper purification have increased
the economics of the new membrane process.
Fig 4.2 represents a condensed overview of a membrane cell process.
89
plastic sheets are porous and chemically active to allow sodium ions to pass
through but reject hydroxyl ions. An example of membrane material is
perfluorosulphonic acid polymer.
The membranes exclude OH- and Cl- ions from the anode chamber thereby
making the product free from the salt contamination experienced in the
diaphragm cell. The membrane cells use more concentrated brine solutions and
produce purer and more concentrated sodium hydroxide, which require less
evaporation during concentration.
90
Ammonia is one of the most highly produced inorganic chemicals in the world
because of its widespread application. Synthetic ammonia is produced from the
reaction between nitrogen and hydrogen. Before synthetic nitrogen fixation was
discovered, manures, ammonium sulfate (a by-product from the coking of coal),
Chilean saltpetre, and later, ammonia recovered from coke manufacture were
some of the important sources of fixed nitrogen. During the first decade of the
twentieth century, the worldwide demand for nitrogen-based fertilizers far
exceeded the existent supply.
4.2.2. Uses of ammonia
Ammonia is the basis from which virtually all nitrogen-containing products are
derived.
The main uses of ammonia include the manufacture of:
Nitric acid
Explosives
Refrigeration for making ice, large scale refrigeration plants, airconditioning units in buildings and plants
Extractive metallurgy
Cleaning solutions
91
500 o
C, Fe
H = 45.7kJ/mol
NH3
92
nitrogen requires a lot of energy to dissociate. In the gas phase this dissociation
occurs only at around 3000C. Even the hydrogen molecule, which has a weaker
molecular bond, only dissociates markedly at temperatures above 1000C.
4.2.6. Catalyst
Since the ammonia synthesis reaction cannot be moved to the right at low
temperature, this calls for temperature increase, which unfortunately drives the
reverse reaction. This is where the role of the iron catalyst comes in. The reaction
when carried out at high pressures and temperatures occurs with large yields
when iron catalysts are present. The hydrogen and nitrogen molecules lose their
translational degrees of freedom when bound to the catalyst surface.
This
reduces the activation energy for the release of atomic nitrogen dramatically, and
thus makes the forward reaction go faster at lower temperatures. The use of
lower temperature reaction conditions means there is limited reverse reaction.
But we still need reasonably high temperatures (250-400C) even with the use of
a catalyst which essentially accelerates the reaction sufficiently so that we can
obtain ammonia at conditions where the equilibrium conversion is large enough
to be useful.
Iron catalyst
The real problem has been to find a suitable catalyst so that the maximum
amount of product is obtained with minimum volume of the catalyst in the
shortest time possible. The catalysts, which Haber initially employed, were
catalytically active pure metals, which were too expensive. They also lost
catalytic activity after a short time due to poisoning. Iron was one of the metals
that showed high activity. However, pure iron has a regular shape with low
porosity which is a disadvantage for a catalyst. The iron can be made irregular by
mixing and fusing iron oxide with other oxides combinations. This is referred to
as structural promotion. A common iron catalyst promoter is a mixture of Al 2O3
and K2O. Its optimal performance requires reaction temperatures around 400C
and pressures from 150-300 atmospheres. Ammonia synthesis reaction is carried
out commercially at 200-500 atm and 450 to 600 oC.
93
94
c CO + H2O + N2
The nitrogen and hydrogen coming out of the secondary reformer are in the ratio
of 3:1. This mixture is known as the synthesis gas.
4.2.8.4. Shift Conversion.
The carbon monoxide is converted to carbon dioxide with the assistance of
catalyst beds at different temperatures.
CO+H2O = CO2+H2
This water-gas shift reaction is favorable for producing carbon dioxide which is
used as a raw material for urea production. At the same time more hydrogen is
produced.
4.2.8.5. Purification.
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2H2O
Note that the first equation is the opposite of the reformer reaction.
4.2.8.6. Ammonia Converter.
After leaving the compressor, the gaseous mixture goes through catalyst beds in
the synthesis converter where ammonia is produced with a three-to-one
hydrogen-to-nitrogen stoichiometric ratio. However, not all the hydrogen and
nitrogen are converted to ammonia. The unconverted hydrogen and nitrogen are
separated from the ammonia in the separator and re-cycled back to the synthesis
gas compressor and to the converter with fresh feed. Because the air contains
argon which does not participate in the main reactions, purging it minimizes its
build up in the recycle loop.
4.2.8.7. Ammonia Separation
The removal of product ammonia is accomplished via mechanical refrigeration or
absorption/distillation. The choice is made by examining the fixed and operating
costs. Typically, refrigeration is more economical at synthesis pressures of 100
atm or greater. At lower pressures, absorption/distillation is usually favoured.
4.2.8.8. Ammonia Storage
Ammonia is stored in tanks as a refrigerated liquid. Some ammonia is used
directly as a fertilizer. Most ammonia is converted in downstream processes to
urea (46% nitrogen) or ammonium nitrate (34% nitrogen) for use as fertilizer.
4.2.9. Some environmental impacts of ammonia production
96
Ammonia is toxic, irritant and corrosive to metal alloys (e.g. copper alloys). In
refrigeration, its replacement by the non-toxic chlorofluorocarbon (CFCs) has
contributed to global warming. In large industrial processes such as bulk ice
making, and food processing and preservation, ammonia is still being used as a
refrigerant.
The toxicity of ammonia solution is usually not harmful to human beings because
it is easily excreted in urine. However, ammonia even in dilute concentrations is
toxic to aquatic animals because they do not have the mechanisms to eliminate it
from their bodies by excretion.
in
chemical
conversions
such
as
nitration,
sulphonation,
and
97
100% H2SO4
Elemental sulphur
back to the chamber to be used again. Sulphuric acid produced in this way is
only about 62 to 70 per cent H2SO4. The rest is water. The chamber process has
become obsolete and has been repalced by the contact process due to the
following reasons:
i. An increased demand for strong, pure acid and oleum
ii. Contact process plants are cheaper and more compact
4.3.4.2. The Contact Process
The second method of manufacturing sulphuric acid, the contact process, which
came into commercial use about 1900, depends on oxidation of sulphur dioxide
to sulphur trioxide, SO3, under the accelerating influence of a catalyst.
The first contact plants (before 1920) were built using platinum catalysts. Finely
divided platinum, the most effective catalyst, has two disadvantages: it is very
expensive, and it is deactivated by certain impurities in ordinary sulphur dioxide.
They include compunds of arsenic, antimony and lead. In the middle of 1920s,
vanadium catalysts started being used and have since then replaced platinum.
By 1930, the contact process could compete with the chamber process and
because it produces high strength acid, it has almost replaced the chamber
process.
Since the oxidation of sulphur and sulphur dioxide releases large amounts of
energy, major changes in the manufacturing plant design were introduced to
utilise this heat energy in the production of steam for generating electrical power.
This combination of a chemical plant and electrical generation is known as cogeneration.
The flow diagram for sulphuric acid manufacture by the contact process is shown
in Fig. 4.5
99
Fig. 4.5. Block diagram for the manufacture of sulphuric acid by the contact
process.
The main steps in the contact plant are:
the gas conversion of SO2 into sulphur trioxide (SO3) by passing it through
a converter containing the catalyst
100
volume and the O2 content is low but higher than 3%. The gases are generally
diluted to 9-12% SO2 before entering the conversion process.
Conversion of SO2 into SO3
The design and operation of sulphuric acid plants are focused on the following
gas phase chemical reaction in the presence of a catalyst:
2SO2+O2(g) = 2SO3(g), H = -98.3kJ at 250C
From thermodynamic and stoichiometric considerations, the following methods
are available to maximise the formation of SO 3 for the O2/SO2/SO3 system.
removal of SO3
This reaction is a reversible reaction and the conditions used are a compromise
between equilibrium and rate considerations.
It is necessary to shift the position of the equilibrium as far as possible to the right
in order to produce the maximum possible amount of sulphur trioxide in the
equilibrium mixture. Even though excess O 2 would move the SO2 formation to the
right, the 1:1 mixture gives the best possible overall yield of sulphur trioxide. The
forward reaction is exothermic and is favoured by low temperature. However, too
low a temperature slows the reaction. To get the gases to reach equilibrium
within a very short time, a compromise temperature of 400450 oC is used.
According to Le Chateliers principle high pressures favour the forward reaction.
However, even at relatively low pressures of 1 to 2 atmospheres, there is a
99.5% conversion of sulphur dioxide into sulphur trioxide. In the absence of a
catalyst the reaction is quite slow and is therefore carried out in the presence of a
vanadium oxide catalyst which has a long life because it is not easily poisoned.
Further more, vanadium catalyst has high conversion efficiency. Its only
101
A pressure of 2 atmospheres
102
103
104
processes. Yellowing, spots of dead tissue, and weak stems and roots are all
indicative of plants that lack enough potassium.
Besides the above three macronutrients, fertilizers also contain trace elements
that improve the growth of plants. Calcium, magnesium, and sulfur are also
important materials in plant growth. They are only included in fertilizers in small
amounts, however, since most soils naturally contain enough of these
components. Other micronutrients include iron, chlorine, copper, manganese,
zinc, molybdenum, and boron, which primarily function as cofactors in enzymatic
reactions. While they may be present in small amounts, these compounds are no
less important to growth, and without them, plants can die. The absence of any
one nutrient in the soil can limit plant growth, even when all other plant nutrients
are present in adequate amounts.
4.4.3. Raw materials
Primary fertilizers include substances derived from nitrogen, phosphorus, and
potassium. Nitrogen is derived from ammonia, phosphorus from phosphate rock
and potassium from potassium chloride, a primary component of potash.
4.4.4. The Manufacturing Process
Fully integrated factories have been designed to produce compound fertilizers
from primary fertilizers. Depending on the actual composition of the end product,
the production process will differ from manufacturer to manufacturer.
