c. Absorbs dissolved oxygen and prevents CO2 pitting d. Prevents the formation of any kind of sludge e. Prevents erosion of the boiler metal . In order to prevent boiler oxygen corrosion, the boiler must control the dissolved oxygen content of the feed water during operation. There are two basic types of electric boilers: resistance and electrode. The tube side of a feedwater heater is treated in the same way the boiler is treated during storage. It is also used widely in condensate systems. The inner layer is relatively thick, compact, and continuous. Distribution ratios are not true physical constants but are a function of pressure (Figure 19-6) and pH. All monitoring data, whether spot sampling or continuous, should be recorded. Oxygen attack is an electrochemical process that can be described by the following reactions: Anode: The influence of temperature is particularly important in feedwater heaters and economizers. Increase in cost of maintenance and repairs. its pH, conductivity, the concentration and the composition of the dissolved salts . Oxygen is highly corrosive when present in hot water. pH should be maintained at 10.0. circulate the boiler water with an external pump, reduce the water level to the normal operating level and steam the boiler for a short time. 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. Boiler feedwater hardness, iron, copper, oxygen, and pH should be measured. Therefore, various combinations and feed rates of phosphate, blowdown adjustment, and caustic addition are used to maintain proper phosphate/pH levels. What is Boiler Corrosion? The second type of iron oxide in a boiler is the corrosion products, which may enter the boiler system with the feedwater. The metal failure occurs at the point of the highest concentration of cyclic stress. At 60F and atmospheric pressure, the solubility of oxygen in water is approximately 8 ppm. Some have stainless steel superheater elements. In general, whenever water and metals are in contact with each other in the presence of air and dissolved salts, corrosion will usually occur. Is oxygen responsible for boiler corrosion? The following practices help to minimize these corrosion problems: Where boiler tubes fail as a result of caustic embrittlement, circumferential cracking can be seen. Galvanic corrosion can occur at welds due to stresses in heat-affected zones or the use of different alloys in the welds. Much is flashed off with the steam; the remainder can attack boiler metal. Although "metal passivation" refers to the direct reaction of the compound with the metal oxide and "metal conditioning" more broadly refers to the promotion of a protective surface, the two terms are frequently used interchangeably. At a certain thickness of the outer layer, an equilibrium exists at which the oxide continually forms and is released into the water. Removal of the last traces of oxygen is accomplished by treating the water with a reducing agent that serves as an oxygen scavenger. Therefore, treatment must be increased gradually for old systems. Problems caused by iron and copper corrosion in condensate systems are not restricted to piping and equipment damage or to the loss of high-quality water and heat energy when condensate is lost. Particular care should be taken to purge water from long horizontal tubes, especially if they have bowed slightly. Corrosion leads to failure of machinery from inside also reduces over all boiler efficiency. In boilers, oxygen is introduced through the raw water supply. Leaking of rivets and joint areas. Most industrial boiler and feedwater systems are constructed of carbon steel. In this reaction a temperature rise provides enough additional . All manholes, handholes, vents, and connections are blanked and tightly closed. Even if the original makeup or feedwater pH is not low, feedwater can become acidic from contamination of the system. All organic chemicals exposed to a high-temperature, alkaline, aqueous environment eventually degrade to some degree. Immediately after surfaces are dried, one of the three following desiccants is spread on water-tight wood or corrosion-resistant trays: The trays are placed in each drum of a water tube boiler, or on the top flues of a fire-tube unit. Based upon the stoichiometric relationship, it should take about 13 parts of sodium erythorbate to react with one part of dissolved oxygen. Dissolved oxygen 2. . References Water treatment handbook Vol. EFFECT OF pH ON CORROSION OF IRON AND COPPER. As the oxide layer becomes thicker, the outer layers begin to slough off as particles of copper oxide. Sodium sulfite. CALL (414) 425-3339 Boiler Oxygen Corrosion Favorite this: There are few problems associated with steam generation equipment that are seen more often than oxygen corrosion. Copper alloy systems can be treated with half the amount of oxygen scavenger, with pH controlled to 9.5. Both copper and iron are oxidized in the presence of hydrogen ions and oxygen and can undergo oxygen pitting. 