CHEMICAL

INDUSTRY
CHEMICAL INDUSTRY

• The chemical industry comprises

the companies that produce
industrial chemicals. Central to the
modern world economy, it converts raw
materials (oil, natural
gas, air, water, metals, and minerals) into
more than 70,000 different products.
THE EARLY YEARS OF CHEMICAL INDUSTRY

• Its history can be traced back to ancient times

when alkali and limestone were combined to
make glass, and sulfur and saltpeter became an
explosive that is similar to modern gunpowder

• Middle Eastern artisans used to refine alkali and

limestone for the production of glass in as early
as 7,000 B.C. and Phoenicians produced soap in
the 6th century B.C.
THE EARLY YEARS OF CHEMICAL INDUSTRY

• The Chinese developed black powder around the

10th century A.D, and it was used as a primitive
explosive.

• In the middle ages, alchemists produced small

amounts of chemicals and by 1635 the Pilgrims
in Massachusetts were producing saltpeter for
gunpowder and chemicals for tanning.
INDUSTRIAL REVOLUTION

• The first sulfuric acid plants were built in Great

Britain in 1740 (Richmond), France in 1766
(Rouen), Russia in 1805 (Moscow Province), and
Germany in 1810 (near Leipzig)
• The development of the textile and glass
industries prompted the initiation of soda
production.
INDUSTRIAL REVOLUTION

• The first soda plants were built in France in 1793

(near Paris), Great Britain in 1823 (Liverpool),
Germany in 1843 (Schönebeck), and Russia in
1864 (Barnaul)

• In the mid-19th century, artificial fertilizer plants

appeared in Britain (1842), Germany (1867), and
Russia (1892).
INDUSTRIAL REVOLUTION

• In 1823, British entrepreneur James Muspratt

started mass producing soda ash (needed for
soap and glass) using a process developed by
Nicolas Leblanc in 1790

• Further advances in organic chemistry in the last

half of the 19th century, allowed companies to
produce synthetic dyes from coal tar for the
textile industry as early as the 1850s.
INDUSTRIAL REVOLUTION

• In the 1890s, German companies began mass

producing sulfuric acid and, at about the same
time, chemical companies began using the
electrolytic method, which required large
amounts of electricity and salt, to create caustic
soda and chlorine.
CHEMICAL INDUSTRY IN THE 19TH CENTURY

• By World War II, petrochemicals were being used

in the United States to produce plastics and
fibers.

• Polymer science uses petrochemicals to make

products such as plastics, resins, paints, and
adhesives.

• After World War II, the industry experienced a

shift in production from organic chemicals, such
as coal, to petrochemicals.
CHEMICAL INDUSTRY IN THE 19TH CENTURY

• The rapid process of concentration in the

chemical industry, the high level of scientific and
technological development, the strengthening of
the monopoly on patents, and commercial
politics led to Germany’s conquest of the world
market.

• Until World War I it retained a monopoly on the

production of organic dyes and intermediates.
CHEMICAL INDUSTRY IN THE 20TH CENTURY

• Man-made fibers changed the textile industry

when rayon (made from wood fibers) was
introduced in 1914; and thus the introduction of
synthetic fertilizers by the American Cyanamid
Company in 1909 led to a green revolution in
agriculture that dramatically improved crop
yields.
CHEMICAL INDUSTRY IN THE 20TH CENTURY

• Advances in the manufacture of plastics led to

the invention of celluloid in 1869 and the
creation of such products as nylon by Du Pont in
1928

• Research in organic chemistry in the 1910s

allowed companies in the 1920s and 30s to
begin producing chemicals for oil

• Synthetic rubber came into existence during

World War II, when the war cut off supplies of
rubber from Asia
CHEMICAL INDUSTRY IN THE 20TH CENTURY

• In the 1960s, there was an increase in the

production of organic chemicals from oil and
natural gas.

• Many oil companies, such as BP, Shell, and

Exxon, also began producing chemicals that were
derived from petroleum feedstock.

• During the 1970s, oil prices increased drastically,

which increased the cost of manufacturing
petrochemicals and polymers
INDUSTRIAL DISASTER OF BHOPAL

• In 1984, the worst industrial disaster in history

occurred when toxic chemicals leaked from a
Union Carbide plant in Bhopal, India

• This disaster led to a period of increased

regulations to protect the air, water, and soil
from chemical contamination.
CHEMICAL INDUSTRY IN THE 21TH CENTURY

• By this century, companies in the chemical

industry include large, medium, and small
companies located all over world.

• Millions of people got employed by the

chemicals industry in production, research and
development, as well as chemists, engineers,
and technicians.

