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Essential Boiler Water Chemistry for Operation & Maintenance Engineers

Essential Boiler Water Chemistry for Operation & Maintenance Engineers


Introduction Boiler is a vessel wherein water is heated to convert into steam, with the application of heat of a burning fuel and/or the hot exhaust gas from some process. The heat potential available in steam is one of the well-known sources of energy to do mechanical work in any steam engine. It is essential to maintain uninterrupted flow of steam to the engines and hence the boiler has to be necessarily fed with adequate supply of water to keep up a safe level in the drum. In order to ensure long life and trouble free operation of a boiler it is important to keep the boiler water chemistry under control. Depending upon the working pressure and temperature of boiler, the quality of Feed Water for the boiler is to be maintained. However, due to continuous evaporation occurring in boiler, the concentration of impurities in the boiler goes on increasing. Therefore, it is necessary to carry out chemical injection in the boiler for forming precipitates of impurities, which are to be drained out at regular intervals. Due to this regular draining or blow down the quantity of water in boiler system has got to be continuously made-up by feeding high purity water which is obtained by appropriate treatment of raw water. Natural Water: Though the water, in nature, is available in plenty, it can not be taken for use in a boiler without a proper chemical treatment. The physical and chemical properties of natural water, which widely vary, depending upon the source and strata on which it flows, makes it unsuitable for direct use in a Boiler. The natural water picks up minerals and salts from the earthen layer, which gets into the solution. Water, therefore, is a mixer of composite mineral salts in dissolved condition, in varying proportions, composition and degree. It gets polluted further with multifarious organic and inorganic impurities, due to disposal of industrial and domestic wastes. Decayed vegetation and marine lives also contribute to water contamination. Not only the dissolved salts in water, but also the presence of the coarse and un-dissolvable substances in suspended form, constituting mainly of silt and clay matters, generally termed as turbidity, make it unsuitable for direct use, without any treatment. Natural water, found on earth, contains siliceous matters, in dissolved as well as in colloidal forms. Impurities: Water as a Solvent Pure water (H20) is colorless, tasteless, and odorless. It is composed of hydrogen and oxygen. 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.

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers

Water Impurities Water impurities include dissolved and suspended solids. Calcium bicarbonate is a soluble salt. A solution of calcium bicarbonate is clear, because the calcium and bicarbonate are present as atomic sized ions which are not large enough to reflect light. Some soluble minerals impart a color to the solution. Soluble iron salts produce pale yellow or green solutions; some copper salts form intensely blue solutions. Although colored, these solutions are clear. Suspended solids are substances that are not completely soluble in water and are present as particles. These particles usually impart a visible turbidity to the water. Dissolved and suspended solids are present in most surface waters. Seawater is very high in soluble sodium chloride; suspended sand and silt make it slightly cloudy. An extensive list of soluble and suspended impurities found in water is given in Table 1-1. Table 1-1. Common impurities found in fresh water. Constituent Chemical Formula 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 corrosion in water lines, particularly steam and condensate lines ion pH varies according to acidic or alkaline solids in water; most natural waters have a pH of 6.0-8.0

Means of Treatment

Turbidity

non-expressed analysis as units

in

coagulation, and filtration

settling,

Hardness

calcium and magnesium salts, expressed as CaCO3

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

Alkalinity

bicarbonate(HCO3 ), carbonate (CO32-), and hydroxide(OH-), expressed as CaCO3

lime and lime-soda softening; acid treatment; hydrogen zeolite softening; demineralization dealkalization by anion exchange neutralization alkalies with

Free Mineral Acid Carbon Dioxide

H2SO4 , HCI. etc., expressed as CaCO3

CO2

aeration, deaeration, neutralization with alkalies pH can be increased by alkalies and decreased by acids

pH

hydrogen concentration defined as: pH = log 1/ [H+]

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers
adds to solids content of water, but in itself is not usually significant, combines with calcium to form calcium sulfate scale adds to solids content and increases corrosive character of water adds to solids content, but is not usually significant industrially: useful for control of boiler metal embrittlement cause of mottled enamel in teeth; also used for control of dental decay: not usually 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 discolors water on precipitation; source of deposits in water lines, boilers. etc.; interferes with dyeing, tanning, papermaking, etc. same as iron usually present as a result of floc carryover from clarifier; can cause deposits in cooling systems and contribute to complex boiler scales 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 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; surface active agents for iron retention same as iron

Sulfate

SO42-

Chloride

Cl

Nitrate

NO3

Fluoride

F-

Sodium

Na

Silica

SiO2

Iron

(ferrous) Fe2+ Fe3+ (ferric)

Manganese

Mn2+

Aluminum

AI3+

improved clarifier and filter operation

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers
corrosion of water lines, heat exchange equipment, boilers, return lines, etc. cause of "rotten egg" odor; corrosion corrosion of copper and zinc alloys by formation of complex soluble ion refers to total amount of dissolved matter, determined by evaporation; high concentrations are objectionable because of process interference and as a cause of foaming in boilers refers to the measure of undissolved matter, determined gravimetrically; deposits in heat exchange equipment, boilers, water lines, etc. refers to the sum of dissolved and suspended solids, determined gravimetrically deaeration; sulfite; inhibitors sodium corrosion

Oxygen

O2

Hydrogen Sulfide

H2 S

aeration; chlorination; highly basic anion exchange cation exchange with hydrogen zeolite; chlorination; deaeration

Ammonia

NH3

Dissolved Solids

none

lime softening and cation exchange by hydrogen zeolite; demineralization, reverse osmosis, electrodialysis, evaporation

Suspended Solids

none

subsidence; filtration, usually preceded by coagulation and settling

Total Solids

none

see "Dissolved Solids" and "Suspended Solids"

Surface Water The ultimate course of rain or melting snow depends on the nature of the terrain over which it flows. In areas consisting of hard packed clay, very little water penetrates the ground. In these cases, the water generates "runoff". The runoff collects in streams and rivers. The rivers empty into bays and estuaries, and the water ultimately returns to the sea, completing one major phase of the hydrologic cycle of the nature. As water runs off along the surface, it stirs up and suspends particles of sand and soil, creating silt in the surface water. In addition, the streaming action erodes rocky surfaces, producing more sand. As the surface water cascades over rocks, it is aerated. The combination of oxygen, inorganic nutrients leached from the terrain, and sunlight supports a wide variety of life forms in the water, including algae, fungi, bacteria, small crustaceans, and fish. Often, river beds are lined with trees, and drainage areas feeding the rivers are forested. Leaves and pine needles constitute a large percentage of the biological content of the water. After it dissolves in the water, this material becomes a major cause of fouling of ion exchange resin used in water treatment.
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers The physical and chemical characteristics of surface water contamination vary considerably over time. A sudden storm can cause a dramatic short term change in the composition of a water supply. Over a longer time period, surface water chemistry varies with the seasons. During periods of high rainfall, high runoff occurs. This can have a favorable or unfavorable impact on the characteristics of the water, depending on the geochemistry and biology of the terrain. Surface water chemistry also varies over multi year or multidecade cycles of drought and rainfall. Extended periods of drought severely affect the availability of water for industrial use. Where rivers discharge into the ocean, the incursion of salt water up the river during periods of drought presents additional problems. Industrial users must take surface water variability into account when designing water treatment plants and programs. Groundwater Water that falls on porous terrains, such as sand or sandy loam, drains or percolates into the ground. In these cases, the water encounters a wide variety of mineral species arranged in complex layers, or strata. The minerals may include granite, gneiss, basalt, and shale. In some cases, there may be a layer of very permeable sand beneath impermeable clay. Water often follows a complex three dimensional path in the ground. The science of groundwater hydrology involves the tracking of these water movements. Table 1-2. A comparison of surface water and groundwater characteristics. Characteristic Turbidity Dissolved minerals Biological content Temporal variability Surface Water high low-moderate high very high Ground Water low high low low

In contrast to surface supplies, ground waters are relatively free from suspended contaminants, because they are filtered as they move through the strata. The filtration also removes most of the biological contamination. Some ground waters with a high iron content contain sulfate reducing bacteria. These are a source of fouling and corrosion in industrial water systems. Groundwater chemistry tends to be very stable over time. A groundwater may contain an undesirable level of scale forming solids, but due to its fairly consistent chemistry it may be treated effectively. Mineral Reactions: As groundwater encounters different minerals, it dissolves them according to their solubility characteristics. In some cases chemical reactions occur, enhancing mineral solubility. A good example is the reaction of groundwater with limestone. Water percolating from the surface contains atmospheric gases. One of these gases is carbon dioxide, which forms carbonic acid when dissolved in water. The decomposition of organic matter beneath the surface is another source of carbon dioxide. Limestone is a mixture of calcium and magnesium carbonate. The mineral, which is basic, is only slightly soluble in neutral water. The slightly acidic groundwater reacts with basic limestone in a neutralization reaction that forms a salt and a water of neutralization. The salt formed by the reaction is a mixture of calcium and magnesium bicarbonate. Both bicarbonates are quite soluble. This reaction is the source of the most common deposition and corrosion problems faced by industrial users. The calcium and
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers magnesium (hardness) form scale on heat transfer surfaces if the groundwater is not treated before use in industrial cooling and boiler systems. In boiler feedwater applications, the thermal breakdown of the bicarbonate in the boiler leads to high levels of carbon dioxide in condensate return systems. This can cause severe system corrosion. Structurally, limestone is porous. That is, it contains small holes and channels called "interstices". A large formation of limestone can hold vast quantities of groundwater in its structure. Limestone formations that contain these large quantities of water are called aquifers, a term derived from Latin roots meaning water bearing. If a well is drilled into a limestone aquifer, the water can he withdrawn continuously for decades and used for domestic and industrial applications. Unfortunately, the water is very hard, due to the neutralization/dissolution reactions described above. This necessitates extensive water treatment for most uses. The Mechanism of Scaling and Corrosion: Scaling: Deposition is a major problem in the operation of steam generating equipment. The accumulation of material on boiler surfaces can cause overheating and/or corrosion. Both of these conditions frequently result in unscheduled downtime. Boiler feedwater pretreatment systems have advanced to such an extent that it is now possible to provide boilers with ultrapure water. However, this degree of purification requires the use of elaborate pretreatment systems. The capital expenditures for such pretreatment equipment trains can be considerable and are often not justified when balanced against the capability of internal treatment. The need to provide boilers with high-quality feedwater is a natural result of the advances made in boiler performance. The ratio of heating surface to evaporation has decreased. Consequently, heat transfer rates through radiant water wall tubes have increased-occasionally in excess of 200,000 Btu/ft/hr. The tolerance for deposition is very low in these systems. The quality of feedwater required is dependent on boiler operating pressure, design, heat transfer rates, and steam use. Most boiler systems have sodium zeolite softened or demineralized makeup water. Feedwater hardness usually ranges from 0.01 to 2.0 ppm, but even water of this purity does not provide deposit-free operation. Therefore, good internal boiler water treatment programs are necessary. Deposits Common feedwater contaminants that can form boiler deposits include calcium, magnesium, iron, copper, aluminum, silica, and (to a lesser extent) silt and oil. Most deposits can be classified as one of two types

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers

scale that crystallized directly onto tube surfaces sludge deposits that precipitated elsewhere and were transported to the metal surface by the flowing water

Scale is formed by salts that have limited solubility but are not totally insoluble in boiler water. These salts reach the deposit site in a soluble form and precipitate when concentrated by evaporation. The precipitates formed usually have a fairly homogeneous composition and crystal structure. High heat transfer rates cause high evaporation rates, which concentrate the remaining water in the area of evaporation. A number of different scale-forming compounds can precipitate from the concentrated water. The nature of the scale formed depends on the chemical composition of the concentrated water. Normal deposit constituents are calcium, magnesium, silica, aluminum, iron, and (in some cases) sodium. The exact combinations in which they exist vary from boiler to boiler, and from location to location within a boiler (Table 1- 3). Scale may form as calcium silicate in one boiler and as sodium iron silicate in another. Compared to some other precipitation reactions, such as the formation of calcium phosphate, the crystallization of scale is a slow process. As a result, the crystals formed are well defined, and a hard, dense, and highly insulating material is formed on the tube metal. Some forms of scale are so tenacious that they resist any type of removal-mechanical or chemical. Sludge is the accumulation of solids that precipitate in the bulk boiler water or enter the boiler as suspended solids. Sludge deposits can be hard, dense, and tenacious. When exposed to high heat levels (e.g., when a boiler is drained hot), sludge deposits are often baked in place. Sludge deposits hardened in this way can be as troublesome as scale. Once deposition starts, particles present in the circulating water can become bound to the deposit. Intraparticle binding does not need to occur between every particle in a deposit mass. Some nonbound particles can be captured in a network of bound particles.