Multicomponent fertilizers are compound fertilizers composed of primary
nitrogen, phosphorus, and potassium (NPK) fertilizers and secondary nutrients.
Generally, each granule of the compound fertilizer contains a uniform ratio of
nutrients, or blends. The three numbers on a bag of such a fertilizer are referred
to as the "analysis." It is the percentage of nitrogen, phosphate and potash that is
available to plants from that bag of fertilizer. N-5-P-10-K-5 or simply 5-10-5
means 5 percent nitrogen, 10 percent phosphate and 5 percent potash. The
analysis found on a bag or bulk shipment of fertilizer tells the farmer or consumer
the amount of nutrients being supplied.
105
The balance 80 percent will contain some micronutrients and filler material, which
allows for even application of the nutrients across the fertilized area.
106
In its unprocessed state, phosphate rock is not suitable for direct agricultural
application, since the phosphorus it contains is insoluble. To transform the
phosphorus into a plant-available form (CaH 4(PO4).H2O) and to obtain a more
concentrated product, phosphate rock is processed using sulphuric acid,
phosphoric acid and/or nitric acid.
Acidulation by means of sulphuric acid converts the rock to monocalcium
phosphate popularly known as normal or single superphosphate (SSP) having a
phosphorus content of 15-20% P2O5.
Ground phosphate rock is thoroughly mixed with metered quantities of 60-70%
sulphuric acid in the ratio of 0.82 to 0.95 acid to phosphate rock. The heat of
dilution serves to heat the acid to proper reaction temperature. Excess heat is
dissipated by evaporation of extra water added. The rate of water and acid
addition is varied to control moisture level. The fresh superphosphate drops to a
slow moving conveyor in a den where it takes I hour in order to solidify. A
disintegrator slices the solid mass of crude product before it is taken to pile
storage. The chemical reaction continues for 4-6 weeks to 15-20% P 2O5. After
curing, the product is bagged and shipped.
2 Ca5(PO4)3F + 7H2SO4 + 3H2O
5CaH4(PO4)2.H2O +HF
Since no CaSO4 is formed, the phosphorus content is not diluted. Therefore, TSP
(0-46-0) has a phosphorus content of 43-48 percent as P2O5.
Two processes are used to produce TSP fertilizers: run-of-pile and granular. The
run-of-pile process is similar to the SSP process. Granular TSP uses lower
107
strength phosphoric acid (40 percent compared to 50 percent for run-of -pile).
Pulverized ground phosphate rock is mixed with phosphoric acid in the reactor.
The resultant slurry is sprayed into the granulator. The product is dried, screened
and cooled. It is stored for 4-6 weeks to cure.
Monoammonium Phosphate (MAP) (11-52-0) and Diammonium Phosphate
(DAP) (18-46-0) are called ammoniated phosphates because phosphoric acid is
treated with ammonia to form these basic phosphate products that also contain
nitrogen. They are widely produced in the granular form for blending with other
types of fertilizers, and are also produced in non-granular forms for use in liquid
fertilizers.
Acidulation of phosphate rock using nitric acid produces NP slurries for use in the
manufacture of compound fertilizers.
4.4.4.3. Potassium fertilizer
Most potassium (K) is obtained from naturally occurring ore deposits. Although
the low-grade unrefined mineral ores can be directly applied, it is normally
purified. Potassium in the form of potassium chloride and potassium magnesium
sulphate are used in the manufacture of multi-nutrient fertilizers. Potassium
chloride is typically supplied to fertilizer manufacturers in bulk. The manufacturer
converts it into a more usable form by granulating it. This makes it easier to mix
with other fertilizer components.
4.4.4.4. Manufacture of NPK fertilizer
The raw materials, in solid form, can be supplied to fertilizer manufacturers in
bulk quantities of thousands of tons, drum quantities, or in metal drums and bag
containers.
Secondary nutrients are added to some fertilizers to help make them more
effective. The different types of particles are blended together in appropriate
proportions to produce a composite fertilizer. Typically, complex NPK fertilizers
are manufactured by producing slurries of ammonium phosphates, to which
potassium salts are added prior to being made into granules. PK fertilizers, on
108
109
in which the chemical variation is reduced. In the wet process, each raw material
is fed with water to the ball mill. This slurry is pumped to blending tanks and
homogenized to correct chemical composition. The slurry is stored in tanks until
required.
4.5.3.2. Pyroprocessing
In the preheater, the raw meal from the mill is heated with the hot exhaust gas
from the kiln before being fed into the rotary kiln to form a semi-product known as
clinker. The ash from fuel used is also absorbed into the clinker. The particle size
range for clinker is from about 2 inches to about 10 mesh.
111
Reaction
Evaporation of water
Remarks
Solid phase reactions,
>500
endothermic
Solid phase reactions,
900
endothermic
Solid phase reactions,
dehydration products
endothermic
CaCO3
Main reactions between lime
1250 - 1280
1280 -1550
Function
Together with 3CaO.SiO2,
responsible for final strength
3CaO.SiO2
3CaO.Al2O3
C3S
C3A
Tricalcium silicate
(I year)
Responsible for early
Tricalcium
aluminate
needs retardation by
gypsum by forming
3CaO.
C4AF
Tetracalcium
112
3CaO.Al2O3CaSo4.3H2O
Improves chemical
Al2O3.Fe2O3
alumino-ferrate
resistance
The rotary kiln discharges the red-hot clinker under the intense flame into a
clinker cooler. The clinker cooler recovers heat from the clinker and returns the
heat to the pyroprocessing system thus reducing fuel demand and cooling the
clinker to a temperature conducive for handling in subsequent steps.
4.5.3.4. Finish Grinding
The final process of cement making is called finish grinding. The clinker is dosed
with a controlled amount of gypsum and fed into a finish mill. Other additives may
be added during the finish grinding process to produce formulated cements such
as waterproofing and corrosion resistant cements.
The cement is stored in a bulk silo for packaging and/or bulk distribution.
Formative Evaluation
1. Write cell reactions for the mercury cell
2. Draw a process flow diagram to show how sodium hydroxide and chlorine are
produced using a membrane cell.
3. Describe briefly with the help of a diagram and equations, the Haber process
for manufacture of ammonia.
4. Why is it necessary to remove sulphur compounds from the feedstocks for the
ammonia process?
5. What are the major industrial and domestic uses of ammonia?
6. Consider the following reaction:
2SO2(g) + O2(g
Temperature: 400-450 oC
Pressure: 2 atmospheres
(iii) 5-10-5
9. What do you understand by the term Portland cement?
10. Explain the role played by various constituents in cement during curing of
plaster.
114
115
Computer with internet facility to access links and relevant copywrite free
resources
117
Process
Atmospheric
Purpose
Produce kerosene
By-Products, etc.
Naphtha, tar, etc.
1870
distillation
Vacuum distillation
118
1913
1916
1930
1932
1932
1933
1935
1935
Thermal cracking
Sweetening
Thermal reforming
Hydrogenation
Coking
Solvent extraction
Solvent dewaxing
Cat. polymerization
feedstocks (1930's)
Increase gasoline yield
Reduce sulfur & odor
Improve octane number
Remove sulfur
Produce gasoline basestock
Improve lubricant viscosity index
Improve pour point
Improve gasoline yield and octane
feedstocks
Residual, bunker fuel
Sulfur
Residual
Sulfur
Coke
Aromatics
Waxes
Petrochemical,
1937
Catalytic cracking
number
Higher octane gasoline
feedstocks
Petrochemical,
1939
1940
Visbreaking
Alkylation
Reduce viscosity
Increase gasoline octane & yield
feedstocks
Increased distillate, tar
High-octane
aviation
1940
1942
Isomerization
Fluid
catalytic
1950
1952
1954
1956
1957
cracking
Deasphalting
Catalytic reforming
Hydrodesulfurization
Inhibitor sweetening
Catalytic
Petrochemical feedstocks
Increase cracking feedstock
Convert low-quality naphtha
Remove sulfur
Remove mercaptan
Convert to molecules with
1960
1974
1975
isomerization
Hydrocracking
Catalytic dewaxing
Residual
octane number
Improve quality and reduce sulfur
Improve pour point
Increase gasoline yield from residual
high
gasoline
Naphtha
Asphalt
Aromatics
Sulfur
Disulfides
Alkylation feedstocks
Alkylation feedstocks
Wax
Heavy residuals
hydrocracking
Source: http://www.setlaboratories.com
5.1.4. Characteristics and classification of Crude Oil
As has been mentioned, crude oils are complex mixtures containing many
different hydrocarbon compounds that vary in appearance and composition from
one oil field to another. Crude oils range in consistency from water to tar-like
solids, and in color from clear to black.
An "average" crude oil contains about 84% carbon, 14% hydrogen, 1%-3%
sulfur, and less than 1% each of nitrogen, oxygen, metals, and salts. Crude oils
are generally classified as paraffinic, naphthenic, or aromatic, based on the
predominant proportion of similar hydrocarbon molecules. Oils with low carbon,
high hydrogen, and high API (American Petroleum Institute) gravity are usually
rich in paraffins and tend to yield greater proportions of gasoline and light
119
petroleum products; those with high carbon, low hydrogen, and low API gravities
are usually rich in aromatics. The former category is known as light crudes and
the latter as heavy crudes.
Crude oils that contain appreciable quantities of hydrogen sulfide or other
reactive sulfur compounds are generally called "sour." while those with lower
sulfur are called "sweet."
5.1.4. Composition of petroleum
Crude petroleum contain hydrocarbon and non-hydrocarbon compounds.
Hyrocarbon compounds
Paraffins - The paraffinic crude oil hydrocarbon compounds found in crude oil
have the general formula C nH2n+2 and can be either straight chains (normal) or
branched chains (isomers) of carbon atoms. The lighter, straight chain paraffin
molecules are found in gases and paraffin waxes. The branched-chain (isomer)
paraffins such as isobutene are usually found in heavier fractions of crude oil and
have higher octane numbers than normal paraffins.
