NFC Institute of Engineering and Fertilizer

Research

Submitted to: Sir Eng. Tayyab Ali

Submitted By: Nida Imran

Roll no.: 19-CHM-02

 Assignment
Manufacturing of CHLORINE
Introduction
Chlorine is a chemical element, one of roughly 90 basic building blocks of matter. Naturally chemically reactive,
chlorine’s tendency to combine with other elements and compounds has been used to produce thousands of
essential products, ranging from drinking water disinfectants to solar energy panels to replacement knee and
hip joints.

Represented by the chemical symbol “Cl,” chlorine is number 17 on the Periodic Table of the Elements,
indicating each atom of chlorine contains 17 protons and 17 electrons. Due to its natural chemical reactivity,
chlorine is rarely present in nature by itself as elemental chlorine, and typically exists bonded to other
elements in the form of chemical compounds such as sodium chloride (table salt)

History of chlorine
In 1774, in his small experimental laboratory, Swedish pharmacist Carl Wilhem Scheele released a few drops of
hydrochloric acid onto a piece of manganese dioxide. Within seconds, a greenish-yellow gas arose. Although
he had no idea at the time, he had just discovered chlorine.

The fact that the greenish-yellow gas was actually an element was only recognized several decades later by
English chemist Sir Humphrey Davy. Until that time, people were convinced that the gas was a compound of
oxygen. Davy gave the element its name on the basis of the Greek word khloros, for greenish-yellow. In 1810
he suggested the name "chloric gas" or "chlorine."

Some of the most effective and economical germ-killers, chlorine disinfectants destroy and deactivate a wide
range of dangerous germs in homes, hospitals, swimming pools, hotels, restaurants, and other public places.

Chlorine's powerful disinfectant qualities come from its ability to bond with and destroy the outer surfaces of
bacteria and viruses.

First used as a germicide to prevent the spread of "child bed fever" in the maternity wards of Vienna General
Hospital in Austria in 1847, chlorine has been one of society's most potent weapons against a wide array of
life-threatening infections, viruses, and bacteria for over 150 years.

Presence in nature
Chlorine is the 19th most abundant chemical element in the Earth. While elemental chlorine (Cl2 gas) is almost
never found in nature, over 2,000 naturally occurring chlorine-containing compounds have been identified in
living organisms. Chlorine is also found at some level in virtually every rock on Earth. The weathering and
erosion of the rocks of the continents cause chloride (a negatively charged form of chlorine) to be dissolved in
rain and melting snow and carried to the oceans by Earth’s rivers. Over long periods of geologic time, the
oceans have become great reservoirs of chloride. Ocean water has evaporated in some places over the
millennia, leaving behind large salt deposits. One of the salts in these deposits, halite (sodium chloride), is used
as common table salt and as the raw material from which elemental chlorine is produced.
Presence in Human Body
Yes, human beings cannot live without chlorine. Our body's cells exist in a sea of fluid. This fluid is mostly
water, along with dissolved charged atoms of sodium and chloride. Chloride plays an essential role in a delicate
balancing act: providing for the electrical neutrality and the correct pressure of body fluid. One result of this
balancing act is that the amount of water we retain and concentrations of salt in our bodies remain relatively
constant over time. We don't dry up, nor do we bloat uncontrollably. When changes occur, the balance
reasserts itself. For example, after heavy exercise and perspiration, the body requires salt; and we are usually
thirsty after eating salty food.

Chloride ions are building blocks of hydrochloric acid, which is essential to our digestive system. Hydrochloric
acid, made in the stomach, has two main purposes: to help destroy germs that arrive with food; and to help
break down foods, ensuring that essential nutrients are made available to the body.

Chlorine is also essential to the immune system, which is charged with fighting off the daily invasion of germs.
When infections take place, hypochlorite—a chlorine-containing compound which is a well-known disinfectant
—forms in white blood cells. Hypochlorite either attacks germs or helps to activate other disinfecting agents.

