1

Chapter no 1
In this chapter, we are going to discuss raw materials for caustic soda and their physical and chemical
appearances and their properties. By proceeding with this we will also discuss the local survey of sodium
hydroxide in Pakistan and the regional survey. And Later on the demand and supply, also production and
consumption of caustic soda, and social benefits.

1.0 Introduction:

Chlorine and Sodium hydroxide are among the top ten chemicals produced in the world and are involved
in the production of a wide variety of products used in day to day life. These comprise pharmaceuticals
and detergents, deodorants, disinfectants, herbicides, pesticides, and plastics. Caustic soda or lye has been
designated as a poor substance and is intensely corrosive used in a variety of manufacturing processes.
Sodium hydroxide is a co-product of chlorine production. It is an inorganic substance and is highly
soluble in water and easily absorbs moisture and carbon dioxide from the air. It makes a chain
of hydrates NaOH·nH2O.

Sodium hydroxide is used in many industries in the manufacture of pulp and paper, textile, drinking

water, soap, and detergent, and drain cleaner. It does not contain odor and comes in the form of either
liquid or solid. It is a simple white substance in the form of solid which is in the form of pellets, chips, or
sticks. In a liquid state, it is in the form of an aqueous solution and easy to handle. Usually, it is produced
in a 50% solution through electrolysis of sodium chloride during which chlorine gas is also produced and
then the water evaporates to achieve the final product in solid form. [1]

1.1 Historical Background:

Throughout the first half of the 19th century, soap makers, bleachers, and paper manufacturers for use in
their plants made caustic soda solution. The solid soda was made from the so-called red 3 liquor i.e.
caustic mother liquor by Le Blanc soap makers in Lancashire, England by the batch-wise lime reaction,
chemically not different from the lime-soda process of the 200 centuries.

Na2CO3 + Ca (OH) 2 → NaOH + CaCO3

Out of all the processes developed the continuous lime process was the only one in important use during
the early years of the 200 centuries. [1]

1.2 Physical and Chemical Properties: [2]

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1.2.1 Physical Properties:

Pure anhydrous sodium hydroxide is a white somewhat translucent crystalline solid having a molecular
weight of 39.99gm/gm. mole. In even moderate conditions it is highly corrosive to the skin. Because of
this property, it is also known as caustic soda. Caustic soda is very soluble in water and is highly alkaline.
The properties of pure, anhydrous caustic soda are given in the table. Although caustic soda is produced
and shipped in the anhydrous state in the form of solid, flakes, or beads, very little is consumed as such.
Because, it is used almost exclusively in water solutions of less than 50% concentration, the properties of
its aqueous solutions are most important to the industry. In solution from depending upon concentration,
caustic soda can form five hydrates containing 1,2,3,4 and 7 molecules of water, respectively. Hydrate
formation is an exothermic caustic solution that generates heat when further diluted with water. With a
concentration of 40% or more, the heat produced can raise the temperature above the boiling point,
resulting in a dangerous eruption of the solution. Any dilution of the caustic from a concentration greater
than 25% should be done carefully.

Table 1.1 Physical Properties of Pure Anhydrous NaOH

Molecular weight (gm./gm. Mole) 39.98

Specific Gravity 2.130

Melting point °C 318

Boling point °C 1390

Index of refraction 1.3576

Latent heat of fusion (J/g) 167.4

The heat of transition, alpha to beta, (J/g) 103.3

The heat of formation from elements: Alpha from, 422.60

KJ/mole)
The heat of formation from elements: Beta from, 422.60
KJ/mole)
Transition temperature °C 299.6

(Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics )

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1.2.2 Chemical Properties:

The aqueous solution of caustic soda is highly basic and especially useful in reaction with weak acidic
materials where a weak base such as sodium carbonate is ineffective. NaOH neither burns nor supports
combustion, although, in its reaction with amphoteric metals, such as Al, Sn, and Zn, hydrogen gas is
produced which may form an explosive mixture. A major use of NaOH is to form sodium salts, thus
neutralizing strong acids makes easier the solubilization of water-insoluble chemicals through the
formation of sodium salts. Sodium hydroxide is also useful in the precipitation of heavy metals as their
hydroxides and the control of the acidic nature of aqueous solutions.

