Table of Contents

1.1

Introduction

1.2

Raw materials

Pages
1
2

1.2.1 Raw material purification

1.3

Production process

1.4

Properties of caustic soda

13

1.5

Uses of caustic soda

16

1.6.1 Caustic soda packaging and storage

1.6.2 Placement unloading

18

1.6.3 Unloading precaution

1.7

17

References

1.1

INTRODUCTION

The Alkali industry also known as chloralkali industry is a chemical technology

industry in which chloralkali processes is carried out. The chloralkali process
(also chlor-alkali) is an industrial process for the electrolysis of sodium chloride.
It is the technology used to produce chlorine and sodium hydroxide (caustic soda),
which are commodity chemicals required by industry. To give some sense of scale,
35 million tons of chlorine were prepared by this process in 1987 (Greenwood etal 1987) Industrial scale production began in 1892.
Usually the process is conducted on a brine (an aqueous solution of NaCl), in
which case NaOH, hydrogen, and chlorine result. When using calcium chloride or
potassium chloride, the products contain calcium or potassium instead of sodium.
Related processes are known that use molten NaCl to give chlorine and sodium
metal or condensed hydrogen chloride to give hydrogen and chlorine.
Brine (salt water), the feedstock of the chlor-alkali industry, is used in the
production of chlorine, caustic soda (sodium hydroxide), soda ash (sodium
carbonate), and a wide range of other products that can be used as raw material in
other processes and industries. Chlorine is used to produce polymers which are
then used in the manufacture of plastics, synthetic fibers, and synthetic rubber.
Caustic soda is used in the production of polyester, other synthetic fibers, plastics,
soaps, and detergents. Soda ash is used in the manufacture of glass, pulp and paper,
and rayon.

The aim of this term paper shall be on the production of caustic soda (sodium
hydroxide) as one part of the products of an alkali industry. We shall also discuss
the various steps that is required for the efficient production of caustic soda.
Caustic soda (sodium hydroxide or NaOH) is most commonly manufactured by the
electrolysis of a sodium chloride (NaCl) solution. Industries manufactures caustic
soda using either membrane or diaphragm electrolytic cells. Some industries do not
use mercury based electrolytic cells to produce caustic soda. The co-products
formed from the electrolytic production of caustic soda are chlorine and hydrogen.
The largest users of caustic soda are the pulp and paper, detergent and chemical
industries. Caustic soda is also used in the alumina, oil and gas and textile
industries, mostly for its alkalinity value.
Liquid caustic soda is available as a 50% solution in two main grades. The names
of these grades correspond to the electrolytic cells used to produce the caustic
soda; membrane grade and diaphragm grade. To be technically correct, only
molten caustic soda should be called liquid, but since the term liquid caustic soda
has historically been used to describe solutions of caustic soda, it is used in this
document interchangeably with the term solution.
There three (3) major procedures in the production of caustic soda and they are
namely:
I.

Membrane cell process

II.

Diaphragm cell process

III.

Mercury cell

These listed processes above will be discussed in details in the later part of this
term paper.
3

1.2

RAW MATERIALS FOR CAUSTIC SODA PRODUCTION

Brine (salt water), sodium and chlorine are the major raw materials for the
industrial manufacture of caustic soda. These are obtained by dissolving rock salt
or naturally occurring brines. The salt solution contains some impurities, these salts
are salts of sodium, and magnesium. A critical parameter in the chlor-alkali process
is determining the purity of the feed brine. In the membrane cell production
process of caustic soda, trace levels of alkaline earth metals (such as calcium and
magnesium) and iodide can shorten the membrane life. To ensure production
efficiencies, the sum of calcium and magnesium must be less than 20 ppb in 30%
sodium chloride (NaCI).

1.2.1 RAW MATERIAL PURIFICATION

The presence of trace metalssuch as magnesium, calcium, and manganesein
the brine feedstock can poison the ion-exchange membrane cell and halt the chloralkali process. Iodide, present at ppb concentrations, is another critical analyte to
measure as it can interact with trace levels of alkaline earth metals at the
membrane surface and compromise the membranes useful life. Soda and milk
slake lime of a lime solution, are used to purify the brine.
1. Treatment with soda
MgSO4 + Na2CO3 MgCO3 + Na2SO4

CaSO4 + Na2CO3 CaCO3 + Na2SO4

2. Treatment with slake lime
Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
Mg(HCO3)2 + 2 Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O

Thickening and filtration are the main methods of removing all suspended
solids and precipitates.