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). Answer (1 of 2): Boilers are made from steel plates and they are continuously are in contact with the water which acts as electrolyte. Hydroquinone. The presence of dissolved oxygen in boiler system is responsible for pitting corrosion. Oxygen corrosion in boiler feedwater systems can occur during start-up and shutdown and while the boiler system is on standby or in storage, if proper procedures are not followed. The dissociation constant Kb is a common measure of basicity. The electrochemical corrosion reaction for iron boiler metal surfaces is generally. Deaerator performance has to be maintained limiting dissolved oxygen to less than 0.01 ppm level. Like those of neutralizing amines, the steam/liquid distribution of each scavenger has a unique temperature dependence. Iron can enter the boiler as soluble ferrous ions and insoluble ferrous and ferric hydroxides or oxides. In practice, the best protection is provided by blended products containing a variety of amines with differing steam/liquid distributions. For example, if cyclohexylamine is used in a second condensate system with two consecutive condensation sites having acetic acid as a contaminant, most of the acetic acid goes into the liquid phase at the first condensation site, while most of the cyclohexylamine remains in the steam. Even small concentrations can cause serious problems. Deposits of rust in a plumbing system is such an example of differential aeration cells and accelerate corrosion. Research has shown that as little as 5 ppb to 10 ppb of dissolved oxygen significantly reduces the rate of . 3 Fe + 4 H2O -> Fe3O4 + 4H2. Where oxygen invades the condensate system, corrosion of iron and copper-bearing components can be overcome through proper pH control and the injection of an oxygen scavenger. At temperatures of 212F and above, the reaction is rapid. The most stable amines commonly used are morpholine and cyclohexylamine. The mechanical degasification is typically carried out with vacuum degasifiers that reduce oxygen levels to less than 0.5-1.0 mg/L or with deaerating heaters that reduce oxygen concentration to the range of 0.005-0.010 mg/L. Hydrazine efficiently eliminates the residual oxygen by reacting with the oxygen to give water and gaseous nitrogen. High-temperature hot water boilers operate at pressures of up to 500 psig, although the usual range is 35-350 psig. Stress cracking of welded components can also be a problem. Copper and Copper Alloys Many factors influence the corrosion rate of copper alloys: The impact of each of these factors varies depending on characteristics of each system. It is important to monitor the feedwater system for corrosion by means of iron and copper testing. Low boiler water alkalinity or exposure of the metal to water containing dissolved oxygen during operating or even non-operating period causes corrosion in the steam boiler. Actual lab and field test data show that much less erythorbate is actually needed than theoretical to scavenge the oxygen. The cost of boiler repairs due to corrosion can be in the order of $50,000 to over $1m, plus cost of time off hire. Boilers that are idle even for short time periods (e.g., weekends) are susceptible to attack. Iron oxides present in operating boilers can be classified into two major types. Dissolved oxygen is given, and temperature at various alloy levels for pH=9.05. Presence of corrosive gases such as Oxygen (O2), Carbon Dioxide (CO2), Hydrogen Sulphide (H2S) in the boiler water The most familiar form of oxygen attack in boilers and condensate systems is oxygen pitting. If levels are left unchecked, DO will destroy a boiler system. Figure 11-13 shows rate of reaction as a function of temperature and hydrazine concentration. A . In modern boiler systems, dissolved oxygen is handled by first mechanically removing most of the dissolved oxygen and then chemically scavenging the remainder. The dissolved oxygen content of water at 20 C is 9ppm, at 60 C is 5 ppm and at 90 C is just under 2 ppm. Usually, a slight excess of scavenger is fed. ammonia feed rates must be carefully controlled to minimize the attack of any copper-bearing alloys (Figure 19-4). The most important factor is temperature. Table 19-1. Corrosion in boilers is due to the following reasons (1) Dissolved oxygen : This is the most usual corrosion causing factor. When contaminants are present in the condensate, filming amines have a tendency to form deposits by reacting with multivalent ions, such as sulfate, hardness, and iron. Two types of corrosion can occur with oxygen present. Field trials in large utility boilers show the intermediate breakdown products to