Lecture 7 and 8

Inorganic Chemical Industries Part II: Chlor-alkali, Ammonia, Sulphur

Acid, Fertilizer and Cement.
Unit objectives

At the end of this unit you should be able to:

a. Describe using equations and diagrams, the electrolytic 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, the process for the

manufacture of Portland cement.

4.1. Manufacture of Sodium Hydroxide and Chlorine by the

Chlor-alkali process

4.1.1. Introduction

Before the electrolytic method of making sodium hydroxide and chlorine (chlor- alkali
process) became widely used, sodium hydroxide was made from soda ash by the lime-
soda process. The soda ash as aqueous Na2CO3 is reacted with slaked lime (Ca (OH)2)
according to the following equation:

Na2CO3 (aq) + Ca (OH) 2(s) = 2NaOH (aq) + CaCO3(s)

The chlor-alkali process has gradually replaced the lime-soda process.

4.1.2. Raw Materials

The chlor-alkali industry uses rock salt, a natural deposit of sodium chloride. The aqueous
sodium chloride solution, referred to as brine contains Na+, Cl-, H+ and OH- ions.
Electrolysis of this solution produces simultaneously chlorine, sodium hydroxide and
hydrogen in the ratio of 1:1.13:0.028
4.1.3. Chlor-alkali process
The term chlor-alkali refers to the two chemicals (chlorine and an alkali) which are
simultaneously produced as a result of the electrolysis of brine. The most common chlor-
alkali chemicals are chlorine and sodium hydroxide (caustic soda) but can include
potassium hydroxide when a potassium brine is used.

Brine electrolysis produces chlorine at the anode and hydrogen along with the alkali hydroxide at
the cathode. The two products are removed in separate streams.

The overall chemical reaction of electrolysis of sodium chloride is:

2NaCl(aq) + 2H2O(l) = 2NaOH(aq) + Cl2(g) + H2(g)

If chlorine is not separated from the sodium hydroxide, side reactions such as the following
would occur:

2NaOH(aq) + Cl2(g) = NaOCl(aq) + NaCl(aq) + H2O(l) H2(g) + Cl(g)

= 2HCl(g)
Three processes are in use: the diaphragm-cell process, the membrane-cell process, and the
mercury-cell process. These are shown in the figures below.

Fig 4.1. Chlor-alkali cells

 4.1.4. Mercury Cells

In the mercury-cell process, a flowing pool of mercury at the bottom of the electro- lytic
cell serves as the cathode. The anodes are graphite or modified titanium. When an
electric current passes through the brine, chlorine is produced at the anode and sodium
dissolves in the mercury, forming an amalgam of sodium and mercury. The amalgam is
then poured into a separate vessel, where it decomposes into sodium and mercury.

Cell reactions

At the anode

2Cl (aq) Cl2 (g) + 2 e -

At cathode
Hg
2Na  (aq)  2e   2Na / Hg

Overall: 2NaCl (aq)  2NaHg  Cl 2( g)

The amalgam (a mercury-sodium alloy) is taken to a different vessel for decomposition

according to the equation:

2Na .Hg + 2H2O = 2NaOH + H2 + Hg

Initially mercury cells seemed to dominate the field because it produced high quality
products. With exactly the required amount of water added, a 50%NaOH solution is
formed which does not greatly require much evaporation for concentration.

However, mercury cells use much more electrical energy than diaphragm and mem- brane
cells. Also, small quantities of mercury discharges into nearby streams. These discharges
were found to be sources of the carcinogenic methyl mercury. This has led to prohibition
and gradual replacement of the mercury cells by diaphragm cells.

4.1.5. Diaphragm Cells

These cells contain a diaphragm, usually made of asbestos fibres that separate the anode
from the cathode. The diaphragm also allows ions to pass by electrical migration but limit
the diffusion of products. The anodes are made of graphite and the cathodes of cast iron.
When an electric current passes through the brine, the chlorine ions and sodium ions
move to the electrodes. Chlorine gas is produced at the anode, and sodium ions at the
cathode react with the water, forming caustic soda. Some salt remains in the solution with
the caustic soda and can be removed at a later stage.