1.3

CAUSTIC SODA PRODUCTION PROCESS

Three production methods are in use. While the mercury cell method produces
chlorine-free sodium hydroxide, the use of several tonnes of mercury leads to
serious environmental problems. In a normal production cycle a few hundred
pounds of mercury per year are emitted, which accumulate in the environment.
Additionally, the chlorine and sodium hydroxide produced via the mercury-cell
chloralkali process are themselves contaminated with trace amounts of mercury.
The membrane and diaphragm method use no mercury, but the sodium hydroxide
contains chlorine, which must be removed Saturated brine is passed into the first
chamber of the cell where the chloride ions are oxidised at the anode, losing
electrons to become chlorine gas (A in figure):

2Cl Cl2 + 2e
At the cathode, positive hydrogen ions pulled from water molecules are reduced by
the electrons provided by the electrolytic current, to hydrogen gas, releasing
hydroxide ions into the solution (C in figure):

2H2O + 2e H2 + 2OH
The ion-permeable ion exchange membrane at the center of the cell allows the
sodium ions (Na+) to pass to the second chamber where they react with the
hydroxide ions to produce caustic soda (NaOH) (B in figure). The overall reaction
for the electrolysis of brine is thus:
5

2NaCl + 2H2O Cl2 + H2 + 2NaOH

A membrane cell is used to prevent the reaction between the chlorine and
hydroxide ions. If this reaction were to occur the chlorine would be
disproportionated to form chloride and hypochlorite ions:

Cl2 + 2OH Cl + ClO + H2O

Above about 60 C, chlorate can be formed:

3Cl9 + 6OH 5Cl + ClO3 + 3H2O

Because of the corrosive nature of chlorine production, the anode (where the
chlorine is formed) must be made from a non-reactive metal such as titanium,
whereas the cathode (where hydroxide forms) can be made from a more easily
oxidized metal such as nickel.
i.

MEMBRANE CELL

In the membrane cell, the anode and cathode are separated by an ion-permeable
membrane. Saturated brine is fed to the compartment with the anode (the anolyte).
A DC current is passed through the cell and the NaCl splits into its constituent
components. The membrane passes Na+ ions to the cathode compartment
(catholyte), where it forms sodium hydroxide in solution. The membrane allows
only positive ions to pass through to prevent the chlorine from mixing with the
sodium hydroxide. The chloride ions are oxidised to chlorine gas at the anode,
which is collected, purified and stored. Hydrogen gas and hydroxide ions are
formed at the cathode. The diagram below shows the process flow chart of
membrane process

Fig1. Process flow chart of a membrane process

The membrane process is summarised in the diagram below. The cathode and
anode compartments are separated by a water-impermeable membrane. This means
that ions can pass, but water cannot. Concentrated sodium chloride solution
(NaCl(aq)) flows though the anode compartment and water flows though the
7

cathode compartment. The sodium ions and hydroxide ions combine in the cathode
compartment to produce sodium hydroxide.

Fig 2. Membrane cell

ii

MERCURY CELL

In the mercury-cell process, also known as the Castner-Kellner process,

a saturated brine solution floats on top of the cathode which is a thin
layer of mercury. Chlorine is produced at the anode, and sodium is
produced at the cathode where it forms a sodium-mercury amalgam with
the mercury. The amalgam is continuously drawn out of the cell and
reacted with water which decomposes the amalgam into sodium
hydroxide and mercury. The mercury is recycled into the electrolytic
cell. Mercury cells are being phased out due to concerns about mercury
poisoning from mercury cell pollution such as occurred in Canada
8

Fig 3. Mercury process for chloralkali

The process chart for the above process is shown below:

Fig.4 process flow chart for a mercury cell process

ii.

Diaphragm Cell
In the diaphragm cell process, there are two compartments separated by a
permeable diaphragm, often made of asbestos fibers. Brine is introduced into
the anode compartment and flows into the cathode compartment. Similarly to
the Membrane Cell, chloride ions are oxidized at the anode to produce
chlorine, and at the cathode, water is split into caustic soda and hydrogen. The
10

diaphragm prevents the reaction of the caustic soda with the chlorine. A
diluted caustic brine leaves the cell. The caustic soda must usually be
concentrated to 50% and the salt removed. This is done using an evaporative
process with about three tonnes of steam per tonne of caustic soda. The salt
separated from the caustic brine can be used to saturate diluted brine. The
chlorine contains oxygen and must often be purified by liquefaction and
evaporation.

Fig 5. Diaphragm Cell

A process flow chart is used to describe the process of diaphragm cell and
amongst the two (2) other manufacturing process of caustic soda its the most
suitable and generally accepted process.

11

Fig 6. Process flow chart of a diaphragm process

Diaphragm cells have the advantage of:
operating at a lower voltage than mercury cells
12

 operating with less pure brine than required by membrane cells

When using asbestos diaphragms, the diaphragm process inherently gives rise to
environmental releases of asbestos.