• The chemicals industry established its

importance in national economies and grew to
about $3.7 trillion USD in sales.
 Industry Description

The chemical industry comprises the companies that produce

industrial chemicals.

Central to the modern world economy, it converts raw materials (oil, natural
gas, air, water, metals, and minerals) into more than 70,000 different products.

The birth of the heavy chemical industry (production of chemicals in large

quantities for a variety of uses) coincided with the beginnings of the Industrial
Revolution in general.
 Industry Description

the chemical industry involves the use of chemical

processes such as chemical
reactions and refining methods to produce a wide
variety of solid, liquid, and gaseous materials.

The industry includes manufacturers

of inorganic- and organic-industrial
chemicals, ceramic products,
petrochemicals, agrochemicals, polymers
and rubber (elastomers), oleochemicals
(oils, fats, and waxes), explosives,
fragrances and flavors.
 Industry Description

Oil refinery in Louisiana

New polypropylene plant PP3 in the Slovnaft oil

refinery (Bratislava, Slovakia)
 Industry Description

What does the chemical

industry produce?

The products of the chemical industry can be divided into

three categories:

Basic chemicals

Specialty chemicals

Consumer chemicals
 Industry Description

Basic chemicals

chemicals derived from oil, known as petrochemicals

Polymers

Basic inorganics
 Industry Description

Speciality chemicals
Crop protection, paints and inks, colorants (dyes and pigments).
It also includes chemicals used by industries as diverse as textiles,
paper and engineering.
 Industry Description

Consumer chemicals

They include, for example, detergents, soaps and other toiletries.

 Industry Description

SULFURIC
ACID

Sulfuric acid is one of the most important compounds

made by the chemical industry.

It is made in greater volume than any other product of the

chemical industry allowing it to be used in producing, literally,
hundreds of compounds needed by almost every industry

In the United States alone, well over 40 million tons of the colorless,
viscous, relatively low-cost liquid are produced each year.
 Industry Description

By far the largest amount of sulfuric acid is used to make phosphoric acid, used, in
turn, to make the phosphate fertilizers, calcium dihydrogenphosphate and the
ammonium phosphates

It is also used to make ammonium sulfate, which is a particularly important fertilizer

in sulfur-deficient.
 Industry Description

Sulfuric Acid
 Sulfuric acid is a odorless, oily and highly
corrosive chemical and is one of the
most important compounds made by
the chemical industry.
 It is used to make, literally, hundreds of
compounds needed by almost every
industry.
 Industry Description

History of Sulfuric Acid Manufacturing

 The preparation by burning sulfur with
saltpeter was first described by
Valentinus in the fifteenth century
 Later its preparation by distilling niter with
green vitriol was mentioned by Persian
alchemist Abu-Bekr-Ahhases, who died in Green Vitriol
(Iron Sulfate)
940
 Industry Description

History of Sulfuric Acid Manufacturing

 Inthe eighteenth and nineteenth centuries, it was
essentially and entirely produced by chamber process, in
which oxides of nitrogen (as nitrosyl compounds) were
used as homogeneous catalysts for the oxidation of sulfur
dioxide.
 The product made by this process were of rather low
concentration (typically 600 Baume or 77 to 78% H2SO4)
not high enough for many commercial uses
 Industry Description

History of Sulfuric Acid Manufacturing

 The contact process was first discovered in 1831 by
Peregrine Phillips, an Englishman whose patent included
the essential features of the modern contact process
namely the passing of the mixture SO2 over a catalyst
followed by absorption of SO3 in 98-99% H2SO4
 Industry Description

History of Sulfuric Acid Manufacturing

A significant change in the
contact process occurred in 1963,
when Bayer AG announced the
first large scale use of Double
Contact Double Absorption
process and granted several
Bayer AG is a German multinational chemical
patents and pharmaceutical company founded in
Barmen, Germany in 1863.
 Industry Description

Sulfuric Acid Manufacturing Processes

 Contact Process

 Double Contact Double Absorption Process

 Lead Chamber Process

SULFURIC ACID
MANUFACTURING
The Contact Process
 The contact process was first discovered in 1831 by
Peregrine Phillips
 The process for producing sulfuric acid has four stages:
a) extraction of sulfur
b) conversion of sulfur to sulfur dioxide
c) conversion of sulfur dioxide to sulfur
trioxide
d) conversion of sulfur trioxide to sulfuric
acid
Step 1: Extraction of Sulfur
 Easily the most important source
of sulfur is its recovery from
natural gas and oil. These
contain sulfur compounds, both
organic and hydrogen sulfide
both of which must be removed
before they are used as fuels or
chemical feedstock.
Step 1: Extraction of Sulfur
 Another important source of sulfur is as sulfur dioxide from
metal refining. Many metal ores occur as sulfides and are
roasted to form an oxide and sulfur dioxide, for example,
in the manufacture of lead:

 Other
metals manufactured from their sulfide ores include
copper, nickel and zinc.
Step 1: Extraction of Sulfur
 Sulfuric
acid is also obtained
from ammonium sulfate, a by-
product in the manufacture of
poly(methyl 2-
methylpropenoate) and also
recovered from 'spent' (i.e.
used) sulfuric acid.

