Boiler Feedwater Treatment

Water for boilers

All natural waters contain varying amounts of suspended and dissolved matter as well as dissolved gases. The type and amount of impurities in fresh water vary with the source (lake, river, well) and with the area of location. Impurities in water become an important consideration when water is to be used for steam generation. With the trend toward higherpressure boilers, pretreatment has become the key to successful operation of industrial power plants. Feedwater must be pretreated to remove impurities to control deposition, carryover, and corrosion in the boiler system. Poor quality water gives poor quality steam. The first step in any treatment is filtration of suspended solids. On the basis of proven satisfactory performance, cost, and other considerations, cartridge filters are a practical solution to most problems of water clean-up.

Physical properties of water

Pure water is a tasteless, odourless, colorless liquid. Because water can be converted to steam at a convenient temperature, it is an ideal medium for generating power or conducting heat.

Chemical composition of water

Pure water, H2O, is a simple combination of hydrogen and oxygen. There are, however, several hybrids forms of water in all supplies. Water often contains about 300 ppm of deuterium oxide, D2O, or heavy water. It has no use as drinking water or in making plants grow, but in pure form has found use in nuclear reactors. For all practical purposes only ordinary water, H2O, is considered for use in boilers.

Boiling temperature
The boiling point of water is dependent on pressure. At sea level atmospheric pressure, water boils at about 212oF. With increasing pressure, the boiling point also increases. At a pressure of 200 psig, for example, water boils at a temperature of about 388oF. At the critical pressure of 3200 psig (where water is converted to steam without change in volume), the boiling point is 704oF. As the pressure decreases, the boiling point of water decreases. Under vacuum water will boil at temperatures as low as 35oF.

Water an ideal medium for carrying heat energy

It takes one BTu (British Thermal Unit) to raise temperature of one pound of water 1oF. It takes an additional 970 Btu to change one pound of water, at boiling point, to steam. This heat energy is stored in the steam and when it condenses, the energy is given off. Thus much of the heat from burning fuel can be absorbed by boiler water, transported with the steam, and released at the points of use.

Impurities in water

All natural waters contain various types and amounts of impurities. These impurities cause boiler problems and as such consideration must be given to the quality and treatment required of the water used for generating steam. For any type of treatment, sediment filtration (usually with cartridge filters) is the first step.

Natural water
Natural waters contain suspended matter, dissolved solids, and dissolved gases. Water being a universal solvent dissolves minerals, rocks and soil that come into contact with it. It dissolves gases from air and gases that are given off from organics in the soil. It picks up suspended matter from the earth. Additionally it may also be contaminated with industrial wastes and process materials. Dissolved minerals Dissolved minerals picked up by the water consist mainly of calcium carbonate (limestone), calcium sulfate (gypsum), magnesium carbonate (dolomite), magnesium sulfate (epsom salts), silica (sand), sodium chloride (common salt), hydrated sodium sulfate (Glauber salt), and smaller quantities of iron, manganese, fluorides, aluminum, and other substances. The nitrates and phosphates found in water are usually due to sewage contamination. Water hardness Water containing high amounts of calcium and magnesium minerals is hard water. The amount of hardness in natural water can vary from a few ppm to 500 ppm. Calcium and magnesium compounds are relatively insoluble in water and tend to precipitate out. This causes scale and deposit problems. Such water must be treated to make it suitable for steam generation. Dissolved gases in water Water contains varying amounts of dissolved air (21% oxygen, 78% nitrogen, 1% other gases including carbon dioxide). Water can contain up to 9 ppm oxygen at room temperature and atmospheric pressure. As the temperature increases, the solubility of oxygen decreases, but water under pressure can hold higher amounts of dissolved oxygen. Nitrogen, being inert, has little effect on water used in boilers. Water can contain 10 ppm of carbon dioxide, sometimes much more than that due to decaying vegetation and organics in soil. Hydrogen sulfide and methane may be dissolved in water but this is rare. These gases can be troublesome when they are present in the feed water. Other impurities in water Natural waters contain varying levels of soil, sand, turbidity, colour, precipitated minerals, oil, industrial wastes and other suspended solid particles. Turbidity is due to very fine organic materials and microorganisms, as well as suspended clay and silt. Colour is due to the decaying vegetable matter.