be lactic and glycolic acids. The most significant contributors to boiler waterside corrosion are dissolved oxygen, acid, or caustic in the water and high temperature. What are boiler corrosion causes ? Learn on the go with our new app. In these applications, the increased dissolved solids contributed by sodium sulfate (the product of the sodium sulfite-oxygen reaction) can become a significant problem. Generally, economizers are arranged for downward flow of gas and upward flow of water. A figure < 0.007 ppm is considered to be very ideal. Finally, as chromium and molybdenum increase, wear rate decreases. Erosion is common in the shell side, due to high-velocity steam impingement on tubes and baffles. In most cases, proper feedwater deaeration and elimination of air infiltration into the condensate substantially reduce oxygen corrosion. Chemical de-oxygenation by use of oxygen scavengers i.e. From a practical standpoint, it is necessary to establish a pH control range that provides the desired protection for the most critical system components. Where two-phase flow (steam and water) exists, failures due to erosion are caused by the impact of the fluid against a surface. Phosphate buffers the boiler water, reducing the chance of large pH changes due to the development of high caustic concentrations. Major factors that determine the best oxygen scavenger for a particular application include reaction speed, residence time in the system, operating temperature and pressure, and feedwater pH. The solubility of oxygen in water is reduced as the temperature of the water increases. Results have also shown that sharp corrosion fatigue and bulbous SAC cracks have similar mechanism but the morphology is different due to availability of oxygen during boiler shutdown conditions. Synthetic polymers have been used for deposit control. Oxygen pitting begins at weak points in the iron oxide film or at sites where the oxide film is damaged. Excess caustic combines with disodium phosphate and forms trisodium phosphate. Among the most commonly used compounds are hydroquinone and ascorbate. Sometimes, a 50/50 water and ethylene glycol mixture is used for freeze protection. Wet storage is usually suitable for shorter down-time periods or if the unit may be required to go on-line quickly. 5 lb of a 35% solution of hydrazine and 0.1 lb of ammonia or 2-3 lb of a 40% solution of neutralizing amine can be added per 1000 gal (minimum 200 ppm hydrazine and 10.0 pH). The most common source of corrosion in boiler systems is dissolved gas: oxygen, carbon dioxide and ammonia. Oxygen corrosion may be highly localized or may cover an extensive area. An amine that is more likely to distribute into the steam, such as cyclohexylamine, is a better choice for the system described above. Water usually contains about 8 ppm of dissolved oxygen at room temp. The second step is to form a protective layer on the inside surface of the tubes which protects the metal surface from any further corrosion attacks. Increasing blowdown lowers both phosphate and pH. Usually, the most suitable point of application is the drop leg between the deaerator and the storage compartment. The point of attack varies with boiler design and feedwater distribution. In determining product feed rates, recycle and recovery ratio are important factors. Distribution of Amines between Steam and Liquid. Caustic corrosion (gouging) occurs when caustic is concentrated and dissolves the protective magnetite (Fe3O4 ) layer. Common causes include the following: Acid corrosion can also be caused by chemical cleaning operations. In water, the predominant copper corrosion product is cuprous oxide (Cu2O). 0% average accuracy. The importance of eliminating oxygen as a source of pitting and iron deposition cannot be over-emphasized. The effect of temperature and pH of the condensation site must also be considered. The inhibition of embrittlement requires a definite ratio of nitrate to the caustic alkalinity present in the boiler water. Feedwater and boiler water residuals provide an indication of excess scavenger feed and verify chemical treatment feed rates. Another approach to controlling condensate system corrosion is the use of chemicals that form a protective film on metal surfaces (Figure 19-7). Proper precautions must be taken in sampling for metal oxides to ensure representative samples. The boiler water should be tested weekly with treatment added as necessary to maintain treatment levels. info@complete-water.com 855-787-4200. . When boilers are removed from the line for extended periods of time, fireside areas must also be protected against corrosion. The third step is to maintain this layer throughout the life of the plant. Off-line boiler corrosion is usually caused by oxygen in-leakage. Water acts as a cathode of any corrosion cell to depolarize, thereby