2.

CHAPTER 2

SALT AND SALT PRODUCTION PROCESS

2.1 IMPORTANCE OF SALT TO MANKIND

Salt or sodium chloride has been in use as a flavoring and taste

improving substance from time immemorial by mankind. Salt is also used as a

preservative of meat, fish and other food products (and even human bodies by

Egyptians). This particular property made salt one of the most important

commodities for centuries. Being salt an important ingredient in our food,

Indians attach much sentiments to salt. It played significant role even in the

Freedom struggle of India (Salt Sathyagraham, April, 1930). Offering salt to

deities to gain health by devotees is a practice of Hindu culture. Gypsum and

halite are co-precipitates. With reference to salt pans and to this study gypsum

certainly deserves a discussion, as in any salt pan operation, gypsum is a by-

product. Gypsum crystallizes as substrates in salt pans. In this chapter is given

a description of gypsum crystallizing in an artificial environment of salt pans.

Almost every person in the world uses salt in one form or the other every

day. The English word “salary” comes from the Latin “salarium”, meaning the

money Roman legionaries were paid to buy salt (Young 1977). Atleast 14000

uses (direct and indirect) have been attributed to sodium chloride by various
 2.2
industries around the world. The US Geological survey recognizes 8 major

categories comprising 29 end uses (Kostick, 2002).

2.2 SALT PRODUCTION

Producing salt from sea water involves the selective recovery of pure

NaCl, free of other soluble or non-soluble salts and other substances. To

achieve this either sea water or bore well brine or large open well brine is

pumped into the initial reservoir ponds, and is concentrated through natural

evaporation, which leads to the fractional crystallisation of all salts contained;

a process based on their varying solubility. Following sections detail the

economics of salt production, salt season, salt pan operations, brine analyses,

technology and the meteorological parameters governing the salt production.

2.3 SALT PRODUCTION SCENARIO

India is the fourth largest salt producing country in the world with an

average annual production of about 145 lakh tones (See Annexure 2.1). Private

sector plays a dominant role contributing over 65 per cent of the salt

production in the country, while the public sector contributes about 2 per cent.

The cooperative sector contributes about 9 per cent whereas the small-scale

sector (less than 10 acres) accounts for nearly 24 per cent of the total salt

production in the country. There are about 13,000 salt works, mostly in small

sector, engaged in the production of salt.

 2.3
Salt is one of the essential items of human consumption. The per-capita

consumption of salt in the country is estimated at about 14 kg per annum which

includes edible as well as industrial salt. The current annual requirement of

salt in the country is estimated to be 60 lakh tonnes for edible use (including

requirement for cattle) and 85 lakh tonnes for industrial use. Caustic soda,

soda ash, chlorine, etc. are the major salt-based industries. Besides, about 24

lakh tonnes of salt is exported every year. Common salt and iodised salt are

exported chiefly to Japan, Philippines, China, USA, Indonesia, Malaysia, Nepal

and Bhutan under open general license (NMCC, GOI, 2007).

2.3.1 Salt season

In northern part of India, salt manufacturing season commences with the

closure of south west monsoon i.e. by October 15 and lasts up to June of the

following year till the onset of the monsoon season in Gujarat, while in Tamil

Nadu it commences from February and ends by October 15, during north east

monsoon (NMCC, GOI, 2007).

2.3.2 Solar salt production process

Although salt from sea water is produced by solar evaporation there are

three systems of evaporating the sea water and/ or brine viz., 1. Single, 2.

Double and 3. Multi-pond systems (Fig. 2.1).

 2.4

Fig. 2.1
 2.5

2.3.2.1 Single - Pond System

Though production cost will be lower, quality of salt is very much

reduced and the production rate is also limited. Impounding of sea water in all

the ponds and after evaporation scrapping of salt from all the ponds - a batch

wise process – reduced the production cost. However, complete evaporation in

the same pond results in the crystallization of all the salts present in sea

water/ brine which makes NaCl impure.