1.3 Raw Material for Sodium Hydroxide Production: [3]

Almost all caustic soda is produced by the electrolysis of sodium chloride solution using one of three cell
types: mercury, diaphragm, and membrane cells. The electrolysis process produces 2.25 tonnes of 50%
caustic soda with each ton of chlorine. The primary raw material is common salt usually in the form of
underground deposits which are brought to the surface as a solution to pump high pressure water supply.
The sodium chloride solution is often called brine.
Salt is the most important raw material for the production of sodium hydroxide. It can be extracted by
seawater, inland brine, rock salt deposits mining, and solution mining. Since the diaphragm cell
requires a low level of purity, the solution can be used directly to the brine produced by mining. Other
types of cells require a certain level of purity. Large deposits of sodium chloride (rock salt) are found
in many parts of the world.  These deposits are almost pure sodium chloride and are often several
hundred meters deep (some are up to 3000 meters deep) from 30 meters to 500 meters thick. They
have vaporized from the seas trapped in the Triassic period 200 million years ago. Solar salt is
produced by the evaporation of seawater using a solar heating system which is also a source of sodium
chloride.

1.3.1 Sources of Rock Salt:

Rock salt which is exported by subsurface mining is used as the primary source for the production of
sodium hydroxide. Some applications including Chlor-alkali manufacturing can use brine solutions that
are obtained directly from rock salt by forcing water into the deposit to dissolve the salt. Rock salt has
been abandoned in the United States, Canada, Germany, Austria, Brazil, Ethiopia, Pakistan, Poland,
Spain, Thailand, the and United Kingdom. So, Sri Lanka has a great opportunity to import rock salt from
Pakistan, Ethiopia, or Thailand. It shows that rock salt has the opportunity to act as the main raw material.
[3]
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1.3.2 Properties of Industrial Salt:

Salt is a chemical compound with many interesting properties that are as follows:

 It forms Crystals or white crystalline powder.

 It is Transparent and colorless in a crystalline form slightly like ice.
 It crystallizes in the isometric system usually in the form of cubes.
 It is soluble in water (35.6g/100g at 0°C and 39.2g/100g at 100°C).
 It is slightly soluble in alcohol but insoluble in concentrated hydrochloric acid.
 It Melts at 801°C and begins to vaporize at a temperature just a little above this boiling point of
1413°C.
 Specific gravity is 2.165.
 It is non-combustible and low toxic.
 It is Hygroscopic in nature and absorbs moisture from damp atmospheres above 75% relative
humidity and below this, it will dry out.

Salt in its natural form often contains traces of magnesium chloride, magnesium sulfate, magnesium
bromide, and others. These impurities can otherwise stain transparent crystals, yellow, red, blue, or
purple. [4]

Table 1.2 Typical chemical composition of industrial salt

(Schw
eitzer, Component Percentage (%)
NaCl
97.94

MgCl2
0.74

MgSO4
0.32

NaOH
0

CaSO4
0.72

Insoluble
0.28

Albert. African Notebook. 1958. Indiana University Press.)

1.4 Local survey of sodium hydroxide in Pakistan: [5]

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Pakistan has a substantial production capacity of caustic soda to satisfy the needs of the local industry.
Currently, there are four major plants in Pakistan with a production capacity of about 435,000 megatons
per year of caustic soda of several grades.

1.4.1 Sodium Hydroxide sector update survey:

A Chlor-alkali business may be designated as a region of the chemical industry that produces liquid
chlorine, hydrochloric acid, sodium hypochlorite, bleaching land, and chlorinated paraffin. However,
caustic Soda is the main product of this sector. Caustic Soda is produced as a 50 % solution by the
deviation of the electrolytic chlor-alkali process. Demand for caustic soda is highly dependent on
manufacturing sector development as it is an essential raw material in industries including textile, soap,
detergent, paper & board, vegetable oil refining, thermal power unit, and food processing sugar, etc.
Presently there are 4 major players in the market with a production capacity of more than 500,000 MT of
caustic soda and chlor alkali-based products. These plants are SCIL, Ittehad Chemicals Limited (ICL),
Engro Polymer Chemicals Limited (EPCL), and NIMIR Industrial Chemicals Limited (NIMIR).
However, NIMIR only produces caustic soda for its internal use. The installed productivity of caustic
soda of the other three commercially challenging players is presented here:

Table 1.3 Annual capacity of industries for sodium hydroxide production [5] (Tons)
Annual FY08 FY09 FY10 FY11 FY13 FY14 FY15
Capacity
SCIL 178200 178200 201300 201300 201300 201300 201300
ICL 143550 143550 143550 143550 150550 125550 125550
EPCL NIL 106000 106000 106000 106000 106000 106000
(JCR VS Chemical Industry Sector Update December 2016)

The total annual output of these 3 units remained at the advanced level of 450,850 MT. Where SCIL has
the largest productivity of 201,300 MT/annum. After ECL entry into the industry, the market has become
more competitive for the other players as all caustic soda producers have been observed in the trend of
decreasing capacity use. SCIL also operates a textile unit that is engaged in the production of a variety of
yarn. Caustic soda represents more than 60% of total revenue in terms of SCIL and ICL revenue. EPCL
operates mainly in Sindh while the other two players are based in Punjab. SCIL has the highest installed
capacity among three players. [6]

1.5 Worldwide Survey of Sodium Hydroxide:

Sodium Hydroxide, commonly called Caustic Soda, is one of the most widely used chemical substances
in the world. Sodium Hydroxide is the natural Co-Product of the Chlorine Industry. Sodium Hydroxide is
a chemical substance that has a high supply and demand in daily domestic activities due to its greater
availability and ease of production. However, the current global market has increased the demand for
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Chlorine. NaOH is a true co-product in Chlorine production. So, with the increased Chlorine production,
the production of NaOH has also increased, and as a result of this continuous production of NaOH, there
has also been a substantial supply of NaOH for the necessary production activities. So, any slight increase
of NaOH demand will not be dealt with any other alternative NaOH production methods (i.e.
caustification Process, where NaOH is produced from lime and Soda). But for any further increase in the
NaOH demand, the Caustification process will be used to increase the production.

Table 1.4 Annual Production of NaOH

World 70 million tons

(http://www.essential
US 11.4 million tons
chemicalindustry.org/ chemicals/sodium-
hydroxide.html.)
Europe 10.7 million tons
1.5.1 Regional Survey: [7]
In the regional survey, we
discuss imports and exports of caustic soda in china and the demand for caustic soda in china.
1.5.2 Imports of caustic soda in China:
Table 1.5 Imports of caustic soda (Value US$)
Years Observation value
2008 1,132,562,161,442,00
2009 1,005,555,225,206,00
2010 1,396,001,565,258,00
2011 1,743,394,866,363,00
2012 1,818,199,227,571,00
2013 1,949,992,314,705,00
2014 1,959,234,625,162,00
2015 1,679,564,324,560,00
2016 1,587,920,688,162,00
2017 1,843,792,938,795,00
2018 2,134,982,614,989,00
2019 2,068,950,254,597,00

(https://trendeconomy.com/data/h2/China)

1.5.3 Exports of caustic soda in China:

Table 1.6 Exports of caustic soda (Value US$)
Years Observation Value
2008 1,430,693,066,080,00
2009 1,201,646,758,080,00
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2010 1,577,763,750,888,00
2011 1,898,388,434,783,00
2012 2,048,782,233,084,00
2013 2,209,007,280,269,00
2014 2,342,292,696,320,00
2015 2,273,468,224,113,00
2016 2,097,637,171,895,00
2017 2,263,370,504,301,00
2018 2,494,230,194,966,00
2019 2,498,569,865,637,00
(https://trendeconomy.com/data/h2/China)

Figure 1 imports and exports of caustic soda in China in 2019

1.5.4 Production Pattern of caustic soda in China: [7]

China is driving the growth in caustic soda demand. China is the world’s largest consumer of caustic
soda accounting for 28% of global demand and is also the largest producer overtaking the US in 2005.
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Figure 2 year’s vs. production

