SODIUM SULPHATE

CHAPTER NO:-01
INTRODUCTION

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SODIUM SULPHATE

1.1 INTRODUCTION

SODIUM SULPHATE (also known as sodium sulfate or sulfate of soda) is the

inorganic compound with the formula of Na2SO4 as well as several related hydrates.

All forms are white solids that are highly soluble in water. With an annual production
of 6 million tonnes, the decahydrate is a major commodity chemical product.

It is mainly used for the manufacture of detergents and in the kraft process for
manufacturing of paper pulping.

Anhydrous sodium sulphate, known as the rare mineral thenardite, using as adrying
agent in organic synthesis.

Heptahydrate sodium sulphate is a very rare form. Decahydrate sodium sulphate

known as the mineral mirabilite widely used by chemical industry. It is also known as
Glauber’s salt.

 CHEMICAL FORMULA:-
Na2SO4

 Other names:-
1) Sodium Sulphate.
2) Sulfate of Sodium.
3) Thenardite (Mineral).
4) Sal Mirabilis (decahydrate).
5) Mirabilite (decahydrate mineral).
6) Disodium sulphate.

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SODIUM SULPHATE

1.2 HISTORY(1)

In 1625, Johann Rudolf

Glauber’s discovered the sodium sulphate
from Austrian spring water there so the
hydrate form is known as Glauber's salt. Due
to its medicinal properties he named it as salt
mirabilis (miraculous salt). The crystals
were used as a general purpose laxative, until
1900s. By reaction with potassium carbonate
or potash, Glauber's salt was used as a raw
material for the industrial production of soda
ash in the 18th century. In the nineteenth
century the demand of soda ash was
increased so the large scale Leblanc process
which produced synthetic sodium sulphate
JOHAAN RUDOLF GLAUBER
became the principal method of soda ash
production.

Sodium sulphate (Na2SO4) is the sodium salt of sulphuric acid. Anhydrous

sulphates is white crystalline solid also known as the mineral thenardite, while the
dehydrate Na2SO4.10H2O has been known as Glauber's salt or mirabilis Na2S04.7H20 is
transformed to mirabilite when it is cooled Mirabilite is the natural mineral form of the
dehydrate. About two-thirds of the world's production of sodium sulphate is obtained
from mirabilite. It is also produced from by-products of chemical processes such as
hydrochloric acid production.

In 1995, bulk sodium sulphate sold for around $70 per ton in the US, making
it a very cheap material. Probably the largest use for sodium sulphate today is as a filler
in powdered home laundry detergents. Total consumption of Na2SO4 in Europe was
around 1.6 million tons in 2001, of which 80% was used for detergents. However this

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SODIUM SULPHATE

use is waning as domestic consumers are increasingly switching to liquid detergents

that do not include the chemical.

Another major use for Na2SO4, particularly in the US, is in the Kraft process
for the manufacture of wood pulp. Organics present in the black liquor" from this
process are burnt to produce heat, needed to drive the reduction of sodium sulphate to
sodium sulphide. However this process is being replaced to some extent by newer
processes; use of Na2S04 in the US pulp industry declined from 9,80,000 tonnes in 1970
to only 2,10,000 tonnes in 1990.

The glass industry also provides another significant application for sodium
sulphate, consuming around 30,000 tonnes in the US in 1990 (4% of total US
consumption). It is used as a “fining agent”, to help remove small air bubble from
molten glass. It also fluxes the glass, and prevent scum formation of the glass melt
during refining.

Sodium sulphate is important in the manufacture of textiles, particularly in

Japan. It helps in “levelling” reducing negative charges on fibres so that dyes can
penetrate evenly.

Unlike the alternative sodium chloride, it does not corrode the stainless steel
vessels used in dyeing, the dehydrate, was formerly used as a laxative It has also been
proposed for heat storage in passive solar heating systems. This takes advantage of the
unusual solubility properties (see above), and the high heat of crystallization (78.2
kJ/mol).

Other uses for sodium sulphate include frosting windows, in carpet

freshener, starch manufacture and as an additive to cattle feed. In the laboratory,
anhydrous sodium sulphate is widely used as an inert drying agent for organic solutions,
Na2SO4 is added to the solution until the crystals no longer clump together.

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SODIUM SULPHATE

1.3 PROPERTIES

Physical properties

 Chemical Formula:- Na2SO4.