Sources of fresh water

Fresh water can be surface water from rivers, streams, reservoirs or ground water from wells. Generally ground water supplies are more consistent in composition than surface water supplies. Surface water quality is effected by rainfall, soil erosion and industrial wastes, but ground water is usually harder than surface water. The composition of fresh water also varies with the location and type and strata of the earth formations. In limestone areas, for example, water contains large quantities of dissolved calcium. Apart from the geographic variations, the local conditions of a particular area may have a great influence in the composition of the water.

Boiler feedwater
Boiler feedwater is the water supplied to the boiler. Often, steam is condensed and returned to the boiler as part of the feedwater. The water needed to supplement the returned condensate is termed make-up water. Make-up water is usually filtered and treated before use. Feedwater composition therefore depends on the quality of the make-up water and the amount of condensate returned. Sometimes people think that there is a great deal of similarity between the requirements for potable (drinking) water and the requirements for boiler feedwater. The minerals in drinking water are considered desirable and are absorbed by the body. On the other hand, minerals in water cannot be handled as well by boilers. Although a boiler is a big mass of steel, it is more sensitive to water impurities than the human stomach. For this reason, a lot of care is needed in filtration and treatment of the boiler water supply.

Purity requirements of feedwater

Feedwater is a matter both of quantity of impurities and the nature of impurities. Hardness, iron, and silica, for example, are of more concern than sodium salts. The purity requirements of feedwater depend on how much feedwater is used as well as toleration of the particular boiler design (pressure, heat transfer rate etc.). In todays high-pressure boilers practically all impurities must be removed. The feedwater (make-up water) from outside needs to be treated for the reduction or removal of impurities by first filtration, and then followed by softening, evaporation, deariation, ion exchange etc. Internal treatment is also required for the conditioning of impurities within the boiler system, to control corrosion, as reactions occur in the boiler itself and the steam pipelines.

Boiler deposits
Water evaporating in the boiler causes impurities to concentrate. Boiler scale results from suspended matter settling out on the metal or dissolved impurities precipitating out on heat transfer surfaces and becoming hard and adherent.

Impurities that form deposits

Bicarbonates of calcium and magnesium dissolved in water break down under heat and give off carbon dioxide forming insoluble carbonates. These carbonates precipitate directly on the boiler metal and or form sludge in the water that deposits on boiler surfaces. Sulfate and silica generally precipitate directly on the boiler metal and are much harder to condition. Silica (sand) if present in water can form exceedingly hard scale. Suspended or dissolved iron

coming in the feedwater will also deposit on the boiler metal. Oil and other process contaminants can form deposits as well and promote deposition of other impurities. Sodium compounds usually do not deposit unless the water is almost completely evaporated to dryness, as may occur in a starved tube. Deposits are seldom composed of one constituent alone, but are generally a mixture of various types of solid sediments, dissolved minerals, corrosion products like rust, and other water contaminants.

Characteristics of phosphate deposit

Phosphate deposits are usually soft brown or gray deposits that can be easily removed by normal cleaning methods. They are normally found in boilers employing a phosphate internal treatment. They are the preferred reaction product when using a residual phosphate treatment on high hardness feed water. Since they are easily conditioned with organic sludge conditioners, they are relatively nonadherent. Calcium phosphate is usually the predominant compound in the boiler deposit.

Characteristics of carbonate deposit

Carbonate deposits are usually granular and sometimes porous. The crystals are relatively large and often matted together with finely divided particles of other materials making the scale look dense and uniform. Carbonate deposit can be easily checked by putting it in an acid solution. Bubbles of carbon dioxide will effervesce from the scale.