2.3.2.2 Double - pond system

The second system, in the process of salt recovery from sea water was

made with the division of the evaporation basin into two: the first basin,

usually called nurse pond, was used for the production of NaCl-saturated brine,

which was fed into the second basin, usually called crystallizer. Thus, it was

made possible to achieve continuous salt production (crystallization) and to

eliminate those seawater salts, with less solubility than NaCl (i.e. CaCO3 and

CaSO4), since these crystallize in the first basin and remain there.

2.3.2.3 Multi - pond system

The third and most decisive system concerned was the division of the

nurse pond into several interconnected basins. With this design, sea water

enters the first basin and, as it flows through successive ponds and evaporates

in the sun, its concentration increases. This production method ensures greater

control over the concentrations and quantities of the brines fed through the

system, thus resulting in the unobstructed production of much better quality

and quantity of the salt. Nursing ponds cover around 90% (to concentrate brine
 2.6
from 3.5 to 26°Be) of the total area of the saltern and create a complete,

living ecosystem.

This production method is still used nowadays for the recovery of salt

from sea water, although there have been improvements and variations,

allowing for the production of some hundred to a few million tonnes of salt,

depending on the size of the area in use (Korovessis and Lekkas, 1994). These

three stages (reservoirs, condensers and crystallizers) constitute the basic steps

towards improving the salt manufacturing technology.

2.3.3 SALT PAN ARCHITECTURE

Figure 2.2 illustrates a typical layout of salt works. Principally, in

Tuticorin coastal areas, any salt pan operation comprises five following

components: 1. Abstraction of brine; 2. impounding of brine in reservoirs; 3.

concentrating in condensers; 4. Precipitating salt in pans and 5. Stock piling or

salt heaps.

Generally, a saltern consists of a system of shallow ponds (15-60 cm

deep), connected mainly in series, with natural clay bottom to ensure very low

water permeability. In principle, operation is not basically different from the

one described previously. Differences could be seen only in optimization, brine

transfer, and collection of salt due to some technological progress. It is

because the whole process relies on natural energy, the solar energy.
 2.7

Fig. 2.2
 2.8
(Brine transfer at the rate of one pond /day enhances the evaporation rate

and thereby increases salt precipitation.). The ponds are divided into two basic

groups. The first group, usually called evaporating ponds, is where sea water is

concentrated up to saturation point in terms of NaCl.

The second group, called crystallizers, consists of the basins where salt

is crystallized and produced via further evaporation of the brine. What

basically elevates saltern to ecosystems is the fact that for sea water to be

concentrated up to the point of salt crystallization, 90% of its water content

has to evaporate, thus requiring a vast surface (approximately 90% of the salt

works area). So it is the concentration of the initial brine available decides the

requirement of reservoirs and concentrating ponds (Korovessis and Lekkas,

1994).

2.3.3.1 Brine concentration

Often the bore well brine concentration is either two or three times the

sea water concentration i.e. 8°Be or even 10°Be. Based on this available brine

source present day salterns are designed.

Crystallizers take up the remaining 10% of the area when sea water is

used as starter brine. The crystallizer basins are specially designed and have

their bottom leveled and concentrated, aiming to facilitate and optimize the

manual or mechanized collection of salt.

 2.9
The first pond of the saltern is fed with sea water (raw material) usually

via pumping. As sea water flows from pond to pond, its concentration rises

continuously through natural evaporation. The evaporation (or concentration)

of brine is achieved by exposure to solar radiation and with the help of the

prevailing microclimate in the area, especially of wind, rainfall, air

temperature, humidity and duration of sunshine.

So an increasing salinity (concentration) gradient is created throughout

the ponds of the saltern with a simultaneous and continuous reduction of the

volume of sea water, which initially entered the system of pans.

2.3.3.2 Pond biogeochemistry

Generally gypsum, a hydrous sulphate of calcium may precipitate within

the fluid and settle down or precipitate at bottom of the sink itself

(Blatt et al., 1980). Moreover, salt pan gypsum acquires interesting bed form

that is curly and layered, differently called as teepees and tumuli. Hence salt

pan gypsum is described hereunder.

2.3.3.3 Gypsum as a mineral

Gypsum is one of the important industrial minerals. In India, cement

industry is the major end use consumer of gypsum followed by industries

producing fertilizer and plaster of Paris. Acidic soil is treated with gypsum.