Aromatics: The aromatic series include simple aromatic compounds such as
benzene, naphthalenes and the most complex aromatics, the polynuclears which
have three or more fused aromatic rings. They have high anti-knock value and
good storage stability.
Naphthenes (Naphtha): These are saturated hydrocarbon groupings with the
general formula CnH2n, arranged in the form of closed rings (cyclic) and found in
all fractions of crude oil except the very lightest. Single-ring naphthenes
(monocycloparaffins) with five and six carbon atoms such as cyclohexane
predominate. Two-ring naphthenes (dicycloparaffins) are found in the heavier
ends of naphtha.
Alkenes (Olefins): Olefins such as ethylene, butene, isobutene are usually
formed by thermal and catalytic cracking and rarely occur naturally in
unprocessed crude oil. They are unstable and also improve the anti-knock
tendencies of gasoline but not as much as the iso-alkanes. When stored, the
olefins polymerise and oxidize. This tendency to react is employed in the
production of petrochemicals.
120
121
122
123
to increase the yield of gasoline from each barrel of crude oil and to decrease the
tendency of gasoline to knock when it burned. It was found that:
Short alkanes (C4H10) burn more evenly than long alkanes (C 7H16).
Heptane
2-Methylheptane
Hexane
2-Methylhexane
1-Heptene
Pentane
1-Pentene
Butane
Number
0
23
25
44
60
62
84
91
124
Cyclohexane
2,2,4-Trimethylpentane
97
100
(isooctane)
Benzene
Toluene
101
112
By 1922 a number of compounds had been discovered that could increase the
octane number of gasoline. Adding as little as 6 ml of tetraethyllead to a gallon of
gasoline, for example, can increase the octane number by 15 to 20 units. This
discovery gave rise to the first "ethyl" gasoline, and enabled the petroleum
industry to produce aviation gasolines with octane numbers greater than 100.
Another way to increase the octane number is thermal reforming. At high
temperatures (500-600oC) and high pressures (25-50 atm), straight-chain
alkanes isomerize to form branched alkanes and cycloalkanes, thereby
increasing the octane number of the gasoline. Running this reaction in the
presence of hydrogen and a catalyst such as a mixture of silica (SiO 2) and
alumina (Al2O3) results in catalytic reforming, which can produce a gasoline
with even higher octane numbers.
The yield of gasoline is increased by "cracking" the long chain hydrocarbons into
smaller pieces at high temperatures (500 oC) and high pressures (25 atm). A
saturated C12 hydrocarbon in kerosene, for example, might break into two C 6
fragments. Because the total number of carbon and hydrogen atoms remains
constant, one of the products of this reaction must contain a C=C double bond.
125
The flow diagrams Fig. 5.2 and 5.3 show the various processes undertaken to
improve the yields and quality of petroleum products. Among them are catalytic
cracking and catalytic reforming.
126
128
other processes. Most processes use platinum as the active catalyst. Sometimes
platinum is combined with a second catalyst (bimetallic catalyst) such as rhenium
or another noble metal.
The conversion is illustrated by the following reaction in which a cycloalkane is
converted to an aromatic compound, usually of higher octane number.
The naphtha feed is mixed with recycled hydrogen and introduced to the feed
preheater to raise the temperature. The hot mixture of hydrogen and naphtha
vapours is passed through a series of four reactors containing the catalyst. The
working temperatures and pressures are usually between 150 oC to 510oC and
1500kPa to 7000kPa respectively. The products are cooled and about 90% of the
hydrogen is compressed and recycled. The main product is fractionated. The
overhead product can be used as a fuel.
Some catalytic reforming systems continuously regenerate the catalyst while in
other systems one reactor at a time is taken off-stream for catalyst regeneration,
Some facilities regenerate catalysts from all of the reactors during shutdown.
5.1.9. Polymerization
This is the joining up of low molecular weight fractions to form high molecular
weight components. This process converts by-products hydrocarbon gases into
liquid hydrocarbons that are suitable for use as high octane number fuels and for
petrochemical industry. The combining molecules are usually unsaturated.
Propylene and iso-butylene are common olefins polymerised in the vapour phase
in reactions such as shown here:
129
5.1.10. Alkylation
Akylation was discussed in Unit 2 under unit processes. In the context of
petroleum processing, it is the combining of an olefin with an aromatic
hydrocarbon. The process is of relatively minor importance compared to the
catalytic cracking and catalytic reforming processes. It is used mainly for
converting gaseous hydrocarbons to gasoline in the presence of an acid catalyst
such as hydrogen fluoride or sulphuric acid. The processes are usually
exothermic and similar to polymerisation. An example is the formation of 2,2Dimethylbutane from ethylene and isobutane:
130
131
of H2S and other undesirable components. In cases where steam is used for
stripping, the product is sent to a vacuum drier for removal of water.
Hydrodesulfurized products are blended or used as catalytic reforming feedstock.
C6H4(CO2H)CO2R
C6H4(CO2R)2 + H2O
132
Two of the most important diesters bis(2-ethylhexyl) phthalate (DEH) and dioctyl
phthalate (DOP) are used as plasticisers in the manufacture of polyvinyl chloride.
Other major uses of phthalic anhydride are in polyester resins and (decreasingly)
in alkyd resins. Alkyd resins containing PA are used in solvent-borne protective
coatings. As paint technology increasingly utilises water-borne technologies,
many PA-based alkyds have lost out to alternative raw materials. Phthalic
anhydride is widely used in industry for the production of certain dyes such as the
well-known anthroquinone dye.
5.2.1.3. Production Process
Phthalic anhydride was first produced by the oxidation of naphthalene from coal
in concentrated sulphuric acid in the presence of mercury sulphate. This route
was later replaced by the catalytic vapour phase oxidation of naphthalene in air
in the presence of a vanadium oxide catalyst. Today, naphthalene feedstock has
been generally superseded by the use of orthoxylene obtained from refineries
and crackers. The commonly used catalyst is vanadium pentoxide with titanium
dioxide-antimony trioxide. Alternative catalysts include molybdenum trioxide and
calcium oxide, or manganese oxides. The respective reactions for the two
feedstocks are as follows:
C10H8 + 4.5 O2
C6H4(CH3)2 + 3 O2
The process technology has changed little although yields have improved and
catalysts in current use have a longer life of three years. Another development
has been the lowering of the air to orthoxylene weight ratio to 9.5:1, down from
about 20:1, thus allowing a reduction in capital costs and energy savings.
In the orthoxylene-based process shown in Fig 5.4, the feedstock is vapourized
and mixed with air. The air-orthoxylene mixture is fed to a reactor with vertical
tubes filled with catalyst. The reaction takes place at 375-425 oC and below 1 bar
pressure.
133
Salt cooler
Reactor
Switch Condensers/
Desublimation/ Melting
Steam
generator
Vapourizer
Vacuum
Distillation
Fig 5.4 Process flow diagram for the manufacture of phthalic anhydride.
Temperature control is important because the main reaction and the side
reactions are exothermic. The reactor is cooled by recirculating a molten salt on
the outside of the tubes.
About 70% of xylene is converted to PA, 15 % is unconverted, 15% is oxidized
into maleic anhydride while the 1% balance forms a heavy impurity. The maleic
anhydride is formed by the following reaction:
C6H4(CH3)2 + 7.5 O2
The gases from the reactor are cooled before entering a series of three switch
condensers which separates phthalic anhydride from the byproducts. Because of
the low partial pressure of phthalic anhydride in the stream, it desublimates
rather than condenses. Phthalic anhydride collects on the walls of the
condensers as a solid. When the load on the heat transfer surface reaches a
certain level, gas flow is stopped and higher temperature oil is circulated in the
tubes to melt the solid. When one condenser is on desublimation mode, the
134
second is in the melting mode while the third is on standby. Purification of the
product is by vacuum distillation. A purified product with a purity of over 99.5 %
phthalic anhydride is obtained. The product is stored either in a molten state or
bagged as flakes.
5.2.2. Adipic Acid
5.2.2.1. Introduction
Adipic acid, COOH-(CH2)3-COOH, is one of the most important commercially
available aliphatic dicarboxylic acids. The two -COOH groups can yield two kinds
of salts. Typically, it is a white crystalline solid,slightly soluble in water and soluble
in alcohol and acetone.
Its consumption and production is dominated by the United States. Of the 2.3
million metric tons of adipic acid produced worldwide, about 42% is produced in
the United States which also consumes 62% of total production. Western Europe
produces about 40%, Asia-Pacific 13%, while the other regions account for the
remaining 5%.
5.2.2.2. Uses
Adipic acid consumption is linked almost 90% to nylon. Nylon is used for
everyday applications such as electrical connectors, cable tires, fishing lines,
fabrics, carpeting, and many other useful products. Technical grade adipic acid is
used to make plasticizers, unsaturated polyesters for production of rigid and
flexible resins and foams, wire coatings, elastomers, adhesives and lubricants.
Food grade adipic acid is used as a gelling aid, acidulant, leavening and
buffering agent.
5.2.2.3. Production Process
Almost all of the commercial adipic acid is produced from cyclohexane in a
continuous process as shown in Fig. 5.5.
135
C6H11OH + C6H11O
+ zHNO3
High
pressure
Scrubber
Low
pressure
Scrubber
Oxidation
Distillation
Refining
KA
Oxidation
Absorber
136
Drying and
Cooling
Crystallization/
Separation
Concentration
Bleacher
The term polymer comes from two Greek words: polys which means many
and meros which means parts. A polymer is therefore a high molecular weight
compound made up of hundreds or thousands of many identical small basic units
(monomers) of carbon, hydrogen, oxygen or silicon atoms. The monomers are
linked together covalently in a chemical process known as polymerization. This is
illustrated in Fig 5.4.
138
are tougher, more opaque, more resistant to solvents, higher density and sharply
defined melting point.