Polymethyl Methacrylate
Step 2: Conversion of Sulfur to Sulfur
Dioxide
 If sulfur is the feedstock, it must
first be converted to sulfur
dioxide. Molten sulfur is sprayed
into a furnace and burnt in a
blast of dry air at about 1300 K.
The sulfur burns with a
characteristic blue flame:
Step 2: Conversion of Sulfur to Sulfur
Dioxide
 As excess air is used the emerging gas contains about 10-
12% sulfur dioxide and 10% oxygen, by volume. The gases
are very hot and so are passed through heat exchangers
(waste heat boilers).
 The gases are cooled to about 700 K and the water in the
surrounding boiler pipes is converted into steam. In
manufacturing one tonne of sulfuric acid, one tonne of high
pressure steam is also produced.
Step 3: Conversion of Sulfur Dioxide to
Sulfur Trioxide
A typical plant contains one cylindrical vessel which acts
as a fixed bed reactor with four separate beds of
catalyst, known as a converter, heated to 700 K, through
which the sulfur dioxide and air pass:
Step 3: Conversion of Sulfur Dioxide to
Sulfur Trioxide
Step 3: Conversion of Sulfur Dioxide to
Sulfur Trioxide
 However,the reaction will reach equilibrium and the
conversion of sulfur dioxide to sulfur trioxide will stop.

 Therefore,
a catalyst shall be employed to assure
optimum conversion to sulfur trioxide
Step 3: Conversion of Sulfur Dioxide to
Sulfur Trioxide
 Thecatalyst, vanadium(V) oxide on silica, is generally in
the form of small pellets, to which caesium sulfate has
been added as a promoter.
Step 3: Conversion of Sulfur Dioxide to
Sulfur Trioxide
 Vanadium(v) oxide catalyst
used for the manufacture of
sulfuric acid. The gas inlet
duct can be seen in the
middle of the picture.
Step 4: Conversion of Sulfur Trioxide to
Sulfuric Acid
 Sulfur trioxide reacts with water and the reaction can be expressed
as:

 However, water itself cannot be used for absorption as there is a

large temperature rise, and a sulfuric acid mist is formed, which is
difficult to handle.
 Instead, sulfuric acid of about 98% concentration is used. This is
kept at this concentration by addition of water and removal of
acid at that concentration.
Step 4: Conversion of Sulfur Trioxide to
Sulfuric Acid
The Contact Process
Step 4: Conversion of Sulfur Trioxide to
Sulfuric Acid
 The gases not absorbed contain about 95% nitrogen, 5%
oxygen, and traces of sulfur dioxide. The gas stream is
filtered to remove any traces of sulfuric acid mist with an
acidic scrubber that contains bases like sodium
bicarbonate and is returned to the atmosphere using a
high stack.
Double Contact Double Absorption
Process
 In the double contact process, the degree of conversion
obtained is about 99.5%, depending on the arrangement of
the contact beds and of contact time preceding the
intermediate absorber.
 After cooling the gases to approximately 160–190 °C in a
heat exchanger, the sulfur trioxide already formed is
absorbed in the intermediate absorber in sulfuric acid with
a concentration of 98.5–99.5 wt%.
Double Contact Double Absorption
Process
 The intermediate absorber is preceded by an oleum
absorber if required.
 The sulfur trioxide formed in the secondary stage is
absorbed in the final absorber.
Double Contact Double Absorption
Process
Lead Chamber Process
 In 1746 in Birmingham, England,
John Roebuck began producing
sulfuric acid in lead-lined
chambers, which were stronger,
were less expensive, and could be
made much larger than the glass
containers
Lead Chamber Process
 Lead Chamber process is one of the sulphuric acid production
methods which gives only about 50-60 Be grade acid.
 The main principle behind the process is that the moist SO2 (sulphur
dioxide) in presence of nitrogenous oxides (active catalyst) is
oxidized to sulphur trioxide with the oxygen present in air.
 Sulphur trioxide is made to react with water to produce sulphuric
acid. The reactions would be like below:
2SO2 + O2 → 2SO3
SO3 + H2O → H2SO4
 Lead Chamber Process
 Sulfurdioxide is generated by burning elemental sulfur or by
roasting pyritic ore in a current of air:
S8 + 8 O2 → 8 SO2
4 FeS2 + 11 O2 → 2 Fe2O3 + 8 SO2
 Nitrogen oxides are produced by decomposition of niter in the
presence of sulfuric acid or hydrolysis of nitrosylsulfuric acid:
2 NaNO3 + H2SO4 → Na2SO4 + H2O + NO + NO2 + O2
2 NOHSO4 + H2O → 2 H2SO4 + NO + NO2
Lead Chamber Process
 In the reaction chambers, sulfur dioxide and nitrogen
dioxide dissolve in the reaction liquor. Nitrogen dioxide is
hydrated to produce nitrous acid which then oxidizes the
sulfur dioxide to sulfuric acid and nitric oxide.