Advantages and disadvantages

i. The electrodes can be placed close together and this permits compactness of
diaphragm cells of low electrical resistance.

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.

v. The release of asbestos to the environment is a major anticipated problem of

diaphragm cells. Diaphragms made of corrosion resistant plastics are a proposed

solution to asbestos pollution.

vi. A major advantage is that diaphragm cells can operate on dilute 20% reasonably

impure brine. Such brines produce dilute sodium hydroxide (about 15%)
contaminated with sodium chloride. Concentrations to about 50% are achieved
by use of multi-effect evaporators. Studies have shown that nearly 2,600kg of
water must be evaporated to obtain 1 ton of 50% caustic soda.

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.

Fig 4.2 Membrane chlor-alkali process

In this process, rather than using a diaphragm, semi permeable membrane made of plastic
sheets is used to separate the anode and cathode compartments. The 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.
 Fig 4.3 Chlor-alkali membrane cell

Brine is pumped into the anode compartment, and only sodium ions pass into the cathode
compartment, which contains pure water. Thus, the caustic soda produced has very little
salt contamination.

4.2. Manufacture of Ammonia

4.2.1. Introduction.
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 world- wide 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:

 Fertilizers ((ammonium sulfate, diammonium phosphate, urea)

  Nitric acid
 Explosives
 Fibres, synthetic rubber, plastics such as nylon and other polyamides
 Refrigeration for making ice, large scale refrigeration plants, air-
conditioning units in buildings and plants
 Pharmaceuticals (sulfonamide, vitamins, etc.)
 Pulp and paper
 Extractive metallurgy
 Cleaning solutions
4.1.3. Raw Materials

The raw materials used to manufacture ammonia are air, water and, hydrocarbons. Coal
can also be used in place of hydrocarbons but the process is complex and expensive.

4.2.4. Nitrogen fixation

For a long time, commercial development of nitrogen fixation ammonia process had
proved elusive. Old methods used to produce ammonia included dry distillation of
nitrogenous vegetable and animal waste products. Here, nitrous acid and nitrites were
reduced with hydrogen according to the following equation:

N2O + 4H2 = 2NH3 + H2O

Ammonia was also produced by the decomposition of ammonium salts using alkaline
hydroxides such as quicklime as shown in the following equation.

2NH4Cl + 2CaCl2 = CaCl2 + Ca(OH)2 + 2NH3

Haber invented a large-scale catalytic synthesis of ammonia from elemental hydrogen and
nitrogen gas, reactants which are abundant and inexpensive. By using high temperature
(around 500 oC), high pressure (approximately 150-200 atm), and an iron catalyst, Haber
could force relatively unreactive gaseous nitrogen and hydrogen to combine into
ammonia.

The collaborative efforts of Haber and Carl Bosch made the commercial high-pressure
synthesis of ammonia possible by 1913. This energy-intensive process has undergone
considerable modification in recent years.
4.2.5. Chemical Reaction and Equilibrium
Ammonia synthesis from nitrogen and hydrogen is an exothermic reversible reaction and
can be described by the following overall reaction.

2 2 3

1/2N + 3/2H 500 oC Fe NH Δ H = 45.7kJ/mol

The reaction is accompanied by decrease in volume and by Le Chatelier’s principle,
increasing the pressure causes the equilibrium to shift to the right resulting in a higher
yield of ammonia. Since the reaction is exothermic, decreasing the temperature also
causes the equilibrium position to move to the right again resulting in a higher yield of
ammonia. We can conclude then that ammonia synthesis as per equation (1) is an
equilibrium reaction that is favoured by low temperature and high pressure.
Thermodynamics gives us equilibrium conditions of the reaction but does not give us any
idea about the rate of reaction. The reaction does not proceed at ambient temperature
because nitrogen requires a lot of energy to dissociate. In the gas phase this dissociation
occurs only at around 3000°C. Even the hydrogen molecule, which has a weaker molecular
bond, only dissociates markedly at temperatures above 1000°C.