Characteristics of sulfate deposit

Sulfate deposit is brittle, does not pulverize easily, and will not effervesce when put in an acid solution. It is much harder and denser than a carbonate deposit due to its smaller crystal structure.

Characteristics of silica deposit

Silica deposits are very hard and resemble porcelain. Their crystals are very small, forming a dense, impervious scale. This scale is extremely brittle, very difficult to pulverize, and not soluble in hydrochloric acid.

Characteristics of iron deposit

Iron deposits are very dark coloured and are due to corrosion products or iron contamination in feedwater. Iron deposits are usually magnetic in nature. They are soluble in hot acid, giving a dark-brown solution.

Problems caused by deposits

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

expenses. Boiler deposits reduce overall operating efficiency resulting in higher fuel consumption.

Corrosion
Corrosion is basically the reversion of a metal to its ore form. Iron, for example, reverts to iron oxide as a result of corrosion. The process of corrosion is actually not so simple, it is a complex electro-mechanical reaction. Corrosion may generally be over a large metal surface but sometimes it results in pinpoint penetration of metal. Though basic corrosion is usually due to reaction of the metal with oxygen, other factors including stresses produce different forms of attack. Corrosion may occur in the feedwater system as a result of low pH water and the presence of dissolved oxygen and carbon dioxide. Corrosion in the boiler itself normally occurs when boiler water alkalinity is too low or too high or when the metal is exposed to oxygen-bearing water during either operation or idle periods. High temperatures and stresses tend to accelerate the corrosion. In the steam & condensate system and pipelines corrosion is generally the result of contamination with carbon dioxide and oxygen.

Corrosion Fatigue
Cracking in boiler metal may occur due to cyclic stresses created by rapid heating and cooling. These stresses are concentrated at points where corrosion has roughened or pitted the metal surface. This is usually because of improper corrosion prevention. Sometimes even with properly treated water corrosion fatigue cracking occurs. These cracks often originate where a dense protective oxide film covers the metal surfaces, and cracking occurs from the action of applied cyclic stresses. Corrosion fatigue cracks are often thick, blunt, and across the metal grains. They start at internal tube surfaces and are most often circumferential on the tube.

Caustic embrittlement
Caustic embrittlement or cracking is a more serious type of boiler metal failure showing up as continuous intergranular cracks. This type of cracking occurs when the metal is stressed, water contains caustic with a trace of silica, and some mechanism, such as a slight leak, is present allowing the boiler water to concentrate on the stressed metal. Caustic embrittlement is more of a problem in older boilers with riveted drums as they cause stresses and crevices in the areas of rivets and seams. In the newer welded drum boilers this type of cracking is less frequent but the rolled tube ends are still vulnerable to attack. The possibility of caustic cracking should be a consideration in water treatment.

Other causes of boiler corrosion

Chelate residuals in excess of 20 ppm as CaCO3 or improperly applied chelate treatment may produce boiler system corrosion. Concentration of boiler solids at high heat input areas might also produce corrosion. The recommendations of a water treatment consultant need to be followed to minimize chances of such corrosion from occurring.

Corrosion problems

Uniform corrosion of boiler metal surfaces is bound to occur and is not of much concern as all boilers experience a small amount of general corrosion. Corrosion, however, takes many forms and deep pitting that causes only a small amount of total iron loss causes penetration and leakage in boiler tubes. Corrosion beneath certain types of boiler deposits can weaken the metal and cause tube failure. Likewise corrosion in steam condensate system can damage pipelines and equipment.

Corrosion measurement
Hydrogen gas sampling of the boiler steam is done to measure the corrosion potential of the boiler water. This test for corrosion is based on the release of hydrogen gas when iron corrodes. Measuring the amount of hydrogen gas released detects boiler water conditions and indicates if corrosion conditions exist in an operating boiler.

