CHAPTER 1 INTRODUCTION

1.0 INTRODUCTION[1]
Industry uses water to generate steam, to cool and heat, and to fill the varied voluminous needs of process and general plant services. Estimating the true economic impact of this water involves determining not only the required flow and available supply but also quality requirements and treatment costs.

In many industrial plants, the water once used in a particular application is still of higher quality than raw water. Therefore it can be cascaded or reused in other application requiring a lesser quality, here it is also important to define water quality criteria for any given usage.

In order to improve economy of industrial water use, it becomes imperative to reduce waste water volumes, recover and reuse wastewater, which can be done effectively by FEEDWATER TREATMENT.

1.1 FEEDWATER DEFINITION

Feedwater can be defined as the water of certain standard that is recommended to be used in process equipment and general plant services. So that equipment performs at its best.

1.2 NEED FOR FEEDWATER

Industry uses water to generate steam, to cool to heat, and to fill the varied and voluminous needs of process and general plant services. During these process impurities present in water causes problems like corrosion, scale formation, embrittlement etc. To minimize such problems it is required that raw is treated first and then allowed to enter the industrial systems.

1.3 BASIC JOBS IN TREATMENT [2]

Feedwater treatment is basically done to minimize following problems:-

1. SCALE. Calcium and magnesium salts, chiefly dissolved in water, deposite on tube
surfaces as scale when water evoporates.This reduces heat transfer, causes overheating of tube metal. Scale formation is avoided by (1) removing these hardness salt before water enters boiler or (2) adding chemicals to the water to cause these solids to form a soft sludge that can be removed by blowdown.

2. CORROSION Boilers, economizer, feedheaters, piping etc. become corroded when (1)
water is acidic or (2) dissolved gases are present. Prescribed remedies are (1) neutralizing water acidity with an alkali (2) removing gases by dearation,followed by chemical scavenger that absorbs remaining traces and (3) feeding a corrosion inhibitor together with organic substances to protect surface of boiler and return lines.

3. CARRYOVER Slugs of water passing over with steam cause erratic superheat,
mechanical troubles with turbines. Solids passing over deposit in super heaters on turbine blades may spoil materials in process. Alkalinity too high, oil in water, suspended solids are main cause of foaming,Bowdown and antifoam agents combat carry over.
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4. EMBRITTLEMENT.Metal failure from embrittlement is along drum seams, under rivets

and at tube ends where water flashing to steam through any small leaks in these stressed areas allows any sodium hydroxide in water to concentrate.Embrittlement can be checked by maintaining low hydroxide alkalinity, avoiding leaks at stressed metal, using special inhibiting agents.

1.4 APPLICATIONS OF FEEDWATER

Water has wide range of application in industries, considering chemical industrial application, feedwater is used in: BOILER FEEDWATER COOLING WATER PROCESS WATER OR DEMINERALIZED WATER

In next chapters sections preparation of these waters from raw water is discussed. But before proceeding to treatment process of feedwater, it is required that raw water characteristics are understood.

CHAPTER 2 RAW WATER

2.1 RAW WATER [5]

Pure water (H2O) is colourless, tasteless, and odourless. Because water becomes contaminated by the substances with which it comes into contact, it is not available for use in its pure state. To some degree, water can dissolve every naturally occurring substance on the earth. Because of this property, water has been termed a "universal solvent." Although beneficial to mankind, the solvency power of water can pose a major threat to industrial equipment. Corrosion reactions cause the slow dissolution of metals by water. Deposition reactions, which produce scale on heat transfer surfaces, represent a change in the solvency power of water as its temperature is varied. The control of corrosion and scale is a major focus of water treatment technology. Constituent Turbidity Chemical Formula/description NTU(nephlometric turbidity unit) Difficulties Caused imparts unsightly appearance to water; deposits in water lines, process equipment, etc.; interferes with most process uses chief source of scale in heat exchange equipment, boilers, pipe lines, etc.; forms curds with soap, interferes with dyeing, etc. Foam and carryover of solids with steam; embrittlement of boiler steel; bicarbonate and carbonate produce CO2 in steam, a source of corrosion in condensate lines. corrosion Means of Treatment coagulation, settling, and filtration

Hardness

calcium and magnesium salts Expressed in terms of CaCO3 conc.or in ppm

softening; demineralization; internal boiler water treatment; surface active agents

Free Mineral Acid H2SO4 , HCI. etc.

Expressed in terms of CaCO3 conc.or in ppm

lime and lime-soda softening; acid treatment; hydrogen zeolite softening; demineralization by anion exchange

Free Mineral Acid

H2SO4 , HCI. etc., ppm

neutralization with alkalis

pH

pH=-log[H+]

pH varies according to pH can be increased by acidic or alkaline alkalis and decreased by solids in water; most acids
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natural waters have a pH of 6.0-8.0 SO42- , ppm

Sulphate

Chloride

Cl -,ppm

Nitrate

NO3- ,ppm

Fluoride

F- ,ppm

Sodium

Na+ ,ppm

Silica

SiO2 ,ppm

adds to solids content of water, but in itself is not usually significant, combines with calcium to form calcium sulphate scale adds to solids content and increases corrosive character of water adds to solids content, useful for control of boiler metal embrittlement cause of mottled enamel in teeth; also used for control of dental decay: not much significant industrially Adds to solids content of water: when combined with OH-, causes corrosion in boilers under certain conditions. scale in boilers and cooling water systems; insoluble turbine blade deposits due to silica vaporization

demineralization, reverse osmosis, electrodialysis, evaporation

demineralization, reverse osmosis, electrodialysis, evaporation demineralization, reverse osmosis, electrodialysis, evaporation adsorption with magnesium hydroxide, calcium phosphate, or bone black; alum coagulation demineralization, reverse osmosis, electrodialysis, evaporation

Iron

Fe2+ (ferrous) Fe3+ (ferric),ppm

Manganese

Mn2+,ppm

Discolours water on precipitation; source of deposits in water lines, boilers. etc.; interferes with dyeing, tanning, papermaking. Discolours water on aeration; coagulation and precipitation; source filtration; lime softening;
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hot and warm process removal by magnesium salts; adsorption by highly basic anion exchange resins, in conjunction with demineralization, reverse osmosis, evaporation aeration; coagulation and filtration; lime softening; cation exchange; contact filtration;