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers

Table 1- 3. Crystalline scale constituents identified by X-ray diffraction. Name Acmite Analcite Anhydrite Aragonite Brucite Calcite Cancrinite Hematite Hydroxyapatite Magnetite Pectolite Quartz Serpentine Thenardite Wallastonite Xonotlite Formula Na2OFe2O34SiO2 Na2OAl2O34SiO22H2O CaSO4 CaCO3 Mg(OH)2 CaCO3 4Na2OCaO4Al2O32CO29SiO23H2O Fe2O3 Ca10(OH)2(PO4)6 Fe3O4 Na2O4CaO6SiO2H2O SiO2 3MgO2SiO22H2O Na2SO4 CaSiO3 5CaO5SiO2H2O

Binding is often a function of surface charge and loss of water of hydration. Iron oxide, which exists in many hydrated and oxide forms, is particularly prone to bonding. Some silicates will do the same, and many oil contaminants are notorious deposit binders, due to polymerization and degradation reactions. Since these scale components have the small thermal conductivities as shown in Table below, the scale adhesion on the heating surface remarkably reduces the thermal efficiency of boiler. Substance Silica scale Calcium carbonate scale Calcium sulfate scale Calcium phosphate scale Iron oxide (hematite) scale Iron oxide (magnetite) scale Carbon steel Copper Thermal conductivity (kcal/mhC) 0.20.4 0.40.6 0.52.0 0.50.7 35 1 4060 320360

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers When the part covered with the scale is locally superheated, the mechanical strength of the tube material is reduced and the bursting may occur eventually. Most scales formed on the heating surface are generally composed of several mixed substances. The thermal conductivity of such mixed scale is approximately 1 to 2 kcal/mhC. Figure below shows a model of heating surface covered with scale and the inner skin temperature of the tube under the scale, obtained from the following equation: t2 = t4 + (1/ + D/ k2) x Q Where, t2 = inner skin temperature of tube (C) t4 = boiler water temperature (bulk)(C) = heat transfer coefficient of boiling surface (kcal/ m2hC) D = scale thickness (m) k2 = thermal conductivity of scale (kcal/ mhC) Q = heat flux (kcal/m2h) Figure in the left shows the relationship between the scale thickness and the inner skin temperature of tube at each heat flux when a scale with thermal conductivity of 2 kcal/mhC adheres on the boiler tube inside with the pressure of 10 kgf/cm2.

Figure in the right shows the relationship between the temperature and the allowable tensile stresses of carbon steels using as boiler tubes. When the temperature exceeds 350 C, the allowable stress starts to decrease and reaches the 50 to 60% of the original value at 450 C. Therefore, the tube wall temperature should be kept below 450C for the safe boiler operation and the scale thickness on the tube has to be controlled thinner STB 410 is equivalent of ASTM grade SA210 GR A1 than 1 to 2 mm as shown in JIS JIS STB 340 is equivalent of ASTM grade SA 192 previous Figure. In addition to causing material damage by insulating the heat transfer path from the boiler flame to the water 9

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers

They roughen the tube surface and increase the drag coefficient in the boiler circuit. Reduced circulation in a generating tube contributes to accelerated deposition, overheating, and premature steam-water separation.

BOILER CIRCULATION Figures below illustrate the process of boiler circulation and how scaling may affect it. The left legs of the U-tubes represent downcomers and are filled with relatively cool water. The right legs represent generating tubes and are heated. The heat generates steam bubbles, and convection currents create circulation. As more heat is applied, more steam is generated and the circulation rate increases. If deposits form (Figure right), the roughened surface and partially restricted opening resist flow, reducing circulation. At a constant heat input the same amount of steam is generated, so the steamwater ratio in the generating tube is increased. The water in the tube becomes more concentrated, increasing the potential for deposition of boiler water salts. In extreme cases, deposition becomes heavy enough to reduce circulation to a point at which premature steam-water separation occurs. When this happens in a furnace tube, failure due to overheating is rapid. When deposits are light they may not cause tube failures, but they reduce any safety margin in the boiler design. Up to the point of premature steam-water separation, the circulation rate of a boiler is increased with increased heat input. When the circuit is dirty, the inflection point of the circulation-to-heat input curve moves to the left, and the overall water circulation is reduced. This is represented by the lower broken line. Circulation and deposition are closely related. If the surface charge on a particle is relatively neutral in its tendency to cause the particle either to adhere to the tube wall or to remain suspended, an adequate water sweep will keep it off the tube. If the circulation through a circuit is not adequate to provide sufficient water sweep, the neutral particle may adhere to the tube. In cases of extremely low circulation, total evaporation can occur and normally soluble sodium salts deposit.

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Corrosion: Corrosion is one of the main causes of reduced reliability in steam generating systems. It is estimated that problems due to boiler system corrosion cost industry billions of Rupees per year. Many corrosion problems occur in the hottest areas of the boiler-the water wall, screen, and superheater tubes. Other common problem areas include deaerators, feedwater heaters, and economizers. Methods of corrosion control vary depending upon the type of corrosion encountered. The most common causes of corrosion are dissolved gases (primarily oxygen and carbon dioxide), under-deposit attack, low pH, and attack of areas weakened by mechanical stress, leading to stress and fatigue cracking. These conditions may be controlled through the following procedures:

maintenance of proper pH and alkalinity levels control of oxygen and boiler feedwater contamination reduction of mechanical stresses operation pressure within design specifications, especially for temperature and

proper precautions during start-up and shutdown effective monitoring and control

Corrosion Tendencies of Boiler System Components Most industrial boiler and feedwater systems are constructed of carbon steel. Many have copper alloy and/or stainless steel feedwater heaters and condensers. Some have stainless steel superheater elements. Proper treatment of boiler feedwater effectively protects against corrosion of feedwater heaters, economizers, and deaerators. The ASME Consensus for Industrial Boilers specifies maximum levels of contaminants for corrosion and deposition control in boiler systems. The consensus is that feedwater oxygen, iron, and copper content should be very low (e.g., less than 7 ppb oxygen, 20 ppb iron, and 15 ppb copper for a 900 psig boiler) and that pH should be maintained between 8.5 and 9.5 for system corrosion protection. In order to minimize boiler system corrosion, an understanding of the operational requirements for all critical system components is necessary. Deaerators Deaerators are used to heat feedwater and reduce oxygen and other dissolved gases to acceptable levels. Corrosion fatigue at or near welds is a major problem in deaerators. Most corrosion fatigue cracking has been reported to be the result of mechanical factors, such as manufacturing procedures, poor welds, and lack of stress-relieved welds. Operational problems such as water/steam hammer can also be a factor.

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Effective corrosion control requires the following practices:

regular monitoring of operation minimization of stresses during start-up maintenance of stable temperature and pressure levels control of dissolved oxygen and pH in the feedwater regular out-of-service inspection using established nondestructive techniques

Other forms of corrosive attack in deaerators include stress corrosion cracking of the stainless steel tray chamber, inlet spray valve spring cracking, corrosion of vent condensers due to oxygen pitting, and erosion of the impingement baffles near the steam inlet connection. Economizers Economizer corrosion control involves procedures similar to those employed for protecting feedwater heaters. Economizers help to improve boiler efficiency by extracting heat from flue gases discharged from the fireside of a boiler. Economizers can be classified as nonsteaming or steaming. In a steaming economizer, 5-20% of the incoming feedwater becomes steam. Steaming economizers are particularly sensitive to deposition from feedwater contaminants and resultant under-deposit corrosion. Erosion at tube bends is also a problem in steaming economizers. Oxygen pitting, caused by the presence of oxygen and temperature increase, is a major problem in economizers; therefore, it is necessary to maintain essentially oxygen-free water in these units. The inlet is subject to severe pitting, because it is often the first area after the deaerator to be exposed to increased heat. Whenever possible, tubes in this area should be inspected closely for evidence of corrosion. Economizer heat transfer surfaces are subject to corrosion product buildup and deposition of incoming metal oxides. These deposits can slough off during operational load and chemical changes. Corrosion can also occur on the gas side of the economizer due to contaminants in the flue gas, forming low-pH compounds. Generally, economizers are arranged for downward flow of gas and upward flow of water. Tubes that form the heating surface may be smooth or provided with extended surfaces. Superheaters Superheater corrosion problems are caused by a number of mechanical and chemical conditions. One major problem is the oxidation of superheater metal due to high gas temperatures, usually occurring during transition periods, such as start-up and shutdown. Deposits due to carryover can contribute to the problem. Resulting failures usually occur in the bottom loops-the hottest areas of the superheater tubes. Oxygen pitting, particularly in the pendant loop area, is another major corrosion problem in superheaters. It is caused when water is exposed to oxygen during downtime. Close temperature control helps to minimize this problem. In addition, a nitrogen blanket and chemical oxygen scavenger can be used to maintain oxygenfree conditions during downtime. Low-Pressure Steam and Hot Water Heating Systems Hot water boilers heat and circulate water at approximately 200F. Steam heating boilers are used to generate steam at low pressures, such as 15 psig. Generally,
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers these two basic heating systems are treated as closed systems, because makeup requirements are usually very low. High-temperature hot water boilers operate at pressures of up to 500 psig, although the usual range is 35-350 psig. System pressure must be maintained above the saturation pressure of the heated water to maintain a liquid state. The most common way to do this is to pressurize the system with nitrogen. Normally, the makeup is of good quality (e.g., deionized or sodium zeolite softened water). Chemical treatment consists of sodium sulfite (to scavenge the oxygen), pH adjustment, and a synthetic polymer dispersant to control possible iron deposition. The major problem in low-pressure heating systems is corrosion caused by dissolved oxygen and low pH. These systems are usually treated with an inhibitor (such as molybdate or nitrite) or with an oxygen scavenger (such as sodium sulfite), along with a synthetic polymer for deposit control. Sufficient treatment must be fed to water added to make up for system losses, which usually occur as a result of circulating pump leakage. Generally, 200-400 ppm P-alkalinity is maintained in the water for effective control of pH. Inhibitor requirements vary depending on the system. Types of Corrosion Corrosion control techniques vary according to the type of corrosion encountered. Major methods of corrosion control include maintenance of the proper pH, control of oxygen, control of deposits, and reduction of stresses through design and operational practices. Galvanic Corrosion Galvanic corrosion occurs when a metal or alloy is electrically coupled to a different metal or alloy. The most common type of galvanic corrosion in a boiler system is caused by the contact of dissimilar metals, such as iron and copper. These differential cells can also be formed when deposits are present. Galvanic corrosion can occur at welds due to stresses in heat-affected zones or the use of different alloys in the welds. Anything that results in a difference in electrical potential at discrete surface locations can cause a galvanic reaction. Causes include:

scratches in a metal surface differential stresses in a metal differences in temperature conductive deposits

Pitting of boiler tube banks has been encountered due to metallic copper deposits. Such deposits may form during acid cleaning procedures if the procedures do not completely compensate for the amount of copper oxides in the deposits or if a copper removal step is not included. Dissolved copper may be plated out on freshly cleaned surfaces, establishing anodic corrosion areas and forming pits, which are very similar to oxygen pits in form and appearance. This process is illustrated by the following reactions involving hydrochloric acid as the cleaning solvent. Magnetite is dissolved and yields an acid solution containing both ferrous (Fe+) and ferric (Fe+) chlorides (ferric chlorides are very corrosive to steel and copper) Fe3O4 + 8HCl FeCl2 + 2FeCl3 + 4H2O

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Metallic or elemental copper in boiler deposits is dissolved in the hydrochloric acid solution by the following reaction: FeCl3 + Cu CuCl + FeCl2

Once cuprous chloride is in solution, it is immediately redeposited as metallic copper on the steel surface according to the following reaction: 2CuCl + Fe FeCl2 + 2Cu0

Thus, hydrochloric acid cleaning can cause galvanic corrosion unless the copper is prevented from plating on the steel surface. A complexing agent is added to prevent the copper from redepositing. The following chemical reaction results: FeCl3 + Cu + Complexing Agent FeCl2 + CuCl