Basic corrosion prevention methods

The common methods for prevention of corrosion include: 1. 2. 3. 4. 5. 6. Filtration of solid suspended impurities & particles from water Removing dissolved oxygen from the boiler feedwater Maintaining alkaline conditions in the boiler water Keeping the boiler internal surfaces clean Protecting boilers during out of service periods Using a chemical treatment programme to counteract corrosive gases in steam and condensate systems

The selection and control of chemicals for preventing corrosion requires an understanding of the causes and corrective measures.

Boiler water carryover

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

Boiler carryover measurement

Steam purity can be measured with the use of a sodium ion analyzer. It measures the sodium ion content in a cooled steam sample that will correspond to the amount of boiler water solids contaminating the steam. The sodium ion analyzer can detect carryover down to 1 ppb sodium in steam.

Affect of oil on carryover

Oil contamination in boiler feedwater is usually from pumps and other lubricated equipment. Oil can cause serious foaming due to saponification of oil by boiler water alkalies.

Affect of suspended solids on carryover

Suspended solids tend to collect on the surface film surrounding a steam bubble, which therefore resists breaking and builds up foam. The finer suspended particles become the greater is their collection on the bubble. The type as well as the quantity of suspended solids can affect carryover. Depending on the type of suspended solids, some boilers having high suspended solids operate without carryover, while others have carryover with low suspended solids.

Selective silica carryover

Silica can be present in the steam as the result of general boiler water carryover, or it can go into the steam in a volatile form. In the later case, silica acts much like gas and is considered to be selectively carried over. As the boiler pressures increase above 400 psi, there is an increase in the tendency for silica to be selectively carried into the steam in amounts proportionate to the amount of silica present in the boiler water.

Problems caused by carryover

Suspended and dissolved solids in the boiler water tend to deposit in the steam and condensate system. Impurities carried over with the steam cause contamination in the many processes for which steam is used, resulting in overheating, corrosion and reduction of efficiency of the boiler itself and other equipment.

Preventing carryover
The basic preventive measure is to maintain the concentration of solids in the boiler water at recommended levels. High water levels, excessive boiler loads and sudden load changes are to be avoided. Very often contaminated condensate returned to the boiler system causes carryover. The return condensate should be filtered to remove suspended solids before being fed back to the boiler. Efforts should be made to trace the source of any excessive contamination and the problem rectified. The use of chemical antifoams is effective in controlling carryover due to concentration of impurities in the boiler water. Steam-separating equipment must be inspected for proper installation.

Removing impurities from boiler feedwater

Feedwater is filtered to remove suspended matter and if the suspended solids are very fine, a flocculation step may be needed to enable effective filtration. The water is then subjected to

other treatments to make it suitable for the boiler. Depending on the quality of water, it may be subjected to one or more treatments like chemical precipitation, lime-soda softening, ion exchange, deaeration, and reverse osmosis.

Filtration
Filtration is the essential first step before the chemical treatment and conditioning of the boiler feedwater. Filtration removes or minimizes all types of suspended solid impurities. If rust, sand (silica) etc. are not filtered out, they lead to severe scale formation, which is difficult to clean and reduce boiler efficiency. Even the condensate feedwater must be filtered before returning to the boiler. The boiler itself and the steam piping produce rust particles etc. due to corrosion and other reactions. Filtration is also necessary for any water treatment process to work properly. For example, softening resins get coated with suspended matter, loosing their effectiveness and capacity to regenerate. Reverse osmosis membranes get fouled up leading to reduced efficiency and shorter life. If the water is very dirty, sand filtration is first done followed by cartridge filtration.

Coagulation and flocculation

Some times the suspended particles in water are so fine that even cartridge filters are unable to remove them. In such a situation, before cartridge filtration, the water is first treated with coagulants. Coagulation is charge neutralization of finely divided and colloidal impurities in water into masses that can be filtered. In addition, particles have negative electrical charges, which cause them to repel each other and resist adhering together. Coagulation, therefore, involves neutralizing the negative charges and providing a nucleus for the suspended particles to adhere to. Flocculation is the bridging together of coagulated particles.