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 (250-400°C) 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 Al2O3 and
K2O. Its optimal performance requires reaction temperatures around 400ºC and pressures
from 150-300 atmospheres. Ammonia synthesis reaction is carried out commercially at 200-
500 atm and 450 to 600oC.
4.2.8. Modern Method of Manufacturing Ammonia

The manufacturing process consists of six stages namely: manufacture of reactant gases,
purification, compression, catalytic reaction, recovery of ammonia formed and recirculation
and ammonia removal as shown in the flow diagram Fig. 4.4.
 Fig. 4.4 Block diagram of an ammonia plant

Hydrogen is obtained by conversion of hydrocarbons such as methane, propane, butane or

naphtha into gaseous hydrogen.

4.2.8.1. Desulphurization

Hydrocarbon feedstocks contain sulphur in the form of H2S, COS, CS2 and mercaptans. The
catalyst used in the reforming reaction is deactivated (poisoned) by sulphur. The problem
is solved by catalytic hydrogenation of the sulphur compounds as shown in the following
equation: H2+RSH = RH + H2S(g)

The gaseous hydrogen sulphide is then removed by passing it through a bed of zinc oxide
where it is converted to solid zinc sulphide:

H2S+ZnO = ZnS+H2O

4.2.8.2. Primary (Steam) Reforming.

Reforming is the process of converting natural gas or naptha (C nH2n+2) into hydrogen,

carbon monoxide and carbon dioxide. Steam and natural gas are combined at a three-to-
one ratio. This mixture is preheated and passed through catalyst-filled tubes in the
primary reformer.

Catalytic steam reforming of the sulphur-free feedstock produces synthesis gas (hydrogen
and carbon monoxide). Using methane as an example:

CH Ni,4 15-20 atm, 1000-1100 oC2 CO + 3H

The reaction is endothermic. It is operated at 1000-1100 oC. It is not favoured by high

pressures, but to reduce volumetric flow rate at high temperature, the steam reforming
reaction is carried out at high pressures of 15 to 20 atm.

4.2.8.3. Secondary reformer

From the primary reformer, the mixture flows to the secondary reformer. Air is fed into
the reformer to completely convert methane to CO in the following endothermic reaction.
 CH + Air Ni, 15-20 atm, 1000-1100 oc CO + H O + N
4 2 2

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.

The carbon dioxide is removed either by scrubbing with water, aqueous monoetha-
nolamine solution or hot potassium carbonate solution.

CO is an irreversible poison for the catalyst used in the synthesis reaction, hence the need
for its removal .The synthesis gas is passed over another catalyst bed in the methanator,
where remaining trace amounts of carbon monoxide and dioxide are converted back to
methane using hydrogen.

CO+3H2 = CH4+H2O

CO2+4H2 = CH4+2H2O

O2 + 2H2 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

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.

4.3. Sulphuric Acid Manufacture

4.3.1. Introduction

During the 19th century, the German chemist Baron Justus von Liebig discovered that
sulphuric acid, when added to the soil, increased the amount of soil phosphorus available
to plants. This discovery gave rise to an increase in the commercial production of
sulphuric acid and led to improved methods of manufacture.

4.3.2. Uses of sulphuric acid

Sulphuric acid is the most widely used chemical. The largest single use of sulphuric acid is
for making phosphate and ammonium sulphate fertilizers. Other uses include production
of phosphoric acid, trisodium phosphates for detergent making. Sulphuric acid is also used
in large quantities in iron and steel making as a pickling agent to remove oxidation, rust
and scale from from the metals. It is an oxidizing and dehydrating agent. Its dehydrating
action is vital in absorbing water formed in chemical conversions such as nitration,
sulphonation, and esterification. It vigorously removes water from, and therefore chars,
wood, cotton, sugar, and paper. As a strong oxidizing agent it is capable of dissolving such
relatively unreactive metals as copper, mercury, and lead to make compounds of these
metals.

It is used in the manufacture of aluminium sulphate for application in paper pulp

production and in water treatment. It is also used as an electrolyte in lead acid batteries
found in cars.