1.6 Pakistan growing Demand: [8]

The actual demand for caustic soda is as follows.
Table 1.7 Demand for caustic soda in various industries
(Unit: 1000tons)
Application 201 201 201 201 201 201
2 3 4 5 6 7
Paper and pulp 302 310 296 306 303 305
Chemical fibers 56 57 55 56 63 59
Dying finishing 48 48 46 46 47 49
Alumina 51 31 26 23 22 23
Foods 88 84 81 88 88 89
Nonferrous metals 92 84 81 88 88 89
Electronic 74 71 70 66 66 66
Pharmaceuticals/agrochemica 57 58 54 51 51 46
ls
Iron & steel 41 44 44 46 46 49
Water supply &sewage 45 45 48 43 48 46
Inorganic chemicals 461 451 446 452 439 455
Organic chemicals 324 292 361` 381 396 407
Dyes/intermediates 73 80 79 77 70 71
Soaps/detergents 44 43 43 44 47 46
Electrolysis soda 58 57 54 53 50 51
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Plastics 126 132 144 157 149 163

Other Chemical applications 638 609 679 621 655 673
Others 599 668 576 634 667 693
Total 317 316 318 323 329 337
7 4 5 0 4 5
(https://trendeconomy.com/data/commodity_h2/281511)

1.6.1 Demand-Supply Gap:

We assume that the available capacity of Caustic soda will remain the same that is 143550 tons.
But the demand and supply gap are as follows:
Table 1.8 Demand supply gap of NaOH
(Tons)

Years Total Demand Available Capacity Demand Supply

1990-00 152,001 143,550 8,491
2000-01 162,801 143,550 19,251
2001-02 173,600 143,550 30,050
2002-03 184,400 143,550 40,850
2003-04 195,199 143,550 51,649
2004-05 205,999 143,50 62,449
2005-06 216,798 143,550 73,248
2006-07 227,598 143,550 84,048
2007-08 238,397 143,550 94,847
2008-09 249,197 143,550 105,647
2009-10 259,996 143,550 116,446
(Encyclopedia of Chemical Processing and Design by John J. Mcketta)
The gap between demand and supply can be enclosed by
1. Increase in imports
2. A new entrant in the market
3. Expansion in installed capacity of existing units
1.6.2 Limitation on Technology:
Pakistan has an abundant production capacity of caustic soda to supply the needs of local industry.
Presently Pakistan has four major plants with a production capacity of around 435,000 megaton per
year of caustic soda of various grades. Caustic soda is the main product of the Pakistan Chlor alkali
industry. The demand for caustic soda is highly dependent on the development of the manufacturing
sector as it is the important raw material needed for processing various industries like textile, soaps,
detergents, paper and pulp, oil refining, thermal power units, food processing. The largest consumer of
caustic soda in Pakistan is the textile sector. [1]
1.7.4 Installed Capacity:
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Following is the per day capacity and an annual capacity of different industries for the production of
caustic soda.
Table 1.9 Installed per day capacity of NaOH

Units Per Day Capacity Annual Capacity

(Tones) (Tones)
Sitara Chemical 400 132000

Etihad Chemical 170 56100

Nimmer Chemical 30 9900

Total 600 198000

(https://www.questia.com/magazine/1G1-11189822/caustic-soda-industry)

1.7 Production Pattern of Caustic Soda:

Local production of caustic soda has been increased during the last two decades. From 1998 to 1999 a
total of 118315 tonnes of caustic soda were manufactured. From 2006 to 2007 this production has
increased to at a total of 194150 tons per annum.
From 2001 to 2008 local production of caustic soda has increased from 118315 tons to 194150 tons,
showing an annual progress rate of 10.83 which is very encouraging for the industry. Production of
caustic soda in the last five years has been increased in various industries through the capacity trend of
caustic soda shows an increasing trend. [9]
Table 1.10 Production of NaOH

Years Caustic Soda(tones)

2015-2016 225250
2016-2017 223855
2017-2018 270126
2018-2019 246613
2019-2020 90586
Monthly Bulletin of Statistics December 2020
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Production of Caustic Soda in Pakistan

300000
270126
246613
250000
Production (Metric Tones)

225250 223855

200000

150000

100000 90586

50000

0
2015-16 2016-17 2017-18 2018-19 2019-20
years

Figure 3 years vs. production

1.8 Basis of Capacity Selection:

The average import of caustic soda in the past few years is increased. Due to ups and downs in the
import of Caustic soda in the past few years, we selected an average value of caustic soda capacity for
the plant which is 250 MTPD.