This can take place as a separate step or during acid cleaning. Both iron and the copper are removed from the boiler, and the boiler surfaces can then be passivated. In most cases, the copper is localized in certain tube banks and causes random pitting. When deposits contain large quantities of copper oxide or metallic copper, special precautions are required to prevent the plating out of copper during cleaning operations. Caustic Corrosion Concentration of caustic (NaOH) can occur either as a result of steam blanketing (which allows salts to concentrate on boiler metal surfaces) or by localized boiling beneath porous deposits on tube surfaces. Caustic corrosion (gouging) occurs when caustic is concentrated and dissolves the protective magnetite (Fe3O4 ) layer. Iron, in contact with the boiler water, forms magnetite and the protective layer is continuously restored. However, as long as a high caustic concentration exists, the magnetite is constantly dissolved, causing a loss of base metal and eventual failure. Steam blanketing is a condition that occurs when a steam layer forms between the boiler water and the tube wall. Under this condition, insufficient water reaches the tube surface for efficient heat transfer. The water that does reach the overheated boiler wall is rapidly vaporized, leaving behind a concentrated caustic solution, which is corrosive. Porous metal oxide deposits also permit the development of high boiler water concentrations. Water flows into the deposit and heat applied to the tube causes the water to evaporate, leaving a very concentrated solution. Again, corrosion may occur. Caustic attack creates irregular patterns, often referred to as gouges. Deposition may or may not be found in the affected area. Boiler feedwater systems using demineralized or evaporated makeup or pure condensate may be protected from caustic attack through coordinated phosphate/pH control. Phosphate buffers the boiler water, reducing the chance of large pH changes due to the development of high caustic concentrations. Excess caustic combines with disodium phosphate and forms trisodium phosphate. Sufficient disodium phosphate must be available to combine with all of the free caustic in order to form trisodium phosphate.
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Disodium phosphate neutralizes caustic by the following reaction: Na2HPO4 + NaOH Na3PO4 + H2O

This results in the prevention of caustic buildup beneath deposits or within a crevice where leakage is occurring. Caustic corrosion and caustic embrittlement does not occur, because high caustic concentrations do not develop. Different forms of phosphate consume or add caustic as the phosphate shifts to the proper form. For example, addition of monosodium phosphate consumes caustic as it reacts with caustic to form disodium phosphate in the boiler water according to the following reaction: NaH2PO4 + NaOH Na2HPO4 + H2O

Conversely, addition of trisodium phosphate adds caustic, increasing boiler water pH: Na3PO4 + H2O Na2HPO4 + NaOH

Control is achieved through feed of the proper type of phosphate to either raise or lower the pH while maintaining the proper phosphate level. Increasing blowdown lowers both phosphate and pH. Therefore, various combinations and feed rates of phosphate, blowdown adjustment, and caustic addition are used to maintain proper phosphate/pH levels. Elevated temperatures at the boiler tube wall or deposits can result in some precipitation of phosphate. This effect, termed "phosphate hideout," usually occurs when loads increase. When the load is reduced, phosphate reappears. Clean boiler water surfaces reduce potential concentration sites for caustic. Deposit control treatment programs, such as those based on chelants and synthetic polymers, can help provide clean surfaces. Where steam blanketing is occurring, corrosion can take place even without the presence of caustic, due to the steam/magnetite reaction and the dissolution of magnetite. In such cases, operational changes or design modifications may be necessary to eliminate the cause of the problem. Acidic Corrosion Low makeup or feedwater pH can cause serious acid attack on metal surfaces in the preboiler and boiler system. Even if the original makeup or feedwater pH is not low, feedwater can become acidic from contamination of the system. Common causes include the following:

improper operation or control of demineralizer cation units process contamination of condensate (e.g., sugar contamination in food processing plants) cooling water contamination from condensers

Acid corrosion can also be caused by chemical cleaning operations. Overheating of the cleaning solution can cause breakdown of the inhibitor used, excessive exposure of metal to cleaning agent, and high cleaning agent concentration. Failure to neutralize acid solvents completely before start-up has also caused problems.

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers In a boiler and feedwater system, acidic attack can take the form of general thinning, or it can be localized at areas of high stress such as drum baffles, "U" bolts, acorn nuts, and tube ends. Oxygen Attack Without proper mechanical and chemical deaeration, oxygen in the feedwater will enter the boiler. Much is flashed off with the steam; the remainder can attack boiler metal. The point of attack varies with boiler design and feedwater distribution. Pitting is frequently visible in the feedwater distribution holes, at the steam drum waterline, and in downcomer tubes. Oxygen is highly corrosive when present in hot water. Even small concentrations can cause serious problems. Because pits can penetrate deep into the metal, oxygen corrosion can result in rapid failure of feedwater lines, economizers, boiler tubes, and condensate lines. Additionally, iron oxide generated by the corrosion can produce iron deposits in the boiler. Oxygen corrosion may be highly localized or may cover an extensive area. It is identified by well defined pits or a very pockmarked surface. The pits vary in shape, but are characterized by sharp edges at the surface. Active oxygen pits are distinguished by a reddish brown oxide cap (tubercle). Removal of this cap exposes black iron oxide within the pit. Oxygen attack is an electrochemical process that can be described by the following reactions: Anode: Fe O2 Overall: Fe + O2 + H2O Fe(OH)2 The influence of temperature is particularly important in feedwater heaters and economizers. A temperature rise provides enough additional energy to accelerate reactions at the metal surfaces, resulting in rapid and severe corrosion. At 60F and atmospheric pressure, the solubility of oxygen in water is approximately 8 ppm. Efficient mechanical deaeration reduces dissolved oxygen to 7 ppb or less. For complete protection from oxygen corrosion, a chemical scavenger is required following mechanical deaeration. Major sources of oxygen in an operating system include poor deaerator operation, in-leakage of air on the suction side of pumps, the breathing action of receiving tanks, and leakage of undeaerated water used for pump seals. The acceptable dissolved oxygen level for any system depends on many factors, such as feedwater temperature, pH, flow rate, dissolved solids content, and the metallurgy and physical condition of the system. Based on experience in thousands of systems, 3-10 ppb of feedwater oxygen is not significantly damaging to economizers. This is reflected in industry guidelines. the ASME consensus is less than 7 ppb (ASME recommends chemical scavenging to "essentially zero" ppb) TAPPI engineering guidelines are less than 7 ppb EPRI fossil plant guidelines are less than 5 ppb dissolved oxygen
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+

Fe2+ H2O

+ +

2e 2e 2OH

Cathode:

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Mechanical Conditions Affecting Corrosion Many corrosion problems are the result of mechanical and operational problems. The following practices help to minimize these corrosion problems:

election of corrosion-resistant metals reduction of mechanical stress where possible (e.g., use of proper welding procedures and stress-relieving welds) minimization of thermal and mechanical stresses during operation operation within design load specifications, without over-firing, along with proper start-up and shutdown procedures maintenance of clean systems, including the use of high-purity feedwater, effective and closely controlled chemical treatment, and acid cleaning when required

Where boiler tubes fail as a result of caustic embrittlement, circumferential cracking can be seen. In other components, cracks follow the lines of greatest stress. A microscopic examination of a properly prepared section of embrittled metal shows a characteristic pattern, with cracking progressing along defined paths or grain boundaries in the crystal structure of the metal. The cracks do not penetrate the crystals themselves, but travel between them; therefore, the term "intercrystalline cracking" is used. Good engineering practice dictates that the boiler water be evaluated for embrittling characteristics. An embrittlement detector (described in Chapter 14) is used for this purpose. If a boiler water possesses embrittling characteristics, steps must be taken to prevent attack of the boiler metal. Sodium nitrate is a standard treatment for inhibiting embrittlement in lower-pressure boiler systems. The inhibition of embrittlement requires a definite ratio of nitrate to the caustic alkalinity present in the boiler water. In higher-pressure boiler systems, where demineralized makeup water is used, embrittling characteristics in boiler water can be prevented by the use of coordinated phosphate/pH treatment control, described previously under "Caustic Corrosion." This method prevents high concentrations of free sodium hydroxide from forming in the boiler, eliminating embrittling tendencies. Caustic Embrittlement Caustic embrittlement (caustic stress corrosion cracking), or intercrystalline cracking, has long been recognized as a serious form of boiler metal failure. Because chemical attack of the metal is normally undetectable, failure occurs suddenly-often with catastrophic results. For caustic embrittlement to occur, three conditions must exist:

the boiler metal must have a high level of stress a mechanism for the concentration of boiler water must be present the boiler water must have embrittlement-producing characteristics

Where boiler tubes fail as a result of caustic embrittlement, circumferential cracking can be seen. In other components, cracks follow the lines of greatest stress. A microscopic examination of a properly prepared section of embrittled metal shows a characteristic pattern, with cracking progressing along defined paths or grain boundaries in the crystal structure of the metal. The cracks do not penetrate the crystals themselves, but travel between them; therefore, the term "intercrystalline cracking" is used.
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Good engineering practice dictates that the boiler water be evaluated for embrittling characteristics. An embrittlement detector (described in Chapter 14) is used for this purpose. If a boiler water possesses embrittling characteristics, steps must be taken to prevent attack of the boiler metal. Sodium nitrate is a standard treatment for inhibiting embrittlement in lower-pressure boiler systems. The inhibition of embrittlement requires a definite ratio of nitrate to the caustic alkalinity present in the boiler water. In higher-pressure boiler systems, where demineralized makeup water is used, embrittling characteristics in boiler water can be prevented by the use of coordinated phosphate/pH treatment control, described previously under "Caustic Corrosion." This method prevents high concentrations of free sodium hydroxide from forming in the boiler, eliminating embrittling tendencies. pH Control Good pH control is essential for effective control of deposition and corrosion in many water systems. Therefore, it is important to have a good understanding of the meaning of pH and the factors that affect it. Pure H2O exists as equilibrium between the acid species, H+ (more correctly expressed as a protonated water molecule, the hydronium ion, H30+) and the hydroxyl radical, OH-. In neutral water the acid concentration equals the hydroxyl concentration and at room temperature they both are present at 10-7 gram equivalents (or moles) per liter. The "p" function is used in chemistry to handle very small numbers. It is the negative logarithm of the number being expressed. Water that has 10-7 gram equivalents per liter of hydrogen ions is said to have a pH of 7. Thus, a neutral solution exhibits a pH of 7. Table 1-3 lists the concentration of H+ over 14 orders of magnitude. As it varies, the concentration of OH - must also vary, but in the opposite direction, such that the product of the two remains constant. Table 1-4. pH relationships.
pHa 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 H+ Concentration Exponential Notation, gram moles/L 100 10 10
-1 -2

OH - Concentration, H Concentration, OH Concentration, Exponential pOH Normality Normality Notation, gram moles/L
+ -

1 0.1 0.01 0.001 0.0001 0.00001 0.000001 0.0000001 0.00000001 0.000000001 0.0000000001 0.00000000001 0.000000000001 0.0000000000001 0.00000000000001

0.00000000000001 0.0000000000001 0.000000000001 0.00000000001 0.0000000001 0.000000001 0.00000001 0.0000001 0.000001 0.00001 0.0001 0.001 0.01 0.1 1

10-14 1010-13 -12

14 13 12 11 10 9 8 7 6 5 4 3 2 1 0

10-3 10-4 10-5 10 10 10 10 10 10 10 10


-6 -7 -8

10-11 10-10 10-9 10 10


-8 -7 -6

10

10-9
-10 -11 -12 -13 -14

10-5 10 10 10
-4 -3 -2 -1 0

10

10

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers

pH+pOH=14.