Applications / Uses
Water
Chlorine chemistry helps keep drinking water and swimming pools safe. Before cities began routinely treating
drinking water with chlorine-based disinfectants, thousands died every year from waterborne diseases such as
cholera, typhoid fever, dysentery and hepatitis A. Chlorine-based pool and spa disinfectants help keep
recreational waters safe by destroying waterborne pathogens that can result in illnesses, such as diarrhea,
swimmer’s ear or skin rashes, including athlete’s foot.

Household Disinfectant
Chlorine chemistry is used to manufacture household chlorine bleach, which whitens and disinfects clothes
and disinfects kitchen and bathroom surfaces. Diluted bleach and water solutions are especially effective at
killing germs that may be found on household surfaces that make people sick, including the norovirus (also
known as the “stomach bug”) and seasonal flu.

Food
Chlorine chemistry helps provide safe and abundant food by protecting crops from pests and keeping kitchen
counters and other food-contact surfaces disinfected, destroying E. coli, salmonella and a host of other
foodborne germs.

Healthcare
Chlorine chemistry is critical to manufacturing medicines we depend on, including some that help lower
cholesterol, control arthritis pain and relieve allergy symptoms. The products of chlorine chemistry can also be
found in blood bags, medical devices and surgical stitches. Chlorine chemistry is also used to manufacture
contact lenses, safety glasses and respiratory inhalers.

Energy and Environment

Chlorine chemistry plays an important role in harnessing solar energy, purifying the silicon in grains of sand
and helping transform them into solar panel chips. Wind turbine blades made from chlorine-based epoxy
resins help convert wind power into electricity.

Advanced Technology
Chlorine chemistry is used to manufacture fast processors that power smart phones, tablets, and computers.
Chlorine chemistry is also used to manufacture residential and commercial air conditioning refrigerants, hybrid
car batteries and high-performance magnets.

Building and Construction

Plastic foam insulation, manufactured using chlorine chemistry, increases the energy efficiency of home
heating and air-conditioning systems, reducing energy bills and conserving natural resources. Energy-efficient
vinyl windows reduce heating and cooling costs and GHG emissions. Research indicates manufacturing vinyl
windows requires one-third of the energy needed to manufacture aluminum windows. And chlorine chemistry
even contributes to the beauty of every room in your home by helping to manufacture durable paints.

Defense and Law Enforcement

Chlorine chemistry is used to manufacture bullet-resistant vests worn by soldiers and police officers. Chlorine
chemistry is also used to produce parachutes and night vision goggles as well as cockpit canopies and missile
guidance technologies.

Transportation
Chlorine chemistry is used on planes, trains, automobiles, and boats, in the manufacture of seat cushions,
bumpers, brake fluid and airbags that help keep passengers safe and comfortable. Chlorine chemistry is also
used to manufacture shatter-resistant windows, wire and cable, steel hulls, and navigation systems.

Manufacturing of Chlorine
Chlorine can be manufactured by the electrolysis of a sodium chloride solution (brine), which is known as the
Chloralkali process. The production of chlorine results in the co-products caustic soda (sodium hydroxide,
NaOH) and hydrogen gas (H2). These two products, as well as chlorine itself, are highly reactive. Chlorine can
also be produced by the electrolysis of a solution of potassium chloride, in which case the co-products are
hydrogen and caustic potash (potassium hydroxide). There are three industrial methods for the extraction of
chlorine by electrolysis of chloride solutions, all proceeding according to the following equations:

Cathode: 2 H+ (aq) + 2 e− → H2 (g)

Anode: 2 Cl− (aq) → Cl2 (g) + 2 e−

Overall process: 2 NaCl (or KCl) + 2 H2O → Cl2 + H2 + 2 NaOH (or KOH)

Mercury cell electrolysis

Castner–Kellner cell: Sodium chloride is electrolyzed between the "A" anode and "M" mercury cathode in the
side cells, with chlorine bubbling up into the space above the NaCl and the sodium dissolving in the mercury.
The sodium–mercury amalgam flows to the center cell, where it reacts with water to produce sodium
hydroxide and regenerate the mercury.

