2.

1 Table of basic properties

Name

Formula

Barium Sulphate
Barium Chloride
Calcium Carbonate
Calcium Chloride
Chlorine
Magnesium
Chloride
Magnesium
Hydroxide

BaSO4
BaCl2
CaCO3
CaCl2
Cl2

Hydrochloric Acid
Sodium Bisulfite

HCl
NaHSO3

Sodium Carbonate
Sodium Chloride
Sodium Hydroxide
(Caustic Soda)
Sulphuric Acid

Molecular
Melting Point Boiling
Solubility in
Weight
(oC)
Point (oC)
Water
(g/mol)
233.43
1345
1600 2.4mg/100ml
244.27
962
1560 35.8g/100ml
100
1339 -------1.3mg/100ml
110.98
773
1935 740g/L
70.9
-101
-34 14g/L

MgCl2

95.21

Mg(OH)2

350
58.32 (decomposes)

Na2CO3
NaCl
NaOH
H2SO4

36.46
104.06

714

-114
150

Solution
Strength

1412 54.3g/100ml
--------

0.6mg/100ml
-85 720g/L
315 42g/100ml

68.50%

34
106 (decomposes) -------34g/L
58.44
801
1413 359g/L
40
98

318
10

1388 111g/L
337 miscible

32%50%
98%

2.2-Reagents and Raw Materials

2.21 Rock Salt
NaCl 94.2%
CaCl2 0.9%
MgCl2 0.8%

H2O 2.0%
Insolubles 2.1%

The rock salt provided for the plant contains NaCl, MgCl2, CaCl2 and a small portion of insolubles, it
is expected that these insolubles are silica based particles that have no chemical interaction at any
stage in the process and are removed to less than 20ppb in the brine pretreatment. The magnesium
and sodium chlorides are impurities in the rock salt that damage the cell membrane if not removed.
The concentrations of calcium and magnesium ions in the brine solution are reduced below 20ppb by
the ion exchange column, these levels are considered to have minimal impact on the efficiency of the
membrane but at higher levels the ions come out of solution across the membrane due to the rapid
change in pH physically impeding the transfer of sodium ions to the cathode.
The purity of the rock salt is typical for solid mined salt, solution mining would increase the purity
however the plant would have to be built next to the mine due to the increased transportation cost and
the pretreatment steps would be the same.
In an effort to support regional business a small portion of the rock salt for the cell electrolysis can be
sourced from the Kilroot mine near Carrickfergus, 250 miles from Shannon. The mine has been
operating since 1965 producing over 500 tonnes of rock salt annually and works with local haulage
contractors to supply Ireland. Our requirements far exceed the capacity of this mine so the majority of
the salt must be sourced from the U.K, the Winsford mine in Cheshire currently averages
900,000tonnes/y of salt production with the capacity for 2.25Mt/y more than sufficient for this plant.
There are no foreseeable issues with rock salt supply in Britain, however the global market is subject
to change due to the rising presence of China as a salt superpower producing 65Mt/y in 2011, a rise
of 18Mt/y since 2006 (USGS/BGS). Salt mining in China is currently monopolized with a large public
motion to privatize the sector potentially decreasing the cost for Chinese salt in the future.

2.22 Sulfuric Acid (H2SO4)

Sulfuric acid is a clear colorless acid supplied at 98% concentration, above 98% the acid is volatile
and quickly evaporates.During the cell process water vapor and brine mist escape in the chlorine gas
stream, these must be removed before the chlorine can be stored or transported, whilst some water is
removed in the demisters further drying is required. The drying process employs a packed column
with 98%conc. Sulfuric acid flowing counter current to the chlorine gas, sulfuric acid is used due to its
hygroscopic properties, readily absorbing water from air and lack of attraction to Cl2. 98% Sulfuric
acid is highly corrosive, dehydrating and oxidizing, the material in the column has to be resistant to
corrosion and care must be taken when storing and handling the acid. The dilution of sulfuric acid is
highly exothermic; because the reaction is in an equilibrium that favours the rapid protonation of
water, addition of acid to the water ensures that the acid is the limiting reagent.