Confusion regarding pH arises from two sources: the inverse nature of the function the pH meter scale

It is important to remember that as the acid concentration increases, the pH value decreases (see Table 1-5). Table 1-5. Comparative pH levels of common solutions. 12 11 10 9 8 7 6 5 4 3 2
a

OH - alkalinity 500 ppm as CaCO3 OH - alkalinity 50 ppm as CaCO3 Columbus. OH, drinking water, a OH - alkalinity 5 ppm as CaCO3 strong base anion exchanger effluents phenolphthalein end point neutral point at 25 C Weymouth, NIA, drinking water, methyl orange end point FMA 4 ppm as CaCO3 FMA 40 ppm as CaCO3 strong acid cation exchanger effluent FMA 400 ppm as CaCO3
a

Extremes of drinking water pH

The pH meter can be a source of confusion, because the pH scale on the meter is linear, extending from 0 to 14 in even increments. Because pH is a logarithmic function, a change of I pH unit corresponds to a 10 fold change in acid concentration. A decrease of 2 pH units represents a 100 fold change in acid concentration. Alkalinity Alkalinity tests are used to control lime-soda softening processes and boiler blowdown and to predict the potential for calcium scaling in cooling water systems. For most water systems, it is important to recognize the sources of alkalinity and maintain proper alkalinity control. Carbon dioxide dissolves in water as a gas. The dissolved carbon dioxide reacts with solvent water molecules and forms carbonic acid according to the following reaction: CO2 + H2O = H2CO3 Only a trace amount of carbonic acid is formed, but it is acidic enough to lower pH from the neutral point of 7. Carbonic acid is a weak acid, so it does not lower pH below 4.3. However, this level is low enough to cause significant corrosion of system metals. If the initial loading of CO2 is held constant and the pH is raised, a gradual transformation into the bicarbonate ion HCO3- occurs.
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers The transformation is complete at pH 8.3. Further elevation of the pH forces a second transformation into carbonate, CO32-. The three species carbonic acid, bicarbonate, and carbonate can be converted from one to another by means of changing the pH of the water. Variations in pH can be reduced through "buffering" the addition of acid (or caustic). When acid (or caustic) is added to water containing carbonate/bicarbonate species, the pH of the system does not change as quickly as it does in pure water. Much of the added acid (or caustic) is consumed as the carbonate/bicarbonate (or bicarbonate/carbonic acid) ratio is shifted. Alkalinity is the ability of a natural water to neutralize acid (i.e., to reduce the pH depression expected from a strong acid by the buffering mechanism mentioned above). Confusion arises in that alkaline pH conditions exist at a pH above 7, whereas alkalinity in natural water exists at a pH above 4.4. Alkalinity is measured by a double titration; acid is added to a sample to the Phenolphthalein end point (pH 8.3) and the Methyl Orange end point (pH 4.4). Titration to the Phenolphthalein end point (the P-alkalinity) measures OH - and 1/2 CO32-; titration to the Methyl Orange end point (the M-alkalinity) measures OH-, CO32- and HCO3 . Silica When not properly controlled, silica forms highly insulating, difficult to remove deposits in cooling systems, boilers, and turbines. An understanding of some of the possible variations in silica testing is valuable. Most salts, although present as complicated crystalline structures in the solid phase, assume fairly simple ionic forms in solution. Silica exhibits complicated structures even in solution. Silica exists in a wide range of structures, from a simple silicate to a complicated polymeric material. The polymeric structure can persist when the material is dissolved in surface waters. The size of the silica polymer can be substantial, ranging up to the colloidal state. Colloidal silica is rarely present in groundwaters. It is most commonly present in surface waters during periods of high runoff. The polymeric form of silica does not produce color in the standard molybdate based colorimetric test for silica. This form of silica is termed "non-reactive". The polymeric form of silica is not thermally stable and when heated in a boiler reverts to the basic silicate monomer, which is reactive with molybdate. As a result, molybdate testing of a boiler feedwater may reveal little or no silica, while boiler blow down measurements show a level of silica that is above control limits. High boiler water silica and low feed water values are often a first sign that colloidal silica is present in the makeup. One method of identifying colloidal silica problems is the use of atomic emission or absorption to measure feed water silica. This method, unlike the molybdate chemistry, measures total silica irrespective of the degree of polymerization. Conductivity: Conductivity is measured at 25C at local continuous flow sampling point at the down stream of a strong cation exchanger with a closed cell provision having no access to atmosphere. The figure is relevant for CO2 free sample only. In case, combined CO2 is present, conductivity through cation column will be higher in proportion to the CO2 concentration. In such cases correction applied for CO2 will give fairly reliable figures.
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Water as feed to boiler: We have seen that water as available in nature cannot be used directly in boilers for raising steam. It has to be treated and chemically conditioned to render it fit for use as feed and make up in the steam generation process. Mechanical and chemical treatments are the primary steps to make it free from suspended, colloidal and dissolved impurities, so that it attains perfectly pure status. It is the process of pretreating and de-mineralizing the water to make it fit for use in any boiler. However, in the actual process of steam generation, it is required to further chemically treat the water at various stages in order to make it suitable as a feed to a boiler, which will be non corrosive and protective to various ferrous and non ferrous alloys, deployed in the design and construction of various equipment. In a nutshell, treatment and further conditioning of water are necessary for the following objectives: a) To prevent scaling internals of pressure vessels due to dissolved and suspended impurities, b) To prevent corrosion of metallic parts of the boiler, with which water / steam come in direct contact, c) To establish protective coating over metallic surfaces to prevent corrosion attack. d) To avoid salt deposits over turbine blades, e) To ensure better utilization of heat energy and to improve on efficiency, In order to ensure to achieve above objectives, following processes of water treatment are adopted: 1. Pre treatment 2. Demineralization 3. Deaeration (De-gasification) 4. Chemical conditioning Pretreatment of water: Clarification: Pre- treatment to raw water is mainly to make it suitable for further processing of water by Deionization units. The water entering Demineraliser plant should be free from suspended, colloidal and organic impurities and the process of pretreatment plays a vital role in ensuring proper feed input is made to Deionization units. Presence of such suspended impurities adversely affects the deionization properties of the resins, which will affect the end quality of Demineralized water. Suspended & colloidal particles are removed by clarifying the water in a clariflocolator aided by suitable coagulating agents. Precipitator Clarifier Section:

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers A precipitator inlet flow control valve controls the raw water inlet flow into the clarified water basin, through a level controller. A manual by-pass valve is also provided to the level control valve, so that in case of problem in the level control valve, manual operation can be done to maintain the level. The precipitator is of a reinforced concrete construction, in the shape of a truncated conical vessel placed in inverted position, with a circumferential channel all around the bigger diameter section at the top. The conical concrete tank consists of a cylindrical tank built internally at the central portion. The inner cylindrical compartment is known as the flocculating mixing-zone and the outer compartment, the sedimentation sludge blanket zone. The raw water enters the inner mixing zone through an open channel from the top and flows downward into the inner conical tank. The precipitator is fitted with a carriage, which can slowly be driven to go round inside the Clariflocculator. The carriage carries a paddle mechanism, with three or four tiers of vanes fixed vertically down and hanging from the paddle mechanism. The carriage is driven by an electric motor and a gear mechanism, with its axis at the center of the conical tank and the other end of the carriage placed with a wheel over a circular rail, fitted along the circumference of the conical tank. When the carriage is driven by the motor it goes round and round the top of the conical tank in a circular motion and the paddle mechanism stirs well the water in the outer conical zone. Chemicals, Alum and Lime, solutions are prepared in separate tanks and the prepared solutions are pumped trough pumps. The chemicals are let into the open channel to get mixed thoroughly with the raw water flowing along the open channel into the mixing chamber. A water flow indicating mechanism is fitted in the open channel to indicate the raw water flow. The precipitator operates on the sludge blanket principle, whereby a bed of sludge particles is retained in suspension at a predetermined level in the outer cone. The slow speed agitator ensures thorough mixing of chemicals and raw water and assists in the completion of precipitator chemical process. The blanket consists of a loose mass of suspended floc constituting of medium sized particles. These attract and retain finer particles rising through the blanket, so that, when the water rises above the blanket zone, it is filtered and is almost clear. Above the blanket zone, some particles of floc remain but these continue to grow and fall back so that water decanting through blankets of sludge and rising to the top of the precipitator is almost free from floc and turbidity. The clear water overflows through the notches and falls into the circumferential channel and from there through open canal flows into the clarified water tanks. Continuous spent large floc desludging of the concentrator on the precipitator is carried out through a pneumatically operated valve which is set to open at regular intervals. 2(two) valves are provided for draining the precipitator. Ferrous sulphate solution is delivered into the Precipitator by means of twin head proportional feed 5% solution dosing pump. (The concentration values for both Lime and Ferrous sulphate dosage for precipitator change according to raw water quality and will be recommended by the Original Equipment supplier.) Chemicals are dosed proportionally to the raw water flow rate by an automatic proportioning system consisting of a flow recorder control totalizer and low flow alarm, which regulates the stroke of the ferrous sulphate pump and the swing angle of the lime dosing device respectively. The raw water is treated in the precipitator with hydrated lime for removal of temporary hardness, caused by bicarbonate in Calcium and Magnesium salts. Hydrated lime reacts chemically with the bicarbonates of Calcium and Magnesium salts in the water, forming a sludge of calcium carbonate and magnesium oxide, which gets settled down in layers. Alum, chemically known as Ferrous Sulphate is also added along with lime dosing, in the clariflocculator to hasten the process of coagulation and assist in settling of the sludge.
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Filtration: Water filtration is the process of separating suspended and colloidal impurities from water by passage through a porous medium. A bed of granular filter material or media is used in most plant application. A filter may be defined simply as a device consisting of a tank, suitable filter media and necessary piping, valves and controls. Filters are designed for the following: Gravity flow, with natural head of water above the filter bed and low point of discharge at the filter bottom, providing the pressure differential needed to move the water through the filter bed.

Pressure units, which, as their name implies, are operated on line, under service pressure, filtering the water as it flows the tank on its way to service or storage Filters are classified in a number of different ways by type or kind of filter medium to be deployed, such as sand, anthracite coal, activated carbon, fabric or porous membranes, or, by the direction of flow upflow or downflow. Also, they are sometimes described hydraulically as the slow rate or rapid rate type. Varied design and process techniques are adopted based on the quality and the quantum of the raw water, to be treated and the quality of the effluent to be achieved. Economy is a vital point to reckon with. Sand Filters are used for this purpose. Gravity Filters: Gravity filters are usually employed where large quantities of filtered water are required. It normally use 8 to 12 feet high tank constructed of steel or concrete. Concrete tanks are usually rectangular; steel tanks are round or rectangular. The end of gravity filter runs is usually determined by the head loss or pressure loss developed across the filter bed, and backwashing is initiated on this basis. Water quality deterioration (turbidity breakthrough) can also be used. Pressure Filters: Three basic types of Pressure Filters are: Vertical Downflow, Horizontal Downflow and Vertical Upflow. Vertical and horizontal downflow pressure filter units are the work horse of the filtration field and most widely used.

Backwashing: When differential head between inlet and outlet increases, the filters must be taken out of service and backwashed for removing accumulated dirt and
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers sludge materials. The filters are nevertheless to be backwashed at least once every operating day. For back wash the flow direction is reversed that is the inlet is given at the bottom and water from the top is delivered out to open canal. When the water flows in reverse direction it carries all the accumulated dirt and sediments and throws out along with the water. The back washing is to be done until the out flowing water is perfectly clear of all accumulated sediments. Chlorine removal: To avoid algae formation chlorine is dosed into raw water, before the process of clarification in the clariflocculator. Presence of chlorine is harmful to the Ion Exchange Resin and it is essential to ensure that even the traces of chlorine are not present in the clarified and filtered water, before admission to deionizing unit. Hence before admission to cation vessel, the water is once again filtered treated in a vessel containing a bed of Activated Carbon. Activated Carbon Bed absorbs left over chlorine and the organic matters and feeds clear water to the ion exchange vessels. Demineralization: Demineralization is the removal of dissolved ionic impurities that are present in water. Demineralized water is commonly produced by one or a combination of the following processes:

Ion exchange Membrane desalination or RO (Reverse Osmosis)

Thermal desalination The method selected to produce demineralized water depends on the quality of the influent water, the required quality of the effluent water, the availability of resources such as regenerant chemicals, and wastewater treatment and disposal requirements. The economics of the processes that produce acceptable effluent quality must be evaluated to determine the most cost-effective method for a specific application. Ion Exchange Process: Basically the minerals present in water are in ionized condition. Ion exchange demineralization therefore is one of the most important and widely applied processes for the production of high-purity water for power plant services, and it is accomplished using resins that exchange one ion for another. Cation resins are solid spherical beads with fixed negatively charged sites and exchangeable positively charged sites. Anion resins are solid spherical beads that have fixed positively charged sites and exchangeable negatively charged sites. In their regenerated state for demineralization applications, cation resins are in the hydrogen form and anion resins are in the hydroxide form. The reactions of the resin beads with the dissolved impurities in the water are represented by the following: Cation resin: R-H+ + C+ R-C+ + H+ 2R-H+ + C2+ R2-C2+ + 2H+ Anion resin: where R = resin matrix and fixed charge site; C = cations such as Ca2+, Mg2+, and Na+; and A = anions such as HCO3-, Cl-, and SO4-2 R+OH- + A- R+A- + OH2R+OH- + A2- R2+A2 + 2OH-