Mercury cell electrolysis, also known as the Castner–Kellner process, was the first method used at the end of
the nineteenth century to produce chlorine on an industrial scale.The "rocking" cells used have been improved
over the years.Today, in the "primary cell", titanium anodes clad with platinum or conductive metal oxides
(formerly graphite anodes) are placed in a sodium (or potassium) chloride solution flowing over a liquid
mercury cathode. When a potential difference is applied and current flows, chlorine is released at the titanium
anode and sodium (or potassium) dissolves in the mercury cathode forming an amalgam. This flows
continuously into a separate reactor ("denuder" or "secondary cell"), where it is usually converted back to
mercury by reaction with water, producing hydrogen and sodium (or potassium) hydroxide at a commercially
useful concentration (50% by weight). The mercury is then recycled to the primary cell by a pump situated at
the bottom.

The mercury process is the least energy-efficient of the three main technologies (mercury, diaphragm and
membrane) and there are also concerns about mercury emissions.

Emission factors in environment components andthe main emission sources of mercury sources at amercury
cell chlor plant(Data from EC, 2011; Euro Chlor, 2011)
Component

Mercury emission factors

g/tonne of annual chlorine capacity*
Sources of mercury release Min Max Median

Cell-room ventilation 0.132 1.298 0.587

Process exhaust-purged air from cell
end boxes-vents from wash water
Air

collection tanks-exhaust from any

vacuum system used to collect spilled
mercury-hydrogen burnt or sold as
-the process waste water: brine
purge, (back)washing water from
brinepurification, condensate and
wash liquor from treatment of
chlorineand hydrogen, condensate
from caustic concentration
chlorine,units,
Water
Products

Mercury in produced
hydrogen and caustic (may therefore
beemitted to the environment during
subsequent uses).Hg contained in 0.01 0.43 0.05
caustic is usually the largest
contributor to emissions via
products
 Wastes
-solids from brine purification-solids
from caustic filtration-solids from
waste water treatment-solids from
sludge (sewer, traps, channels)-
activated carbon from treatment of 0 98 0.5
gaseous streams-graphite from
decomposer packing-residues from
retorts-wastes from maintenance and
renewal.

Globally, the number of mercury-cell facilities is on the decline, consistent with theend of the economic life of
these facilities. The number ofmercury cell chlor-alkali plants inoperationshows a worldwide decrease from 91
to 53 overthe period 2002-2011 (-42%) andthe global mercury cell chlorine capacity is estimated to have
declined by about 42%, thereremains approximately 5.3 million metric tons per year of mercury cell
chlorine productioncapacity worldwide, compared to about 9.1 million metric tons per year in 2002

Trend of number of plants and capacity of mercury electrolysis units in USA/Canada/Mexico,Europe, Russia,
India and Brazil/Argentina/Uruguay(Source: WCC, 2011 and UNEP, 2011

Even though the mercury cell chlor-alkali technique has been replaced by alternativetechniques in
many locations or the chlor-alkali plants were decommissioned, historicalaccumulation of Hg could still
be a secondary contamination source to the environment(Olivero-Verbel et al., 2008; Ullrich et al., 2007a,
2007b)
 Trend of the total mercury emissions (air + water + products) for the mercury cell chlor-alkaliplants
(USA/Canada, Europe, India and Brazil/Argentina, Uruguay and Russia)(Source: WCC, 2011 and UNEP, 2011

Diaphragm cell electrolysis (Bipolar)

In diaphragm cell electrolysis, an asbestos (or polymer-fiber) diaphragm separates a cathode and an anode,
preventing the chlorine forming at the anode from re-mixing with the sodium hydroxide and the hydrogen
formed at the cathode.[6] This technology was also developed at the end of the nineteenth century. There are
several variants of this process: the Le Sueur cell (1893), the Hargreaves-Bird cell (1901), the Gibbs cell (1908),
and the Townsend cell (1904).[7][8] The cells vary in construction and placement of the diaphragm, with some
having the diaphragm in direct contact with the cathode.