Aluminium

AI3+,ppm

Oxygen

O2,ppm

Hydrogen Sulphide Ammonia

H2S,ppm

of deposits in water lines, boilers. etc.; interferes with dyeing, tanning usually present as a result of floc carryover from clarifier; can cause deposits in cooling systems and contribute to complex boiler scales corrosion of water lines, heat exchange equipment, boilers, return lines, etc. cause of "rotten egg" odour; corrosion corrosion of copper and zinc alloys by formation of complex soluble ion high concentrations are objectionable because of process interference and as a cause of foaming in boiler deposits in heat exchange equipment, boilers, water lines, etc.

cation exchange; contact filtration;

improved clarifier and filter operation

deaeration; sodium sulphite

NH3,ppm

aeration; chlorination; highly basic anion exchange cation exchange with hydrogen zeolite; chlorination; deaeration lime softening and cation exchange by hydrogen zeolite; demineralization, reverse osmosis, electrodialysis, evaporation subsidence; filtration, usually preceded by coagulation and settling

Dissolved Solids

May contain salts in ppm

Suspended Solids

Undissolved matter in ppm

So, these are the contents in the raw water that are required to be removed to make it usable in industry.

CHAPTER 3 BOILER FEEDWATER TREATMENT

3.1 Boiler feedwater [4]

Feedwater can be defined as the water of certain standard that is recommended to be used in process equipment and general plant services. Treatment of boiler feedwater aims at preventing scale and sludge depositions, corrosion and carryover. All natural waters contain varying amounts of suspended and dissolved matter as well as dissolved gases Impurities in water become an important consideration when water is to be used for steam generation. With the trend toward higher pressure boilers, pretreatment has become the key to successful operation of industrial power plants. Poor quality water gives poor quality steam.

3.2 Problems caused in boiler systems [3] 3.2.1 Boiler Deposits

Impurities that form deposits Bicarbonates of calcium and magnesium dissolved in water break down under heat and give off car bon dioxide forming insoluble carbonates. These carbonates precipitate directly on the boiler metal and or form sludge in the water that deposits on boiler surfaces. Sulfate and silica generally precipitate directly on the boiler metal and are much harder to condition. Silica (sand) if present in water can form exceedingly hard scale. Suspended or dissolved iron coming in the feedwater will also deposit on the boiler metal. Oil and other process contaminants can form deposits as well and promote deposition of other impurities. Sodium compounds usually do not deposit unless the water is almost completely evaporated to dryness, as may occur in a starved tube. Deposits are seldom composed of one constituent alone, but are generally a mixture of various types of solid sediments, dissolved minerals, corrosion products like rust, and other water contaminants.

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The major problem that deposits cause is tube failure from overheating. This is due to the act that the deposits act as an insulator and excessive deposits prevent efficient heat transfer through the tubes to the water. This causes the metal to become overheated and over time the metal fails. These deposits can also cause plugging or partial obstruction of boiler tubes, leading to starvation and subsequent overheating of the tubes. Underneath the deposit layer corrosion may also occur. Deposits cause unscheduled outages, increased cleaning time and expenses. Boiler deposits reduce overall operating efficiency resulting in higher fuel consumption.

3.2.2 Boiler scale formation

At prevailing temperatures in a steam boiler, both carbonate and non-carbonate hardness forms a scale. Breakdown of hardness is shown by following equations. Ca(HCO3)2 = CaCO3 + H2O+CO2 Mg(HCO3)2=MgCO3+ H2O+CO2 MgCO3+H2O=Mg(OH)2+CO2 Another source of boiler scale is Silica. Its thermal conductivity is very low and causes tube failures often even with very thin silica scales. Scale formation occurs when the salts present crystallize from a solution which is locally supersaturated.Feedwater forms a thin film along the boiler surface and tends to concentrate, causing hard layer formation on heating surface itself. Scale creates problem in boiler operation because it has low degree of heat conductivity, it causes rise in temperature causes tube and equipment failures. Scale causes 2-3% loss in boiler efficiency.

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3.2.3 Corrosion in Boiler systems [4]:Though basic corrosion is usually due to reaction of the metal with oxygen, other factors including stresses produce different forms of attack. Corrosion may occur in the feedwater system as a result of low pH water and the presence of dissolved oxygen and carbon dioxide. Corrosion in the boiler itself normally occurs when boiler water alkalinity is too low or too high or when the metal is exposed to oxygenbearing water during either operation or idle periods. High temperatures and stresses tend to accelerate the corrosion. In the steam & condensate system and pipelines corrosion is generally the result of contamination with carbon dioxide and oxygen. Corrosion Fatigue Cracking in boiler metal may occur due to cyclic stresses created by rapid heating and cooling. These stresses are concentrated at points where corrosion has roughened or pitted the metal surface. This is usually because of improper corrosion prevention. Sometimes even with properly treated water corrosion fatigue cracking occurs. These crack often where a dense protective oxide film covers the metal surfaces, and cracking occurs from the action of applied cyclic stresses. Corrosion fatigue cracks are often thick, blunt, and across the metal grains. They start at internal tube surfaces and are most often circumferential on the tube. Caustic embrittlement Caustic embrittlement or cracking is a more serious type of boiler metal failure showing up as continuous intergranular cracks. This type of cracking occurs when the metal is stressed, water contains caustic with a trace of silica, and some mechanism, such as a slight leak, is present allowing the boiler water to concentrate on the stressed metal. Caustic embrittlement is more of a problem in older boilers with riveted drums as they cause stresses and crevices in the areas of rivets and seams. In the newer welded drum boilers this type of cracking is less.

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3.2.4 Boiler water carryover

Boiler water carryover is the contamination of steam with boiler water solids. Common causes of boiler water carryover are: 1. Bubbles or foam form on the surface of the boiler water and leave with the steam. This is due to high concentrations of insoluble or soluble solids in the boiler water. Substances like alkalis, greases, oils, fats, organic matter and suspended solids are known to cause foaming. 2. Fine droplets of water in the form of spray or mist are thrown up into the steam space by the bursting of rapidly rising bubbles at the steam- release surface. 3. Priming is a sudden surge of boiler water caused by a rapid change in load. It may be caused by damaged steam-separating equipment, operation above the boiler rating, sudden fluctuations in steam demand, or carrying too high of a water level in the steam- release area. 4. Steam contamination may also occur from leakage of water through improperly designed or installed steam-separating equipment in the boiler drum.

3.3 Boiler Water Treatment:Feedwater is filtered to remove suspended matter and if the suspended solids are very fine, a flocculation step may be needed to enable effective filtration. The water is then subjected to other treatments to make it suitable for the boiler. Depending on the quality of water, it may be subjected to one or more treatments like chemical precipitation, lime-soda softening, ionexchange, deaeration, and reverse osmosis.

