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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.
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.
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.
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.
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.
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.
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.
The selection and control of chemicals for preventing corrosion requires an understanding of the causes and corrective measures.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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
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.
removal. Sodium sulfite and hydrazine chemicals are commonly used for this purpose. Catalysts are sometimes also used to speed up the reaction.
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.