Glass transition temperature: At low temperature, even amorphous polymers are
hard and brittle (glass-like). As temperature is increased, kinetic energy
increases. However, motion is restricted to short-range vibrations and rotations
as long as glass-like structure is retained. At a certain temperature called the
glass transition temperature, a polymer loses glass-like properties. It becomes
softer and more elastomeric but it does not melt. If heating is continued further,
the polymer will lose elastomeric properties and melt to a flowable liquid.
5.3.4. Types of polymer products
Plastics
A plastic is a material that contains as an essential ingredient, an organic
substance of a large molecular weight, is solid in its finished state, and, at some
stage in its manufacture or in its processing into finished articles, can be shaped
by flow.
In practice, a plastic is usually considered to be an amorphous or crystalline
polymer which is hard and brittle at ordinary temperatures. If crystalline regions
are present, they are randomly oriented.
Thermoplastics
A thermoplastic material is one which can be softened and molded on heating.
They are elastic and flexible above a certain glass transition temperature. Nylon
is a thermoplastic and it was the first commercial polymer to be made as a
substitute for silk for making parachutes, vehicle tires, garments and many other
products. Current uses include: fabrics, footwear, fishnets and carpets to mention
but a few. The two special grades of Nylon are Nylon 6-6 and Nylon 6. Other
thermoplastic materials and their uses are given in Table 5.2
Table 5.2. Uses of various thermoplastic materials
Plastic type
Low density polyethylene (LDPE
Uses
Packaging films, wire and cable
139
houseware
Bottles, drums, pipes, films, sheets,
Polypropylene PP
packaging
Construction, rigid pipes, flooring, wire
Polystyrene
Thermosetting plastics
A thermosetting material is one which involves considerable crosslinking, so that
the finished plastic cannot be made to flow or melt. Thermosetting plastics
(thermosets) are polymer materials that cure or are made strong by addition of
elements (e.g. sulphur) or addition of energy in form of heat (normally above
200oC) through some chemical reaction. Before curing process, they are usually
in liquid form, powder or malleable forms that can be moulded to a final form or
used as adhesives. The curing process transforms these materials into plastic or
rubber through a cross linking process. The cross links produce a three
dimensional rigid structure of the material with large molecular weight and a high
melting point. The three dimensional network of bonds in thermosets generally
makes them much stronger than thermoplastics. This makes them suitable for
high temperature applications up to the decomposition temperature of the
material. A thermoset material cannot be melted and reshaped after forming and
curing and therefore cannot be recycled unlike thermoplastics. Examples of
thermosets include: polyester resin, vulcanized rubber, bakelite and epoxy resin.
Table 5.3. gives uses of various thermosetting plastics.
Table 5.3. Principal thermosetting plastics
Thermosetting plastic
Phenol-formaldehyde (PF)
Uses
Electrical and electronic equipment,
140
binder
Similar to PF, textile treatment, coating
Construction, automobile parts, marine
Epoxy
accessories
Protective coating, adhesives, electrical
and electronics, industrial flooring,
material composites
Similar to UF, decorative panels,
Melamine-formaldehyde (MF)
Nitrile rubber
Butyl rubber
Silicone rubber
Polyurethane rubber
141
Polysulphide rubber
Poly butadiene
Styrene-butadiene
Polyisoprene
Tetrafluoroethylene
Tetrafluoropropylene
Adhesives
The heated glue-pot which traditionally contained glues based on animal
products such as hoof, horn and fish residues has been replaced by adhesives
based on synthetic polymers. There is now a wide range of adhesives and
sealants suited to a variety of tasks from polyvinyl acetate (PVA) wood, board
and paper glues to two-part epoxide resins for rivet-less bonding of metal panels.
Fibres
Animal fibres, such as wool or silk, and vegetable fibres, such as cotton, continue
to be used although there is a wealth of synthetic fibres such as cellulose acetate
and nylon, acrylic and polyester. Carbon fibres for making advanced composites
are produced by heat treatment of polyacrylonitrile and other synthetic fibres.
Films
Animal membranes were the only non-metallic film forming materials used before
the availability of rubber and these found little application. The successful
development of a drum for casting films from viscose led in the 1920s to the
production of 'Cellophane'- still a widely used material. In the 1930s, unsupported
PVC films were manufactured but it was not until polyethylene was available in
the 1940s that the production of films for bagging materials became
commonplace.
142
Surface finishes
The paint industry was traditionally based on naturally occurring 'drying' oils such
as linseed but since the 1930s these have gradually been replaced by synthetic
polymers. Because of toxicity problems from using paints based on solvents,
many more finishes are now water-based polymer emulsions.
5.3.5. Polyethylene
5.3.5.1. Introduction
There are three major classes of polyethylene. These are low density
polyethylene (LDPE), high density polyethylene (HDPE) and linear low density
polyethylene (LLDPE). Pellets of these plastics are extruded and blown to
produce film. This film is used for packaging and making plastic bags.
Ethylene is derived from either modifying natural gas (a methane, ethane,
propane mix) or from the catalytic cracking of crude oil. In a highly purified form,
it is piped directly from the refinery to a separate polymerization plant. Here,
under the right conditions of temperature, pressure and catalysis, the double
bond of the ethylene monomer opens up and many monomers link up to form
polyethylene. In commercial polyethylene, the number of monomer repeat units
ranges from 1000 to 10 000. Molecular weight ranges from 28,000 to 28,0000.
5.3.5.2.The Polyethylene Manufacturing Process
Today, polyethylene manufacturing processes are usually categorized into "high
pressure" and "low pressure" operations. The former is generally recognized as
producing conventional low density polyethylene (LDPE) while the latter makes
high density (HDPE) and linear low density (LLDPE) polyethylenes. The
difference between these polyethylene processes and types is outlined below.
High pressure
Polyethylene was first produced by the high pressure process by ICI, Britain, in
the 1930's. They discovered that ethylene gas could be converted into a white
solid by heating it at very high pressures in the presence of minute quantities of
oxygen:
143
polyethylene
80 - 300 oC
Reactor
High
pressure
Separator
Low
pressure
Separator
Secondary
Compressor
Extruder /
Pelletizer
Primary
Compressor
Fig. 5.5 High pressure process for the manufacture of polyethylene (LDPE)
Low pressure
The initial discovery of LDPE was an accident. So was the discovery of HDPE in
1952. Researchers in Germany and Italy had succeeded in making a new
aluminium based catalyst which permitted the polymerization of ethylene at much
lower pressures than the ICI process:
Ethylene
10 - 80 bar
polyethylene
stiffness and density were found to be due to a much lower level of chain
144
branching. The new HDPE was found to be composed of very straight chains of
ethylene with a much narrower distribution of molecular weights (or chain
lengths) and a potentially very high average chain length.
In the late 1950's, DuPont Canada first applied the low pressure process to the
production of LLDPE. LLDPE is made by copolymerizing of ethylene with a small
amount of another monomer, typically butene, hexene or octene.
The most common method used in industry is to polymerize ethylene by means
of a fluidized reactor bed. A fluidized reactor bed consists of metallic catalyst
particles that are 'fluidized' by the flow of ethylene gas. This means that the
catalyst particles are suspended in the ethylene fluid as ethylene gas is pumped
from the bottom of the reactor bed to the top.
Before the late 1970's an organic peroxide catalyst was employed to initiate
polymerization. However, because the organic peroxide catalyst is not as active
as the metallic catalyst, pressures in excess of 100 times the pressure required
with metallic catalysts were necessary.
Before ethylene is sent to the fluidized bed, it must first be compressed and
heated. Pressures in the range of 100-300 pounds per square inch (psi) and a
temperature of 100 oC are necessary for the reaction to proceed at a reasonable
rate. The catalyst is also pumped with the ethylene stream into the reactor. This
is because polyethylene molecules remain stuck to the catalyst particle from
which they were produced thus incorporating the catalyst within the polyethylene
product. Hence the need to replenish the consumed catalyst
The conversion of ethylene is low for a single pass through the reactor and it is
necessary to recycle the unreacted ethylene. Unreacted ethylene gas is removed
off the top of the reactor. After purification, ethylene gas is then recompressed
and recycled back into the reactor. Granular polyethylene is gradually removed
from the bottom of the reactor as soon as reasonable conversions have been
achieved. Typically, a residence time of 3 to 5 hours results in a 97% conversion
of ethylene.
Polyethylene comes out of the reactor as granular powder, which is then melted
and flows through a film extruder.
145
Compressor
Fluid bed
reactor
Compressor
Separator
Extruder
146
5.3.6.2. Uses
SBR is widely used for rubber belting, hose, flooring, molded goods, rubber
soles, coated fabrics etc. It is compatible with natural rubber and has equal
performance for automobile tyres. But it is inferior to natural rubber for heavy
duty truck tyres.
5.3.6.3. Manufacturing Process
SBR is produced by the copolymerization of butadiene with styrene in the
approximate proportion of 3:1 by weight.
In the emulsion process, which produces general purpose grades, the
feedstocks are suspended in a large proportion of water in the presence of an
initiator or a catalyst and a stabiliser. A continuous process is employed.
In the solution process, the copolymerisation proceeds in a hydrocarbon solution
in the presence of an organometallic complex. This can be either a continuous or
batch process.
The emulsion polymerization process has several advantages. It is normally used
under mild reaction conditions that are tolerant to water and requires only the
absence of oxygen.
147
Fe(III)EDTA + SFS
Fe(II)EDTA
148
P-H + RS.
RS. + M
RS-M.