3.3.1 Filtration
Filtration is the essential first step before the chemical treatment and conditioning of the boiler feedwater. Filtration removes or minimizes all types of suspended solid impurities. If rust, sand (silica) etc. are not filtered out, they lead to severe scale formation, which is difficult to clean and reduce boiler efficiency. Even the condensate feedwater must be filtered before returning to the boiler. The boiler itself and the steam piping produce rust

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particles etc. due to corrosion and other reactions. Filtration is also necessary for any water treatment.

3.3.2 Coagulation and flocculation

Sometimes the suspended particles in water are so fine that even cartridge filter s are unable to remove them. In such a situation, before cartridge filtration, the water is first treated with coagulants. Coagulation is charge neutralization of finely divided and colloidal impurities in water into masses that can be filtered. In addition, particles have negative electrical charges, which cause them to repel each other and resist adhering together. Coagulation, therefore, involves neutralizing the negative charges and providing a nucleus for the suspended particles to adhere to. Flocculation is the bridging together of coagulated particles. Types of coagulants Iron and aluminum salts such as ferric sulfate, ferric chloride, aluminum sulfate (alum), and sodium aluminate are the most common coagulants. Ferric and alumina ions each have three positive charges and therefore their effectiveness is related to their ability to react with the negatively charged colloidal particles. These coagulants form a floc in the water that serves like a net for collecting suspended matter. Polyelectrolytes, which are synthetic materials, have been developed for coagulation purposes. These consist of long chain-like molecules with positive charges. In some cases organic polymers and special types of clay are used in the coagulation process to serve as coagulant aids. These assist in coagulation by making the floc heavier.

3.3.3 Chemical precipitation

Chemical precipitation is a process in which chemical added reacts with dissolved minerals in the water to produce a relatively insoluble reaction product. Precipitation methods are used in reducing dissolved hardness, alkalinity, and silica. The most common example is lime-soda treatment.

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Lime - soda in softening process Calcium hydroxide (hydrated lime) reacts with soluble calcium and magnesium carbonates to form insoluble precipitates. They form a sludge that can be removed by settling and filtration. Lime, therefore, can be used to reduce hardness present in the bicarbonate form (temporary hardness) as well as decrease the amount of bicarbonate alkalinity in water. Lime reacts with magnesium sulfate and chloride and precipitates magnesium hydroxide, but in this process soluble calcium sulfate and chlorides are formed. Lime is not effective in removing calcium sulfates and chlorides (permanent hardness). Soda ash is used primarily to reduce non-bicarbonate hardness (permanent hardness). The calcium carbonate formed by the reaction precipitates as sludge and can be filtered out. The resulting sodium sulfate and chloride are highly soluble and non-scale forming.

Methods of lime-soda softening. The older method of intermittent softening consists of mixing the chemicals with the water in a tank, allowing time for reaction and forming of sludge, and filtering and drawing off the clear water. The modern method of continuous lime-soda softening involves use of compartmented tanks with provision for (a) Proportioning chemicals continuously to the incoming water (b) Retention time for chemical reactions and sludge formation, and continuous draw-off of softened water. Lime-soda softening is classified as hot or cold, depending on the temperature of the water. Hot process softeners increase the rate of chemical reactions, increase silica reduction, and produce over-all better quality water. Coagulants used in lime-soda process In the initial clarification process, coagulants are used to agglomerate fine suspended particles, which can then be filtered out. Likewise, in the softening process, coagulants speed up settling of sludge by 25 -50%. Sodium aluminate used as a coagulant in lime-soda softening being alkaline, also contributes to the softening reactions, particularly in reducing magnesium. Proper uses of coagulants help remove silica in the softening process. Silica tends to be adsorbed on the floc produced by coagulation of sludge.
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Advantages of lime-soda softening The main advantage is that in reducing hardness, alkalinity, total dissolved solids, and silica are also reduced. Prior clarification of the water is not usually necessary with the lime-soda process. Another advantage is that with continuous hot process softening some removal of oxygen and carbondioxide can be achieved. Fuel savings can be realized with hot process softening because of solids reduction. This reduction decreases the conductivity of the feedwater, thereby decreasing blowdown and conserving heat.

Disadvantages of lime-soda softening The main disadvantage is that while hardness is reduced it is not completely removed. Variations in raw water composition and flow rate also make control of this method difficult since it involves adjusting the amounts of lime and soda ash being fed.

3.3.4 Deaeration of water

Dissolved oxygen in water is a major cause of boiler system corrosion. It should be removed before the water is put in the boiler. Feedwater deaeration removes oxygen by heating the water with steam in a deaerating heater. Part of the steam is vented, carrying with it the bulk of the dissolved oxygen.

3.3.5 Internal treatment

Internal treatment of water inside the boiler is essential whether or not the feedwater has been pretreated. Internal treatment compliments external treatment and is required regardless of whether the impurities entering the boiler with the feedwater are large or small in quantity. Internal treatment can constitute the sole treatment when boilers operate at low pressure, large amounts of condensed steam are used for feedwater, or the raw water available is of good quality. However, in moderate or high-pressure boilers, External treatment of the make-up water is mandatory for good results.
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The purpose of an internal water treatment program is: 1. To react with incoming feedwater hardness and prevent it from precipitating on the boiler metal as scale 2. To condition any suspended matter such as hardness sludge in the boiler and make it non-adherent to the boiler metal 3. To provide antifoam protection to permit a reasonable concentration of dissolved and suspended solids in the boiler water without foaming 4. To eliminate oxygen from the feedwater 5. To provide enough alkalinity to prevent boiler corrosion 6. To prevent scaling and protect against corrosion in the steam-condensate systems.

Chemicals used in internal treatment Phosphates used to be the main conditioning chemical, but nowadays chelate and polymer type chemicals are mostly used. These new chemicals have the advantage over phosphates of maintaining scale-free metal surfaces. All internal treatment chemicals, whether phosphate, chelate, or polymer, condition the calcium and magnesium in the feedwater. Chelates and polymers form soluble complexes with the hardness, whereas phosphates precipitate the hardness. Sludge conditioners are also used to aid in the conditioning of precipitated hardness. These conditioners are selected so that they are both effective and stable at boiler operating pressures. Synthetic organic materials are used as antifoam agents. For feedwater oxygen scavenging, chemicals used are sodium sulfite and hydrazine.