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers The hydrogen ions (H+) displaced from the cation resin react with the hydroxide ions (OH-) displaced form the anion resin. The net effect is the dissolved ions are removed from the water and replaced by pure water (H2O). The ion exchange resins are contained in ion exchange pressure vessels. The ion exchange resin in the vessels is referred to as the resin bed. This process of exchanging dissolved impurities is cyclic. When a resin bed site is exchanged with a dissolved ion, the site becomes exhausted and cannot remove other impurities without releasing an impurity. Exhausted resins must be regenerated to return the resin beads to the original hydrogen form for cations and hydroxide form for anions before further ion exchange can take place. Cation resins are commonly regenerated with a strong acid solution of either sulfuric or hydrochloric acid. Anion resins are commonly regenerated with a sodium hydroxide solution. As can be seen from the regeneration reactions listed below, regeneration is the reverse reaction to the impurity exchange reactions. Cation resin regeneration: 2R-C+ + H2SO4 2R-H + C2+SO42R2-C2+ + H2SO4 2R-H+ + C2+SO42Anion resin regeneration: R+A- + NaOH R+OH- + Na+AR2+A2- + 2NaOH 2R+OH- + Na2+A2Ion Exchange Resins: Cation resins are commercially available in strong-acid and weak-acid forms. Strongacid cation resins can remove all cations in the influent water whereas weak-acid cation resins generally are restricted to the removal of hardness associated with carbonate alkalinity. Anion resins are commercially available in strong-base and weak-base forms. Strongbase anion resins are capable of removing both weakly dissociated and strongly dissociated acids. Weak-base anion resins primarily provide removal of the strongly dissociated acids (such as hydrochloric, sulfuric, and nitric) and have only limited capability for removal of weakly dissociated acids. Cation and anion resins have different affinities for the different dissolved ions. Consequently, the cation and anion resins display a selectivity series for dissolved ions. Listed below is a representative selectivity series for commonly used strong-acid cation resins and strong-base anion resins with the ion having the greatest affinity for the resin at the bottom of the list. Selectivity of strong-acid cation and strong-base anion resins Cations Calcium (Ca ) Magnesium (Mg2+) Ammonium (NH4+) Potassium (K ) Sodium (Na+) Hydrogen (H+) Back Wash: Water is passed upwards in reverse flow through the column and then thrown to drain. This loosens and cleans the ion exchange material and prevents it from becoming packed. When the water enters at the bottom the whole bed is loosened and lifted up. The swollen bed height can be seen through a glass window. The top level of resin bed to which it has to raise is marked on the glass window. Quantity of back wash water is
25
+ 2+

Anions Sulfate (SO42-) Chloride (Cl-) Bicarbonate (HCO3-) Silica (exchanges as HSiO3-) Hydroxide (OH-)

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers to be maintained such that the resin bed is always raised and held at that level marking through out the back wash process. During back wash air scoring is also given to loosen the impurities got accumulated in the bed. Acid wash: The required amount of hydrochloric acid is injected into the units after diluting it to required concentration. Proportioning of 30% acid solution into 7% dilution is done through a water injector. When water flows through the injector it creates vacuum at the throat and the acid is sucked through line, which is connected to the throat. After the throat the acid and the water get mixed up thoroughly and the effluent is let out to sewer canal. Usually the sewer canal consists of a level mark. The acid water mix flow is always to be maintained to corresponding level mark during acid dosing. The acid effluent is taken to a neutralizing tank, where the solution can be mixed with required quantity of bleaching powder or lime soda so increase its PH to +8 and pumped out to sewage system. Rinse: Water is passed downwards through the column. This brings the regenerant into contact with the whole of the exhausted resin bed. The rinse is continued till excess regenerant has been removed. Deaeration (Degasification): Deaeration is the process of removing dissolved corrosive gases (O2 and CO2) from water. This process is also called degasification. Dissolved oxygen acts as a depolarizer and contributes to the corrosion of metal Whereas Carbon dioxide dissolved in water liberates H+ ions that attack metal CO2 + H2O H2CO3 H+ + HCO3- (carbonic acid) The process of deaeration is most frequently applied in boiler feed water heaters to protect piping, boilers and condensate equipment from corrosion. Deaeration is a thermal method where water is heated to bring about degasification, unlike de-oxygenation where it is carried out mainly by chemical techniques. The three cardinal principles that must be satisfied in any mechanical deaerator are: Heating: Water must be heated to full saturation temperature (boiling point), corresponding to the steam pressure in the unit. Since, theoretically, the solubility of any gas is zero at the boiling point of the liquid, complete gas removal is not possible unless the liquid is kept at boiling temperature. Mechanical agitation: The heated water must be mechanically agitated, by spraying, cascading over trays, or by atomization, to expose maximum surface contact to the scrubbing atmosphere, thus permitting complete release and removal of gases. Complete gas removal: adequate steam must be passed through the water to scrub out and carry away the gases after release. Extremely low partial gas pressure must be maintained since Henrys law states that the amount of gas which will dissolve in a liquid is proportional to the partial gas pressure in the atmosphere contacting the liquid. It is mandatory that the volume of scrubbing steam be high to produce the low partial gas pressure, and it is equally mandatory that the conditions prevail through out the deaeration process. Deaerator: A deaerator is the apparatus wherein deaeration is carried out. Deaerators can be classified in accordance with the mode of steam-water distribution in them. 1. Atomizing deaerator
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers 2. Tray-type deaerator 3. Film-type deaerator. A direct-contact deaerator consists of a deaerator column fitted on the top of the storage tank. The deaerator column is a hollow cylindrical vessel provided with (a) Perforated, horizontal trays arranged one above the other. (b) Water distribution device at the top. (c) Steam distributor at the bottom. Feedwater enters the deaerator from the top and is evenly distributed, by means of the distributing device, into the perforated trays fitted at the bottom. Water fills the perforations (dia 5-7 mm) and rains down and comes in contact with heating steam dissolved into the lower portion of the deaerator column through the steam distributor. As a result of heat exchange between the steam going up and the feedwater stream flowing down, the water gets heated up to its boiling point and the gases (O2, CO2) dissolved in it are transferred to the gas phase. These gases together with non-condensing vapour are vented into the atmosphere through a vent valve or pass into a vent condenser where the steam is condensed and the O2 and CO2 are vented. The deaerated water is collected in the storage tank which is fitted with gauge glass, pressure gauge and hydraulic seal to avoid the formation of high pressure or vacuum in the deaerator. Degasifier: Carbon dioxide can be removed by either vacuum degasification or forced draft degasification. A vacuum degasifier is a packed tower in which the water is sprayed and the gases are removed to a low level by maintaining a vacuum in the tower. A schematic representation of a typical two-stage vacuum degasifier is given here. A forced draft degasifier is a packed tower in which the water is sprayed down the column and the carbon dioxide is removed by air that is blown up the column. Determination of whether a gasifier is to be used and the type of degasifier used depends on the amount of CO2 produced following cation exchange and the effluent water quality (dissolved oxygen content) required. For moderate to large concentrations of carbon dioxide, it is more economical to remove the CO2 by degasification than by anion exchange.

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Mixed Bed: The effluent water from anion exchanger may still have some silica. The water needs to be polished. Hence the water drawn from DM tank before it is supplied to boiler feed is passed through mixed bed exchanger. The mixed bed exchanger is similar to Cation or Anion exchangers. It consists of both Cation and Anion resins mixed together and filled up. Hence the DM storage water is flowing through the mixed bed resins the traces of all Cation and Anions are totally absorbed and removed. The process of regeneration is similar to the regeneration process of Cation and anion exchangers. After back washing the Cation gets settled at the bottom and the anion resin at the top of the Cation bed. For regeneration the acid is introduced at the middle and is taken out at the bottom. For anion regeneration the alkali is introduced at the top and drained from the middle. Conductivity meter: The purpose of the conductivity meter is for continuously controlling the Demineralized water effluent and signaling the exchange process exhaustion and consequent necessity to regenerate the exhausted train. Due to the extremely low salinity content of Demineralized water it would be impractical to measure it gravimetrically. For this reason the more accurate and immediate electrical conductivity measure of the Demineralized water is used, by taking advantage of the capability of ions to conduct electric current in an aqueous solution. The higher the salinity, the number of ions present the higher will be the electrical conductivity. Under present circumstances 1 ppm of residual salinity corresponds to an electrical conductivity of 5 micro-Siemens (at 20`C), thus giving a measure of operational leakage from the Demineralized trains (normally ranging around 10 micro-Siemens or 2 ppm residual salinity consisting of NaOH traces). When a stage of the Demineralized train is exhausted the effluent salinity will rapidly increase and be signaled by a corresponding increase in conductivity. As a general rule, under normally experienced conditions, a sharp increase in the effluent conductivity is also matched by an increase (a marked increase) in the silica content of the effluent. For this reason and to avoid over exhaustion of the resins it is strongly recommended to regenerate the train as soon as a sharp increase in conductivity is experienced (conductivity higher than 3 to 5 micro-Siemens). Slight fluctuations in the recorded conductivity of effluent might be experienced without any special significance on the train operation, being due to slight fluctuations in filtered water quality or rate of changes through the train. Membrane Desalination Process (Reverse osmosis): Reverse osmosis is a pressure driven membrane process capable of removing small particles, dissolved in salts and low molecular weight organics from a feed water stream. If two aqueous solutions containing differential salt contents are kept separated by a semi-permeable membrane, the system develops an inherent tendency for water molecules (not the salt) to permeate across the membrane layer to dilute the more concentrated solution.
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers This process is called osmosis. The driving force per unit membrane cross-section, dependent on the concentration difference, is the osmotic pressure. However, this natural process can be reversed if some external pressure higher than the systems osmotic pressure is applied on the concentrated solution side whereupon water will pass from the more concentrated solution, through the membrane boundary, to the less concentrated solution. This is the basis of reverse osmosis. If one compartment contains pure water and the other salt or mineral-rich water, the process of reverse flow will produce pure water, since the membrane is not permeable to salt. The RO process cannot go on indefinitely. The salt solution would require increasingly higher pressure to force water through the membrane; ultimately the membrane could become clogged by precipitated salts and other impurities. In actual practice, RO devices employ crossflow filtration as shown in the figure here This method uses a pressurized feed stream which flows parallel to the membrane surface. Only a portion of this feed stream passes through the membrane as permeate and the remainder of the stream known as the reject or concentrate provides a continuous sweep of rejected ions and particles from the membrane surface. Osmotic Pressure: A simple equation relates osmotic pressure to concentration: P = C x R x T Where, P is osmotic pressure in Pa, C is difference in concentration in mol.m-3 [mol.m-3 = concentration in kg.m-3/ mol. Weight in kg.mol-3] R is constant of an ideal gas = 8.314 (J/mol.K), T is the temperature in K Example: Concentration in solution = 100 kg.m-3; T = 300 K; for a compound with A molecular weight of 0.050 kg.mol-1 C = 100/ 0.05 = 2000, P = 2000 x 8.3143 x 300 = 50 x 105 Pa = 50 bar In fact, to produce "pure" water from a saline solution, the osmotic pressure of the solution must be exceeded. In the same way, it may be said that in order to obtain economically viable flows, at least twice the osmotic pressure must be exerted. As shown in figure left, when water is transferred, the molecules and ions retained by the membrane tend to accumulate along its entire surface, thereby increasing both the salinity actually "treated" by the membrane and the osmotic pressure that must be "overcome" in order to desalinate the solution.

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers This results in higher energy costs, as well as in the risk of causing precipitation if the solubility product of one of the canon-anion couples is exceeded in the boundary layer all along the membrane. This phenomenon is known as concentration polarization of the membrane and is defined by the coefficient: = Cm/ Ce Where, Cm is concentration of the liquid in contact with the membrane, and Ce is the concentration of the liquid to be treated. This phenomenon can be reduced to a minimum by maintaining a circulation flow across the upstream surface of the membrane, which limits the thickness of the boundary layer and facilitates the reverse diffusion of the rejected solutes; however, this limits the fraction of desalinated water. This technique is used in industrial systems to maintain the coefficient between 1 and 1.4. For a saline solution, the water flux rates may be obtained by Fick's and Henry's laws. Qp = Kp x S x (P - p) x Kt/e Where, Qp = flow of water through the membranes, Kp = membrane permeability coefficient for water, S = membrane surface area, e = thickness of the membrane, P = hydraulic pressure differential across the membrane, p = osmotic pressure differential across the membrane, Kt = temperature coefficient. Thus, the flow of water through the membrane is directly proportional to the effective pressure gradient, represented by the difference between the hydraulic and the osmotic pressure. The coefficient Kt takes the viscosity of water into account. The latter decreases when the temperature rises. Therefore, the flow is greater when the temperature rises (2.5 to 3% difference per degree at about 15C). Thermal Desalination Process: It is based on using heat to vaporize a portion of the fluid (brackish water or sea water) treated. The vapour is subsequently condensed as pure water. Basically, there are three commercially available technologies by which thermal desalination can be accomplished: Multiple effect distillation Multistage flash evaporation Vapour compression

The thermodynamic principles of operation for the processes are same; the processes vary in method and operating conditions used to accomplish the desalination.