Various concentrations of sulphuric acid are available depending on the application

purpose. These include:

 10% dilute acid for laboratory use, pH = 1

 33.3% for lead acid batteries, pH = 0.5
 62.2% for chamber and fertilizer manufacture, pH = 0.4
 77.7% tower or Glover acid pH = 0.25
 93.2% Oil of Vitriol
 98% conc acid, pH = 0.1
 100% H2SO4
 20% oleum (104.5% H2SO4)

4.3.3. Raw Materials

Raw materials for sulphuric acid are those that produce sulphur dioxide when reacted with
oxygen. The commonly used raw materials are:
 • Elemental sulphur

• Sulphides such as pyrites

• Hydrogen sulphide from petroleum refineries

4.3.4. Manufacturing process

Two processes, the lead-chamber and contact processes, are used for the production of
sulphuric acid. In their initial steps, both processes require the use of sulphur dioxide.

4.3.4.1. The Lead-chamber process

This process employs as reaction vessels large lead-sheathed brick towers. In these towers,
sulphur-dioxide gas, air, steam, and oxides of nitrogen react to yield sulphuric acid as fine
droplets that fall to the bottom of the chamber. Almost all the nitrogen oxides are
recovered from the outflowing gas and are brought 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 replaced 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 co-generation.

The flow diagram for sulphuric acid manufacture by the contact process is shown
in Fig. 4.5
 Fig. 4.5 Block diagram for the manufacture of sulphuric acid by the contact
process.

The main steps in the contact plant are:

 production of sulphur dioxide gas

 purifying and cooling the gas
 the gas conversion of SO2 into sulphur trioxide (SO3) by passing it
through a converter containing the catalyst
 absorbing the sulphur trioxide in sulphuric acid
4.3.4.3. Production of SO3

Sulphur is burned in the Sulphur burner to produce Sulphur dioxide:

S(s)+O2(g) = SO2(g), ΔH = -298.3 Kj at 250C

Before combustion, Sulphur, is first melted by heating it to 135°C. Combustion is carried

out at between 900 and 1800°C. The combustion unit has a process gas cooler. The SO2
content of the combustion gases is generally around 18% by volume and the O 2 content is
low but higher than 3%. The gases are generally diluted to 9-12% SO 2 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), ΔH = -98.3kJ at 250C

From thermodynamic and stoichiometric considerations, the following methods are

available to maximise the formation of SO3 for the O2/SO2/SO3 system.

 heat removal: the formation of SO3 is exothermic, so a decrease of

temperature will be favourable
 increased oxygen concentration
 removal of SO3
 raising the system pressure
 catalyst selection to reduce the working temperature
 longer reaction time

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 O2 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 400–
450 oC is used. According to Le Chatelier’s 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. Furthermore, vanadium
catalyst has high conversion efficiency. Its only disadvantage is that it requires use of low
sulphur dioxide concentration which makes plant capital cost to be high.

In summary, optimum conditions for sulphuric acid production in the contact process are:
  A temperature of about 4300C
 A pressure of 2 atmospheres
 Vanadium pentoxide catalyst.

A diagram of the converter is shown in Fig. 4.6

Fig 4.6 Converter for SO2 into SO3

4.3.4.4. Absorption of SO3

Sulphuric acid (H2SO4) is obtained from the absorption of SO 3 into sulphuric acid with a
concentration of at least 98%, followed by the adjustment of the strength by the
controlled addition of water. SO 3, will react with water to form sulphuric acid. However,
converting the sulphur trioxide into sulphuric acid cannot be done by simply adding water
to the sulphur trioxide. Direct mixing of sulphur trioxide with water by the following
reaction is uncontrollable. The exothermic nature of the reaction means it generates a fog
or mist of sulphuric acid, which is more difficult to work with than a liquid.

SO3 (g) +H2O (l) = H2SO4 (l), ΔH = -130.4kJ at 250C

Instead, the sulphur trioxide is first dissolved in concentrated (98%) sulphuric acid
to form a product known as fuming sulphuric acid or oleum.

SO3+H2SO4 (l) + = H2S2O7 (l)

The oleum can then be reacted safely with water to produce concentrated sulphuric acid.