Parts by Weight
Cold
HOT
Styrene
25
25
Butadiene
75
70
Water
180
180
Dodecyl mercaptan
0.2
0.8
Cumene hydroperoxide
0.17
FeSO4
0.017
EDTA
0.06
Na4P2O7.10H2O
1.5
Potassuim persulfate
0.3
SFS
0.1
Stabilizer
varies
stripping the latex in a column. The latex is then stabilized with the appropriate
antioxidant and transferred to blend tanks. In the case of oil-extended polymers
or carbon black masterbatches, these materials are added as dispersions to the
stripped latex. The latex is then transferred to finishing lines to be coagulated
with sulfuric acid, sulfuric acid/sodium chloride, glue/sulfuric acid, aluminum
sulfate, or amine coagulation aid. The type of coagulation system is selected
depending on the end-use of the product. Sulfuric acid/sodium chloride is used
for general purpose. Glue/sulfuric acid is used for electrical grade and low water
sensitivity SBR. Sulfuric acid is used for coagulations where low-ash-polymer is
required. Amine coagulating aids are used to improve coagulation efficiency and
reduce production plant pollution. The coagulated crumb is then washed,
dewatered, dried, baled and packaged.
Formative
Evaluation
1. From what you have read about crude oil and natural, what is the
composition of
(i)
Crude oil
(ii)
(iii)
LPG?
2. Explain how petroleum refining has evolved over the years as product
specifications changed.
3. Why is sulphur undesirable in fuel and how is it removed by
hydrodesulphurisation?
4. Write short notes on
(i)
cracking
(ii)
reforming
150
(ii)
6. Write all the equations using the structural formula of the main raw
materials and products for the main reactions that take place during the
manufacture of phthalic anydride and adipic acid.
7. Name 10 materials that you use daily which are made of synthetic organic
polymers
8. Vinyl chloride undergoes copolymerization with 1,1-dichloroethylene
to
151
INDUSTRIES,
PHARMACEUTICALS,
SOAPS
AND
DETERGENTS
At the end of this unit you should be able to:
a. Discuss factors that affect the viability of the fermentation route and
those that affect fermentation yield
b. Describe the process of manufacuring fermentation ethanol
c. Give a brief history of the pharmaceutical industry and the role played
by antibiotics
d. Describe production processes of two pharmaceuticals: penicilin and
aspirin
e. Outline the soap manufacturing process
f. Discuss the various types of surfactants
g. Explain how detergents are manufactured
Summary of Learning Activity
In this unit, you will learn how microorganisms under certain optimum conditions
are exploited commercially to produce chemical products. You will learn about
the production of ethanol and pencillin by fermentation followed by purification of
the producs by distillation and solvent extraction respectively. You will also learn
how aspirin is produced synthetically. The study of soaps and detergents is
covered in the last section of this unit.
List of relevant reading
1. George T. A. (1977). Shreves Chemical Process Industries. 5 th edn.
McGraw-Hill
International
Edition.
Chemical
Engineering
Series.
Singapore.
2. Stephenson R.M. (1966). Introduction to the Chemical Process Industries,
Reinhold Publishing Corporation, New York
152
Computer with internet facility to access links and relevant copywrite free
resources
153
Micro-organisms
154
First, it is important to appreciate that conditions that achieve maximum cell mass
may not necessarily be those that give maximum yield of some product of
metabolism. It may sometimes be necessary to semi-starve the micro-organisms
to obtain optimum yield of products. However, it is necessary to grow sufficient
cell mass to catalyze the fermentation process.
In most fermentations, the following are the factors that affect product yield.
Inoculum amount, i.e., the initial amount of cells fed into the fermenter,
will determine whether the cells are sufficient or not to fuel production.
mesophilic.
Those
that
grow
better
at
higher
temperatures
Micro-organisms vary in their need for oxygen. Fungi, algae and a few
bacteria are aerobic while a few bacteria are anaerobic. For those which
are aerobic, a too low oxygen level leads to poisoning of fermentation
while too high oxygen content causes excessive growth of microorganisms at the expense of the product. The level of nutrients in the
substrate may not be sufficient to give a fast fermentation rate. Nutrients
include energy sources such as starch or sugar. The cell mass is 50%
carbon, therefore, carbon sources such as starch, sugar and carbon
dioxide are required. The cell mass also contains 10% nitrogen. Nitrogen
sources include ammonia, ammonium salts such as diammonium
phosphate (DAP), amino acids and vitamins. Minerals including
phosphorus, potassium, sulphur, magnesium, traces of iron, copper,
cobalt, manganese, zinc and molybdenum are added as water-soluble
salts.
156
157
The seed tanks are equipped with mixers, which keep the growth medium
moving, and a pump to deliver sterilized, filtered air. After about 24-28 hours, the
material in the seed tanks is transferred to the primary fermentation tanks.
Fermentation
The fermentation tank is essentially a larger version of the steel, seed tank. It is
filled with the same growth media found in the seed tank and also provides an
environment conducive to growth. Here the microorganisms are allowed to grow
and multiply. During this process, they excrete large quantities of the desired
product. The tanks are cooled to maintain the right temperature. The
fermentation tank is constantly agitated, and a continuous stream of sterilized air
is pumped into it. Anti-foaming agents are periodically added to inhibit foaming.
Acids or bases are added to control pH to the level which is optimal for the
growth of the microorganism.
The fermenter is the heart of any fermentation process. The design of
fermentation equipment and the operation of the fermentation process must
ensure the process is contamination free, and in the case of pathogens, they
must be contained with high degree of safety. Most production fermenters are
made of stainless steel construction with impellers for good bulk liquid mixing
characteristics to ensure homogeneity within the vessel. Air is sparged into the
vessel below the bottom impeller. Fermenters produce heat through dispersion of
kinetic energy and metabolism, therefore the vessel must have a cooling system.
Aseptic operation at prolonged time periods demands that pipelines transporting
sterile air, seed and other materials required for the fermentation be sterilized by
exposure to steam, usually at 120oC for 20 to 30 minutes. Below is a schematic
diagram of a typical fermenter.
158
inside the cells and are not released or are only partially released to the medium.
It may be possible or necessary to wash the cells to remove impurities before
breaking them to get the product. Some cells have high resistance to shear and
require specialized equipment to rupture them. Ultrasonic vibrations, grinding in
mills and high pressure can be used to rupture cells.
Centrifuges and rotary-drum filtering are commonly used in the separation of the
cells from the broth. Products in the broth may be recovered by a variety of unit
operations among them distillation, extraction with salts and solvents, membrane
ultra filtration, precipitation and chromatography.
159
C6H12O6 + C6H12O6
glucose
fructose
yeast
2C2H5OH + 2CO2
160
Several viable yeast strains exist but the most commonly used strain is
saccharomyces cerevesie. These yeasts produce enzymes that catalyze the
reaction that converts substrate into energy for the yeast and ethanol. During
reproduction, the fermentation yeast produces enough enzymes needed for the
alcoholic fermentation. These enzymes will continue fermenting far beyond the
yeasts need for energy and even long after reproduction has stopped. This is
the fact that is exploited industrially.
6.2.3. Production Process Using Starch Raw Materials
Enzymatic hydrolysis of carbohydrates
Ground raw material is heated to about 55 oC. Starch liquefying enzymes which
are either bacterial or fungal -amylase, are added. The starch is then heated to
about 95oC. When starch is heated, viscosity increases drastically due to
gelatinisation. The enzymes assisted by mechanical agitation attack the
gelatinized long starch molecules forming water-soluble dextrins. This results into
an instant fall in viscosity. This process is called liquefaction or hydrolysis.
The dextrin mash is then diluted with water and cooled to 55 oC. A second
enzyme, glucoamylase is added to hydrolyse dextrins into glucose.
Fermentation
Fermentation can be carried out either batch or continuously.
Batch fermentation is the simplest and most commonly used especially for small
alcohol plants.The yeast inoculum is prepared in a 10-20% solution in sterilized
water and added to the mixture of substrate and nutrients in the fermentation
vessel. After addition of the inoculum, the yeast cells constitute about 2 to 4% by
weight in the fermentation mash. The inoculum size greatly affects fermentation
time.
161
Fermentation conditions
Yeast metabolism is inhibited by a concentration of sugar higher than 20%.
Typical substrate concentrations are in the range of 10-14%w/v. Some of the raw
materials used, namely barley, wheat, rye and molasses have enough nutrients
to give efficient fermentation. But small amounts of nutrient sources such as
ammonium phosphate, ammonium sulphate or urea are added such that nitrogen
content is about 0.6g/l of the fermentation mash.
For most yeasts, activity is highest at 29-32 oC.
fermentation and cooling coils and jackets are installed in the most conventional
fermentation equipment. The temperature range between 29 and 32 oC is ideal
for yeast growth. The principal microbial contaminants in a distillery are lactic
acid formers whose development is severely suppressed at pH values below 5.
The pH is normally adjusted at 4.8 to 5 with sulphuric acid or the acidic media. If
starch raw materials are used and dextrinization is not complete, the -amylase
may be inactivated at pH values below 4.
Lack of enough oxygen reduces the viability of the yeast.
162
Rectifyi
ng
column
Beer
column
163
In the ancient times a large part of medicinal products used were natural
products mostly derived from plants. In subsequent centuries, it was agreed that
such products must be pure for effective utilization as pharmaceutical products.
Pharmaceuticals
are
produced
either
synthetically
or
biosynthetically.
Fermentation has long been used to manufacture most of the important drug
classes such as antibiotics, vitamins and hormones. Micro-organisms growing
under
controlled
fermentation
conditions
perform
complex
chemical
164
6.3.2. Antibiotics
Antibiotics are chemical substances that can inhibit the growth of, and even
destroy, harmful microorganisms. They are derived from special microorganisms
or other living systems, and are produced on an industrial scale using a
fermentation process.
The great medical advantage of antibiotics in healing infections is that the
purified forms of antibiotics are more or less harmless to most humans. This
means that they must act on some aspect of the growth of micro-organisms
which differs from ordinary mammalian cells. Antibiotics are either bactericidal or
bacteriostatic. They kill bacteria or inhibit bacterial growth respectively.
Antibiotics work by stopping bacterial enzymes that control cell-wall creation and
activating other enzymes that break apart the bacterium's defenses. Without the
protection of the outer wall the bacteria die due to osmotic damage.