 Molecular Weight:- 142.42gm/mol.
 Appearance:-White Crystalline solid (Hygroscopic).
 Odour:- Odourless.
 Density:-2.664 gm/mol (anhydrous)
:-1.464 gm/mol (hydrous).
 Melting Point:- 8440C (1623 0F; 1157 K).
 Boiling Point:- 14290C (2604 0F; 1702 K).
 Solubility in Water:-
Anhydrous: 4.76gm/100ml (00C), 13.9gm/100ml (200C), 42.7gm/100ml
(1000C).
Heptahydrate: 19.5gm/100ml (00C), 44gm/100ml (200C).
 Solubility:- insoluble in enthanol, soluble in glycerol,water and hydrogen iodide.

Chemical properties

Sodium sulfate is a typical electrostatically bonded ionic sulfate. The existence of free
sulfate in solution is indicated by the easy formation of insoluble sulfates when these
solutions are treated with Ba2+ or Pb2+ salts:

Na2SO4 + BaCl2 → 2 NaCl + BaSO4

Sodium sulfate is unreactive toward most oxidizing or reducing agents. At high

temperatures, it can be converted to sodium sulfide by carbothermal reduction (high
temperature heating with charcoal, etc.):

Na2SO4 + 2 C → Na2S + 2 CO2

This reaction was employed in the Leblanc process, a defunct industrial route to sodium
carbonate.

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SODIUM SULPHATE

Sodium sulfate reacts with sulfuric acid to give the acid salt sodium bisulfate:

Na2SO4 + H2SO4 ⇌ 2 NaHSO4

Sodium sulfate displays a moderate tendency to form double salts. The

only alums formed with common trivalent metals are NaAl(SO4)2(unstable above
39°C)and NaCr(SO4)2, in contrast to potassium sulfate and ammonium sulfate which
form many stable alums. Double salts with some other alkali metal sulfates are known,
including Na2SO4·3K2SO4 which occurs naturally as the mineral aphthitalite.
Formation of glaserite by reaction of sodium sulfate with potassium chloride has been
used as the basis of a method for producing potassium sulfate, a fertiliser. Other double
salts include 3Na2SO4·CaSO4, 3Na2SO4·MgSO4 (vanthoffite) and NaF·Na2SO4.

1.4 APPLICATIONS

 Sodium sulfate is used to dry an organic liquid.

 As filler in powdered home laundry detergents.
 As a fining agent which removes small air bubbles from molten glass.
 Glauber’s salt, the decahydrate was used as a laxative which removes the
certain drugs such as acetaminophen from the body.
 For de-frosting windows, in carpet fresheners, starch manufacture.
 As additive to cattle feed.
 In the manufacture of detergents and in the Kraft process of paper pulping.
 Used to dry an organic liquid, here clumps form, indicating the presence of water
in organic liquid.
 Used in Kraft process in USA & Canada for mfg. Of pulp.
 Manufacturing in textile industries.
 Helps in levelling, reduces negative charges on fibres so that dyes can penetrate
evenly.
 It helps in "levelling". reducing negative charges on fibres so that dyes can
penetrate evenly.
 Other uses for sodium sulphate include frosting windows, in carpet fresheners,
starch, manufacture and as an additive to cattle feed.
 It also fluxes the glass, and prevents scum formation of the glass melt during
refining

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SODIUM SULPHATE

CHAPTER NO:–02
MARKET SURVEY

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SODIUM SULPHATE

2.1 WORLD CONSUMPTION

Sodium sulfate is used mostly in detergents but also finds use in sodium
sulfide production and glass, pulping, and textile applications. Detergent applications
have shown steady growth, especially in developing countries; in 2016, detergent uses
account for about 39% of global consumption.

Sodium sulfide production accounts for 19% of total sodium sulfate

consumption in 2016; this market is almost exclusively in China, where sodium sulfide
is still produced by reduction of sodium sulfate with powdered coal. Glass is the third-
largest use for sodium sulfate, and is also the market most impacted by economic
conditions (especially for construction markets and automobile production).

Sodium sulfate can be recovered from naturally occurring brines or lakes

that contain significant amounts of the product. It is also obtained as a by-product of the
production of man-made fibers, chromium chemicals, hydrochloric acid, and formic
acid, as well as from lead-acid battery recycling or desulfurization of flue gases. By-
product sodium sulfate can have purity similar to that of the natural product.