Internal treatment for hardness At boiler operating temperatures, calcium carbonate in the feedwater breaks down to form calcium carbonate. Since it is relatively insoluble, it precipitates. Sodium carbonate in the water partially breaks down to sodium hydroxide and car bon dioxide. Internal treatment with phosphates transforms calcium bicarbonate to calcium phosphate and sodium carbonate. In the presence of hydroxide alkalinity, magnesium bicarbonate
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precipitates as magnesium hydroxide or reacts with silica to form magnesium silicate. These minerals are precipitated from solution in form of sludge, which must be conditioned to prevent its sticking to the boiler metal. The conditioned sludge is then removed from the boiler by blowdown. When chelate is used for internal treatment, it reacts with calcium and magnesium salts to form soluble complexes. These complexes are in the form of dissolved solids and are removed by blowdown. Dispersant polymers used in conjunction with chelate produces reaction products, which are better conditioned. They do not precipitate and are more easily removed by blowdown.

Internal treatment for sulfates The boiler temperature makes the calcium and magnesium sulfates in the feedwater insoluble. With phosphates used as internal treatment, calcium reacts with the phosphate producing hydroxyapatite, which is much easier to condition than calcium sulfate. With chelates or polymer used as internal treatment, calcium and magnesium react with these materials producing soluble complexes that are easily removed by blowdown. Internal treatment for silica If silica is present in the feedwater, it tends to precipitate directly as scale at hot spots on the boiler metal and or combines with calcium forming a hard calcium silicate scale. In the internal treatment for silica, the boiler water alkalinity has to be kept high enough to hold the silica in solution. Magnesium, present in most waters, precipitates some of the silica as sludge.

Internal treatment for sludge conditioning Internal treatment for hardness results in insoluble precipitates in the boiler that form sludge. In addition, insoluble corrosion particulate (metal oxides) is transported to the boiler by condensate returns and from preboiler feedwater corrosion resulting in suspended solids. Suspended solids, carried to the boiler by feedwater or subsequently formed within the boiler, adversely affect both boiler cleanliness and steam purity. These solids have varying

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tendency to deposit on the boiler metal. Conditioners prevent these solids from depositing and forming corrosive or insulating boiler scale. Some of the principal types of sludge conditioners are: 1. Starches effective on high silica feedwater and where oil contamination is a problem 2. Lignins effective on phosphate type sludge 3. Tannins fairly effective on high hardness feedwater

Internal treatment advantages Internal treatment is basically simple and with the help of a qualified consultant an effective program is easily established. Scales or deposits, corrosion and carryover are minimized thereby improving efficiency and reducing energy consumption, preventing tube failures and unscheduled costly repairs, and reducing deposits, corrosion and contamination in equipment or processes.

3.3.6 Blowdown [8]

Blowdown is the discharge of boiler water containing concentrated suspended and dissolved feedwater solids. As the blowdown water is replaced with lower solids feedwater, the boiler water is diluted. With proper regulation of blowdown, the amount of solids in the boiler water can be controlled. The amount of blowdown needed depends on how much feedwater impurities a given boiler can tolerate. For example if a particular boiler can tolerate 500 ppm maximum dissolved solids, and the feedwater contains 50 ppm, it can be concentrated only about 10 times. This means that for every 100 pounds of water fed to the boiler about 10 pounds of boiler water must be blown down to keep the dissolved solids from exceeding 500 ppm. Total dissolved solids is not the only limiting factor in deter mining blowdown, other considerations include suspended solids, alkalinity, silica and iron.

Continuous and intermittent blowdown Boilers incorporate blowdown valves at low points where sludge is likely to collect. Opening these blowdown valves for short intervals provides intermittent removal of sludge and concentrated solids. In addition, some boilers also have a blowdown off take located slightly below the water level in the steam release area. A small amount of water is
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continuously removed through these connections. This procedure is called intermittent blowdown. The use of continuous blowdown in addition to manual (bottom) blow down maintains the residuals at more consistent levels in the boiler water. Continuous blowdown also minimizes the amount of bottom blowdown required, with resultant savings in fuel and chemicals. Continuous blowdown helps minimize upsets in boiler water circulation and operation.

3.3.7 Corrosion in steam condensate system

Corrosion in steam condensate system is caused by carbon dioxide and oxygen carried into the system by steam. Dissolved carbon dioxide in condensed steam forms corrosive carbonic acid. If oxygen is present with carbondioxide, the corrosion rate is much higher, and is likely to produce localized pitting. Ammonia, in combination with oxygen, attacks copper alloys.

Prevention of steam condensate corrosion Generally corrosion prevention is by removing oxygen from the feedwater by mechanical (deaerator) means, by use of suitable chemicals, and pretreatment of the make-up water to minimize potential carbon dioxide formation in the boiler. Further boiler water treatment is done by use of volatile amines to neutralize carbon dioxide or volatile filming inhibitors to form a barrier between the metal and the corrosive condensate. Mechanical conditions need to checked and corrected, like poor trapping and draining of lines. Deaerator can reduce oxygen to as low as 0.007 ppm. Since very small amounts of oxygen can cause boiler and steam condensate system corrosion, chemical treatment is needed to assure complete oxygen removal. Sodium sulfite and hydrazine chemicals are commonly used for this purpose.

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3.4 Boiler feedwater specifications [3]

Table 1

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CHAPTER 4 COOLING WATER TREATMENT

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4.1 Cooling water [3]

Cooling water systems remove heat generated from a variety of industrial processes. General schematic showing operation of cooling water Fig 1:-

4.2 Objectives of Cooling Water Treatment

The primary objectives of cooling water treatment are to maintain the operating efficiency of the cooling water system and to protect the equipment that contacts the cooling water. These objectives are accomplished by controlling or minimizing deposition, corrosion, and microbiological growth on the cooling water equipment. Treatment programs must also address requirements for environmental compliance, safety, water conservation, and limitation of chemical costs.