H2S2O7 (l) +H2O (l) = 2H2SO4 (l)

4.3.4.5. Environmental Issues

Sulphuric acid is a constituent of acid rain, formed by atmospheric oxidation of sulphur

dioxide in the presence of water. Sulphur dioxide is released when fuels containing
sulphur such as oil and coal are burned. The gas escapes into the atmosphere forming
sulphuric acid. Sulphuric acid is also formed naturally by oxidation of sulphide ores.

4.4. Manufacture of Fertilizers

4.4.1. Introduction

Fertilizer is a substance added to soil to improve the growth and yield of plants. Mo- dern
synthetic fertilizers are composed mainly of nitrogen, phosphorus, and potassium compounds
with secondary nutrients added.

The process of adding substances to soil to improve its growing capacity was developed in
the early days of agriculture. Ancient farmers knew that the first yields on a plot of land
were much better than those of subsequent years. This caused them to move to new,
uncultivated areas, which again showed the same pattern of reduced yields over time.
Eventually it was discovered that plant growth on a plot of land could be improved by
spreading animal manure throughout the soil. Over time, fertilizer technology became
more refined. New substances that improved the growth of plants were discovered.

4.4.2. Uses of fertilizer

The use of synthetic fertilizers has significantly improved the quality and quantity of the
food available today, although their long-term use is an environmental subject of debate.

As has been mentioned, fertilizers are typically composed of nitrogen, phosphorus, and
potassium as micronutrients. Nitrogen helps make plants green and plays a major role in
boosting crop yields. It plays a critical role in protein formation and is a key component of
chlorophyll. Plants with adequate nitrogen show healthy vigorous growth, strong root
development, dark green foliage, increased seed and fruit formation and higher yields.
Plants also need phosphorus, a component of nucleic acids, phospholipids, and several
proteins. Phosphorus is also needed to provide the energy to drive metabolic chemical
reactions. Without enough phosphorus, plant growth is reduced.

Potassium helps plants grow strong stalks, in the same way that calcium gives people strong
bones. It is used in protein synthesis and other key plant 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.

The balance 80 percent will contain some micronutrients and filler material, which
allows for even application of the nutrients across the fertilized area.

Fig 4.7 A bag of fertilizer showing analysis

4.4.4.1. Nitrogen fertilizer

Ammonia (82-0-0) is a basic nitrogen fertilizer. Stored as a liquid under pressure or

refrigerated, it becomes a gas when exposed to air and is injected into the soil. It is also
used as a building block to make other easy to handle nitrogen fertilizer products, including
urea, ammonium nitrate, ammonium sulfate and water-based liquid nitrogen fertilizers. Nitric
acid and ammonia are used to make ammonium nitrate (34-0-0), a solid granular fertilizer
with a high concentration of nitrogen. The two materials are mixed together in a tank and
a neutralization reaction occurs, producing ammonium nitrate. This material can then be
stored until it is ready to be granulated and blended with the other fertilizer components.

Urea (46-0-0) is a solid nitrogen product typically applied in granular form. It can be
combined with ammonium nitrate and dissolved in water to make a highly soluble liquid
nitrogen fertilizer known as urea ammonium nitrate (UAN) solution typically containing
28 to 32 % nitrogen.

Ammonium sulfate (21-0-0) is another solid nitrogen fertilizer.

4.4.4.2. Phosphate fertilizer

Phosphate rock, Ca5(PO4)3F which contains 27 to 38% phosphorus pentoxide (P2O5), is

the main raw material source from which most types of phosphate fertilizers are produced.

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 (CaH4 (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 + 3H 3CaH4 (PO4)2.H2O + 7CaSO4 + 2HF

Sulphuric acid is also used to manufacture phosphoric acid, an intermediate product in

the production of triple superphosphate (TSP).

Acidulation of the phosphate rock using phosphoric acid produces triple superphos- phate
by the following reaction:

Ca5 (PO4)3F + 7H3PO4 + 5H2O 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 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 contai- ners.

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 the other hand, are generally produced by granulation of
superphosphates (SSP or TSP) with potassium salts.