Antibiotics differ chemically so it is understandable that they also differ in the
types of infections they cure and the ways in which they cure them. Certain
antibiotics destroy bacteria by affecting the structure of their cells. This can occur
in one of two ways. First, the antibiotic can weaken the cell walls of the infectious
bacteria, which causes them to burst. Second, antibiotics can cause the contents
of the bacterial cells to leak out by damaging the cell membranes. Another way in
which antibiotics function is by interfering with the bacteria's metabolism. Some
antibiotics such as tetracycline and erythromycin interfere with protein synthesis.
Still other antibiotics, such as sulfonamide or trimethoprim have a general
blocking effect on cell metabolism.
The development and use of antibiotics have had a tremendous impact on
human health. Tuberculosis, caused by Mycobacterium tuberculosis was a
serious disease until the advent of streptomycin. Syphilis and bacterial dysentery
are now only encountered rarely. Average life expectancy in the world has
increased due to antibiotics. Infant mortality has dropped. In addition to these
and other medical benefits, antibiotics help to stabilise food supply by controlling
animal, fish and plant diseases therefore leading to higher agricultural
productivity.
165
166
In addition to its high order of activity, penicillin is nontoxic. Its main bad feature is
that about 5% of those receiving the drug suffer from some degree of allergic
response.
All penicillin type antibiotics operate by inhibiting the production of cell walls by
bacteria, which therefore prevents growth. It is now known that penicillin has a
bactericidal rather than a bacteriostatic action, i.e. it kills the bacteria, rather
than merely inhibiting their growth, as some antibiotics do. The bacteria may die
due to osmotic damage because they are not protected by their outer wall.
Various other antibiotics have also been developed with different modes of
action, e.g. interfering with bacterial protein synthesis.
Penicillin is a generic name referring to a class of compounds with the formula
shown below.
is the one in greatest demand by the medical profession. Its main flaw is that it
tends to break down very easily in acid. It therefore must be administered
by intramuscular injection. The potassium salt is the most commercially available
form of penicillin G.
The second form of penicillin is known as semi synthetic penicillin. Most fungi
that produce penicillin can easily incorporate a variety of compounds into the acyl
portion of the penicillin molecule. The synthesized compounds must have the
initial beneficial traits of Penicillin G along with additional advantages such as
acid stability (allowing for oral ingestion), lowered allergenicity and greater
resistance to penicillinase.
6.4.2. Penicillin Production Process
Spores of P. chrysogenum are used to inoculate 100ml of growth medium in a
500ml shake flask. After 4 days incubation, the contents are transferred to growth
medium in a 500L reactor. After three days incubation, this culture is used to
inoculate a 180m3 reactor. Final Fermentation at about pH 6.5 and 23-28 oC is
completed in 5-6 days. With good microorganism strains, about 10% of the
carbon in the glucose finds its way into penicillin G whose final concentration
may reach almost 30g/L.
Filtration
The broth contains 20-35g/L of penicillin. It is pumped to a reservoir tank from
where it is fed to a continuous rotary vacuum filter which may use filter aids to
form a precoat. The mycelium is separated from the liquor and washed on the
filter. It is discharged from the filter as a thick blanket (cake) resembling paper
pulp. The penicillin-rich filtrate is chilled to 2-4 oC to minimize chemical and
enzyme degradation during solvent extraction. This operation is necessary since
filtration process is not sterile. Growth of bacteria should not be allowed to build
in the filtration process because this can result in severe destruction of penicillin
by the action of bacterial penicillinases. Therefore, the filter is usually sterilized
between runs with steam or germicidal solutions.
168
169
170
6.6.2. Properties
Aspirin is an acetyl derivative of salicylic acid. It is a white, crystalline, weakly
acidic substance, with a melting point of 135C. Acetylsalicylic acid decomposes
rapidly in solutions of ammonium acetate or of the acetates, carbonates, citrates
or hydroxides of the alkali metals. Acetylsalicylic acid is stable in dry air, but
gradually hydrolyses in contact with moisture to acetic and salicylic acids. In
solution with alkalis, the hydrolysis proceeds rapidly and the clear solutions
formed may consist entirely of acetate and salicylate. Formulations containing
high concentrations of aspirin often smell like vinegar. This is because aspirin
can decompose in moist conditions, yielding salicylic acid and acetic acid. The
acid dissociation constant (pKa) for acetylsalicylic acid is 3.5 at 25 C.
6.6.3. Manufacture
The synthesis of aspirin is classified as an esterification reaction, where the
alcohol group from the salicylic acid reacts with an acid derivative (acetic
171
anhydride), yielding methyl acetyl ester and acetic acid as a byproduct. Small
amounts of sulfuric acid are often used as a catalyst.
The manufacture follows carboxylation reaction by the Schmitt modification of the
Kolbe reaction as shown. The salicylic acid is refluxed with acetic anhydride in
toluene at about 900C for 20 hours. The reaction mixture is then cooled and the
acetylsalicylic acid precipitates out as large crystals. The crystals are separated
either by filtration or by centrifuging, then washed thoroughly and dried.
172
Soap is integral to our society today. However, the current widespread use of
soap is only a very recent occurrence, despite the fact that it has been made for
more than 2500 years.
Soaps and detergents contain a surfactant1 as their active ingredient. This is a
compound consisting of a long, linear, non-polar (hydrophobic)tail with a polar
(hydrophilic) head. The tail is water insoluble and the head is water-soluble. This
difference in solubility has two important implications. Firstly, this makes the
surfactant molecule a wetting agent. The tails migrate to align themselves with
the solid-water interface, thus lowering the surface tension at that point so that
the surfactant penetrates the fabric better. Secondly, it allows the oily dirt
particles to form an emulsion with the water. The tails of many surfactant
molecules surround an oily dirt particle, forming a micelle with the oil in the centre
and the ionic heads of the surfactant molecules pointing outwards and hence
keeping the micelle in the polar solution.
Surfactants perform other important functions in cleaning, such as loosening,
emulsifying (dispersing in water) and holding soil in suspension until it can be
rinsed away. Surfactants can also provide alkalinity, which is useful in removing
acidic soils.
Animal fats and plant oils contain compounds known as fatty acids. These fatty
acids are bound to glycerol to form triglycerides. In the presence of a strong base
such as sodium hydroxide, the triglycerides breakdown to form the metal salt of
the fatty acid. This reaction which is shown below is called saponification which
literally means the making of soap.
The main sources of fats are beef and mutton tallow, while palm and coconut oils
are the principal oils used in soap making.
173
2+
insoluble in water. When these cations are present in water e.g. in seawater or
hard water, they displace Na (or K) from the soap and form their own salts which
are insoluble in water, hence precipitates. Examples are scum and linings in
bathtubs, discolouration and hardening of fabrics. This precipitate reduces the
emulsifying action of soap and more soap is consumed.
Soap has retained its dominance as the active surfactant ingredient in toilet soap.
The main reasons are:
1) lower cost of soap in comparison with synthetic detergents.
2) difficulties of producing bars of synthetic detergents.
3) greater degreasing and wetting power of synthetic detergents that can be
harmful to the skin.
6.7.2. Batch process for soap manufacture
Step 1 - Oil preparation
The mostly commonly used oils are tallow and coconut oil. These are blended
together and dried in a vacuum chamber. Once the oils are dry, bleaching earth
is added to remove any coloured impurities. After removing the bleaching earth
by filtration, the oils are stored ready for saponification.
Step 2 - Saponification
The mixture of bleached oils is mixed with recycled spent lye from the washing
stage downstream and fresh caustic soda solution. The mixture is boiled for
several hours after which it settles into two layers with the mixture of soap and
unreacted oils at the top. The bottom layer i.e. the lye which contains glycerine is
pumped off. More caustic liquor is added to this and the mixture reheated to
saponify the remaining free oils.
174
Step 3 - Washing
The crude soap is washed with a mixture of fresh caustic solution and nigre lye
(see below). The washed soap is sent to the fitting pans, while the lye is used in
the next saponicaion.
Step 4 - Fitting
Here the remaining unwanted glycerine is removed from the soap by reboiling
with water, NaCl and a small amount of NaOH solution. The electrolyte
concentration in the water is such that the soap and water separates out into two
layers. The top layer is neat wet soap, which is pumped off to be dried. The
bottom layer is known as the nigre layer, and consists of a solution of soap,
glycerine and NaCl. This is left in the pan, reboiled with further salt and left to
stand, forming a soap crust over a lower layer of nigre lye (salt and glycerine).
This soap is left in the pan and is mixed with the next batch of washed soap,
while the nigre lye is used to wash the next batch of crude soap.
Step 6 - Drying
Finally, the water level is reduced down to about 12% by heating the soap to
about 125 oC under pressure and then spraying it into a flash tank at vacuum
pressure of about 40 mm Hg (5.3 kPa). Some of the liquid vapourizes into a
vapor which is condensed in a barometric condenser. The latent heat of
evaporation lost as the water boils off reduces the soap temperature down to 45
o
The soap chips are scraped off the walls and formed into soap noodles in an
equipment known as plodder. The soap is now known as base or neat soap, and
can be converted into a variety of different soaps in the finishing stages.
In the final processing step, the dry soap pellets pass through a bar soap
finishing line. The first unit in the line is a mixer, called an amalgamator, in which
the soap pellets are blended together with fragrance, colorants and all other
ingredients. The mixture is then homogenized and refined through rolling mills
and refining plodders to achieve thorough blending and a uniform texture. Finally,
the mixture is continuously extruded from the plodder, cut into bar-size units and
stamped into its final shape in a soap press.
175
176
This precipitate is filtered out and then excess ferrous chloride removed with
caustic:
2NaOH + FeCl2 Fe(OH)2 (s) + 2NaCl
This is filtered out, leaving a soap-free lye solution.