2 NO2 + H2O → HNO2 + HNO3

SO2 (aq) + HNO3 → NOHSO4
NOHSO4 + HNO2 → H2SO4 + NO2 + NO
SO2 (aq) + 2 HNO2 → H2SO4 + 2 NO
Lead Chamber Process
 Nitricoxide escapes from the reaction liquor and is
subsequently reoxidized by molecular oxygen to nitrogen
dioxide
2 NO + O2 → 2 NO2

 Nitrogen oxides are absorbed and regenerated in the

process, and thus serve as a catalyst for the overall
reaction:
2 SO2 + 2 H2O + O2 → 2 H2SO4
Lead Chamber Process
Applications of
 APPLICATION of SULFURIC ACID
 ‘Universal chemical’
 Annual production: reaches 200 million tons

Pie chart of the applications of sulfuric acid.

Phosphate Fertilizers Production
- major use of sulfuric acid (75% of total worldwide)
• Phosphoric Acid
– Intermediary product for the production of high grade phosphate
fertilizers
“Wet Method”
Trisodium phosphate (detergent)
Phosphate Fertilizers Production

Fluorapatite,
Ca5F(PO4)3

93 percent

Phosphogypsum
(byproduct)

Ca5F(PO4)3 + 5 H2SO4 + 10 H2O → 5 CaSO4•2 H2O + HF + 3 H3PO4

Chemical Production

Sulfuric acid is a highly chemical compound for it is used in

the manufacturing process of a number of well-known
chemicals ( HCl, HNO3, H3PO4) and many other industrial
chemicals.
Industrial Cleaning Agent
IRON and STEEL INDUSTRY
• Sulfuric acid is used as pickling-acid
used to remove oxidation, rust and scale from rolled sheet and billets
(prior to sale into the automobile and white-goods business)
Carbon steels (alloy content ≤ 6%)
• Used acid is re-cycled using a Spent Acid Regeneration (SAR)
plant
combustion of spent produces sulfur dioxide
acid with natural gas, (SO2) and sulfur trioxide
refinery gas, or other (SO3) - used to
suitable fuel source manufacture "new"
sulfuric acid
Catalyst
• Nylon Production
– Sulfuric acid acts as a catalyst for the conversion of cyclohexanone
oxime to caprolactam, used for making nylon

• Petroleum Refining
- Example is H2SO4 as a catalyst for the reaction of isobutane with
isobutylene to give isooctane (raises the octane rating of gasoline (petrol))
Pulp and Paper Industry
• Sulfuric acid is used in large volumes for chlorine dioxide
generation, tall oil splitting and pH-adjustments (bleaching)
• Sulfuric acid is used in production manufacture of aluminium
sulfate, also known as papermaker's alum
– This can react with small amounts of soap on paper pulp fibers to
give gelatinous aluminium carboxylates, which help to coagulate the
pulp fibers into a hard paper surface
Water Treatment
• Aluminum sulfate
– Flocculating agent
– used at water treatment plants to filter out impurities, as well as to
improve the taste of the water
– Aluminum sulfate is made by reacting aluminum hydroxide with
sulfuric acid:
2Al2(OH)3 + 3 H2SO4 → Al2(SO4)3 + 6 H2O
Rayon Manufacture
• Rayon
– good semi-synthetic textile
– ‘art silk’
– made from cellulose fibres derived from wood

Cellulose fibres A thick blue liquid

dissolved in a is produced is then Rayon fibres are
solution of Tetra injected into formed.
Amine Copper (II) sulfuric acid.
Sealed-unit lead-acid type batteries
• Sealed-unit lead-acid type batteries
– used in the automotive industry
for cars and trucks; invented by
Frenchman Gaston Plants in 1859