One method of granulation involves putting the solid materials into a rotating drum
which has an inclined axis. (Refer to drum agglomerator in Unit 2). As the drum rotates,
pieces of the solid fertilizer take on small spherical shapes. They are passed through a
screen that separates out adequately sized particles. A coating of inert dust is then applied
to the particles to make them remain discreet and to inhibit moisture retention. Finally,
the particles are dried, thus completing the granulation process. The fertilizer is emptied
onto a conveyor belt, which transports it to the bagging machine.

4.4.5. Quality Control

To ensure the quality of the fertilizer that is produced, manufacturers monitor the product
at each stage of production. The raw materials and the finished products are all subjected
to a battery of physical and chemical tests to show that they meet the specifications
previously developed. Some of the characteristics that are tested include pH, appearance,
density, and melting point. Since fertilizer production is government- regulated, tests are
run on samples to determine total content of nitrogen, phosphate, and other elements in
the specifications.

4.5. Manufacture of Portland cement

4.5.1. Introduction

Historically, cement can be traced back to the early Roman Empire. It contributed to the
building of the great structures of the Roman Empire. Portland cement is a fine powder,
generally gray in colour. It is composed primarily of calcium silicates, calcium aluminates,
and calcium ferrites. When mixed with water (hydrated), cement solidifies to an artificial
rock, similar to Portland stone. A Portland stone is a yellow limestone from the Isle of
Portland, in Great Britain. Hence the name Portland cement. By varying the amounts and
types of the same basic ingredients, cement with various properties may be obtained.
Concrete is a mixture of gravel, sand and cement.

4.5.2. Raw materials

The major components of cement in terms of metal oxides are CaO, SiO 2, Al2O3, and
Fe2O3. Typically, Ca is provided from limestone, Si from sand or flyash, Al from flyash or
clay, and Fe from iron ore or slag.

4.5.3. Manufacturing process

Fig 4.8 is a process flow diagram for a typical cement manufacturing plant.
 Fig 4.8. A cement manufacturing process

4.5.3.1. Grinding

The feed to the grinding process is proportioned to meet a desired chemical compo- sition.
Typically, it consists of 80% limestone, 9% silica, 9% flyash, and 2% iron ore. These
materials are ground to 75 micron in a ball mill. Grinding can be either wet or dry. The
“raw meal” from dry milling is stored in a homogenizing silo 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. Pyro processing

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.
 Fig 4.9. A cement kiln

4.5.3.3. Reactions in the kiln

Basic chemical reactions are: evaporating all moisture, calcining the limestone to produce
free calcium oxide, and reacting the calcium oxide with the minor materials (sand, shale,
clay, and iron). This results in a final black, nodular product known as “clinker” which has
the desired hydraulic properties.

A summary of the physical and chemical reactions that take place in the kiln are shown in
Table 4.1.

Table 4.1. Reactions in a cement kiln

T oC Reaction Remarks
100 Evaporation of water Solid phase reactions,
endo- thermic
>500 Evolution of combined Solid phase reactions,
water from the clay endo- thermic
900 Crystallization of Solid phase reactions,
amor- phous endo- thermic
dehydration prod-
ucts

Carbon dioxide
evolution from
 CaCO3
900 -1200 Main reactions Fusion reactions,
between lime and clay exothermic
to form clinker
1250 - 1280 Beginning of liquid for- Fusion reactions,
mation endothermic
1280 -1550 Further liquid Fusion reaction,
formation and final endothermic
cement forma- tion

The main reactions which give the real strength of cement are as follows:
900-100 1200-1500
2CaO + CaO.SiO 2 > CaO + 2CaO.SiO 2 > 3CaO.SiO 2

The main constituents of clinker are shown in Table 4.2.

Table 4.2. Main constituents of clinker

Abbreviatio Common name Function

n
2CaO.SiO2 C2S Dicalcium Together with
silicate 3CaO. SiO2,
responsible for
final strength (I
year)
3CaO.SiO2 C3S Tricalcium Responsible for
sili- cate early strength i.e. 7-
8 days
3CaO.Al2O3 C3A Tricalcium Causes fast
alumi- nate harden- ing; needs
retarda- tion by
gypsum
by forming 3CaO.
 Al2O3CaSo4.3H2O

3CaO. C4AF Tetracalcium Improves

Al2O3. alumino- chemical
Fe2O3 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 pyro
processing 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.