BY-PRODUCTS OF A DIAPHRAGM
During electrolysis, some side reactions occur. One of which is

2OH - 2e- 0.5O2 + H2O

Also chlorine librated at the anode is partially dissolved in the electrolyte and it
hydrolyses as follows

Cl2 + H2O HOCI + HCl

There might be diffusion of the alkali (OH) ions to the anode resulting in
neutralization of the hypochloric and hydrochloric acids to form sodium
hypochlorite.

HOCI + NaOH NaOCl + H2O

HCl + NaOH NaCi + H2O
Hence as a result of side reactions, sodium hypochlorite, chloride and chlorate are
formed which led to a drop in the efficiency of the process. To retard this side
reactions some conditions must be followed which prevents the mixing of the
cathode and anode products.

13

 Separation of cathode and anode with a diaphragm and filtering the

electrolyte through the diaphragm counter current to the flow of OH ions
to the anode
Raising NaCl concentration of the electrolyte
Reduce NaOH concentration to the cathode
Raising temperature of electrolysis

1.4

PROPERTIES OF CAUSTIC SODA

Physical properties
Pure sodium hydroxide is a whitish solid, sold in pellets, flakes, and granular form,
as well as in solution. It is highly soluble in water, with a lower solubility in
ethanol and methanol, but is insoluble in ether and other non-polar solvents.

Fig. 7 Whitish pellets of Caustic soda

Similar to the hydration of sulfuric acid, dissolution of solid sodium hydroxide in
water is a highly exothermic reaction in which a large amount of heat is liberated,
posing a threat to safety through the possibility of splashing. The resulting solution

14

is usually colourless and odorless with slippery feeling upon contact in common
with other alkalis.
Chemical properties
Reaction with acids
Sodium hydroxide reacts with protic acids to produce water and the corresponding
salts. For example, when sodium hydroxide reacts with hydrochloric acid, sodium
chloride is formed:
NaOH(aq) + HCl(aq) NaCl(aq) + H2O
In general, such neutralization reactions are represented by one simple net ionic
equation:
OH(aq) + H+(aq) H2O(l)
This type of reaction with a strong acid releases heat, and hence is exothermic.
Such acid-base reactions can also be used for titrations. However, sodium
hydroxide is not used as a primary standard because it is hygroscopic and absorbs
carbon dioxide from air.
Reaction with acidic oxides
Sodium hydroxide also reacts with acidic oxides, such as sulfur dioxide. Such
reactions are often used to "scrub" harmful acidic gases (like SO2 and H2S)
produced in the burning of coal and thus prevent their release into the atmosphere.
For example,
2 NaOH + CO2 Na2CO3 + H2O
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Reaction with amphoteric metals and oxides

Glass reacts slowly with aqueous sodium hydroxide solutions at ambient
temperatures to form soluble silicates. Because of this, glass joints and stopcocks
exposed to sodium hydroxide have a tendency to "freeze". Flasks and glass-lined
chemical reactors are damaged by long exposure to hot sodium hydroxide, which
also frosts the glass. Sodium hydroxide does not attack iron since iron does not
have amphoteric properties (i.e., it only dissolves in acid, not base). A few
transition metals, however, may react vigorously with sodium hydroxide.
In 1986, an aluminium road tanker in the UK was mistakenly used to transport
25% sodium hydroxide solution, causing pressurization of the contents and damage
to the tanker. The pressurization was due to the hydrogen gas which is produced in
the reaction between sodium hydroxide and aluminium:
2 Al + 2 NaOH + 6 H2O 2 NaAl(OH)4 + 3 H2
Precipitant
Unlike sodium hydroxide, the hydroxides of most transition metals are insoluble,
and therefore sodium hydroxide can be used to precipitate transition metal
hydroxides. The following colours are observed: blue-copper, green-iron(II),
yellow/brown-iron(III). Zinc and lead salts dissolve in excess sodium hydroxide to
give a clear solution of Na2ZnO2 or Na2PbO2.
Aluminium hydroxide is used as a gelatinous flocculant to filter out particulate
matter in water treatment. Aluminium hydroxide is prepared at the treatment plant
from aluminium sulfate by reacting it with sodium hydroxide.
Al2(SO4)3 + 6 NaOH 2 Al(OH)3 + 3 Na2SO4
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Saponification
Sodium hydroxide can be used for the base-driven hydrolysis of esters (as in
saponification), amides and alkyl halides. However, the limited solubility of
sodium hydroxide in organic solvents means that the more soluble potassium
hydroxide (KOH) is often preferred.

