Tribhuvan University

IOE Pulchowk Campus

Applied Sciences & Chemical
Engineering

Presented by: Presented to:

Raj Chapagain [’032] Sir Bikash Kumar Mahato
Ramani Pradhan [’034] Assistant Professor
Chemical Process
Industries
• Prelude
Water is probably the most important resource in
the world since it is required for:

Sustenance of human life- physiological processes,

sanitation
Agricultural activities- for food production,
evaporative cooling of earth

Industrial needs- heat transfer processes, chemical

reactions, nuclear fusion power

The largest users of Water by Industry Classification

are:
üSteel
üOil Refineries
üPulp & Paper
 Introduction to Water Conditioning

Water conditioning and waste-water treatment have long been essential

functions of municipalities.
However, the importance of suitably preparing water for the chemical industry is sometimes
underemphasized, although the chemical manufacturing processes consume large quantities
of water ranging in quality from untreated to deionized.

Industrial waste waters present a complex and challenging problem to the chemical
engineer.
The solution is
industry-
specific, but,
A few general principles in water-
conditioning & treatment may be observed:
üreuse of waste waters

ürecovery of by-products to lessen the

expense of treatment

üa n d p o o l i n g o f w a s t e s t o d i s t r i b u t e
pollution or to effect a saving in
neutralization costs.
Water Hardness & Softening
Hard waters contain objectionable amounts of dissolved salts of calcium
and magnesium present as bicarbonates, chlorides or sulfates.

These salts give insoluble precipitates with soap and form clogging scales
with low thermal conductivities when used in boilers.

Hardness is usually expressed in terms of the dissolved calcium and

magnesium salts calculated as calcium carbonate equivalent.
Water hardness may be divided into two classes:
• carbonate
• and, non-carbonate, also frequently known as temporary and permanent.

Temporary hardness can usually be greatly reduced by boiling; permanent hardness requires
the use of chemical agents.

Carbonate or temporary hardness is caused by bicarbonates of lime and magnesia;

noncarbonate / permanent hardness is due to the sulfates and chlorides of lime and magnesia.

Other water impurities that may be present are suspended insoluble matter (classed usually as turbidity), organic matter,
color, and dissolved gases. Such gases are carbon dioxide (largely as bicarbonate), oxygen, nitrogen, and, in sulfur waters,
hydrogen sulfide.
Disadvantages of Hard
Water
Operational Challenges

Reduced efficiency: Hard water deposits (scale) form on heat exchange surfaces in boilers, reactors, and
other equipment, reducing heat transfer and increasing energy consumption.

Clogged pipes and equipment: Scale buildup can restrict flow in pipes, valves, and other
equipment, hindering operations and requiring more frequent maintenance.

Increased corrosion & Higher maintenance costs: Scale deposits can create uneven surfaces and
microenvironments that accelerate corrosion of equipment, and the need for frequent cleaning, descaling, and
repairs of equipment due to hard water increases maintenance costs significantly.

Economic Impacts

Increased energy consumption, Downtime, and Lost Production: Reduced efficiency due to scale formation
leads to higher energy costs for heating and cooling processes, while equipment failures and maintenance
shutdowns due to hard water problems can disrupt production and lead to lost revenue.
Water conditioning must be adapted to the particular use for which the water is designed.

Each industry has its

e.g., Laundries require zero hardness to
prevent precipitation of calcium and
magnesium soap on the clothes. Likewise,
calcium and magnesium salts cause special water-
undesirable precipitates with dyes in the c o n d i t i o n i n g
requirements.
textile industries or with the dyes in paper
manufacture.

This hard water needs to be softened for many uses.

Furthermore, as the advantages of really soft water are recognized; more and more, even fairly soft waters
are being completely softened for laundries, homes, textile mills, and certain chemical processes.
 Methods of Conditioning Water-
The end use of water determines the
treatment chosen

The purification and softening of water may be accomplished by different

methods.
Softening is the term applied to those processes which remove or reduce the hardness of
the water.