The salt solution is continuously fed to the anode compartment and flows through the diaphragm to the
cathode compartment, where the caustic alkali is produced and the brine is partially depleted. As a result,
diaphragm methods produce alkali that is quite dilute (about 12%) and of lower purity than do mercury cell
methods.

Diaphragm cells are not burdened with the problem of preventing mercury discharge into the environment;
they also operate at a lower voltage, resulting in an energy savings over the mercury cell method,[8] but large
amounts of steam are required if the caustic has to be evaporated to the commercial concentration of 50%.

Membrane cell electrolysis

The chloralkali process consists of two half-cells, which are known as anode cell and cathode cell. In the anode
cell, oxidation of chloride ions takes place. And electrons are driven towards the cathode by an external
electric potential. Within the cathode cell, the transferred electrons reduce hydronium ions. The chemical
reactions, which are considered in the developed model, can be expressed as:

Anode cell: 2Na+ + 2Cl-  Cl2 + 2Na+ + 2e-

 2Cl-  Cl2 + 2e-

Cathode cell: 2H2O + 2e-  H2(g) + OH-

Na+ + OH-  NaOH(aq)

Total reaction: 2H2O + 2NaCl  H2(g) + Cl2(g) + 2NaOH(aq)

The developed model consists of material balances for all ions, liquids and gases and the energy balance in
terms of voltage in the electrochemical cell.

The reactor was modelled as a continuously stirred tank reactor, which makes the electrolyte concentration
uniform in each cell compartment. The material balance considers sodium ions, hydroxide ions, water, and
chloride. The liquid volume of each half cell is assumed to be constant. Based on Faraday’s Law, redox reaction
rates .

Model Validation
The modelling and simulation process is shown by fig 3 The equations are developed and integrated in the
MOSAIC modelling environment. Then, the developed model is simulated in MATLAB.
A model validation was done by comparing steady-state simulation data with experimental data provided by .
The model is constructed in MOSAIC and then simulated in MATLAB. Dias measured some variables from a
laboratory-scale chloralkali electrolyser to investigate and characterize the membrane cell. The comparison
results are expressed in FigIt shows the polarization curve of the chloralkali cell model and the chloralkali
electrolyzer. These figures show that the trend in polarization diagrams of both have similar trends, although
there is an offset between the model values and the experimental

Advantages of the Membrane Cell as compare to Disadvantages of the Membrane Cell as compare to
diaphragm and mercury cell diaphragm and mercury cell
a) Does not use harmful a) Higher quality salt and brine required. Resulting in
substances such as mercury or higher
asbestos and hence there can be cost
no potential release of these b) More processing steps required to purify the brine,
materials into the product, again
ground or environment. higher cost
c) Higher unit consumption of salt
b) Lowest power consumer when d) Lower quality sodium hydroxide vs mercury grade
compared to mercury and in terms
diaphragm cells. of sodium chloride content.
(Elecrtric power consumed in e) The sodium hydroxide produced may contain
kWhr/t Cl2 (Moussallem and higher
others 2008) chlorate levels than mercury grade.
Mercury cell – 3100-3400 f) Higher internal consumption of sodium
Diaphragm cell – 2300-2900 hydroxide and
Membrane cell – 2100-2600 hydrochloric acid for regeneration of the ion-
exchange
Total power consumed resins and for brine acidification for chlorate
Mercury – 3100-3400 decomposition.
Diaphragm – 3200-3800 g) Higher maintenance or operating cost for
Membrane – 2400-2900) replacement of
c) Higher quality of sodium membranes – typically needs to be replaced every 4
hydroxide when compared to years
the diaphragm cel (or earlier depending on treated brine quality).
h) The purging of brine streams will release
chlorate to the
environment through the waste water. Chlorates are
known
to be persistent and records show that it can
adversely affect
certain strains of algae such as fucus vesiculousus
or
bladder-wrack (brown algae) at μg/l levels
(Rosemarin and
others 1994). Safe limits as specified in Canada are
at 5
μg/l level (Warrington 2002).
i) The production of perfluorocarboxylic acid and
perfluorosulfonic acid used in the membranes also do
result
in the release of pollutants (Kärrman and others
2010)(Jeon and others 2010).
Process Flow Sheet Diagram
Physical and chemical properties
 Physical Properties