sustaining the corrosion process. This method should not be used for boilers equipped with nondrainable superheaters. Edit. After 25 seconds of contact, catalyzed sodium sulfite removed the oxygen completely. The ASME Consensus for Industrial Boilers (see Chapter 13) specifies maximum levels of contaminants for corrosion and deposition control in boiler systems. In any event, pitting would not occur in this type of boiler if no oxygen were present in the water. Dissolved oxygen in boiler system water causes corrosion and pitting of metal surfaces, which can lead to boiler inefficiency, equipment failure, and system downtime. Many have copper alloy and/or stainless steel feedwater heaters and condensers. As long as the magnetite layers are left undisturbed, their growth rate rapidly diminishes. Practically all ground surface supplies of water contain dissolved air in quantities depending on its source, time of exposure and its temperature. Pits can penetrate deep into the metal that can result in rapid failure of feed lines, Ultimate failure of boiler metal, steam mains and condensate lines, Presence of corrosive gases such as Oxygen (O2), Carbon Dioxide (CO2), Hydrogen Sulphide (H2S) in the boiler water, Acidity imparted to water due to decomposition of Carbon Dioxide (CO2) or Hydrogen Sulphide (H2S). Soluble copper ions and particulate copper oxides are also formed by the normal oxidation processes. The overall reaction is: Low pH causes a generalized loss of metal rather than the localized pitting caused by oxygen corrosion. The pits vary in shape, but are characterized by sharp edges at the surface. Dissolved oxygen (DO) refers to the volume of oxygen that is contained in In low-flow areas of the condensate system, Fe(OH)2deposits near the oxidation site, forming a porous oxide layer. Oxygen corrosion may be highly localized or may cover an extensive area. Actual behavior involves some loss of amine additive and some recirculation of carbon dioxide. The deaerator storage system and the feedwater storage tank are commonly used feed points. Oxygen enters the water by photosynthesis of aquatic biota and by the transfer of oxygen across the air-water interface. Decomposition begins at approximately 400F and is rapid at 600F. Water acts as a cathode of any corrosion cell to depolarize, thereby sustaining the corrosion process. Following chemical cleaning with a water solution, the fireside should be dried by warm air or a small fire. Coordinated phosphate/pH control can be used to minimize the decrease in boiler water pH that results from condenser leakage. Hydroquinone reacts with dissolved oxygen as shown in the following reactions: Benzoquinone reacts further with oxygen to form polyquinones: These reactions are not reversible under the alkaline conditions found in boiler feedwater and condensate systems. Dissolved oxygen (DO) refers to the level of free, noncompound oxygen (O 2) dissolved in water or other liquids. The problem usually occurs only in units operating at or above 1,500 psi. In the absence of contaminants, this oxide layer greatly retards any further oxidation reactions. During the period of initial film formation, old, loosely adherent corrosion products are lifted off the metal surface due to the surfactant properties of the amine. Its dissolved oxygen attacks systems between the point of condensation and the deaerating heater. Based on experience in thousands of systems, 3-10 ppb of feedwater oxygen is not significantly damaging to economizers. 12th grade . Copy and Edit. . Magnetite forms on boiler system metal surfaces from the following overall reaction: The magnetite, which provides a protective barrier against further corrosion, consists of two layers. water. It is caused by excessive heat input or poor circulation, resulting in insufficient flow to cool the tubes. Regardless of feedwater heater design, the major problems are similar for all types. If the fireside is to be left open, the metal sur-faces must be maintained above the dew point by circulation of warm air. It is estimated that problems due to boiler system corrosion cost industry billions of dollars per year. In such cases, operational changes or design modifications may be necessary to eliminate the cause of the problem. For effective yet simple boiler storage, clean, warm, continuous blowdown can be distributed into a convenient bottom connection on an idle boiler. Advances have been made in formulating filming amine treatments. The stability of the passivating iron or copper oxide layer is critically dependent on condensate pH. Boilers can be protected with nitrogen or another inert gas. The behavior of amine bicarbonate in the deaerator affects amine requirements for the system. Deposits due to carryover can contribute to the problem.
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