Purification, as distinguishable by its name, refers to the removal of organic matter and
microorganisms from the water.
 Zeolite Exchange

The most important method for softening

water is the cation-exchange system
commonly referred to as the zeolite system.
The present-day usage of the term "zeolite"
loosely covers a variety of ion exchangers, such
as processed greensand, bentonitic clay,
synthetic gel-type minerals, and the new
synthetic-resin exchangers.
Inorganic zeolites are composed principally of hydrated Alkali alumina-
silicates that contain easily exchangeable ions such as sodium or
potassium.
During the softening process, the Ca and Mg ions are exchanged from the
hard water by the zeolite for the Na ions. When the zeolite becomes
almost all changed to calcium and magnesium compounds, it is
regenerated to restore the sodium zeolite. This is usually done with salt
solution and in the pH range between 6 and 8. Industry largely uses the
sodium cycle for softening water.
Regeneration is with common salt, at a chemical efficiency which varies
between the limits of 0.275 and 0.5 Ib. of salt per 1000 grains of
hardness removed as compared with the stoichiometric efficiency of 0.17
Ib. of salt.
Using water containing calcium bicarbonate, for example, a typical
equation for zeolite softeners follows, where Z represents the complex
cation exchanger radical:

Ca(HCO3)2 + Na2Z → CaZ + 2NaHCO3

CaCl2 + Na2Z → CaZ + 2NaCl

Similar reactions may be written for the other bicarbonates found in

water such as magnesium. For regeneration the reaction is

CaZ + 2NaCl (excess)→ Na2Z + CaCl2 + [excess — 2(NaCl)]

 The equipment for the process,
as shown, is a large closed
cylindrical tank in which the
zeolite is supported on graded
The great advantage of the zeolite softeners is their gravel.
convenience and the fact that they furnish water of zero
hardness without attention or adjustment until regeneration is
required even though the raw water varies in hardness from The water to be softened may
one day to the next.
flow down through the tank.
Auxiliary apparatus includes
both brine- and salt-storage
tanks. The washing and
regeneration may be carried
Efficiency & Effectiveness Limitations

Softens water: Effectively removes hardness- Not effective for all contaminants: Does not remove
causing calcium and magnesium ions through ion other impurities like iron, manganese, or nitrates.
exchange.

Simple operation: Requires minimal operator Waste brine generation: Regeneration process
intervention and is relatively easy to operate produces brine waste requiring proper disposal or
compared to other methods. treatment.

No chemicals added: Regeneration process pH sensitivity: Requires stable pH levels for optimal
typically uses salt brine, avoiding the need for performance.
harsh chemicals used in other methods.
Organic Ion Exchange
Because of the development of the organic ion exchangers, this process
is now used in many industries other than water treatment. Some of
these industries are chemical, especially process liquor and waste
treatment, biological, drug and pharmaceutical, glues and gelatine,
insecticide, rare earth separations, and sugar. These ion exchangers may
be divided into two classes: cation and anion.
The cation organic exchangers are employed to treat solutions in a
relatively wide pH range. They may be roughly divided into:

1.Synthetic organic resins (sulfonated styrene resins, sulfonated phenolic

resins, etc.)
2. Processed natural organic materials (sulfonated coal, coke, lignin,
etc.)
These contain an exchangeable hydrogen ion and can be employed to
remove all cations according to the following reactions:

Ca(HCO3)2+ 2HSO3R → Ca(SO3R)2 + 2C02 + 2H2O

The acid formed; H 2 CO 3 in this case, decomposes and can be removed
easily. A similar reaction would be true for magnesium or sodium
bicarbonates. Sulfates and chlorides react as follows:

CaSO4 + 2HSO3R → Ca(SO3R)2 + H2SO4

NaCl + HSO3R → NaSO3R + HCI
CaCl2 + 2HSO3R → Ca(SO3R)2 + 2HCI

The regeneration is usually affected by sulfuric acid as follows:

Ca(SO3R)2 + H2SO4(excess) → 2HSO3R + CaSO4

2NaSO3R + H2SO4 (excess) → 2HSO3R + Na2SO4
Lime-Soda Process

The use of slaked lime and of soda ash to remove hardness in water has
long been important. The modern application has been divided into the
cold lime process and the hot lime soda process. Typical equations for
these reactions are:
For carbonate hardness,
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 +2H2O
Mg(HCO3)2 + Ca(OH)2 → MgCO3 + CaCO3 + 2H2O
The cold lime process is employed chiefly for partial softening and
ordinarily uses only the cheaper lime for its reagent reactions. This
cold lime process is particularly applicable to partial softening for
municipal water, to the conditioning of cooling water where calcium
bicarbonate hardness may be the scale former, and to certain paper-
mill waters where calcium bicarbonate is troublesome.