2.23 Hydrochloric Acid (HCl)

Hydrochloric acid is a clear colorless acid supplied at or below 38%conc.
The membrane inside the cell is pH sensitive, hydrochloric acid is used to lower the pH of the brine
solution before it enters the cell. HCl is a simple acid that forms H+ and Cl- ions in solution, both ions
are already present in the brine and the HCl poses no threat to the cell process.
Hydrochloric acid is also used to lower the pH of the depleted brine after it leaves the cell, the
decreased pH increases the efficiency of the dechlorination process. Industrial HCl is produced in
concentrations up to 38%, whilst it is possible to obtain higher concentrations the rate of evaporation
is so high special procedures must be used in handling. HCl is a highly corrosive acid at 38%
o
concentration with a boiling point of 45 C, care must be taken when handling and transporting the
acid. Whilst it is possible to synthesize HCl from the products of the electrolysis that is beyond the
scope of the project and the HCl used will be sourced from chemical suppliers in Ireland such as
Gouldings Chemicals.

2.24 Sodium Bisulfite (NaHSO3)

Sodium bisulfite is a white powder formed by bubbling sulfur dioxide through sodium carbonate
solution.
With uses as a food additive to prevent spoiling the key property of sodium bisulfite in industry is as a
mild reducing agent, efficiently removing remove traces or excess amounts of chlorine, bromine,
iodine, hypochlorite salts. Chlorine and hypochlorite are both prevalent in the depleted brine from the
electrolytic cell and need to be removed before being recycled. Sodium bisulfite is added with sodium
hydroxide and they react with free chlorine to produce sodium chloride, water and sodium sulfate.
Sodium bisulfite is a stable non-toxic non-harmful chemical and no special care needs to be taken, it
is readily available from bulk chemical suppliers such as Gouldings.

2.25 Sodium Carbonate (Na2CO3)

Commonly known as soda ash, sodium carbonate is required as a filtration aid in the brine treatment,
it reacts with calcium chloride in solution to form sodium chloride and calcium carbonate which then
precipitates out of solution as a suspended solid. Sodium Carbonate is commercially produced from
the reaction between sodium chloride and limestone according to the Solvay process. The biggest
consumer of sodium carbonate is the glass industry acting as a flux lowering the melting point of
silica, hence the term soda glass. Sodium carbonate is also readily available from bulk chemical
suppliers such as Gouldings Chemicals though the true source is likely to be Solvay, the market
leader, from their plant in France.

2.25 Barium Chloride (BaCl2)

Barium Carbonate is a naturally occurring mineral in Barium deposits that can be reacted with
hydrochloric acid to form barium chloride. A white powder in the anhydrous form a clear solution at
40% concentration it is required in the purification of the brine recycle. The barium chloride reacts with
the sodium sulfate to from barium sulfate and sodium chloride.
With little barium carbonate present in America and the British mine out of production it is likely that
barium chloride must be sourced from China, the largest producer in the world. The Bashan mine in
Chengkou County produces over 50,000t/y of barium carbonate and nearby plants convert it to
barium chloride. It is possible that the price of import changes due to the political tension between
America and China, an issue that has already led to anti-dumping legislation on Chinese barium
chloride in America.

2.26 Ion-Exchange Resin

The Ion-exchange column is a crucial part of the brine treatment process removing the hardness ions
that would otherwise damage and impede the membrane cell. The resin used in the exchange unit is
dependent on the ions being removed; for hardness ions a cation resin in the sodium form is required.
The resin is prepared in the form of small beads with fixed structure and fixed negatively charged
+
sites, a positively charged ion (Na ) is attracted to the site but is interchangeable in solution with an
2+
2+
alternative cation, Mg and Ca . The resin used has differing affinity for different ions and must be
regenerated after use by a solution of sodium hydroxide. The resin is dependent on the solution being
treated and is bought as a unit from a supplier such as Dow Water and Process Solutions.