PIE CHART OF CONSUMPTION/DEMAND OF SODIUM SULPHATE IN WORLD.

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SODIUM SULPHATE

TABLE-2.1.1 MARKET CONSUMPTION IN WORLD.

INDUSTRY LOCATION CONSUMPTION

Elite Chemicals Shanghai, China 2,20,000 kg/year

Joel John Florida, USA 1,90,000 kg/year

Charles & Laurence industry .ltd Florida, USA 1,60,000 kg/year

TABLE-2.1.2 MARKET CONSUMPTION IN INDIA.

INDUSTRY LOCATION CONSUMPTION

A.B. Enterprise Mumbai, Shardanand 20,000 per metric

Power pack chemicals Mumbai, kabadevi 28,000 per metric

United Enterprises Mumbai, mulund west 25,000 per metric

TABLE-2.1.3 MARKET CONSUMPTION IN GUJARAT.

INDUSTRY LOCATION CONSUMPTION

Uma Organics Lamdapura, Vadodara 23,000 per metric

Vinayak Enterprise Parvat patiya, Surat 12,000 per metric

Krishna Chemicals Vatva, Ahmedabad 22,000 per metric

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SODIUM SULPHATE

2.2 MANUFACTURERS OF SODIUM

SULPHATE

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SODIUM SULPHATE

CHAPTER NO:–03
VARIOUS
MANUFACTURING
PROCESSES

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SODIUM SULPHATE

3.1 VARIOUS MANUFACTURING

PROCESSES.
Major manufacturing processes for production of Sodium Sulphate are as follows:

a) From Salt (NaCl) and Sulphuric acid (H2SO4).

b) From natural brine.

DETAILED DESCRIPTION OF PROCESSES

a) Production of Sodium Sulphate From Salt (NaCl) and Sulphuric acid

(H2SO4).

 Raw Material:-

BASIS: For production of 1 ton of Sodium Sulphate,

Salt 750kg

Sulphuric Acid 675kg

Coal 530kg

 Chemical Reaction:-

2NaCl + H2SO4 → HCl + Na2SO4

Na2SO4 + 10H2O → Na2SO4. 10H2O

 Description:-

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SODIUM SULPHATE

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SODIUM SULPHATE

 Block Diagram:-

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SODIUM SULPHATE

(b) Production of Sodium Sulphate From natural brine.

 Raw Material:-

BASIS: For production of 1ton of Sodium Sulphate,

Natural Brine (10%Na2SO4) 10,000kg (theoritical)

Salt (Sodium Chloride) Variable

Natural Gas 5000cu.ft

 Chemical Reaction:-

Na2SO4 + 10H2O → Na2SO4. 10H2O

Na2SO4 + 10H2O → Na2SO4. 10H2O

 Desciption:-

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SODIUM SULPHATE

 Block Diagram:-

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SODIUM SULPHATE

CHAPTER NO:–04
SELECTION OF
MANUFACTURING
PROCESSES

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SODIUM SULPHATE

4.1 COMPARISION OF
MANUFACTURING PROCESS.
 Production of Sodium Sulphate from salt and sulphuric acid is less costly

compared to Natural Brine process.

 Raw materials of production by Salt and Sulphuric acid are easily available.

 Estimation of raw material Quantities is easier in Salt & Sulphuric acid Process.

 Selection of Plant site is easier in manufacturing by Salt and Sulphuric Acid

process.
 More over, Availability of the equipements and utilities necessary for production

by Salt and Sulphuric Acid Process is easy.

CONCLUSION:-

Therefore Production of Sodium Sulphate from Salt and Sulphuric Acid is more
suitable then Production of Sodium Sulphate from Natural Brine.