Types of coagulants
Iron and aluminum salts such as ferric sulfate, ferric chloride, aluminum sulfate (alum), and sodium aluminate are the most common coagulants. Ferric and alumina ions each have three positive charges and therefore their effectiveness is related to their ability to react with the negatively charged colloidal particles. These coagulants form a floc in the water that serves like a net for collecting suspended matter. Polyelectrolytes, which are synthetic materials, have been developed for coagulation purposes. These consist of long chain-like molecules with positive charges. In some cases organic polymers and special types of clay are used in the coagulation process to serve as coagulant aids. These assist in coagulation by making the floc heavier.

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

Reaction of lime and soda in softening process

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

Methods of lime-soda softening

The older method of intermittent softening consists of mixing the chemicals with the water in a tank, allowing time for reaction and forming of sludge, and filtering and drawing off the clear water. The modern method of continuous lime-soda softening involves use of compartmented tanks with provision for (a) proportioning chemicals continuously to the incoming water, (b) retention time for chemical reactions and sludge formation, and continuous draw-off of softened water. Lime-soda softening is classified as hot or cold, depending on the temperature of the water. Hot process softeners increase the rate of chemical reactions, increase silica reduction, and produce over-all better quality water.

Coagulants used in lime-soda process

In the initial clarification process, coagulants are used to agglomerate fine suspended particles, which can then be filtered out. Likewise, in the softening process, coagulants speed up settling of sludge by 25-50%. Sodium aluminate used as a coagulant in lime-soda softening being alkaline, also contributes to the softening reactions, particularly in reducing magnesium. Proper uses of coagulants help remove silica in the softening process. Silica tends to be adsorbed on the floc produced by coagulation of sludge.

Disadvantages of lime-soda softening

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

Advantages of lime-soda softening

The main advantage is that in reducing hardness, alkalinity, total dissolved solids, and silica are also reduced. Prior clarification of the water is not usually necessary with the lime-soda process. Another advantage is that with continuous hot process softening some removal of oxygen and carbon dioxide can be achieved. Fuel savings can be realized with hot process softening because of solids reduction. This reduction decreases the conductivity of the feedwater, thereby decreasing blowdown and conserving heat.

Ion Exchange

Minerals dissolved in water form electrically charged particles called ions. Calcium carbonate, for example, forms a calcium ion with positive charges (a cation) and a bicarbonate ion with negative charges (an anion). Some synthetic and natural materials have the ability to remove mineral ions from water in exchange for others. For example, in passing water through a simple cation exchange softener all the calcium and magnesium ions are removed and replaced with sodium ions. Ion exchange resins usually are small porous beads that compose a bed several feet deep through which the water is passed.

Types of ion exchange resins

Ion exchange resins are two types: cation and anion. Cation exchange resins react only with positively charged ions like Ca+2 and Mg+2. Anion exchange resins react only with the negatively charged ions like bicarbonate (HCO3-) and sulfate (SO4-2). Although there are many types of cation exchange resins, they usually operate on either a sodium or hydrogen cycle. That is, they are designed to replace all cations in the water with either sodium or hydrogen. The anion resins are of two types: weak base and strong base. Weak base resins will not take out carbon dioxide or silica, but will remove strong acid anions by a process more similar to adsorption than ion exchange. Strong base anion resins, on the other hand, can reduce carbon dioxide and silica as well as strong acid anions to very low values. Strong base anion resins are normally operated on a hydroxide cycle. Chloride anion exchange resin is also used in dealkalization where alkalinity is reduced.