4.3 Problems occurring in cooling water systems

Water-related problems can cause system downtime, loss of equipment efficiency, the need for capital replacement of equipment, and can increase the risk of disease from pathogenic microorganisms. An open recirculating cooling tower system has a greater potential for these problems than does a once-through cooling water system, due to the air- and water-mixing design of the open recirculating system. These problems are associated with water-caused deposits, corrosion, or microbiological organisms, and occur for various reasons: The cooling tower is essentially a huge air scrubber that can introduce materials such as microorganisms, gases, dust, and dirt into the circulating water, which provides an excellent growth environment for pathogenic microorganisms. These materials can contribute to the formation of deposits and cause corrosion. If the water is not properly treated and its quality maintained, corrosion and scale and solids deposition can occur. The potential for these problems results from the nature of the cooling
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system design and the operating conditions, including water evaporation, mineral concentration, and water temperatures of up to 54 C (130 F). The constant addition of makeup water results in increased quantities of mineral constituents that can form scale, deposits, and corrosion. Blowdown control and proper water treatment can minimize these problems. The film fill contains small water and air passages that can become plugged, thereby causing a reduction in cooling tower operational efficiency due to reduced water evaporation

4.3.1 Deposit Formation Deposits that occur in cooling water systems are usually divided into two categories: scale and fouling. The presence of either type of deposit in the heat exchangers or in the film fill can interfere with heat transfer, thereby reducing the efficiency of operation. Deposits can also promote under-deposit corrosion. 4.3.2 Scale formation. Scale is formed from minerals, formerly dissolved in water, that were deposited from the water onto heat transfer surfaces or in-flow water lines. As water is evaporated in a cooling tower, the concentration of dissolved solids becomes greater until the solubility of a particular scale-causing mineral salt is exceeded. When this situation occurs in an untreated cooling water system, the scale will form on any surface in contact with the water, especially on heat transfer surfaces. The most common scaling minerals are calcium carbonate, calcium phosphate, calcium sulphate, and silica, usually in that order. Formation of magnesium silicate scale is also possible under certain conditions. Most other salts, including silica, are more soluble in hot water than in cold water; however, most calcium and magnesium salts, including calcium phosphate and calcium carbonate, are more soluble in cold water than in hot water. This is called reverse solubility. The water temperature will increase as recirculating water passes through the cooling system. As a result, calcium and magnesium scales may form anywhere in the system, but most likely on heated surfaces such as heat exchangers or surface condensers. Silica will form in areas having the lowest water temperature, such as in the cooling tower fill.

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4.3.3 Fouling The term fouling refers to the deposition of materials that are normally held in suspension in the cooling water: mud, silt, and other SS brought into the system with the makeup water; dust, dirt, and debris scrubbed out of the air passing through the tower; product leakage such as oils; corrosion products from the system; and biological organisms, both living and dead. Combinations of any or all of these materials can be present in the cooling water. 4.3.4 Cooling water corrosion The term corrosion (in a cooling water system) is defined as the electrochemical deterioration of a metal that is in contact with cooling water. Corrosion occurs when an electric current flows from one part of the metal (anode) through the water (electrolyte) to another part of the metal (cathode). Corrosion takes place at the anode only. The cathode is the driving force of the corrosion action. Specific type of corrosion called White Rust occurs in cooling water systems. Some cooling towers are constructed with galvanized steel components and must not be exposed to conditions of high pH (high alkalinity). The galvanizing process deposits a protective zinc coating on a mild steel metal surface, resulting in increased resistance to corrosion. Failure to avoid such exposure can result in production of white rust due to the corrosion of the galvanizing coating. Eventually, this corrosion process exposes the mild steel underneath, which then starts to corrode. White rust failures have been a common occurrence throughout the country, mainly with newer cooling towers. Proper protection of the galvanizing material is necessary both during start-up of a new cooling tower and during normal operations. Specific water treatment chemicals are needed to provide this protection. Examples include pretreatment with a high level of orthophosphate.

4.4 Treatment methods

4.4.1 Scale Control Methods. Three basic methods are used to prevent the formation of scale in cooling water systems: a) Remove the water scaling ingredients from the water before use. This includes softening, RO etc. b) Keep the scale-forming ingredients in solution. This is the most common scale-control method used for cooling water, and it can be achieved by use of either or both of the following two methods: adding acid, which lowers the pH of the recirculating water, or adding a scale inhibitor (phosphonate or specific polymer), which allows higher COC (Cycles of Concentration. COC in a steam boiler is a term that refers to the number of times the minerals in the feedwater have been concentrated in the boiler by its operation.) to be
25

maintained without scaling. Acid neutralizes (destroys) mineral alkalinity, one of the constituents forming calcium carbonate scale; however, because of the hazards associated with handling strong acids and the potential damage from an acid spill, the use of acid in cooling towers is not recommended. c) Allow the water-scaling ingredient to precipitate as sludge. Modern chemical treatment can distort or modify scale crystals such that they cannot adhere to each other to form a hard deposit; instead, they become a sludge that can be removed through filtration or blowdown. 4.4.1.1 Calcium Carbonate Scale Control Using Chemicals. Acids and phosphonates are chemicals that keep scale from forming. The use of acid in cooling towers may not be appropriate for use at sea side installations due to the associated risk of corrosion. 4.4.1.2 Acids. The acid most commonly used is sulphuric acid used as a diluted solution (e.g., 40% sulphuric acid in water). The use of acids requires adequate pH control. 4.4.1.3 Phosphonates. The phosphonates used most frequently for calcium carbonate scale control in recirculating cooling water systems are AMP (amino-tri [methylene] phosphonic acid); HEDP (1hydroxyethylidene 1,1-diphosphonic acid); and PBTC (2-phosphonobutane-1,2,4tricarboxylic acid). The chemical reaction of all phosphonates is similar; however, their stability varies greatly. The presence of chlorine or other oxidants in treated cooling water favours the use of PBTC, which is very resistant to decomposition, followed by HEDP, and finally AMP. An active dosage of 3 to 5 ppm of either AMP or HEDP, or 1.5 to 2.5 ppm PBTC, will increase the solubility of calcium carbonate by a factor of 3 or more relative to using no chemical treatment. Rather than operating at a PSI of 6.0 (stable water, no scale) in an untreated system, the cooling tower water can be used at a PSI of 4.0 without the occurrence of scale however, in the absence of calcium scaling conditions, phosphonates can increase the corrosion of both mild steel and copper. 4.4.1.4 Calcium Carbonate Scale Control Using Polymers. Many different polymers are used in water treatment. For the most part, they have multifaceted performance capability; they can inhibit various types of scale formation. Often water treatment products will include more than one type of polymer in the product formulation. For control of calcium carbonate, homopolymers such as polyacrylate, polymethacrylate, and polymaleate are used to keep calcium carbonate in solution. Dosages of 3 to 5 ppm of active
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polymer in the cooling tower water can control calcium carbonate scale formation very effectively.