Step 2 - Salt removal
Water is removed from the lye in a vacuum evaporator, causing the salt to
crystallise out as the solution becomes supersaturated. This is removed in a
centrifuge, dissolved in hot water and stored for use as fresh lye. When the
glycerine content of the solution reaches 80 - 85% it is pumped to the crude
settling tank where more salt separates out.
Step 3 - Glycerine purification
A small amount of caustic soda is added to the crude glycerine and the solution
then distilled under vacuum in a heated still. Two fractions are taken off - one of
pure glycerine and one of glycerine and water. The glycerine thus extracted is
bleached with carbon black then transferred to drums for sale, while the
water/glycerine fraction is mixed with the incoming spent lye. This repeats the
treatment cycle.
6.7.6. Disadvantages of soap
Although soap is an excellent detergents and 100% bidegradable, it has two
main disadvantages:
1. Soap forms an insoluble precipitate when hard water is used. Hard water
contains dissolved minerals such as calcium and magnesium which react
with soap to form insoluble calcium and magnesium soaps. This results in
soap wastage as well as the soiling of laundry by the sticky precipitate.
2. Soap cannot be used in acidic solutions such as used during textile
processing. Strong acids will react with soap to precipitate fatty acids
177
which adhere to the fabric and even prevent the application of dyestuffs.
6.8. Detergents
6.8.1. Historical Development of Detergents
In the early 1930s both the alcohol sulphates and the alkyl aryl sulphonates were
the main cleaning materials. The alkyl portion of the sulphonate was from a
kerosene fraction hence referred to as keryl benzene sulphonate. At the end of
the Second World War alkyl aryl sulphonates dominated in general cleaning
materials while the alcohol sulphates found wide application in the shampoo field.
The use of alkyl benzene sulphonate grew rapidly because of their ease of
manufacture. The existing keryl benzene was quickly replaced by an alkyl
benzene made from propylene tetramer coupled to benzene (PT benzene). In a
short span of time, more than half the detergents used throughout the world were
based on PT benzene. The rapid rise in synthetic detergents saw the decline of
soap consumption to a constant level.
6.8.2. Detergency improvement
When detergents started appearing in appreciable quantities on the retail market,
it was noted that white cotton articles were not being washed as white as they
should be. Although the active material was able to lift the dirt from the cloth it
could not keep it in suspension. Hence small spots of dirt were being redeposited
uniformly over the whole surface area of the cloth thus giving the cloth a grey
appearance.
Use of the sodium salt of carboxymethylcellulose (CMC) as an additive to
synthetic detergent powders was found to eliminate the redeposition problem.
To improve the heavy-duty washing properties, manufacturers started to build
their products with alkaline materials such as carbonates, silicates, borax, and
orthophosphates. All of these singly and in combination were tried with moderate
success. Heavy-duty detergent formulations were introduced, initially with tetra
sodium pyrophosphate and then with sodium tripolyphosphate with startling
178
success. With the advent of CMC and tripolyphosphate builders the detergent
industry established itself.
Enzymes, which can be called organic catalysts, tend to hasten reactions and
the proteolytic enzymes convert or 'break down' proteins wholly or partially into
amino acids. They were initially added together with a proportion of amylase
which breaks down starches, to 'pre-soak' detergents. Better and better strains of
enzymes were developed, with stability to a wider pH spectrum, stability against
perborate and quicker action. Today enzymatic powders are now holding a large
proportion of the household detergent. Some washing-machine manufacturers
produce automatic washing machines with a 'Bio' programme which allows the
washing to remain in contact with the detergent solution for an extended period
of time at a relatively low temperature before beginning the washing and heating
cycle. Safety and health concerns cause some enzymes to be excluded in some
detergent formulations.
6.8.3. Detergent Raw materials
A detergent is a formulated product which is specially designed to promote
the cleaning action. Each individual component in the formulation has its own
specific functions in the washing process but it can also produce synergistic
effect with other components. Some components are added to aid or improve
efficiency of the production process while others are added to improve the
appearance and odour of the product. The major components can be categorized
into:
Surfactants
Builders
Bleaching agents
Surfactants
A surfactant ( surface active agent) is a compound with a water-soluble oilinsoluble (hydrophilic) portion on one side and an oil-soluble water-insoluble
(hydrophobic) portion on the opposite side. Generally, the hydrophobic portion is
179
180
surfactants
biodegradeable.
in
terms of tonnage
readily
as in toilet soaps. They are chemically stable on the alkaline side and are easily
hydrolysed on the acid side. They are incorporated in spray-dried formulations.
They can be converted to the ammonium or sodium salts.
Alkyl ether sulphates are obtained by ethoxylation of natural and synthetic
alcohols. The optimal carbon chain length is C 12-C14 with about 2 moles ethylene
oxide. They are highly foaming and have low sensitivity to water hardness. They
also have high solubility and good storage stability at low temperatures in liquid
formulations. They are preferred for easy care and wool detergents as well as
dishwashing liquids, hair shampoos and foam baths.
Nonionics
The most widely used nonionic detergents include:
Alkyl polyglycol ethers (AEO): Ethylene oxide reacts with any compound having
reactive hydrogen atoms. This reaction is called ethoxylation. The polyglycol
ethers of straight chain alcohols i.e. RO(CH 2CH2O)nH are presently becoming
the most important surfactants because of their improved biodegradability,
replacing the older polyglycol ethers based on nonylphenol polyethylene glycol.
Most of these non-ionics are viscous liquids or soft pastes. Aqueous solutions
exhibit an inverse solubility behaviour i.e. the solubility decreases with increasing
temperature. The temperature at which dilute aqueous solutions clouds up
because of insolubility of the surfactant is referred to as the cloud point.
Alkylolamides of fatty acids: These surfactants have the structure RCON(CH 2
CHOH)2
(diethanolethamide)
and
RCONHCH2CHOH
(monoethanolamide).
181
Cationics
Since the surfactant molecules bears a positive charge, their adsorption reduces
the negative zeta-potential of solids present in aqueous solutions. They therefore
reduce mutual repulsions including that between soil and fibres. Excess use
causes charge reversal with adverse effect. They are not used for the sole
purpose of soil removal because charge reversal in the direction of negative
zeta-potential occurs during rinsing causing previously remove soil to be
attracted to the fibres. They are used for special effects for example as antistatic
agents, fabric softening and as microbicides.
Quaternary ammonium compounds (QAC) RRN(CH3)2Cl are among the most
widely used cationic detergents. QAC RHN(CH 3)2Cl having a single long aliphalic
chain possess bacteriological properties. Quaternary ammonium compounds
such as dialkyldimethyl ammonium chloride possessing two aliphatic chains are
used as textile softeners for both household and industrial use.
Since cationics display behaviour opposite to that of anionics, the two are
incompatible. They are incompatible with anionic antibacterial agents like
hexachlorophene but are compatible with cationic germicides such as mercurials.
Nonionic surfactants are more tolerant of cationics than anionics.
Amphoterics
These surfactants possess both anionic and cationic groups in the same
molecule. Amphoterics show the properties of anionics at high pH and those of
cationics at low pH. They are therefore compatible with either cationic or anionic
surfactants. They are used to overcome problems associated with high
electrolyte levels and corrosion. They also have other interesting properties such
as:
1. excellent foaming and lime soap dispersing properties.
2. antistatic properties
3. textile softening
They include dicarboxylic acids such as RN(CH2 COOH). Alkyl aminopropionic
acids have antistatic and hair softening properties.
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N-Alkylbetains RN+ (CH3)2 CH2COO-. These are rarely used because they are
expensive.
Builders
These are used to support detergent action and to deal with the problem of water
hardness caused by the presence of calcium and magnesium ions. They include
alkalis, complexing agents and ion exchangers.
Bleaching agents
Bleaches increase the reflectance of visible light at the expense of absorption. It
involves the removal or change of dyes and soil by mechanical and/or physical
means. Hydrogen peroxide is the main bleaching agent. Sodium perborate
NaBO3 is incorporated in detergents as a source of hydrogen peroxide.
6.8.4. Powder Detergent Manufacture
Powder detergents are produced by spray drying, agglomeration, dry mixing or
combinations of these methods.
In the spray drying process, dry and liquid ingredients are first combined into a
slurry, or thick suspension, in a tank. The slurry is heated and then pumped to the
top of a tower where it is sprayed through nozzles under high pressure to
produce small droplets. The droplets fall through a current of hot air, forming
hollow granules as they dry. The dried granules are collected from the bottom of
the spray drier where they are screened to achieve a relatively uniform size.
After the granules have been cooled, heat sensitive ingredients such as bleach,
enzymes and fragrance that cannot withstand the high temperatures in the spray
drier are added. Traditional spray drying produces relatively low density powders.
New technology has enabled the soap and detergent industry to reduce the air
inside the granules during spray drying to achieve higher densities. The higher
density powders can be packed in much smaller packages than were needed
previously.
Agglomeration, which leads to higher density powders, consists of blending dry
raw materials with liquid ingredients. Helped by the presence of a liquid binder,
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rolling or shear mixing causes the ingredients to collide and adhere to each other,
forming larger particles.
Dry mixing or dry blending is used to blend dry raw materials. Small quantities of
liquids may also be added.
6.8.4. Detergent manufacture by the spray drying
Step 1 - Slurry making
The solid and liquid raw ingredients are fed into a large tank known as a slurry
mixer or clutcher. As the ingredients are added the mixture heats up as a result of
two exothermic reactions: the hydration of sodium tripolyphosphate and the
reaction between caustic soda and linear alkylbenzenesulphonic acid. The
mixture is then further heated to about 85 oC and stirred until it forms a
homogeneous slurry.
Step 2 - Spray drying
The slurry is deaerated in a vacuum chamber and then separated by an atomiser
into finely divided droplets. These are sprayed into a column of air at about
425oC, which dries them instantaneously. The resultant powder is known as
base powder from which other products are made. The ingredients normally
found in base powder and their functions are shown in Table 6.1.