Gypsum occurs in nature as sedimentary evaporitic deposits on land.

 2.10
Gypsum is found extensively all over the World. It is believed that most

gypsum deposits were formed by precipitation from saline waters and the

theory of deposition of gypsum bodies from seawater by evaporation is

generally accepted. Usually it is associated with salt deposits, limestones,

shales, sandstones and clays. Exploration in the Naica mine (Chihuahua,

Mexico) recently unveiled several caves containing giant, faceted, and

transparent single crystals of gypsum as long as 11 m.

2.3.3.3.1 Properties of gypsum

Gypsum is colourless when perfectly crystallized. But the massive

gypsum is colourless to white, when pure. It is grey or black or pink or brown or

yellow when impure. Gypsum is a hydrous calcium sulphate (CaSO4.2H2O)

having a composition of 79% calcium sulphate and 21% water. Crystalline

variety of gypsum has pearly to sub-vitreous luster, whereas massive varieties

have a dull earth appearance. It is very soft; its hardness varies from 1.5 to 2.0

on the Moh’s scale of hardness. Its specific gravity ranges from 2.2 to 2.4

depending upon its purity. Gypsum is easily distinguished from anhydrite by its

inferior hardness (1.5-2 against 3-3.5) and lower specific gravity (2.2-2.4

against 2.7-3.0). Anhydrous gypsum is called anhydrite (CaSO4).

2.3.3.3.2 Marine gypsum

The seawater contains about 3.6% of CaSO4, whereas the practical

recovery is around 2.5%. Marine gypsum is inexhaustible and renewable.

 2.11
Crystals of marine gypsum are usually needle shaped and are known as

selenite.

2.3.3.3.3 Gypsum nucleation and crystal morphology

The most influential parameters potentially affecting gypsum

crystallization processes are water salinity, temperature, type and amount of

dissolved organic compounds, and pH. System of crystallization of gypsum is

monoclinic.

The morphology of gypsum precipitated in continental environments is

characterized by marked variability and includes prismatic, lenticular,

irregular, rosette, and numerous other habits. These habits may provide clues

to the depositional environment during the growth of gypsum; for example

rosettes found in ancient rocks have been used as evidence of deposition under

desert conditions during the geologic past (Lacorix, 1910).

2.3.3.3.4 Factors affecting Gypsum crystallization

The solubility of gypsum changes slowly with temperature and passes

through a very weak maximum at about 40ºC. Gypsum loses all its hydration

water at 57ºC (Hardie, 1967).

Like organic waste products from microorganisms, the inorganic waste

product, ammonia can modify the precipitation of evaporites. These

observations stress the fact that many processes in hypersaline environments

 2.12
are under biogeochemical control. The most convincing arguments show that

dolomitization of CaCO3 can trigger the precipitation of gypsum with the excess

of sulphate during the process:

2CaCO3 + Mg2+ + SO42- → CaMg(CO3)2 + CaSO4.

The role of bacteria in such secondary dolomitization of CaCO3 is not known

with any certainty, but carbon of dolomite formed in a sabkha in Mexico was

found to be isotopically light due to biogenic influence.

Thus the “sulphate problem” in evaporites may be influenced by

bacterial activity but only through the mechanism of dolomitization (Holser et

al., 1981). Microbial mats are highly productive aquatic ecosystems. This

remarkable productivity reflects the efficient recycling of key nutrients within

the mat ecosystem. The participation of cyanobacterial mats and Dunaliella, in

the cycling of hydrogen, oxygen, dissolved inorganic carbon and organic acids

could substantially affect biogeochemical function and community composition

(Javor, 1983; Hoehler, et al., 2001; Canfield and Des Marais, 1993; Des Marais

et al., 2002b).

Solar salterns provide ideal systems for studying evaporative sequences

of minerals, biological composition and activity over a broad range of salinities.