Sulfuric acid is used in a dilute form to act as an

electrolye to allow the flow of electrons between
the plates in the battery. (Battery Acid)
Pharmaceutical Industry
• Chemotherapy drugs
– Sulphuric acid is used in
the manufacturing process
– Cancer cells are more sensitive to DNA damage than normal cells so
in chemotherapy treatment cancer cells are destroyed by damaging
their DNA (alkylation of DNA )
– drug is known as alkylating antineoplastic agents
 Other Applications of Sulfuric Acid
• Agricultural chemicals
• Aluminum Sulfate
• Amino acid intermediates
• Cellophane
• Coloring agents
• Explosives
• Gasoline
• Herbicides
• Jet Fuel
• Kerosene Leather
• Lubricating oils
• Oil additives
• Regeneration of ion exchange resins
• Sugar
• Sulfonation agents
• Synthetic fibers
• Veterinary drugs
• Water softener regeneration
• Water treatment
• Yellow pigments
• Chemical Manufacturing
 Market Players

ECO Services is the #1 provider of Sulfuric Acid

Regeneration services and the #1 supplier of Merchant Virgin
Sulfuric Acid in the USA.

ECO Services also produces liquid Aluminum Sulfate,

processes Hazardous and Non-Hazardous waste with
our Treatment Servicesbusiness, and provides state of the
art Sulfuric Acid tank cleaning technology through Industrial
Field Services
 Market Players

Chemtrade provides industrial chemicals and services

to customers in North America and around the world.
Chemtrade obtains its products from its own production
facilities and through long-term marketing services
agreements.

The industrial producers include base metal

smelting and oil refinery operations that generate
sulphuric acid, spent acid, liquid SO2 and sulphur as by-
products of their production processes.
 Market Players

The Company is mainly engaged in the

manufacturing of Single Super Phosphate
(Fertilizer), Sulphuric Acid (Chemical) and Soya
Edible Oil.

The Company has India’s largest Single Super Phosphate (SSP)

production capacity of 11,13,500 MT alongwith Sulphuric Acid (SA)
production capacity of 2,70,600 MT. .

Mr. Shailesh Khaitan promoted Khaitan Chemicals & Fertilizers Ltd. (KCFL) in 1982. The Company is
engaged in the manufacture of Single Super Phosphate (SSP), Sulphuric Acid (SA) Oleum 65%,
Oleum 23%, Liquid SO3, Labsa, Soya Oil and De-oiled Cake. It is today the largest manufacturer of
Single Super Phosphate (SSP) in India and plans to remain number one at country level for the
coming years
 Market Players

Ineos is an acronym of Ineos manufactures and

INspec Ethylene distributes a wide range of
OxideSpecialities, a name derived from petrochemicals, specialty chemicals
their first acquisition in 1998 and oil products.

Ineos Group Limited (styled as INEOS) is a privately

owned multinational chemicals company headquartered in Rolle,
Switzerland, and with its registered office in Lyndhurst, Hampshire,
UK. Jim Ratcliffe is the founder, Chairman and 60 percent shareholder.
 Market Players

Southern States Chemical is the largest ISO 9001-2008 Certified

manufacturer/supplier of Sulfuric Acid for industrial use in the Southeastern United
States.
 Environmental Aspects
• Emissions into air/water, waste generation
– Emissions into air CO2, SOx, Nox
• Absorption improvements
– Absorbing tower design (velocity)
– Acid distribution (flow and repartition)
– Packing efficiency
– Acid temperature (vapour pressure)
– SO2 emissions
• Origin: bad conversion efficiency
• Minimization technique
– Velocities of gases through catalyst and repartition
– Single absorption double absorption (if gases are higher
– than 6% SO2)
– SO2 weak H2SO4 possible to recycle
 Environmental Aspects
– Emission into water
• Any acidic washings resulting from spillage or leakage are treated with
alkaline solution before disposal to the pit or for domestic usage.

– Solid Wastes
• Sulphuric acid spent catalysts
Types of Landfill Disposal
• Fixation – catalyst is ‘fixed’ in an inert matrix, usually concrete or glass
- designed to prevent metals leaching into the landfill site
• Direct landfilling - catalyst is deposited directly into a suitably
licensed landfill site
- It is common practice to mix the catalyst with
lime to neutralise residual acidity
 Environmental Aspects
• Accidental pollution
– highest risk for accidental pollution is during the transportation of
the product
– different transport regulations such as those of ADR/RID and IMO

• Areas of concern
-- Risk to personnel during the loading and unloading of sulphuric acid
•All producers are responsible for the personals safety of their employees