4.2 DETAILED DESCRIPTION OF

SELECTED PROCESS.
4.2.1 Raw Material:-

BASIS: For production of 1 ton of Sodium Sulphate,

Salt 750kg

Sulphuric Acid 675kg

Coal 530kg

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SODIUM SULPHATE

4.2.2 Chemical Reaction:-

2NaCl + H2SO4 → HCl + Na2SO4

Na2SO4 + 10H2O → Na2SO4. 10H2O

4.2.3 List of Utilities:-

1. Synthesis Fuel.
2. Air.

4.2.4 Description:-
 Salt and 600Be sulfuric acid in an excess were charged to the Mannheim
furnace.
 It is equipped with a rake agitator, where the reacting mass was slowly heated
to a temperature just below fusion temperature 8430C.
 During process hydrogen chloride was evolved from the furnace.
 Salt cake contains crude sodium sulfate was then continuously discharged from
the periphery of the furnace.
 To produce Glauber's salt, the salt cake was charged in to the solution tank where
it was dissolved in hot water to form the 320Be solution.
 Also soda ash or lime was then added to neutralize excess sulfuric acid present
in the system and to precipitate iron and alumina.
 The precipitate was allowed to settle for a layer separation.
 The clear supernatant liquor was pumped to the crystallizer where crystallization
take place and the muddy bottom layer was filtered and also charged into the
crystallizer while the filtered mud cake was discarded.
 After crystallization, to prevent desiccation, the Glauber's salt was stored in
closed bins.
 The mother liquor from crystallizer was returned to the solution tank for reused.
In order to obtain colourless crystals, the crystallizer liquor must be maintained
on the acid side of neutral.

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4.2.5 Major Equipements:-

 Furnance.
 Solution tank.
 Filters.
 Crystallizer.
 Storage Tank: Hydrochloric Acid Storage tank,
Sulphuric Acid Storage tank,
Sodium Sulphate Storage tank,
NaCl Storage tank.

4.2.6 Unit Operations:-

1. Filtration.
2. Extraction.
3. Neutrilization.
4. Crystallization.

4.2.7 Unit Processes:-

1. Sulphonation.

2. Oxidation.

3. Hydrogenation.

4.2.8 Flow Diagram:-

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SODIUM SULPHATE

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SODIUM SULPHATE

1.3Selected Process with CriteriaFrom salts & sulphuric acidThere are so many processes for
manufacturing of sodium sulphate. But this process is more suitable because this process is less costly,
also the raw materials are easily available, and utilities are also less in process, because of that this
process is more suitable1.4 Important Properties Na Solis chemically very stable, being unreactive
toward most oxidising or reducing agents at normal temperatures. At high temperatures, it can be
reduced to sodium sulphide. It is a neutral salt, which forms aqueous solutions with pH of 7, The
neutrality such solutions reflects the fact that Na2SO4 is derived, formally speaking from a strong acid
(sulphuric acid) and a strong base(sodium hydroxide). Sodium sulphate reacts with an equivalent
amount of sulphuric acid to givean equilibrium concentration o the acid salt sodium hydrogen
sulphate.

In fact the equilibrium is very complex and dependent on concentration and temperature, withother
acid salts being presentNa SOn is a typical ionic Sulphate, containing Na ions and SO ions. Aqueous
solutions eanproduce precipitates when combined with salts of Baar PB- which form insoluble
sulphates.

sodium Sulphate has unusual solubility characteristics in water, 3 as shown in the graphSolubility roses
more than tenfold between 0 to 32.4 °C where it reaches a mas49.7 g Na:SO per 100 g water. At this
point the solubility curve changes slope andsolubility becomes almost independent of temperature.
In the presence of NACLof Na SO, is markedly diminished. Such changes provide the basis for the use
of sodiumsulphate in passive solar heating system

s, as well is in the preparation and purification of SodiumSulphateThis nonconformity can be explained

in terms of hydration since 32.4 °C corresponds wintemperature at which the crystalline dehydrate
cheese to give a sulphate liquid phaseanhydrous solid phase1.5Applications of Sodium SulphateUsed
to dry an organic liquid, here clumps form, indicating the presence of water inorganic liquidLargest

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SODIUM SULPHATE

use as fillers in powder home laundry detergent.Used in Kraft process in USA & Canada for mfg. Of
pulpUsed as fining agent to remove of air bubble from molten glassManufacturing in textile
industries,Helps in levelling,reduces negative charges on fibres so that dyes can penetrate easilyIt
helps in "levelling" reducing negative charges on fibres so that dyes can penetrateevenlyOther uses
for sodium sulphate include frosting windows, in carpet fresheners, starchmanufacture and as an
additive to cattle feed.It also fluxes the glass, and prevents scum formation

REFERENCE
BOOKS:-
1) Kirk and Othmer, Encyclopedia of chemical technology,Volume-22, 4th ed.
2) Aun Bhal, B.S. Bhal, G.D. Tuli, Essentials of physical chemistry, Multicolour
volume.

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3)

WEBSITES:-
https://ihsmarkit.com/products/sodium-sulfate-chemical-economics-
handbook.html for consumption in world for market survey.

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