Ion exchange regeneration

Ion exchange resins have a certain capacity for removing ions from water and when their capacity is used up they have to be regenerated. The regeneration is essentially reversing the ion exchange process. Cation exchangers operating on the sodium cycle, salt (NaCl) is added to replenish the sodium capacity. Resins operating on the hydrogen cycle are replenished by adding acid (H2SO4 or HCl). Anion exchangers are normally regenerated with caustic (NaOH) or ammonium hydroxide (NH4OH) to replenish the hydroxide ions. Salt (NaCl) may also be used to regenerate anion resins in the chloride form for dealkalization. Regeneration process involves taking the vessel off line and treating it with concentrated solution of the regenerant. The ion exchange resin then gives up the ions previously removed from water and these ions are rinsed out of the vessel. After the regeneration has been completed, the vessel is ready for further service.

Split-stream softening
When the effluents from a cation exchanger operating on sodium cycle are blended with effluents from a cation exchanger operating on a hydrogen cycle. The purpose is to reduce the alkalinity of the water. Since the hydrogen cycle produces acid water while the sodium cycle does not affect alkalinity, the two effluents can be blended together to give the desired reduction in alkalinity.

Dealkalization
One of the ion exchange processes for reducing water alkalinity is referred to as dealkalization. In this process the water passes through an ion exchanger operating on the chloride cycle. The exchanger removes alkaline anions such as carbonate, bicarbonate, and

sulfates, replacing these ions with chloride. Cation exchange softening precedes dealkalization process.

Demineralization
When the water is passed through both cation and anion exchange resins it is known as demineralization. In this process the cation exchange is operated on the hydrogen cycle. That is, hydrogen is substituted for all the cations. The anion exchanger operates on the hydroxide cycle, which replaces hydroxide for all of the anions. The final effluent from the process consists essentially of hydrogen ions and hydroxide ions or pure water. The demineralization process can be done by several methods. In the mixed-bed process, the anion and cation exchange resins are intimately mixed in one vessel. Multi-bed arrangements may consist of different combinations of cation exchange beds, weak and strong-based anion exchange beds, and degasifiers.

Disadvantages of ion exchange

Sodium cycle ion exchange softening disadvantage is that the total solids, alkalinity, and silica contents of the raw water are not reduced. In the case of cation exchange on the hydrogen cycle, the disadvantage is the corrosion from the acid pH of the effluent. With demineralization, the main difficulty is higher cost, particularly on high solids raw water. Without an excellent pre-filtration arrangement, fouling of the ion exchange material with suspended and colloidal matter in the raw water can produce short runs, ion-exchange degradation, and regeneration difficulties.

Advantages of ion exchange

A major advantage of ion exchange softening is the ease of process control. Variations (within reasonable limits) of hardness in raw water or in flow rate do not have an adverse effect on the completeness of softening. The ion exchange system takes up less space than the lime-soda system. Generally the ion exchange demineralization has the ability to produce better quality boiler feedwater at an economical cost than most other methods.

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

Combination of ion exchange and lime process

As mention earlier, water containing suspended solids, organics, or turbidity requires filtration/clarification prior to ion exchange. Because simple cation exchange does not reduce the total solids of the water supply, it is sometimes used in conjunction with precipitation softening. A common combination treatment is the hot lime-zeolite process. This involves pretreatment of the water with lime to reduce hardness, alkalinity, silica, and subsequent filtration and a cation exchange softening. This combination accomplishes several functions

like softening, alkalinity and silica reduction, some oxygen reduction, and removal of suspended matter and turbidity.

Reverse osmosis
To understand reverse osmosis (RO), one must first understand osmosis. Osmosis uses a semi-permeable membrane that allows ions to pass from a more concentrated solution to a less concentrated solution without allowing the reverse to occur. Reverse osmosis overcomes the osmotic pressure with a higher artificial pressure to reverse the process and concentrate the dissolved solids on one side of the membrane. Operating pressures of about 300 to 900 psi are required to achieve this. Reverse osmosis reduces the dissolved solids of the raw water, making the final affluent ready for further treatment. This process is suitable for any type of raw water, but sometimes the installation and operation cost may not be economical.