2.3-Products and by-products

2.31 Chlorine (Cl2)
The desired product of the process, chlorine gas is pale yellow gas under standard conditions with a
distinct strong odour. Chlorine is a member of the halogens, a highly reactive area of the periodic
table and will react with most other elements to form chlorides. Chlorine gas is an irritant at low
concentrations and deadly above 1000ppm, it reacts with water in the eyes and lungs to form
hydrochloric and hypochlorous acids, activated charcoal and other common gas filtration methods are
effective at preventing chlorine inhalation. Chlorine is used in a wide range of industrial applications
from degreasers to plastics and is an active ingredient of some form in a large number of household
cleaners as an oxidising agent. Chlorine is commonly used in water treatment, both potable and as a

sanitiser for swimming pools chlorine is also used as a bleaching agent in household bleach and hair
dyes. Some chlorine compounds are serious pollutants. These are produced either as by-products or
end products of industrial processes which are persistent in the environment, such as certain
chlorinated pesticides and chlorofluorocarbons. Chlorine is added both to pesticides and
pharmaceuticals to make the molecules more resistant to enzymatic degradation by bacteria, insects,
and mammals, but this property also has the effect of prolonging the residence time of these
compounds when they enter the environment. Chlorine radicals are formed when chlorine gas
undergoes heterolytic fission by ultraviolet radiation, these radicals react with the ozone in the
atmosphere to form oxygenated chlorine and oxygen, depleting the ozone layer.

2.32 Sodium Hydroxide (NaOH)

Sodium hydroxide, also known as caustic soda is a strong chemical base with applications in textiles,
water purification and detergents. Whilst the caustic produced in the cell is 32% concentration
industrial caustic is required to be 50%concentration, a saturated solution. At 50% concentration the
solution is colorless and odourless whilst also being highly corrosive. Anhydrous sodium hydroxide
forms flakes and reacts violently with water in an exothermic reaction causing chemical burns,
household uses include making soap and unblocking drains. Sodium hydroxide plays a key part in the
refinement of aluminium ore, the aluminium ore dissolves in the high pH leaving behind impurities as
an alkaline mud. In 2010 the wall of a mud reservoir in Hungary ruptured spilling a million cubic
metres of alkaline mud killing ten people and having a disastrous effect on the ecology of the nearby
Danube river, exemplifying the need for proper safety regulation. The concentration process for
sodium hydroxide involves multiple-effect evaporators with the final effect operating at temperatures
o
near 200 C, at this temperature sodium hydroxide can corrode stainless steel.

2.33 Barium Sulphate (BaSO4)

Barium sulfate is a white, odourless, insoluble solid considered non-toxic due to its insolubility. It is
however hazardous to the respiratory system as an insoluble powder so occupational exposure limits
3
are set at 5mg/m . Barium sulfate is an off product of the brine treatment process and is ejected as a
suspended solid. The major consumer of barium sulfate is the drilling industry due to its ability to
increase the density of a fluid without dissolving into solution. Alternatively barium sulfate is used in
white paint as well as a base layer for certain types of photography paper due to its ability to reflect
light.

2.33 Calcium Carbonate and Magnesium Hydroxide (CaCO3), (Mg(OH)2)

Byproducts of the brine treatment process these compounds are ejected in the filtration sludge,
neither is toxic or harmful to the environment and each has their own applications however due to the
low volume ejected it is not economically viable to separate them from the sludge. Calcium Carbonate
is a large component of both chalk and limestone and occurs naturally in many animal shells. As an
insoluble hygrophobic solid calcium carbonate finds industrial application as an additive to other solid
flows preventing them from sticking together under humid conditions. Magnesium hydroxide is
commonly known as milk of magnesia as it forms a milky white suspension in water. Magnesium
hydroxide is often used as an antacid or as a laxative with the term Milk of Magnesia being
registered to Bayer Pharmaceuticals.