Step 3 Post dosing
Other ingredients are now added, and the air blown through the mixture in a
fluidiser to mix them into a homogeneous powder.
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Ingredients
Sodium tripolyphsophate (STP)
Function
Water softener, pH buffer (to reduce
Sodium sulphate
Soap noodles
alkalinity).
Bulking and free-flowing agent
Causes rapid foam collapse during
Zeolite
rinsing
Water softener (absorbs Ca2+ and Mg2+)
in countries where STP is not used;
granulating
agent
for
concentrated
detergents
Increases the negative charge on
cellulosic fibres such as cotton and
rayon, causing them to repel dirt
particles (which are positively charged)
Table 6.2 Some Laundry liquid detergents ingredients and their functions
Linear alkylbenzene sulphonic acid
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(LAS)
Caustic soda solution
Neutralizes the LAS
Coconut diethanolamide or a fatty Nonionic detergent and foam former
alcohol ethoxylate:
Absorbs UV light and emits blue light,
Fluorescer
Water
ingredients,
(usually
sodium
NaBO3)
breaks
down
at
high
activator
(e.g. Catalyses
tetraacetylethylenediamine)
Enzymes (e.g. alkaline protease)
sodium
perborate
product.
Protects product from microbial attack
6.8.6. Packaging
Detergents, including household cleaners, are packaged in cartons, bottles,
pouches, bags or cans. The packaging materials and containers are selected on
the basis of product compatibility and stability, cost, package safety, solid waste
impact, shelf appeal and ease of use.
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rancidity.
Formulations
are
also
constantly
checked
for
cost
effectiveness, and soaps are frequently reformulated for cost and supplier
considerations. When a new formula has been agreed the laboratory will lay
down the specifications that the finished soap and its intermediary stages must
meet. These could be colour, odour, moisture or electrolyte concentrations, or the
concentrations of impurities or additives. These specifications are also constantly
being revised as the production equipment is improved, or consumer demands
change.
The laboratory lays down all the specifications for raw materials to be purchased
against. These specifications become the basis for the supplier to quote against.
The materials are constantly tested against these specifications, either on a
shipment basis or suppliers batch size. In some cases the manufacturing plant is
inspected and approved, and if the supplier can validate their process, then the
need for many routine or expensive tests can be reduced or eliminated.
In most cases quality testing is performed at the process, by the process
operators. The laboratory hold samples of every batch of finished goods for some
months, so that if there are any consumer complaints, an original sample can be
tested against the defect sample to determine the cause of the complaint.
Tests carried out on some particular products are listed below.
Batch process soap
The incoming tallow and coconut oil are tested for colour (after bleaching) and
free fatty acid content. The neat liquid soap is tested for free alkali, salt content
and glycerol content, while the soap chips are tested for moisture and fatty acid
content.
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Detergent powder
The laboratory tests for the concentrations of active detergent, sodium
tripolyphosphate, moisture, soda ash, enzymes and bleach, and monitors
physical properties such as dynamic flow rate, compressibility, particle size,
colour and perfume.
Liquid detergent
The product is typically tested for viscosity, pH, cationic detergent (fabric
conditioner) content, enzyme content, conductivity (a measure of detergent
stability), colour and perfume.
Environmental Issues
Propylene tetramer (PT) benzene sulphonate held almost undisputed sway as
the major ingredient used in washing operations till the early 1960s. Around this
time it was noted, however, that sewage treatment problems were arising. The
amount of foam on rivers was increasing and where water was being drawn from
wells located close to household discharge points, the water tended to foam
when coming out of the tap. This was attributed to the fact that propylene-based
alkyl benzene sulphonates are not completely degraded by the bacteria naturally
present in effluents. It was found out that it was the branched-chain formation of
the alkyl benzene which hinders the attack by the bacteria. It was proved that
linear alkyl benzene is biodegradable. Several countries introduced legislation
prohibiting the discharge of non-biologically degradable material into sewer
systems. This promoted the change to linear alkyl benzene (LAS) which had 10
per cent better detergency than PT benzene sulphonate in heavy-duty
formulations. Solutions of the neutralized sulphonic acid had a lower viscosity, an
advantage when the product was spray-dried to a powder. However, powders
made from LAS became sticky and lost their free-flowing characteristics.
Having successfully coped with the problem of biodegradation the industry faced
a new attack. It appeared that in certain lakes and ponds algae started
reproducing at an unprecedented rate. This was blamed on the extensive use of
phosphates in the form of sodium tripolyphosphate. The term eutrophication,
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189
a. Ethanol
b. Penicillin
6. Explain how antibiotics work and the role they have played in the
improvement of human health.
7. Write short notes on the uses of aspirin.
8. Describe the steps that come after saponification in toilet soap production.
9. What is the function of the following ingredients in a detergent powder
a. fluorescer
b. bleach
c. sodium carboxymethylcellulose.
10. Explain why propylene tetramer (PT) benzene was replaced by linear
alkylbenzene sulphonate (LAS).
Practical
Draw the block diagrams for the following processes:
1. Penicillin production
2. Soap manufacture
3. Glycerol purification
XV. Synthesis of the Module
This is the only industrial chemistry module in the whole chemistry course. There
are six units in the module. The first unit covers definitions, classifications, inputs
and outputs of the manufacturing industry and the chemical industry in particular.
The use of flow diagrams to supplement description of chemical processes and
as tools for material balance calculations is presented.
The second unit deals with unit operations and unit processes which are the
building blocks of chemical processes. Included in this Unit are size reduction,
unit operations dealing with separation of materials and important chemical
reactions. This knowledge prepares you for the study of industrial processes.
In unit 3 we apply the knowledge in unit operations and unit processes in the
study of extractive metallurgy and in particular the manufacture of iron, copper
and aluminium. The fourth unit is also on industrial inorganic chemistry and deals
190
with the manufacture of six basic chemicals namely, sodium hydroxide and
chlorine, ammonia, sulphuric acid, fertilizer and cement.
The fifth unit is one of two units dealing with industrial organic processes.
Petroleum processing, manufacture and uses of some petrochemicals and
polymers are presented. These are phthlic anydride and adipc acid, polyethylene
and styrene butadiene rubber respectively.
The sixth and last unit in the module focuses on some organic products some of
them the fermentation products. These are ethanol and penicillin. Aspirin is also
covered under pharmaceuticals. We close the module with the study of soap and
detergent production.
23
H2SO4
57
H2O
20
27
H2SO4
60
H2O
13
by addition of 93% w/w sulphuric acid and 90% w/w nitric acid. Use material
balance to calculate the amount of waste acid, sulphuric acid and nitric acid
needed to produce 100kg of concentrated nitration acid.
2. How are particles made hydrophobic for the purpose of flotation?
3. Explain the following with respect to free radical polymerization:
a. Initiation
b. Propagation
191
c. Termination
4. What are the advantages and disadvantages of emulsion polymerization?
5. List down 10 reasons why material size enlargement is carried out in
industry.
6. Write blast furnace equations for:
a. Iron ore reduction
b. Fuel reactions
c. Slag formation.
7. Describe the Hall-Heroult aluminium electrolysis process
8. Explain how blister copper is produced.
9. Describe the reactions that take place in a cement kiln at various
temperatures
10. Draw diagrams to illustrate mercury, diaphragm and membrane cells as
used in the manufacture of chlorine and sodium hydroxide. What are the
advantages of the diaphragm cell over mercury cell?
11. Explain why in the Haber process, the temperature is increased rather
than decreased as per prediction by the Le Chateliers principle. Why is it
necessary to remove sulphur compounds from the feedstocks?
12. Converting sulphur trioxide into sulphuric acid cannot be done by simply
adding water to sulphur trioxide. Why?
13. Explain using equations, how super-phosphate and triple phosphate
fertilizer is made
14. Discuss the term octane number and explain why iso-alkanes are more
preferred than the n-alkanes for use as internal combustion engine fuels?
15. Describe how phthalic anhydride is manufactured
16. Explain the role of the various ingredients used in the emulsion
polymerization of styrene and butadiene to make SBR polymer.
17. How are the following products recovered from their respective
fermentation mash:
(i)
Ethanol
(ii)
Penicillin
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XVII. References
1. George T. A. (1977). Shreves Chemical Process Industries. 5th edn.
McGraw-Hill
International
Edition.
Chemical
Engineering
Series.
Singapore.
2. Chang R. and Tikkanen W. (1988). The Top Fifty Industrial Chemicals.
Random House, New York.
3. Price R.F. and Regester M.M. (2000), WEFA Industrial Monitor, 20002001, John Wiley & Sons Inc., New York.
4. Chang R. (1991). Chemistry, 4th Edition, McGraw-Hill Inc. New York.
5. Shukla S. D and Pandey G. N, (1978). A Textbook of Chemical
Technology. Vol.1 (Inorganic/Organic). Vikas publishing House PVT Ltd.
New Delhi.
6. Stephenson R.M. (1966). Introduction to the Chemical Process Industries,
Reinhold Publishing Corporation, New York.
7. Groggins P.H. (1958). Unit Processes in Organic Synthesis, 5 th Edition,
McGraw-Hill Book Company, New Delhi.
8. Das R.K. (1988) Industrial Chemistry: Metallurgy, Kalyani Publishers, New
Delhi.
9. Gerhartz, W. (Editor), (1987). Ullmanns Encyclopaedia of Industrial
Chemistry Vol A8, 5th Edition, VCH Verlagsgesellschaft mbH, Weinheim.
10. Clearing House for Inventories and Emissions, U.S.A. Environmental
Protection Agency, Organic Process Industry AP. 42, Vol. 1, 5 th Edition.
11. Underkoffer L.A, Hickey R.J. (1954) Industrial Fermentation Vol. I,
Chemical Publishing Co. Inc. New York.
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12. Price R.F. and Regester M.M. (Editors), (2000). WEFA Industrial Monitor
2000-2001, John Wiley & Sons, Inc.New York.
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