Formula Cl2

Molecular Weight (lb/mol) 70.91

Critical Temp. (°F) 291.2

Critical Pressure (psia) 1118.4

Boiling Point (°F) -29.3

Melting Point (°F) -149.8

Psat @ 70°F (psia) 98.4

Liquid Density @ 70°F (lb/ft3) 88.83

Gas Density @ 70°F 1 atm (lb/ft3) 0.1858

Specific Volume @ 70°F 1 atm (ft3/lb) 5.38

Specific Gravity 2.524

Specific Heat @ 70°F (Btu/lbmol-°F) 8.16

 Chemical Properties
Properties Definitions Conditions Values

Boiling Point

(Liquefying Point) The temperature at which liquid chlorine vaporizes 14.696 psia -29.15F

(101.325 kPa) (-33.97C)

Critical Density The mass of a unit volume of chlorine at the 35.77lb/ft

critical pressure and temperature (573.0kg/m)

Critical Pressure The vapor pressure of liquid chloride at the 1157.0 psia

critical temperature (7977 kPa)

Critical Temperature The temperature above which chlorine exists 290.75 F

only as a gas no matter how great the pressure (143.75 C)

Critical Volume The volume of a unit mass of chlorine at the 0.02795 ft/lb

critical pressure and temperature 0.001745m/kg

Density The mass of a unit volume of chlorine at

specified conditions of temperature and

pressure.

Density of Cl2 32 F,53.51psia 0.7632lb/ft

Gas 0 C, 368.9kPa 12.23kg/m

Density of Saturated 32 F,53.51psia 0.7632lb/ft

Cl2 Gas 0 C,368.9kPa 12.23kg/m

Density of Saturated Cl2 Liquid 32F,14.696psia 91.56lb/ft

0C, 101.325kPa 1467kg/m

Latent Heat of

Vaporization The heat required to evaporate At normal boiling point 123.9Btu/lb

a unit weight of chlorine 288.1KJ/kg

Liquid-Gas

Volume Relationship The weight of one volume of liquid 32F,14.696psia

chlorine equals the weight of 456.5 0C,101.325kPa

volumes of chlorine gas.

Melting Point

(Freezing Point) The temperature at which solid 14.696psia -147.69F

chlorine melts or liquid chlorine 101.325kPa -100.98C

solidifies

Solubility in Water The weight of chlorine which can 60F,14.696psia 6.93lbs/100gal

be dissolved in a given amount of water

 at a given temperature when the total

vapor pressure of chlorine and the water

equals a designated value.

Specific Gravity

of Cl2 Gas The ratio of the density of chlorine 32 F, 14.696psia 2.485

gas at standard conditions to the

density of air under the same conditions:

Specific Gravity of

Cl2 Liquid The ratio of the density of 32 F 1.467

saturated liquid chlorine to the

density of water at its maximum

density - 39°(4°C)

Specific Heat The heat required to raise the

temperature of a unit weight

of chlorine one degree.

Saturated Gas at

constant pressure 32 F, 77 F 0.1244 Btu/lb F

Saturated Gas at constant

volume 32 F, 77 F 0.08887 Btu/lb F

Saturated Liquid 32 F, 77 F 0.2264 Btu/lb F

Ratio for Saturated Gas Ratio of gas specific heat 32 F, 77 F 1.44

At constant pressure to gas

specific heat at constant

volume

Specific Volume The volume of a unit mass of

chlorine at specified conditions

of temperature and pressure.