Biogeochemical processes in salterns not only provide a frame work for

assessing the interplay between biology and geochemistry across salinities, but

also for comparing seasonal and temperature effects on rates of processes

within a narrow range of salinities. Seasonal differences in both salt production

 2.13
and biological productivity are notable. In the summer are brine temperature

increase and longer day length, both due to increased solar radiation, and

biological activity in solar ponds. It has been popularly accepted by saltern

managers that red-coloured brines (due to Dunaliella and / or Halobacteria)

increase solar absorption and cause the temperature of the brines to rise, but

there are no published data documenting this effect (Javor, 1989).

According to Javor (1983) the maximum temperature attained by

densely – coloured brine was 46°C while the clear brine reached only 39°C. In

that saltern, mid-morning brine temperatures typically varied between 19° and

30°C. Temperatures up to 41°C were recorded in a Spanish saltern (Rodriguez-

valera et al., 1985).

When the biological system of saltern is upset – due to either negligent

operation or generally deficient design, or to the pollutants carried in the sea

water, which is fed into the saltern – an excessive quantity of organic matter is

produced. Thus, the biological chain is altered and the saltern become

downgraded with the reduction of the surface of the ponds and increased

viscosity of the brine resulting in the production of bad and sometimes

potentially not marketable quality salt. Therefore, it is clear why the optimal

operation of modern salt works is impossible without maintaining, at the same

time, a healthy and stable ecosystem. It is worth noting that salt works are

totally free of pesticides or other chemical compounds used in farming

(Korovessis and Lekkas, 1994).

 2.14

2.3.3.4 Sequential precipitation of minerals

In the evaporation path of seawater gypsum appears as second mineral

after CaCO3 (when 1 litre seawater was concentrated to 276.3 ml) followed by

anhydrite which is formed from gypsum at an ionic strength of 6.6 (after

seawater was concentrated to 101.8 ml) and halite mineral crystallization

starts, when one litre was concentrated to 92.4 ml (7.2 ionic strength) and on

further evaporation halite may resorb anhydrite (Eugester et al., 1980)and

form glauberite mineral (when 1 litre seawater becomes 76 ml where ionic

strength = 7.5). In another study (Mc Caffrey et al., 1987), it has been

suggested that calcium carbonate begins to precipitate at a brine

concentration of about 1.8 times that of seawater. Gypsum begins to

precipitate at a brine concentration of 3.8 times that of seawater and halite at

a concentration factor of 10.6. About 92% of water from sea water (3.44°Be)

should be evaporated to get a saturated brine (24.5°Be) that begins to

crystallize. About 5.4% of the water evaporates between 24.5° and 29°Be

during crystallization of NaCl (at this density (29°Be) about 72% of salt has

been crystallized).

The concentration of sea water through solar evaporation results in the

successive crystallization of the less soluble salts (CaCO3, CaSO4) first, followed

by NaCl and finally magnesium salts. Salt workers use the empirical Baume

(°Be) scale, to denote the concentration of brines. According to that scale the
 2.15
sea water concentration is 3.5°Be. The crystallization of CaCO3 begins at

4.6°Be and that of CaSO4 at 13.2°Be. NaCl crystallizes at 24.5°Be, followed by

the more soluble Mg salts at 30°Be (Korovessis and Lekkas, 1994).

2.4 SUMMARY

This chapter narrates salt and salt production from an industrial stand

point of view. Importance of salt, salt production and its scenario, salt season,

solar salt production process, salt pan architecture, brine concentration, pond

biogeochemistry are discussed. In India, on an average, 145 million metric

tonnes of salt is being annually produced in solar evaporating sea water or

brine impounded ponds. Gypsum is dealt here as a by-product of salt producing

firms. Properties of gypsum as a mineral and crystallization environment are

given. Primarily gypsum crystallizes as mats along with microbial layers and

manifest in the form of tumuli, which is a typical bed form acquired by gypsum

which further grows laterally forming ridges and crests and these are

frequently broken to form teepees. It is followed by a description of sequential

precipitation of minerals in salt pans. Sea water with a salinity of 3.5 oBe

through evaporation crystallizes into magnesium salts at 30oBe through

intermediate salts of calcium carbonate, calcium sulphate and sodium chloride.

Sodium chloride crystallizes at 24.5 oBe. With 14000 uses, salt certainly

occupies an important place in the society. Following the convention, the

following chapter discusses on materials and methods.

2.16