4.4.1.5 Calcium Phosphate Scale Control Often calcium phosphate scale is formed in cooling water systems treated with a phosphate based corrosion inhibitor program or when phosphate is present in the makeup water (i.e., potable or recycled water). Calcium phosphate is much less soluble in water than is calcium carbonate. If the calcium hardness is 500 ppm and the pH is above 7.0, without any polymer treatment calcium phosphate scale will likely form, even at the low level of 10 ppm phosphate (as PO4) in the cooling water. Calcium phosphate solubility can be increased by a factor of a little less than 3 by the addition of 4-ppm phosphonate or by the use of 6 to 8 ppm of a copolymer or terpolymer specific for calcium phosphate inhibition. 4.4.1.6 Calcium Sulphate Scale Control Calcium sulphate formation can result from high concentrations of calcium ions and sulphate ions in the recirculating water; however, calcium sulphate is the most soluble of the scaleforming calcium salts found in cooling tower waters having pH levels of greater than 8.0. This means that calcium sulphate scale will not form unless some calcium ions (hardness) remain in solution after the calcium reacts with all the carbonate and phosphate in the water. Calcium sulphate scale may occur when the recirculating water contains calcium hardness in the range of 500 to 700 ppm as CaCO3 and sulphate in the range of 500 to 700 ppm SO4 The addition of 3 to 5 ppm of a copolymer of acrylate and acrylamide will allow calcium sulphate to remain in solution at a level almost 3 times the level allowed when using no treatment. Calcium sulphate scale rarely forms at pH levels above 8.0 in the cooling water. 4.4.1.7 Magnesium Silicate Scale Control. Formation of magnesium silicate is possible in cooling systems, but only under certain rare conditions. Magnesium ions (hardness) first react with hydroxyl ions (OH-) to form magnesium hydroxide, which then react, with (absorbs) dissolved or colloidal silica. A deposit analysis often reports this material as magnesium silicate. Since magnesium hydroxide solubility decreases at pH levels above 9.0, this scale will usually occur only at a pH level above 9.0 and when the magnesium hardness concentration is greater than 100 ppm. 4.4.1.8 Silica Scale Control. Silica solubility is dependent upon temperature and pH. At pH levels greater than 8.5, silica remains soluble (no scale) at a concentration of 250 ppm as SiO2. At pH levels of 7.5 or below, maximum silica solubility is 150 ppm as SiO2. At maximum silica levels, silica will
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first deposit on the cooling tower slats rather than in the heat exchanger because silica is more soluble in hot water than in cold water.

If the concentration of silica in the makeup water is above 30 ppm, it will usually be the parameter that controls the adjustment of cooling water system COC. If the silica concentration is high, external treatment can reduce the level of silica in the makeup water.

Summary of scale control methods

Table 2

4.4.2 Fouling Control

Fouling occurs mainly due: Inorganic matter (mud, dirt, and corrosion products) Organic matter (algae, bacteria, and fungus.)

4.4.2.1 Inorganic fouling control Fouling from mud, dirt, and corrosion products can be controlled by the addition of a watersoluble polymer dispersant, such as a polyacrylate. The addition of about 4 to 5 ppm of active polymer, together with sufficient water velocity (e.g., 1 meter per second), can keep foulants in suspension and prevent them from being deposited on heat transfer surfaces. Higher dosages (5 to 20 ppm) of active polymer can be required for heavily fouled systems. It is best to reduce the loading of SS (suspended solids) by mechanically removing them from the system through blowdown, filtration, and physical sump cleaning.
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4.4.2.2 Organic Fouling control Chlorine and Chlorine Release Agents. Chlorine (Cl2) compounds are the most effective industrial oxidizing biocides and the most widely used. Chlorine is available as a chlorine gas, dry calcium hypochlorite (HTH), liquid sodium hypochlorite (bleach), plus several other dry products that release chlorine. When chlorine is introduced into water, it hydrolyses to form hypochlorite ion (OCl-) and hypochlorous acid (HOCl); it is the latter chemical that is the stronger oxidizing biocide. The presence of hypochlorous acid is greater, proportionate to hypochlorite ion, at low pH levels. At a pH of 5.0, hypochlorous acid exists almost exclusively. At a pH of 7.5, there are approximately equal amounts of hypochlorous acid and hypochlorite ion. Chlorine is effective, but to a lesser degree, as a biocide at a pH of 7.5 or greater because the hypochlorite ion has about one-tenth the biocidal efficacy of hypochlorous acid. A pH range of 6.5 to 7.5 is considered optimal for chlorine or chlorine-based microbiological control programs. Above pH 7.5, relatively higher levels of chlorine are required to be effective. Bromine Release Agents. Bromine (Br2) compounds are very similar to chlorine compounds. Although more expensive than chlorine compounds, their main advantage is that bromine is more effective at higher pH ranges (7.5 or greater) than chlorine. Bromine has a lower vapour pressure than chlorine and is 6 times as soluble in water, making it less subject to vaporization loss from a cooling tower. When bromine is introduced to water, it hydrolyses to form hypobromite ion (OBr-) and hypobromous acid (HOBr). A pH range of 7.5 to 10.0 is considered optimal for the use of bromine. Bromine release agents include dry chemicals called hydantoins and bromine salts, such as sodium bromide. When a salt solution is mixed with an oxidizing agent, such as bleach, and a reaction occurs, bromine is produced. In water, bromine degrades more rapidly than chlorine. Recent developments in bromine chemistry have resulted in the production of a bromine solution (liquid). Ozone. Ozone (O3) is a gas produced by passing dry air either through a strong electric field or near an ultraviolet light. If ozone is dissolved in water, the resulting solution can be added to cooling water. Ozone is a very strong oxidizing biocide that, if properly applied, can provide effective control of microorganisms in cooling tower systems; however, because of safety and operational problems associated with its manufacture and use, and the resulting high capital and operating costs, it is neither the most economical method nor the preferred
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method for microbiological control in cooling towers under normal operations. Ozone can increase metal corrosion and does not prevent scale. Chlorine Dioxide. Chlorine dioxide (ClO2) is a gas generated by mixing several chemicals. The chlorine dioxide gas produced in this manner is subsequently dissolved in water, with the water containing the chlorine dioxide then added to the cooling water. Chlorine dioxide must be produced in close proximity to the point of use. It is not recommended for use on normal installations due to the complexity of its production and safety concerns associated with its production and handling. Hydrogen Peroxide. Hydrogen peroxide (H2O2) is a liquid that is usually used at a concentration of 30% in water. Hydrogen peroxide is considered one of the most environmentally friendly oxidizing biocides because it degrades to water; however, concentrated hydrogen peroxide will react in a violent manner when it comes into contact with organic chemicals and materials. Non-Oxidizing Biocides. Non-oxidizing biocides are microbiocides that act as poisons; they disrupt the metabolic or reproductive processes of micro- and macro-organisms and are therefore toxic. Nonoxidizing biocides are organic compounds that are very toxic to organisms, including human beings and animals. They are usually liquids, but some are available as dry products (e.g., pellets, solids). A major consideration for their use is their persistence with respect to the discharge limitations for water (effluent) containing these toxic substances. Also, when choosing and applying a non-oxidizing biocide, you must consider the cooling tower systems operating parameters, such as pH and retention time. The applied dosages of microbiocides should never exceed EPA maximum limits, which are always printed on the container labels. E.g. Quaternary ammonium salts, Dibromo-nitrilo-propionamide, Methylene bisthiocynate