Gas 32 F, 14.696psia 4.9896 ft/lb

Saturated Gas 32 F 1.310 ft/lb

Saturated Liquid 32 F 0.01092 ft/lb

Vapour Pressure The absolute pressure 32 F , 77 F 53.51psia, 112.95 psia

of chlorine gas above liquid

chlorine when they are in

equilibrium

Viscosity The measure of internal

molecular friction when

chlorine molecules are

in motion

Saturated Gas 32 F 0.0125 cP

Liquid 32 F 0.3863 cP

Reference
1. Chlorine, Gas Encyclopaedia, Air Liquide
2. Magnetic susceptibility of the elements and inorganic compounds, in Lide, D. R., ed. (2005). CRC
Handbook of Chemistry and Physics (86th ed.). Boca Raton (FL): CRC Press. ISBN 0-8493-0486-5.
3. Weast, Robert (1984). CRC, Handbook of Chemistry and Physics. Boca Raton, Florida: Chemical Rubber
Company Publishing. pp. E110. ISBN 0-8493-0464-4.
4. "The earliest salt production in the world: an early Neolithic exploitation in Poiana Slatinei-Lunca,
Romania". Archived from the original on April 30, 2011. Retrieved 2008-07-10.
5. Greenwood and Earnshaw, p. 789–92
6. Scheele, Carl Wilhelm (1774). "Om Brunsten, eller Magnesia, och dess Egenskaper" [On braunstein
[i.e., pyrolusite, manganese dioxide], or magnesia, and its properties]. Kongliga Vetenskaps
Academiens Handlingar [Proceedings of the Royal Scientific Academy] (in Swedish). 35: 89–116, 177–
194. In section 6 on pp. 93–94 of his paper, Scheele described how chlorine was produced when a
mixture of hydrochloric acid and manganese dioxide (Brunsten) was heated: "6) (a) På 1/2 uns fint
rifven Brunsten slogs 1 uns ren Spiritus salis. … samt lukten fo̊ rsvunnen." ( 6) (a) On one half ounce of
finely ground Braunstein [pyrolusite] was poured one ounce of pure spiritus salis [spirit of salt,
hydrogen chloride]. After this mixture had been standing in the cold for one hour, the acid had
assumed a dark brown colour. One part of this solution was poured into a glass, which was placed
over the fire. The solution gave off an odour like warm aqua regia and after one quarter’s hour
duration, it was as clear and colourless as water, and the smell had disappeared.) For an English
translation of the relevant passages of this article, see: The Early History of Chlorine : Papers by Carl
Wilhelm Scheele (1774), C. L. Berthollet (1785), Guyton de Morveau (1787), J. L. Gay-Lussac and L. J.
Thenard (1809) (Edinburgh, Scotland: Alembic Club, 1912), pp. 5–10.
 7. Fengmin Du, David M Warsinger, Tamanna I Urmi, Gregory P Thiel, Amit Kumar, John H Lienhard
(2018). "Sodium hydroxide production from seawater desalination brine: process design and energy
efficiency". Environmental Science & Technology. 52: 5949–5958. doi:10.1021/acs.est.8b01195.
hdl:1721.1/123096. PMID 29669210.
8. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-
Heinemann. ISBN 978-0-08-037941-8.
9. R. Norris Shreve; Joseph Brink (1977). Chemical Process Industries (4th ed.). p. 219. ASIN
B000OFVCCG.
10. D. J. Harvey and J. R. Fowler, Chem. Eng. Prog., p. 47 (April 1976).Google Scholar

11. A. B. Nisercola, R. P. Tracy, I. A. Franson, and R. J. Knoth, Abstract No. 37, Meeting of Electrochemical
Society, Washington, D.C., May 1976.Google Scholar

12. H. C. Twiehaus and N. J. Ehlers, Chem. Ind., p. 230 (August 1948).Google Scholar

13. P. E. Feathers and J. E. Wyche, Chem. Eng., p. 122, (May 14, 1973).Google Scholar

14. F. Hine, M. Yasuda, I. Sugiura, and T. Nöda, J. Electrochem. Soc. 121, 220 (1974).CrossRefGoogle Scholar

15. F. Hine and M. Yasuda, Denki Kagaku (J. Electrochem. Soc. Jpn.) 39, 530 (1971).Google Scholar

16. R. B. MacMullin, Denki Kagaku (J. Electrochem. Soc. Jpn.) 38, 570 (1970).Google Scholar