Internal treatment of boiler feedwater

Internal treatment of water inside the boiler is essential whether or not the feedwater has been pretreated. Internal treatment compliments external treatment and is required regardless of whether the impurities entering the boiler with the feedwater are large or small in quantity. In some cases feedwater supply needs to be only filtered without the need for any other external treatment. Internal treatment can constitute the sole treatment when boilers operate at low pressure, large amounts of condensed steam are used for feedwater, or the raw water available is of good quality. However, in moderate or high-pressure boilers, External treatment of the make-up water is mandatory for good results. With todays boilers having higher heat transfer rates, even a small deposit can cause tube failure or wasted fuel.

Internal water treatment program

The purpose of an internal water treatment program is: 1. To react with incoming feedwater hardness and prevent it from precipitating on the boiler metal as scale 2. To condition any suspended matter such as hardness sludge in the boiler and make it nonadherent to the boiler metal 3. To provide antifoam protection to permit a reasonable concentration of dissolved and suspended solids in the boiler water without foaming 4. To eliminate oxygen from the feedwater 5. To provide enough alkalinity to prevent boiler corrosion 6. To prevent scaling and protect against corrosion in the steam-condensate systems.

Chemicals used in internal treatment

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

operating pressures. Synthetic organic materials are used as antifoam agents. For feedwater oxygen scavenging, chemicals used are sodium sulfite and hydrazine. Condensate system protection can be accomplished by the use of volatile amines or volatile filming inhibitors. A reputable company supplying treatment chemicals should be consulted. These companies supply the chemical formulations under their brand names and they provide details on the dosage and methods.

Internal treatment for hardness

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

Internal treatment for sulfates

The boiler temperature makes the calcium and magnesium sulfates in the feedwater insoluble. With phosphates used as internal treatment, calcium reacts with the phosphate producing hydroxyapatite, which is much easier to condition than calcium sulfate. With chelates or polymer used as internal treatment, calcium and magnesium react with these materials producing soluble complexes that are easily removed by blowdown.

Internal treatment for silica

If silica is present in the feedwater, it tends to precipitate directly as scale at hot spots on the boiler metal and or combines with calcium forming a hard calcium silicate scale. In the internal treatment for silica, the boiler water alkalinity has to be kept high enough to hold the silica in solution. Magnesium, present in most waters, precipitates some of the silica as sludge. Special organic materials or synthetic polymers are used to condition magnesium silicate from adhering to the boiler metal.

Internal treatment for sludge conditioning

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

to deposit on the boiler metal. Conditioners prevent these solids from depositing and forming corrosive or insulating boiler scale. Some of the principal types of sludge conditioners are: 1. Starches effective on high silica feedwater and where oil contamination is a problem 2. Lignins effective on phosphate type sludge 3. Tannins fairly effective on high hardness feedwater 4. Synthetic polymers Highly effective sludge conditioners for all types of sludges

Internal treatment advantages

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

Internal treatment chemical dosage

Chemical dosages are based on the amount and type of impurities in the feedwater. For example, the amount of boiler treatment chemicals depends on the feedwater hardness; the amount of sodium sulfite depends on the amount of dissolved oxygen in the feedwater. In addition, a certain amount of extra chemicals are added to provide a residual in the boiler water. Feeding methods include chemical solution tanks and proportioning pumps with the chemicals being added directly before entrance to the boiler. Ortho type phosphates are fed through a separate line directly into the steam drum of the boiler. Chemicals used to prevent condensate system corrosion can be fed directly to the feedwater, boiler, or steam, depending on the type of chemical used. Continuous feeding is the preferred method but intermittent feeding may also suffice in some cases.