4.4.3 Effective Corrosion Control.

Effective corrosion control requires maintaining appropriate pH levels, plus adding maintenance dosages of chemical corrosion inhibitors. Chemical corrosion inhibitors form a protective film or barrier on the cooling system metal surfaces that have been cleaned prior to adding an initial high dosage of inhibitor. The initial high dosage of inhibitor passivates (protects) the metal. The appropriate dosage of corrosion inhibitor must be maintained continuously in the cooling water to ensure continuing protection. Corrosion inhibitors are divided into three classes: cathodic, anodic, and general filmers. Corrosion inhibitors form a protective film on either the anode, the cathode, or over the entire metal surface.
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Anodic Inhibitors. Anodic inhibitors form a protective film coating on the anodic metal (where the metal is lost) and thus directly control corrosion by preventing the reaction that results in corrosion. Any unprotected areas will corrode at a much faster rate than the protected areas, a factor that could result in pitting or localized attack of the unprotected areas. Examples of anodic inhibitors include orthophosphate, nitrite, and orthosilicates. Under certain conditions, molybdate can function as an anodic inhibitor. Cathodic Inhibitors Cathodic inhibitors form a protective film coating of the cathodic metal (where metal is not lost) and thus indirectly prevent corrosion by interfering with the current flow required for the electrochemical reaction to proceed. General Inhibitors. General inhibitors produce a protective film on the surfaces of all metals. These corrosion inhibitors are organic compounds, such as certain phosphonates, amines, and other nitrogen chemicals. They may be used in cooling water systems. Corrosion Inhibitors for Specific Metals. Some corrosion inhibitors provide corrosion control for specific metals. The protection of copper and copper alloys requires the use of azoles, such as tolyltriazole (TTA), benzotriazole (BZT), and butylbenzo-thiazole, which can be added to the system separately from, or as part of a blend of, other treatment chemicals. Galvanic or Crevice Corrosion Control Control of galvanic or crevice corrosion is achieved primarily by engineering and mechanical design. These types of corrosion can also be partially controlled by physical and chemical considerations. A dielectric coupling (insulator), used to separate two different metallurgies, can help to prevent galvanic corrosion. From a chemical perspective, adjusting pH and using proper corrosion inhibitors will reduce corrosion.

MIC (Methyl Isocynate) MIC is best prevented by stopping conditions that foster biological growth and by using an effective microbiological control program. A MIC prevention program includes adequate control (prevention) of deposits and fouling.

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Deposit Corrosion Control Control of deposit corrosion requires maintaining deposit-free metal surfaces. This applies to any form of deposit, such as scale, biomass, corrosion products, or foulants. The occurrence of most types of deposits is prevented by dispersants, scale inhibitors, or biocides, along with the maintenance of adequate flow velocities. Routine, adequate cleaning of filters and tower sumps will help reduce deposits.

4.5 Cooling water specifications

Suspended solids Conductivity Hardness pH CO2 content Iron Manganese Sulphate Chloride COD None 50-600 uS/cm 0.44 ppm 7.8 None <0.3 mg/L <0.05 mg/L <250 mg/L < 250 mg/L < 40 mg/L

Table 3

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CHAPTER 5 PROCESS WATER TREATMENT

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5.1 Process water [5]

All natural waters contain, in various concentrations, dissolved salts which dissociate in water to form charged ions. Positively charged ions are called cations; negatively charged ions are called anions. Ionic impurities can seriously affect the reliability and operating efficiency of a boiler or process system. Overheating caused by the build-up of scale or deposits formed by these impurities can lead to catastrophic tube failures, costly production losses, and unscheduled downtime. Hardness ions, such as calcium and magnesium, must be removed from the water supply before it can be used as boiler feedwater. This type of water is virtually free of all contaminants both dissolved and suspended, organic and inorganic as well free from ions, which gives it the name Demineralized (DM) water. This high purity water is used in pharmaceuticals, electronic chip processing, high-pressure boiler feedwater systems, power plant turbines etc.

5.2 Methods of Preparation of DM water: Distillation process (unable to remove volatile impurity such as alcohol) Water softening (chemical treatment, ion exchange softening) Reverse Osmosis (RO) (expensive method ) Ion-exchange process (most widely used and preferable)

Industrially, Ion-exchange process is preferred for producing DM water so Ion-exchange technique is discussed in brief.

5.3 Ion-exchange process:Demineralization of water is the removal of essentially all inorganic salts by ion exchange. In this process, strong acid cation resin in the hydrogen form converts dissolved salts into their corresponding acids, and strong base anion resin in the hydroxide form removes these acids. Demineralization produces water similar in quality to distillation at a lower cost for most fresh waters. 5.3.1 Principle of ion-exchange process:Ion exchange is a process, which removes unwanted ions i.e. exchanges the mineral ions present in the water with exchangeable counter ions. In the process of exchange, the ion exchanger (RESIN) exchanges an equivalent number of ions. The ion exchanger has a limited capacity for storage of ions in its skeleton (called its exchange capacity). When the ion exchanger is exhausted the process known as regeneration revives the capacity. In short we can say ion exchange is a stoichiometric process, every ion, which is removed from the solution/ water, is replaced by an equivalent amount of another ionic species of the same
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charge. Resins are high molecular weight cross-linked polymer having exchangeable counter ions. The polymer part is inert and inactive. Exchange takes place on the counter ions as follows:Cation resin: R-H + M+ <====> RM + H+ Anion resin: R-OH + X- <====> RX + OHR - is the inert polymer part and H and OH are exchangeable parts. 5.3.2 Theory of Ion-Exchange Process [7]:A) Cation Resin:The raw material used for the preparation of the cation resin is styrene and divinyl benzene. They are first polymerized and then sulphonated to get the exchangeable sites. After polymerization it is sulphonated with sulphuric acid. Degree of cross linkage affects pore size and stability of the resin. More the cross linkage more the stability and less the pore size. For hydrogen based resin, Ion-exchange takes place in following ways:-