1.9 Consumption Pattern of Caustic Soda:

Consumption of caustic soda in the last five years has been increased in various industries through the
capacity trend of caustic soda shows an increasing trend. Textile and paper and pulp are the two major
industries for the consumption of caustic soda.

Table 1.11 Consumption pattern of NaOH

Item Percentage of Total

Viscous rayon 10
Staple fiber 17
Aluminum 13
Soaps 12
Textile 10
Paper and Pulp 24
Vanaspati 2
iscellaneous 12
Total 100

(Encyclopedia of Chemical Processing and Design by John J. Mcketta)

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Percentage of Total
10 Viscous rayon
17 Staple fiber
Aluminum
13
Soaps
Textile
12
100 Paper and Pulp
10 Vanaspati
Miscellaneous
Total
24

12
2

As it is shown from local survey and an increase in demand for caustic soda, production and
consumption have been increased in future and production of caustic soda shows an increasing
trend with time.

1.10 Uses and Social Benefits: [10]

Sodium hydroxide is used to produce many daily products, such as paper, aluminum, commercial drain
and oven cleaners, and soap and detergent.

Sodium Hydroxide in Cleaning and Disinfectant Products:

Sodium hydroxide is used to produce soap and a variety of detergents used in homes and commercial
applications. Chlorine bleach is produced by mixing chlorine and sodium hydroxide.

Sodium Hydroxide in Pharmaceuticals and Medicine:

Sodium hydroxide is used to produce a variety of medicines and pharmaceutical products, from common
pain relievers like aspirin to anticoagulants that can help prevent blood clots or cholesterol-reducing
medications.

Sodium Hydroxide in Water Treatment:

Municipal water treatment facilities use sodium hydroxide to help control the acidity of water and remove
heavy metals from water. Sodium hydroxide is also used to produce sodium hypochlorite, a water
disinfectant.
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Sodium Hydroxide in Food Production:

Sodium hydroxide is used for canning to remove skins from tomatoes, potatoes, and other fruits and
vegetables and also as a component in food preservatives that help prevent mold and bacteria from
growing in food.

Sodium Hydroxide in Wood & Paper Products:

In many processes of making paper, wood is treated with a solution containing sodium sulfide and sodium
hydroxide. It helps to dissolve most unwanted materials into the wood, which leaves relatively pure
cellulose, which forms the basis of the paper. In the process of paper recycling, sodium hydroxide is used
to separate ink from paper fibers allowing the paper fibers to be reused again. Sodium hydroxide is also
used to improve raw materials in wood products such as cabinets and furniture and the bleaching and
cleaning of wood.

Sodium Hydroxide in Other Industrial Manufacturing Uses:

Sodium hydroxide is used in many other industrial and manufacturing processes. It is used to produce
rayon, spandex, explosive, epoxy resins, paints, glass, and ceramics. It is also used in making dye in
textile industry, processing cotton fabric and laundering and bleaching, as well as in metal cleaning and
processing, oxide coating, electroplating, and electrolytic extraction.

Paint stripper:

A solution of sodium hydroxide in water was traditionally used as the most common paint strippers on
wooden objects. Due to its caustic nature and the fact that it can damage the wood surfaces by raising
grain and tarnishing color, it has become less common to use.

Alumina production –Bayer’s process:

Sodium hydroxide is used in the refining of alumina containing ore (bauxite) to produce aluminum oxide
which is the main raw material used to produce aluminum metal through the smelting process.
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References:

[1] 2005-handbook of chlor-alkali technology volume 1 (Fundamentals)

[2] Occidental Chemical Corporation (OxyChem) caustic soda Handbook

[3] “The Sri Lanka Forester 1977”

[4] “Industrial Chemistry, 1991”

[5] JCR-VIS caustic soda sector update June 2016

[6] JCR-VIS Chemical industry sector update December 2011

[7] UN of statistics trend economy

[8] Pakistan Caustic Soda Production Bureau of Statistics

[9] Monthly Bulletin of Statistics December 2020

[10] Sodium Hydroxide Chemical safety facts.org