The hot lime-soda process is employed almost entirely for

conditioning boiler feed water. Since it is operated near the boiling
point of the water, the reactions proceed faster, the coagulation and
the precipitation are facilitated, and much of the dissolved gases such
as carbon dioxide and air is driven out.
Advantage Lime-Soda Process in Water
Conditioning?
Advantages Limitations

Effective Hardness Removal: Removes both Incomplete Softening: Not as effective as some
calcium and magnesium hardness, achieving methods, leaving residual hardness (30-50 mg/L).
significant softening.

Economical: Relatively inexpensive compared Large Sludge Generation: Produces significant amounts
to other softening methods like ion exchange. of sludge requiring proper disposal, adding costs and
environmental concerns.
Precipitates Iron and Manganese: Can High Chemical Consumption: Requires consistent addition
remove certain contaminants like iron and of lime and soda ash, increasing chemical costs.
manganese along with hardness.

Increases pH & provides Partial Disinfection: Strict Control Needed: Demands precise control of
Elevates water pH, r educ i ng c or r os i on chemical dosing and pH to avoid over or under-treatment.
potential in pipes and distribution systems
and the high pH can inhibit some bacterial
growth, providing partial disinfection.
Phosphate Conditioning

Various phosphates are employed, usually in conjunction with one of the

previously described procedures.

Monosodium, disodium, and trisodium phosphates are often added to

water to precipitate the hardness ions in the form of easily removed soft
phosphate sludges.
Sodium hexametaphosphate, (NaPO 3 ) 6 , likewise softens water but
instead of precipitating the hardness ions it forms soluble complexes with
the Ca, Mg, Fe, and Al ions and sequesters them or prevents the
formation of scale or insoluble soaps when the phosphate is present in
excess and when the water is not too hot.
The addition of sodium hexametaphosphate also reduces corrosion,
particularly in non-aerated waters.
Silica Removal

Silica is not removed by hydrogen cation exchange or sodium zeolite

exchange, and usually is only partially removed in the cold or hot
lime-soda processes.
It may be a very objectionable impurity, especially in boiler feed water,
as it can form a tenacious scale. Its presence may be due to dissolved
silica in the feed water, or it may be introduced by filtering hot
alkaline waters through sand in preliminary softening treatments.

Silica may be removed from the feed water by the use of dolomitic
lime or activated magnesia. If preliminary coagulation and settling are
carried out, the use of a ferric coagulant will remove some silica.
Deaeration
The removal of oxygen dissolved in water is often necessary condition the
water properly for industrial purposes, although his is unnecessary for
municipal waters. Dissolved oxygen hastens corrosion by a number of
reactions, depending on conditions. The following is a typical presentation
of an important phase of iron water corrosion accelerated by oxygen in
alkaline or neutral conditions. Iron in contact with water exerts a certain
solution pressure and sets up the oxidation or anodic half reaction:
Fe(s) → Fe++(aq) + 2e

This would cease after a certain potential was reached. However, oxygen
can react with water to give OH ions at cathode areas:
O2(g) + 2H2O(l) + 4e → 4OH-(aq)
The Fe ++ and the OH -­ ions would react and the electrons would
neutralize by flow of current between the adjacent anode and
cathode areas:
Fe++(aq) + 2OH-(aq) → Fe(OH)2(s)

The initial reactions would then proceed further. This electrochemical

corrosion can be summarized:

2Fe(s)+ O2(g)+ 2H2O (l) → 2Fe(OH)2(s)

Naturally air and water can change the ferrous into ferric hydroxide.
Anything that stops the foregoing sequences will stop the corrosion. This
may be by the removal of the dissolved oxygen, by electrode polarization,
by organic inhibitors, or by protective salts. Such protective salts would be
chromates, silicates, phosphates, or alkalies which probably act as anodic
inhibitors by forming a film over the anodic or active areas and thus
interrupting the electrochemical sequences.
Water ordinarily saturated with air at 50°F contains about 8 cc oxygen
per liter. Oxygen is removed by spraying or by cascading the water down
over a series of trays contained in a tank. During the downward flow the
water is scrubbed by uprising steam. An open feed-water heater of the
spray type will usually lower the dissolved oxygen content to below 0.3 cc.
per liter. Scrubbing devices will remove even this small amount, or it can
be chemically combined using a scavenger like sodium sulfite:
O2 + 2Na2SO3 → 2Na2SO4
Such complete deoxygenation is necessary to avoid corrosion in the modern
high-temperature high-pressure boiler.
 References

• Norris Shreve, R. (1956). Chemical process industries (2nd ed.) [Print]. McGraw
Hill Book Company, Inc., Kogakusha Company, LTD.