It will be seen from the equations that the alkaline salt Calcium Bicarbonate, has been splitted into Carbonic acid which is being weakly ionized can also be represented as free carbon dioxide and water. This Carbondioxide formed has to be removed as it forms carbonic acid with water and reduces capacity of ion-exchange resins. b) Anion Resin:It is prepared by the co-polymerization of styrene and Divinyl benzene followed by chloromethylation and their interaction with amine. The polymerization step is same as in cation resin. The basic group may be derived from ammonia or an amine, and in order to facilitate the introduction of the basic group into the polymer.
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The anion resin is much prone to get damaged than cation resin. At elevated temperature oxidation can cause serious degradation thereby contaminating the water flowing through the resin bed and the strong resin may be converted into a weak resin. In the dematerializing process, the anion exchange resin that is used is in the form of R-OH. The exchange process can be shown as:HCl + R-OH <====> R-Cl + H2O H2SO4 + 2 R-OH <====> R2SO4 + 2H2O c) Mixed Resin The mixed bed exchanger containing both cation exchange resins and anion exchange resins intimately mixed together. These exchangers act as polishing units, removing the ions leaking through cation and anion exchanger. When water is passed through it, it comes into contact alternatively with grains of cation and anion resins so that the water is subjected to an almost infinite number of demineralization. During operation both Cation and Anion Resins are present in equal amount in the bed. The proper mixing of bed is very important for proper working of bed. 5.3.3 Working of a DM plant Equipments used in DM plant i. Alum dosing tank ii. Alum dosing pumps iii. Contact tanks iv. Pressurized sand filters v. Activated charcoal filters vi. Strong acid cation bed Vii. Degasser System viii. Strong base anion exchangers ix. Mixed bed exchangers x. Neutralizing pit

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Schematic of DM plant

fig:-2

Various steps involved in treatment of raw water are briefed as under1. Water is passed through activated carbon filter for removal of free chlorine present in water, which otherwise will be an extra load for anion bed. The activated carbon filter can also remove traces of organic impurities, if present in water. 2. Water is then treated in strong acid cation unit where calcium, sodium, magnesium and other cations are replaced by hydrogen ions from the resin or in other words the neutral salts are converted into their respective mineral acids. Hence the pH of the cation bed outlet decreases drastically and the carbonates and bicarbonates are converted into weak carbonic acid. Sodium being monovalent is less efficiently removed by the cation exchanger. There is therefore a very slight leakage of sodium (known as sodium slip) into the treated water from the cation bed. The actual leakage of sodium is dependent on the sodium content of the raw water and regeneration level and is not uniform throughout a run. It begins with high, gradually reduces to a minimum then increases steadily and sharply.
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3. The water from cation bed is then passed through the degasser tower where decomposition of carbonic acid and removal of carbon dioxide occurs. Hence the free carbon dioxide present in the water as well as that produced by the splitting up of alkaline salts is almost all removed by it. 4. The degassed water temporarily stored in degassed water tank, which is then pumped to strong base anion exchanger by, degassed water pumps. 5. In anion exchanger all anions such as sulphates chlorides, dissolved silica, traces of carbonic acid left after the degasser and other anions in the water are removed. 6. Then the water is passed through mixed bed exchanger, where traces of cations and anions slipped through cation bed exchanger and anion bed exchangers are removed. Thus the demineralised water is produced at the outlet of Mixed Bed unit. 7. DM water from MB outlet is stored in DM storage tanks from which it is distributed to different consumption points of both the units. REGENERATION:When the supplies of the exchangeable ions within the resins are exhausted, the treated water quality deteriorates and the resin requires the reconversion of the resin into operating form. This process is called as the regeneration. For CATION exchange resins a mineral acid such as Hydrochloric acid is used for regeneration:NaR + HCl Hydrochloric acid <====> HR Hydrogen resin + NaCl

Sodium Resin

Sodium Chloride

For ANION exchange resins sodium hydroxide is used for regeneration:RCl + NaOH Sodium acid <====> ROH Hydrogen resin + NaCl Sodium Chloride

Sodium Resin

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5.4 DM / Process water specification: PARAMETER Total Dissolved Solids (TDS) Conductivity Silica Hardness

Table 4 AMOUNT < 0.1mg/l < 0.5S/cm. < 0.02mg/l Nil

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6.0 CONCLUSION
In this report, various types of Industrial feedwaters and their preparation techniques are discussed in detail. Feedwater considered in this for topic for discussion were:1. 2. 3. BOILER FEEDWATER COOLING WATER PROCESS WATER/DM WATER Table 5

Comparison between Various Industrial Feedwaters

Note:-Here Some parameters of boiler feedwater & cooling water are higher than raw water because data here considered for both boiler feedwater & cooling water is considered after recycle, thus average specifications are mentioned. Data obtained from actual working equipment from Power plant (TAPP-3&4, Tarapur,Maharashtra,India).
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7.0 LIST OF FIGURES

FIGURE DESCRIPTION NO. 1 2 Schematic for showing cooling water operation Schematic of DM plant

PAGE NO. 23 36

8.0 LIST OF TABLES

TABLE DESCRIPTION NO. 1 2 3 4 5 Boiler feedwater specifications Scale control method for cooling Cooling water specifications DM water specifications Comparison between various industrial feedwaters

PAGE NO. 21 28 32 39 40

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9.0 BIBLIOGRAPHY: BOOKS 1. Robert Parlante, Water In Industry, Handbook of Water Resource and Pollution Control, 1971, Pg-385-426 2. Philip Swan & William Arrot, power Handbook Part-II, 1951.pg-34-36

3. Unified Facilities Criteria (UFC), Industrial Water Treatment Operation and Maintenance Report, UFC 3-240-13FN, pg-33-138, 25 May 2005 4. Parsons, A.J.: Some Aspects of Locomotive Boiler Feed Water Treatment. Of the Institution of Locomotive Engineers, London.pg-572-575 27th February 1957 5. Degrmonte Handbook of water treatment, Haslted press, pg-350-462, 1979 WEB REFERENCES
6. Chemicals used for internal treatment http://www.gewater.com/products/chemical_water/index.jsp 7. General methods of water treatments http://www.gewater.com/handbook/index.jsp

8. Boiler water treatment

http://www.lenntech.com/applications/process/boiler/boiler-feed-water.htm

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