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Zeolite Softening Processes This process, also known as zeolite softening, passes water through a filter containing resin granules. In the filter, known as a softener, calcium and magnesium in the water are exchanged for sodium from the resin granules. The calcium and magnesium in the hard water are replaced by sodium ions This method of water softening is been used extensively for feed water treatment for smaller pressure boiler. It is based on the ability of the ion-exchange resin Zeolite to exchange one ion from the water being treated with another ion in the resin. Zeolite resin exchanges sodium ions for ions causing hardness in the water. Such ions are the ions of calcium and magnesium present in the water that flows through the Zeolite resin bed. The water treated ends up with more sodium ions than before. The ion-exchange softening process does not alter the water's pH or alkalinity. In fact it actually induces an increase in dissolved solids in the water. For each mg/l of calcium removed and replaced by sodium, the total dissolved solids increases by 0.15 mg/l. For each mg/l of magnesium removed and replaced by sodium, the total dissolved solids will increase by 0.88 mg/l. Therefore by Zeolite Softening Processes, water doesnt become De-mineralized but only becomes soft. The regeneration is done by concentrated Brine solution. Chemical conditioning of Boiler water: Demineralization of water renders raw water fit for use as make up and feed to a boiler. Just feeding a boiler with Dematerialized water, which is free of all impurities, alone, will not suffice in reality due to the following reasons. a) When the steam is continuously being generated and released for process, the water inside the drum gets more and more concentrated, even with the very little and negligible level of impurity in feed water. b) Further the pH of Demineralized water normally remains to be close to neutral and will induce low pH corrosion of tube and pipe materials. c) Demineralized water when under storage absorbs atmospheric air and the level of dissolved Oxygen in water increases. Presence of Oxygen in feed water again renders it corrosive. Hence it is essential and pertinent to further chemically treat the demineralised water, which is taken as make up feed to boiler. Chemical treatment is done at various stages for feed and boiled water, steam and return condensate, in order to ensure adequate protection is established over the entire system, to help prevention of direct attack on parent metal by the corrosive elements present in water / steam cycle. We will learn about boiler water internal treatment process and its needs and effects in detail in the following. Chemical Treatment of Water in Steam Generating Systems: The inhibition of corrosion in steam generators and auxiliary equipment during operation is essential, for preventing damage to tube material and innumerous hazards caused, generally resulting in equipment damage. Due to such damages, repairs and maintenance expenditure increases demanding costly replacement of spare parts, in addition to unwanted downtime, with corresponding loss of production. The iron and
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers copper corrosion products, from pre-boiler system, are often carried away into the boiler and cause harmful scale deposits, contributing to caustic or hydrogen attack, as dictated by conditions within the system. Oxygen scavengers: Feed water treatment with Sodium Sulfite (Na2SO3): Sodium sulfite has long been used as an oxygen scavenger in boiler feed water treatment. It reacts readily with oxygen, particularly at elevated pH and temperature, to form sodium sulfate by the following reaction: 2 Na2SO3 + O2 2 Na2SO4 When any oxygen scavenger is used, it is essential to ensure total chemical deaeration before the feedwater reaches the boiler. Especially it is essential to ensure this aspect, while using sulfite, since oxygen remaining in the feedwater when it reaches the boiler will flash into the steam phase, whereas the sulfite will remain in the water phase since it is nonvolatile. It is advisable to dose sodium sulfite to the condensate water or at the feed water storage tank to ensure complete chemical deaeration in the preboiler section, so that it is possible to allow sufficient reaction time for deaeration. The reaction rate of sodium sulfite with oxygen is proportional to the concentration of both sulfite and oxygen and to the temperature and pH of the feedwater. To ensure complete oxygen removal when one of these factors is unfavourable, or when the retention time allowed for the reason is short, a catalyst is often added to the sodium sulfite to increase its reaction rate. Cobalt salts are the most commonly used materials to catalyze the reaction. Feed water treatment with Hydrazine (N2H4): The widely used chemical oxygen scavengers in high pressure boiler operations is hydrazine (N2H4). The advent of an organically catalyzed hydrazine suitable for use in boilers made the full benefits of hydrazine available to low and medium pressure applications and more extensive in high pressure systems. The reaction of hydrazine with oxygen is as follows: N2H4 + O2 2H2O + N2 It is important to note that the products of the hydrazine reaction are inert and volatile. They will, therefore, not add any dissolved solids in the boiler water. Hydrazine will also react with: Ferric oxide: N2H4 + 6Fe2O3 4Fe3O4 + N2 + 2H2O and Cupric oxide: N2H4 + 4CuO 2Cu2O + N2 + 2H2O Magnetite, Fe3O4, and cuprous oxide, Cu2O, are the passivated oxide states of iron and copper. Hydrazine, therefore, renders iron and copper surfaces less susceptible to corrosion by reducing them to a passive state. The reduction reactions take place on metal surfaces in the pre-boiler, the boiler and the after-boiler, as well as on suspended ferric oxide or cupric oxide. Hydrazine is fed in amounts required to react with dissolved oxygen, ferric ions, and cupric ions, plus a small excess. Initially the use of hydrazine was most extensive in high pressure boilers in which sulfite would cause problems (as previously discussed). Hydrazines relatively sluggish reaction with oxygen prevented its use in low pressure boilers. In high pressure systems, the temperature of the boiler feedwater is usually sufficient to permit the effective use of hydrazine. An organic catalyst was then developed which increased the 32

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers reaction rate of hydrazine with oxygen, permitting its effective use in boilers utilizing lower temperature feed water. The increased reaction rate with catalyzed hydrazine brought the added benefit of metal passivation and low temperature condensate protection to both high and low pressure systems, even when a catalyst was not necessary for effective feedwater oxygen scavenging. The basic reactions of catalyzed or uncatalyzed hydrazine are identical except that in the case of the catalyzed version, reactions occur 10-100 times faster.

Alternative of Hydrazine for oxygen scavenging Due to the inclusion of hydrazine on the OSHA and NIOSH lists as a suspect carcinogen, Hydrazine is being replaced by other chemicals as oxygen scavenger by many industries. There are a number of alternatives; each claims to be a safe and effective material for boiler protection through oxygen scavenging, but the levels required and optimum conditions for use vary. Carbohydrazide is a volatile oxygen scavenger, contributes no solids to the system, reacts readily with oxygen at low temperatures and pressures, and passivates the metal of the boiler system. Carbohydrazide can (and does) break down to hydrazine above temperatures of 180C to scavenge oxygen, but this conversion is not necessary for oxygen scavenging activity because it reacts directly with oxygen: H6N4CO + 2O2 CO2 + 2N2 + 3H2O The theoretical dosage required to scavenge one part O2 is 1.4 parts carbohydrazide. It should be noted that in its reaction with oxygen, carbohydrazide creates carbon dioxide, a gas that when dissolved in the condensate as carbonic acid, H2CO3, results in corrosion in the return line. Carbohydrazide cannot be used in applications where the steam comes into contact with food. Erythorbate, however, is generally regarded as safe by the FDA and can be used in food processing applications. It, too, is a metal passivator and contributes no solids to the system. It has a theoretical dosage level of 11 parts per oxygen (as O2). Erythorbic acid is non-volatile. It will remain in the boiler, and will not travel with the steam to control oxygen corrosion in the condensate. Methylethylketoxime, or MEKO, is a volatile oxygen scavenger which displays metal passivating characteristics. It reacts with oxygen to form methyl ethyl ketone, nitrous oxide, and water: 2 H3C(C=N-OH) CH2CH3 + O2 2 H3C (C=O) CH2 CH2 + N2O + H2O Its theoretical dosage is 5.4 parts per part of oxygen. Hydroquinone, which has been used to catalyze the reaction with O2 of some of these oxygen scavengers, has been examined and proven to be effective itself in lowering O2 levels to the 1-2 ppb range. It reacts with oxygen to form benzoquinone: HO CH6 OH + O2 H2O + O = (double bond) CH6 (db) = O and has a theoretical dosage level of 6.9 parts per part O2. It is extremely reactive with oxygen at the lower boiler temperatures and pressures, and is volatile in higher pressure systems. It does not degrade to ammonia, so it is safe for use with coppercontaining alloys. Diethylhydroxylamine, or DEHA, is a volatile metal-passivating oxygen scavenger which reacts with oxygen to form acetate, nitrogen and water: 4 (CH3CH2)2 NOH + 9O2 8 CH3 COOH + 2 N2 + 14 H20 In theory, 1.24 parts of DEHA react with 1 part of oxygen, but in application, a dosage of 3 : 1 DEHA to O2 is recommended. It is generally true that all oxygen scavenger requirements in the field are larger (by up to a factor of 10) than projected by calculations.
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers DEHA has other advantages over each of the above-mentioned O2 scavengers. It has higher volatility and metal passivating characteristics than sulfite, hydrazine and erythorbate, and can be used more safely than hydrazine. Less DEHA is required than erythorbate and methylethylketoxime in theoretical considerations. It offers toxicity advantages over carbohydroxide in that it does not yield hydrazine under use conditions. Relative to the other scavengers, catalyzed and uncatalyzed DEHA show excellent reactivity (e.g., rate of reaction) with oxygen. Catalyzed sodium sulfate is by far the most reactive oxygen scavenger available in the industry which accounts for its use in low pressure systems. Among the preferred scavengers for higher pressure systems, DEHA has the highest rate of reaction with oxygen At 21 C and pH 8.5, DEHA lowers the level of dissolved oxygen from 9-4 ppm in 10 minutes, whereas with carbohydrazide, catalyzed hydrazine, and erythorbate, dissolved oxygen levels are still above 7 ppm. In thirty minutes, the O2 levels for DEHA were below 1 ppm compared to levels near 6 ppm for the other scavengers. At pH 11, catalyzed DEHA compared favorably in rate of reaction with catalyzed sulfite. In both cases, the DEHA was catalyzed with hydroquinone. In considering thermal and oxidative degradation products, DEHA generates dialkyl amines, acetaldehyde, acetaldoxime and acetic acid, the last of which can promote low pH corrosion in the system and add to boiler deposits as sodium or calcium acetates. Several of the other scavengers, including erythorbate, MEKO, and hydroquinone also degrade into organic acids and negatively affect the boiler and after-boiler actions. As well, carbohydrazide produces CO2 in its reaction with O2, requiring additional prevention of corrosion due to low pH levels (as carbonic acid, H2CO3) in condensate return-lines. For the most part, DEHA will find application as a replacement for hydrazine in medium and higher pressure boilers. In changing a steam-generating system from one to the other, a higher level of DEHA will be required at start-up to passivate the after-boiler and return-line sections of the system. After this has been accomplished, a 3 part DEHA per part oxygen dosage corresponds to a DEHA to hydrazine replacement ratio of 1.5. Phosphate dosing and Corrosion in water tubes: The total free sodium hydroxide or free caustic defines the amount of sodium hydroxide in solution in excess of that derived from the hydrolysis of trisodium phosphate according to the following equation: Na3PO4 + H2O Na2HPO4 + NaOH With controlled dozing, Boiler water pH is maintained at the required level. In addition to increasing the pH of the Boiler water, Phosphate helps 1. By reacting with hardness components (Ca2+, Mg2+) in water and converting them into the suspended solids to be easily discharged from boiler with blow down water, 2. By keeping silica in the water soluble form. Among the hardness components in water, calcium ion forms calcium carbonate (CaCO3) and calcium silicate (CaSiO3), and deposits as the scale without boiler compounds. Under the coexistence of phosphates, calcium ions form the suspended fine particles of hydroxyapatite {[Ca3(PO4)2]3Ca(OH)2} which scarcely form the scale. That reaction is expressed in the equation below. 10Ca2+ + 6PO43 + 2OH [Ca3(PO4)2]3Ca(OH)2 In this case, the required amount of phosphate against 1 mg CaCO3/l of calcium hardness is 0.57 mg PO43/l.
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Magnesium ions never react with phosphates but react with alkalis to form suspended magnesium hydroxide [Mg(OH)2] and magnesium silicate (MgSiO3). Mg2+ + 2OH Mg (OH)2 Mg2+ + HSiO3 + OH MgSiO3 + H2O The magnesium silicate tends to form the scale if the pH of boiler water is low. The larger amounts of acid insoluble matter (silica) and magnesium oxide (MgO) are found in the scale of the internal feed water pipe comparing with the other scales. The lower water pH near the feed water pipe may cause such silica scale formation. Therefore, the control of the pH and P alkalinity of boiler water is important for preventing magnesium scales. Silica is stabilized in the form of water soluble sodium metasilicate (Na2SiO3) by reacting with alkalis. H2SiO3 + 2NaOH Na2SiO3 + 2H2O The above reaction shows that the required amount of alkali as P-alkalinity to keep silica in the soluble form in boiler water is 1.7 times of silica concentration in mg SiO2/l. Accordingly, the pH and phosphate concentration of boiler water must be maintained in the appropriate ranges for preventing the scale problems of boilers. Another function of boiler compounds is the adjustment of pH and P-alkalinity of boiler water. In general, the M-alkalinity components in raw water mainly exist in the form of bicarbonates. Those bicarbonates are converted to sodium bicarbonate by treating with softener. The sodium bicarbonate is thermally decomposed to sodium carbonate and carbon dioxide in boiler water. Then, the sodium carbonate, further decomposes into sodium hydroxide and carbon dioxide. 2NaHCO3 + (Heat) Na2CO3 + CO2 + H2O

Na2CO3 + H2O + (Heat) 2NaOH + CO2 Thus carbonate alkali changes to caustic alkali (P-alkalinity) in boilers. This decomposition of bicarbonate is essentially affected by temperature, pH, heating period, etc. For obtaining the thermal decomposition rate in boilers, Figures below are generally used.