Tests for treatment control

Boiler water control tests include tests for alkalinity, phosphate, polymer, hydrazine, chelate, sulfite, pH, organic colour, and total dissolved solids. If sulfite test shows adequate residual is present (this test is not valid with use of uncatalyzed sodium sulfite), the feedwater oxygen has been removed. Testing for organic colour gives an indication for both sludge conditioner and antifoam level. Chelate testing can be either for total chelate or residual chelate.

Tests for checking contaminants

These tests depend on what type of contaminants is suspected. Common checks are for iron, oil and silica. Total iron test serves as a check on corrosion products brought back by the condensate return. This test is also used to check iron present in the make up water. Laboratory facility is required for oil test but visual inspection can reveal gross contamination. Periodic checking should be done to detect unusual silica contamination and to determine when blowdown is needed.

Blowdown

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

Test for regulating blowdown

A practical method for regulating blowdown is by routinely checking the electrical conductivity of the water with a simple measuring instrument. Electrical conductivity gives an estimate of the dissolved solids in the boiler water. By checking both the feedwater and boiler water dissolved solids, one can easily calculate the number of feedwater concentrations.

Continuous and intermittent blowdown

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

Corrosion in steam condensate system

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

Prevention of steam condensate corrosion

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

removal. Sodium sulfite and hydrazine chemicals are commonly used for this purpose. Catalysts are sometimes also used to speed up the reaction.

Prevention of deposits and water corrosion in feedwater systems

Deposits in feedwater systems are usually caused by hardness precipitation as the water goes through feedwater heaters or as the feed lines enter the boilers. Deposits can also occur from premature reaction of treatment chemicals with hardness in the feedwater. Prevention is by means of the use of stabilizing chemicals fed continuously to retard hardness precipitation. The corrosion of feedwater system is due to the low alkalinity or dissolved oxygen in the water. Raising the pH of the water with caustic or amines and feed of catalyzed sodium sulfite minimizes this problem.

Prevention of caustic embrittlement

Organic materials like lignins applied to the boiler water are effective in preventing caustic embrittlement of boiler metal. Sodium nitrate inhibits embrittlement at low concentrations ranging to 0.4 part of sodium nitrate per part of caustic soda in boiler water. Maintaining an organic content of 50-100 ppm and a sodium nitrate content of 50 ppm is a commonly used embrittlement prevention program.

Oil contamination, problem & remedies

Main problems caused by oil in the boiler water are: 1. Oil can coat metal surfaces, cut down heat transfer, and produce metal overheating 2. Oil can cause sludge to become sticky and adhere to heat transfer surfaces 3. Oil can produce foaming and boiler water carryover Oil contamination should be completely eliminated whenever possible. Organic chemicals help counteract the effects of small amounts of oil contamination, but not of gross contamination. When sudden boiler water oil contamination is experienced, normal procedure is to blow down heavily to remove oil and to check for the source of contamination. In case of severe contamination, the boiler needs to be taken off the line and cleaned out to remove the oil from the boiler surfaces. When oil contamination is continuous and unavoidable, some of the methods used are: 1. 2. 3. 4. 5. Free oil can be reduced by passing the water through absorbent cartridge filters Emulsified oil is broken down by chemical additives and filtered Special filters are used with aids like diatomaceous earth Flotation method Coalescence method

Care of out-of-service boilers

Much of the corrosion damage to boilers and condensate equipment results during idle periods due to corrosion caused by the exposure of wet metal to oxygen in the air. Wet boiler lay-up method is of storing boilers full of water. Extra chemicals (alkalinity, oxygen scavenger, and a dispersant) are added to the boiler water and the water level is raised in the

idle boiler to eliminate air spaces. Nitrogen gas can also be used on airtight boilers to maintain positive pressure on the boiler, thereby preventing oxygen from entering. Dry boiler lay-up method is usually for longer boiler outages. The boiler is drained, cleaned and dried out. Material, such as hydrated lime or silica gel, which absorb moisture, is placed in trays inside the boiler. The boiler is then sealed to prevent air from entering. Periodic replacement of the drying chemical is required during long storage periods.