1.5

USES OF CAUSTIC SODA

Caustic soda, is used for many household and industrial purposes. The chemical
forms a strong alkaline solution when you mix it with water.
a) It is used for household purposes in cleaning
b) It is used in many industries like paper and pulp, textiles, and used in the
manufacturing of soaps, detergents and cleaners.
c) Since it is cheaply available, many educational institutions use it in student
labs. In labs, it is generally used to drive chemical reactions.
d) It is a very good neutralizing agent, especially when used for neutralizing
acids and also for refining petrol
e) It is used in oil refineries and for oil drilling, since it increases the viscosity
and prevents heavy materials from settling.
f) Sodium hydroxide is also used in the manufacturing process of soaps and
detergents.
g) Sodium Hydroxide is used along with sodium sulfide to separate lignin from
cellulose. It can also be used as a bleaching agent to bleach brown pulp.
Anhydrous sodium hydroxide can be used as a catalyst for preparing
biodiesel because it is cheaper than any other alkalines
h) It is used as cleaner in breweries and wineries and also for etching aluminum
surfaces, as it gives it a polished look.

17

i) Out of the many uses of sodium hydroxide one major use is that it can be
used for washing and chemical peeling of fruits and vegetables, chocolates
and cocoa processing, as well as soft drink processing

1.6

CAUSTIC SODA PACKAGING AND STORAGE

Liquid caustic soda is available from many plants and terminals in tank truck, rail
tank car, barge and ship quantities. Each form of transportation has its own
advantages. The type of service selected will depend upon such factors as size and
location of storage, rate of consumption, plant location, freight rates, etc.

1.6.1 UNLOADING AND HANDLING CAUSTIC SODA IN

RAILCARS
GENERAL INFORMATION
Liquid Caustic soda has a markedly corrosive action on all body tissue. Even dilute
solutions may have a destructive effect on tissue after prolonged contact. Inhalation
of mists can cause damage to the upper respiratory tract, while ingestion of liquid
caustic soda can cause severe damage to the mucous membranes or other tissues
where contact is made.
It is important that those who handle caustic soda are aware of its corrosive
properties and know what precautions to take. In case of accidental exposure,
immediately flush the exposed area with large amounts of water and seek medical
attention.
1.6.2 PLACEMENT OF THE RAILCAR FOR UNLOADING
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1. After the car is at the loading spot, DOT regulations require that the hand brake
be set and the wheels blocked (chocks).
2. DOT regulations require caution sign(s) be placed on or next to the rail track to
warn persons approaching the car from the access track end(s). Caution signs must
be left up until the railcar is completely unloaded and disconnected from the
customers connections. Signs must be made of metal or other suitable material, at
least 12x15 inches in size, and bear the words, STOP-TANK CAR
CONNECTED, or STOP-MEN AT WORK.
3. It is recommended that a locked switch or derail device be placed at the access
track end(s), a minimum of one car length away from the railcar to be unloaded.
4. A railcar of caustic soda should only be unloaded when adequate lighting is
available.
5. A suitable ramp should be used to access the railcar top operating or safety
platform. The access ramp chosen should accommodate a variety of platform
widths because of variations in rail car manufacturers, and railcar heights since the
railcar will rise while unloading.
1.6.3

UNLOADING PRECAUTIONS

Before making any connections, verify the content of the railcar is caustic
soda.
Avoid skin and eye contact and breathing in vapour, mists and aerosols

19

 Test the nearest eyewash and safety shower per your facility procedure.
Only responsible and properly trained personnel should unload liquid
caustic soda.
Unloading operations must be monitored while the car is connected.
NOTES:
Do not exceed a steam pressure of 15 psig on the jacket. Certain railcar linings can
be damaged using steam pressure above15 psig.
Do not keep steam on while emptying the railcar. Exposing the steam coils without
fluid present to dissipate the heat can damage the lining due to local heating.
Do not heat the product over 120oF to minimize corrosion of unlined steel piping
systems and equipment.

20

REFFERE NCE
1. Sodium Hydroxide - Compound Summary". Retrieved June 12, 2012.
2.
Zumdahl, Steven S. (2009). Chemical Principles 6th Ed. Houghton Mifflin
3.

Company.
Cetin Kurt, Jrgen Bittner (2005), "Sodium Hydroxide", Ullmann's

4.

Encyclopedia of Industrial Chemistry, Weinheim: Wiley-VCH,

Kirk-Othmer Encyclopedia of Chemical Technology 5th edition (online,

5.

account needed), John Wiley & Sons. Accessed November 21, 2005.
Deming, Horace G. (1925). General Chemistry: An Elementary Survey
Emphasizing Industrial Applications of Fundamental Principles (2nd ed.).

6.

New York: John Wiley & Sons

Thacker, H. Leon; Kastner, Justin (August 2004). Carcass Disposal: A
Comprehensive Review. Chapter 6. National Agricultural Biosecurity

7.

Center, Kansas State University, 2004. Retrieved 2010-03-08

Morfit, Campbell (1856). A treatise on chemistry applied to the manufacture
of soap and candles. Parry and McMillan.

21