Relationship between the decomposition rate of carbonate alkali to caustic alkali and boiler pressure

Relationship between the M-alkalinity of feed water and P-alkalinity of boiler water under various boiler pressure and cycles of concentration

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers When the P-alkalinity to be maintained in the boiler water is higher than the Palkalinity given by the feed water, the difference must be supplied by a boiler compound. In this case, an alkaline boiler compound is used. While, if the Palkalinity given by the feed water is in an excess, the P alkalinity of boiler water must be lowered to the desired level by using an acidic boiler compound. When the acidic boiler compound is used, the corrosion of the chemical injection line and the feed water line may be sometimes promoted due to the acidity of the compound. Therefore, the dealkalization softening of feed water is sometimes employed to avoid the use of acidic boiler compounds. The following measures should be carried out for obtaining the sufficient effects provided by boiler compounds: Analysis of phosphate ion concentration: When the phosphate ion concentration is analyzed, the sample water must be filtered. If not, the suspended hydroxyapatite will be dissolved by the analytical reagent and will give a positive error. Boiler compounds for medium or high pressure boilers: Generally, alkaline or coordinated phosphate treatments are applied for medium pressure boilers. For high pressure boilers with the high heat flux, coordinated phosphate treatments are employed in order to prevent the alkali corrosion of the heating surfaces. That is, the boiler compounds for the coordinated phosphate treatment of medium or high pressure boilers must be designed so as to yield no free alkali in boiler water and to have the optimum Na/PO4 mole ratio suitable for the water quality control standard of each boiler. The relationship among pH, phosphate ion concentration and the Na/PO4 mole ratio of boiler compound is shown in Figure below.

Phosphate based boiler compounds of the mole ratio 2.6 to 3.0 are generally employed for medium or high pressure boilers. The pH of boiler water sometimes decreases due to the contamination with organic matters, such as humic and fulvic acids, which are hardly removed by external water treatments. In that the case, the boiler compounds of the Na/PO4 mole ratio of more than 3.0 may be applied to prevent the pH drop of boiler water.

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Coordinated Phosphate-pH Control This system, which is called coordinated phosphate-pH control, depends on the feed of mixtures of orthophosphate or a mixture of caustic and disodium phosphate to control pH in an otherwise un-buffered water. Monosodium, disodium, and trisodium phosphates can accomplish this purpose as a result of their ability to hydrolyze to H2PO4 -, HPO4-2 and PO4-3 and to establish an equilibrium among these forms, in conjunction with OH-concentration or, by inference, the pH. In water containing a low concentration of dissolved solids other than sodium phosphate, the equilibrium between various forms of phosphate ion can be utilized to control the acidity or alkalinity of the whole system. The ratio of one phosphate to the other can be controlled to produce any desired sodium to phosphate (Na/PO4) ratio. If all of the phosphate is present in the trisodium form, the Na/PO4 ratio is obviously 3.0. At or just below this level there will be no free hydroxide present. The pH range for coordinated phosphate control should be 10.0 to 10.6. This corresponds to an orthophosphate residual in the range of 15 to 50 ppm. The molar ratio of sodium phosphate in the boiler water should be less than 3.0:1. Today, coordinated phosphate control programs maintain a 2.8:1 Na/PO4 ratio. The phosphate residual is generally controlled between 5 and 10 ppm as PO4 and the pH between 9.6 and 9.9. The upper limit on operating pressure for this program is regarded as 100 kg/sq.cm Caustic Corrosion Concentration of caustic (NaOH) can occur either as a result of steam blanketing (which allows salts to concentrate on boiler metal surfaces) or by localized boiling beneath porous deposits on tube surfaces. Caustic corrosion (gouging) occurs when caustic is concentrated and dissolves the protective magnetite (Fe3O4 ) layer. Iron, in contact with the boiler water, forms magnetite and the protective layer is continuously restored. However, as long as a high caustic concentration exists, the magnetite is constantly dissolved, causing a loss of base metal and eventual failure (see Figure). Steam blanketing is a condition that occurs when a steam layer forms between the boiler water and the tube wall. Under this condition, insufficient water reaches the tube surface for efficient heat transfer. The water that does reach the overheated boiler wall is rapidly vaporized, leaving behind a concentrated caustic solution, which is corrosive. Porous metal oxide deposits also permit the development of high boiler water concentrations. Water flows into the deposit and heat applied to the tube causes the water to evaporate, leaving a very concentrated solution. Again, corrosion may occur. Caustic attack creates irregular patterns, often referred to as gouges. Deposition may or may not be found in the affected area. Boiler feedwater systems using demineralized or evaporated makeup or pure condensate may be protected from caustic attack through coordinated phosphate/pH control. Phosphate buffers the boiler water, reducing the chance of large pH changes due to the development of high caustic concentrations. Excess caustic combines with disodium phosphate and forms trisodium phosphate. Sufficient disodium phosphate must be available to combine with all of the free caustic in order to form trisodium phosphate.
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Disodium phosphate neutralizes caustic by the following reaction: Na2HPO4 + NaOH Na3PO4 + H2O
Disodium phosphate sodium hydroxide trisodium phosphate water

This results in the prevention of caustic buildup beneath deposits or within a crevice where leakage is occurring. Caustic corrosion (and caustic embrittlement) does not occur, because high caustic concentrations do not develop (see Figure).

Figure shows the phosphate/pH relationship recommended controlling boiler corrosion. Different forms of phosphate consume or add caustic as the phosphate shifts to the proper form. For example, addition of monosodium phosphate consumes caustic as it reacts with caustic to form disodium phosphate in the boiler water according to the following reaction: Conversely, addition of trisodium phosphate adds caustic, increasing boiler water pH: Na3PO4 + H2 O Na2HPO4 + NaOH
trisodium phosphate

water

Disodium phosphate

sodium hydroxide

Control is achieved through feed of the proper type of phosphate to either raise or lower the pH while maintaining the proper phosphate level. Increasing blowdown lowers both phosphate and pH. Therefore, various combinations and feed rates of phosphate, blowdown adjustment, and caustic addition are used to maintain proper phosphate/pH levels.

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Elevated temperatures at the boiler tube wall or deposits can result in some precipitation of phosphate. This effect, termed "phosphate hideout," usually occurs when loads increase. When the load is reduced, phosphate reappears. Clean boiler water surfaces reduce potential concentration sites for caustic. Deposit control treatment programs, such as those based on chelants and synthetic polymers, can help provide clean surfaces. Where steam blanketing is occurring, corrosion can take place even without the presence of caustic, due to the steam/magnetite reaction and the dissolution of magnetite. In such cases, operational changes or design modifications may be necessary to eliminate the cause of the problem. Volatile treatment A review of high pressure boiler water treatment would not be complete without looking at the alternative to phosphate programs. This program uses all-volatile treatment chemicals and is commonly referred to as AVT or zero solids treatment. Sodium is eliminated from the feedwater by evaporation and/or demineralization of the makeup water and full flow, mixed bed demineralization of return condensate. No chemicals containing sodium are added for internal treatment. The chemicals used are all volatile materials are ammonia and/or morpholine or cyclohexylamine for pH control, and hydrazine, catalyzed hydrazine or a volatile hydrazine substitute as an oxygen scavenger and corrosion inhibitor. The control limits for an AVT program are total solids less than 2 ppm and a pH range of 8.5 to 9.0. Such treatment is limited to very high pressure boilers, usually in steam-electric generating systems. It is the only treatment system possible for once-through or monotube boilers, and most manufacturers of PWR-type nuclear reactors favor its use in the secondary steam generating loop to overcome unique crevice corrosion problems. It is occasionally employed in drum-type boilers operating at 200 kg/sq.cm and above but provides less safety and corrosion resistance against a temporary disturbance particularly that of a condenser leak, than does the phosphate-pH treatment system. In actual operation, most systems using volatile chemistry provide a phosphate feeding facility for emergency use during a period when feedwater is contaminated with dissolved salts. As pressures increase, film boiling and other causes of local overheating are most prevalent. This has led to the phenomenon known as caustic corrosion. Over concentration of sodium hydroxide destroys the protective magnetic iron oxide film (magnetite-Fe3O4), and the base metal is then attacked by the concentrated sodium hydroxide as shown in the following two equations: 4NaOH + Fe3O4 Na2FeO2 + 2NaFeO2 + 2H2O 2 NaOH + Fe0 Na2FeO2 + 2H0 Caustic corrosion manifests itself as gouging and is fairly easy to identify. The tube does not lose ductility and, unless arrested, the gouging proceeds until thinning eventually causes tube failure. It is generally accepted that caustic concentration in excess of 50,000 ppm or 5% is necessary for the above reactions to occur. While there is never caustic present to these levels in the bulk boiler water when using precision control, the concentrating mechanism at the tube surfaces that can occur above 900 psig limits its use to lower pressures.

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Control items for boiler water quality: Table below shows the control items of boiler water quality and their purposes. Control item
pH P-alkalinity Electrical conductivity Total dissolved solids Chloride ion Phosphate ion hydrazine Silica

or

Purpose Corrosion inhibition Scale prevention due to silica and hardness Prevention of silica scaling Control of corrosion, sludge and scale Prevention of carryover Corrosion inhibition Determination of the cycles of concentration of boiler water Inhibition of calcium scale Control of boiler water pH Corrosion inhibition Prevention of silica scale Prevention of carryover

(a) pH: The corrosion rate of carbon steel at high temperature is minimized in the pH range of 11 to 12 as shown in Figure below.

Thus the corrosion of boilers is prevented by controlling the pH between 11 to 12. However, the pH on the boiler tube surface becomes higher than that of boiler water because the concentration film is formed on the heating surface. Therefore, the boiler water pH is controlled lower than 11 in case of medium or high pressure boilers. The pH of boiler water is mainly adjusted by using sodium hydroxide for low pressure boilers applying the alkaline phosphate treatment. Under the coordinated phosphate treatment for medium or high pressure boilers, trisodium phosphate and/or disodium hydrogen phosphate are used for the pH control to avoid the alkaline corrosion. For preventing the hide-out of sodium phosphate, the boiler water pH is adjusted by using volatile substances like hydrazine, ammonia, or volatile amines.
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers To minimize the silica transfer from the boiler water into the steam in medium or high pressure boilers, the boiler water pH is controlled at the upper limit of the control range. To prevent the scaling of hardness components or silica in low pressure boilers, the boiler water pH is controlled in the range of 11 to 12 under the presence of a sufficient concentration of phosphate ion. (b) Alkalinity: Substances analyzed as alkalinity of boiler water include sodium hydroxide, sodium carbonate, sodium phosphate, sodium silicate and so on. These substances originate from the feed water or additives, such as boiler compounds. In the case of boilers feeding raw or softened water including higher silica, the scale with a large silica content tends to be formed. To prevent silica scaling, the Palkalinity (mg CaCO3/l) of boiler water should be controlled at 1.7 times or more of the silica concentration (mg SiO2/l), as well as controlling the silica concentration of boiler water. The softening of feed water is also effective to prevent silica scale. The pH and P-alkalinity of boiler water are important factors to prevent the corrosion and scaling problems. However, the increase of silica concentration in boiler water decreases the boiler water pH under the same P-alkalinity level as shown in Figure below.

Therefore, in the case of high silica boiler water, both the pH and P-alkalinity of boiler water should be strictly controlled. In the case of boilers feeding with demineralized water, the alkali of boiler water is supplied by only boiler treatment chemicals and the silica concentration is kept at very low level. In that case, since the pH and P-alkalinity have the close correlation, the pH control of boiler water results to control the P-alkalinity. (c) Total solids or electrical conductivity: The total solids in boiler water consist of dissolved solids and suspended solids. The increase of the total solids causes the deposition and scaling of the dissolved solids with lower solubilities on the heat transfer surfaces. The suspended solids may accumulate at the sections with the low water flow velocity and disturb the water circulation in the evaporation tubes. Therefore, the total solid concentration should be controlled below a specified upper limit. In addition, a higher total solids cause the carryover and lower the steam purity. The total solids of the boiler water should be kept at the lower level to maintain the steam purity as the pressure becomes higher. Since almost all of the dissolved solids are electrolytes, the electrical conductivity of boiler water increases as the total solid concentration increases. 41

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Therefore, the total solid concentration is appropriately controlled by controlling the electrical conductivity analyzed easily. (d) Chloride ion: Since the chloride ion always exists in the dissolved state without precipitation, the cycles of concentration of boiler water is calculated from the chloride ion concentrations of feedwater and boiler water. Since the anions, such as chloride and sulfate ions, in the boiler water deteriorates the passivation film of steel, they promotes the corrosion under the presence of oxygen. Thus the chloride ion concentration in the boiler water is maintained as low as possible. (e) Phosphate ion: In boilers feeding with softened water, phosphate ion concentration should be controlled at the upper limit to cope with any unexpected leakage of hardness from the softener. In boilers fed with fresh water, phosphate ion concentration in boiler water is maintained in the range of 20 to 100 mg PO4/l considering the fluctuation in the hardness of feed water. In water tube boilers feeding with demineralized water, since the feedwater includes no hardness, phosphate is used for controlling the boiler water pH mainly. In that case, the boiler water pH is determined by the Na/PO4 ratio of the phosphate and the phosphate ion concentration. The lower pH and the lower phosphate concentration ranges are applied for boilers with the higher pressure. (f) Hydrazine: In the case of boilers with the pressure below 20 kgf/cm2, the boiler corrosion is prevented by keeping the hydrazine in the boiler water above 0.1 mg/l regardless of the installation of deaerator. The hydrazine is generally injected into the feed water to maintain the specified concentration in the boiler water. In the boiler of which the pressure is higher than 20 kgf/cm2 and the deaerator is installed, the dosage of hydrazine in the feed water is specified in the range of above 0.01 mg/l to above 0.2 mg/l according to the pressure range. (g) Silica: The silica concentration is generally high in the boiler water of low pressure boilers fed with softened water. For preventing the silica scale, the P alkalinity of boiler water is maintained more than 1.7 times of the concentration of silica to keep the silica as water soluble sodium metasilicate. The silica concentration in boiler water should be controlled below the specified concentration to keep the silica concentration in the steam lower than 0.02 mg SiO2/l for preventing the silica scaling on turbine blades and so on. The upper limit of silica in boiler water has to be lowered as the boiler pressure increases, because the solubility of silica increases as the steam temperature increases. Recommended Quality Parameters of Treated Water at Different Stages of Treatment: Clarified and filtered water (inflow to D.M. Plant): We have seen in section 1.6 above what is meant by process of clarification and filtering. The input to Demineralization plant must be clarified and filtered. The water inflow to D.M. plant should be clear, colorless and odorless. It should be free from organic matters, free from chlorine and other oxidizing agents. Presence of oxidizing agents, organic matters etc. will affect the resin exchanging capacity and lead to total collapse of the resin by way of decrosslinking. It should be free from iron, which leads
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers to resin surface contamination. pH control is equally important for maintaining raw water quality. A preferable range would be 7 to 9.0. Strongly acidic Cation effluent: The quality of effluent water of strongly acidic cation exchanger will have the following property: PH at 25 C Free mineral acidity ppm as CaCO3 (FMA) [ HCl + H2SO4 + HNO3 + H3PO4 ] = [ Cl + SO4 + NO3 + PO4 ] Hardness (Ca + Mg ) ppm as CaCO3 Sodium ppm as Na+ Degasifier effluent: Residual free CO2 ppm Strongly basic anion effluent: The quality of effluent water of strong base anion exchanger will have the following property: pH at 25 C Hardness (Ca + Mg) ppm as Ca CO3 Total silica SIO2 ppm Electrical conductivity MICROMHOS/Cm at 25 C Chloride ( ppm as Cl ) Organic matter ( mg of KMn O4/Litre ) Mixed bed effluent: The quality of effluent water of mixed bed exchanger will have the following property: pH at 25 C 6.8 to 7.2 PH less than 6.8 is an indication of leakage of acidic sulphate and chloride salts and organic acids. D.M. plant performance needs checking up. Electrical conductivity micromhos/cm at 25 C through closed cell provision without any access to the atmosphere Total hardness ( Ca + Mg ) ppm CaCO3 Total silica ; ( SiO2 ppm :) Chloride ( ppm as NaCl ) ( By selective ion electrode ) Sodium ( ppm as Na ) < 0.003
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2.8 to 3.5 Should be equal to the total equivalent mineral acidity (EMA) NIL < 0.005

< 5.0

7.5 to 9.0 NIL Less than 0.05 < 2.0 preferably < 1.0 NIL Practically free

< 0.2 micro seimensper sq.cm

NIL < 0.02 (< 0.01 is preferable ) NIL

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Organic matter mg of KmnO4/Litre Should be practically free : There may be slight consumption of permanganate. It should be < 0.5 at any stage. < 0.2 is preferable. Blank comparison is essential. For blank test use reagent grade water. Clear, free from odour, colour and haziness. No glittering to tyndal effect.

General appearance

Condensate and Return condensate: The quality of condensate depends upon the quality and the quantitative addition of make up water. It is, hence, imperative to control CBD in order to limit make up consumption. If auxiliary steam for various purposes is consumed, this will boost the make up consumption. Under such circumstances, quality of make up should be closely monitored to achieve the recommended values, so that, the quality of extracted condensate is maintained. These recommendations are relevant for samples collected at the condensate extraction pump delivery, prior to hydrazine (L.P.) dosing point.

Quality of extracted condensate water: pH at 25 C Electrical conductivity Micro mhos/Cm at 25 C 8.5 to 8.8 < 0.3 (with correction for ammonia and hydrazine through strong cation column alone would ensure the desired purity.) < 0.02 NIL < 0.01 < 0.003 < 0.01 NIL < 0.01 < 1.0 ( < 0.5 is preferable )

Dissolved oxygen ( O2 ppm ) Dissolved carbon dioxide ( CO2 ppm ) Total iron ( Fe ppm ) Total copper ( Cu ppm ) Total silica : (SiO ppm ) Total hardness ( Ca + Mg ) ppm as CaCO3 Sodium + potassium ppm Free ammonia : ppm

In order to get a reliable Conductivity and pH measurement the sample is to be cooled to 25 C with continuous flow of sample flowing with a closed cell provision having no contact with atmosphere. The sample has to be passed through a strong acidic cation column to avoid the influence of dissolved Ammonia and Hydrazine. In case carbon dioxide is present in condensate water, the conductivity measured even after passing through cation column will be indicated high, which will be proportional to the concentration of carbon dioxide in the sample. Sample should flow at a regular and constant rate and should be clear and colourless. Drum sample quality is mainly dependent on the quality of the condensate extraction and make up water. Feed flow requirement is decided by leakages and is dependent on the drum operating pressure too.
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Quality of feed water to boiler Quality requirement for feed water is very much dependent on drum operating pressure. Hence recommended feed water quality is always expressed for a particular range of boiler operating pressure. Drum operating Pressure Kg/Cm2 pH at 25 C Electrical conductivity at 25 C in micro mhos/cm Economizer inlet Total iron ( Fe ppm ) Total copper ( Cu ppm ) Total iron copper & nickel ppm Total silica ( SiO2 ppm ) Carbonic acid (CO2 ppm ) Organic matter KmnO4/Litre Oil ppm Hydrazine N2H4 ppm ) mg 8.5~9.0 < 0.5 < 0.01 < 0.03 < 0.005 < 0.03 < 0.02 Nil 8.5 ~ 9.0 8.7 ~ 9.0 8.8 ~ 9.2 < 0.5 < 0.01 < 0.01 < 0.005 < 0.02 < 0.02 Nil < 0.4 < 0.005 < 0.01 < 0.003 < 0.02 < 0.02 Nil < 0.3 < 0.005 < 0.01 < 0.003 < 0.02 < 0.02 Nil 60 80 100 120 130 & above 8.8~ 9.2 < 0.2 < 0.005 < 0.01 < 0.003 < 0.01 < 0.01 Nil

Less than 0.1 ppm is considered tolerable Nil < 0.1 Nil < 0.05 Nil < 0.05 Nil < 0.02 ~ 0.05 Nil < 0.02

Boiler water: General requirements: The sample collected through CBD line should flow continuously at a steady rate through a cooler. Temperature of the well condensed sample should not be more than 25 C. There should be no appearance of red water when the flow is disturbed. Sample collection with partial choking of line can lead to misleading results. Lines may get choked with ferric and magnetic oxides. These oxides behave like weak ion exchange resins and render the samples representation poor. Boiler kg/cm2 drum pressure 60 < 300 < 125 10.0 10.5 <5 80 < 200 < 75 9.8 ~ 10.2 <3 100 < 100 < 50 9.8 ~ 10.2 < 1.8 120 < 50 < 20 9.4 ~ 9.7 < 1.0 130 & above < 50 < 15 9.4 ~ 9.7 < 0.5

Electrical conductivity micro mhos/cm at 25 C Total solids ( ppm ) pH at 25 C Total silica ( SiO2 ppm )

< 0.3 above 130Kg/Cm2 Phosphate (PO4 ppm ) Chloride (NaCl ppm ) 7.0 11.0 < 5.0 ~ 5.0 ~ 10.0 < 5.0 5.0 10.0 < 3.0 ~ 3.0 ~ 6.0 < 3.0 3.0 ~ 6.0 < 2.0

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Essential Boiler Water Chemistry for Operation & Maintenance Engineers Free Hydroxide ( NaOH ppm ) Phenolpthalene alkalinity (CaCO3 ppm ) Conductivity: Conductivity should be measured at 25 C at continuously flowing local point. pH : It is necessary to maintain pH/PO4 in accordance with coordinate control technique. Na to PO4 ratio should be 3:1. For drum pressure rating of 130 Kg/Cm2 and above congruent control is preferable. Here Na to PO4 ratio is kept at 2.6:1. Ideal range is 2.6/2.8 to 1; a combination of trisodium phosphates and disodium phosphates or sodium hexameta phosphate and sodium hydroxide is used to pH/PO4 relation. Chloride: Presence of chloride is not desirable. Chloride ion impairs magnetite layers growth and coherence. It retards healing mechanism. Even neutral or alkaline chloride may produce acid. It is desirable to shut the unit if chloride ingress is from cooling water leakage, D.M. plant leakage or from impure chemicals. In case of chloride contamination, adequate pH and b/d control becomes necessary till normalcy is restored. Free Hydroxide: Free hydroxide should be maintained as low as possible, made practically free by adopting coordinate/congruent technique. Na to PO4 ratio at 2.8 to 1, under normal operating condition without any sulphate/chloride contamination, is ideal. Saturated and Superheated Steam: The objective is to obtain steam of very high purity, without any contamination from dissolved and entrained solids and acidic gasses, in order to prevent fouling of super heaters and turbine blades. Besides, the steam generated should be non corrosive to ferrous and copper alloys and conducive to the preservation of protective Fe/cu passive oxide layers. Broad guide lines : Solids ppm in steam < 0.01 0.01 to 0.1 0.1 to 1.0 > 1.0 Turbine blade deposition No Possible Yes Yes Super heater deposition No No Possible Yes < 25 < 15 < 10 <5 <3 To keep practically free

Steam sample should be collected through a well designed sampling device and cooler, so that the sample collected is well condensed to a temperature of 25 C without suffering solid separation or concentration. pH at 25 C 8.9 to 9.2
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Essential Boiler Water Chemistry for Operation & Maintenance Engineers The range is prescribed just to provide a safe guide line. It cannot be provided with certainty for want of reliable and established data. However, to a great extent, pH corresponding to a quantity of ammonia present in the steam, which when condensed shall not exceed an average value of 0.5 ppm in the return condensate and at any time a maximum value of 1.0 ppm can be relied upon. In the absence of carbon dioxide the recommendation made is reliable and workable. Electrical conductivity Micro mhos/cm at 25 C Conductivity is measured at 25 C at local continuous flow sampling point at the down stream of a strong cation exchanger. Sample at a constant flow rate is passed through a closed cell having no access to atmosphere. This in valid for CO2 free sample only. If CO2 is present, correction to the effect may give a value which may not be very reliable and accurate. < 0.3 and < 0.2 is ideal

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