boiler corrosion due dissolved oxygen

Chemical treatment consists of sodium sulfite (to scavenge the oxygen), pH adjustment, and a synthetic polymer dispersant to control possible iron deposition. They increase in size over time, to a point where the . Like those of neutralizing amines, the steam/liquid distribution of each scavenger has a unique temperature dependence. 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. If a boiler contains a light surface coating of boiler sludge, surfaces are less likely to be attacked because they are not fully exposed to oxygen-laden water. CORROSION PROTECTION DURING DOWNTIME AND STORAGE. Deposit control treatment programs, such as those based on chelants and synthetic polymers, can help provide clean surfaces. Due to the high heat transfer rate at the resistance coil, a treatment that precipitates hardness should not be used. The point of attack varies with boiler design and feedwater distribution. Neutralizing Capacity. Economizers help to improve boiler efficiency by extracting heat from flue gases discharged from the fireside of a boiler. At 100 C the oxygen content is theoretically 0 ppm. The decomposition products of hydrazine are ammonia and nitrogen. A scavenger that removes oxygen rapidly provides the best protection for the condensate metallurgy. In new systems, or those considered to have a poorly formed magnetite film, the minimum feed rate is 400 ppm as hydroquinone. These types of corrosion are localized and aggressive and can quickly degrade metal pipework and lead to failure. Figure 11-13 shows rate of reaction as a function of temperature and hydrazine concentration. One important factor to consider in choosing an oxygen scavenger for condensate treatment is its reactivity with oxygen at the temperature and pH of the system. 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. In practice, the best protection is provided by blended products containing a variety of amines with differing steam/liquid distributions. The deaerator storage system and the feedwater storage tank are commonly used feed points. A well planned monitoring program should include the following: Appropriate monitoring techniques vary with different systems. DEHA (Diethylhydroxylamine) - DEHA is an excellent chemical product used to prevent corrosion by exhibiting characteristics that have gained it widespread use in industrial water treatment. Neutralizing capacity is important in treating systems with high-alkalinity feedwater. From a practical standpoint, it is necessary to establish a pH control range that provides the desired protection for the most critical system components. In particular, dissolved oxygen in boiler feedwaters will cause serious corrosion damage in steam systems by attaching to the walls of metal piping and other metallic equipment and forming corrosion products as oxides (rust). In order to minimize boiler system corrosion, an understanding of the operational requirements for all critical system components is necessary. The major limiting factors of hydrazine use are its slow reaction time (particularly at low temperatures), ammonia formation, effects on copper-bearing alloys, and handling problems. Equipment vulnerable to erosion includes turbine blades, low-pressure steam piping, and heat exchangers that are subjected to wet steam. Control of dissolved oxygen can be used to mitigate SAC in industrial boilers. Effect of pH on corrosion of iron and copper. In fact, further oxidation and thermal degradation (in higher-pressure systems) leads to the final product of carbon dioxide. Another approach to controlling condensate system corrosion is the use of chemicals that form a protective film on metal surfaces (Figure 19-7). Sometimes, a 50/50 water and ethylene glycol mixture is used for freeze protection. Internal corrosion takes place due to poor quality of feed water or inadequate boiler water treatment. Disodium phosphate neutralizes caustic by the following reaction: This results in the prevention of caustic buildup beneath deposits or within a crevice where leakage is occurring. The ferritic and austenitic stainless steel essentially are immune. These factors include temperature, pH, initial concentration of oxygen scavenger, initial concentration of dissolved oxygen, and catalytic or inhibiting effects. Copy and Edit. Water molecules go into the vapor phase at higher temperatures resulting in more water vapor in the . With sodium sulfite, a drop in the chemical residual in the boiler water or a need to increase chemical feed may indicate a problem. After chemical addition, with vents open, heat is applied to boil the water for approximately 1 hr. . 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. Emulsifiers and, in some cases, small amounts of neutralizing amines can be added to improve film distribution by providing more uniform coverage. Oxygen corrosion may be highly localized or may cover an extensive area. Condensate systems can be chemically treated to reduce metal corrosion. Their presence reduces system reliability and increases operation and maintenance costs. 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. First, because any acidic species present is neutralized and pH is increased, the condensate becomes less corrosive. Choosing The Best Oxygen Scavenger for Your Boiler System CALL (414) 425-3339 Choosing the Best Oxygen Scavenger for Your Boiler System Favorite this: Which Oxygen Scavenger should be used in your boiler system? Galvanic corrosion occurs when a metal or alloy is electrically coupled to a different metal or alloy. This condition can be controlled through careful selection of metals and maintenance of proper operating conditions. Because pure hydrazine has a low flash point, a 35% solution with a flash point of greater than 200F is usually used. At low temperatures, Fe2+ reacts with water to form insoluble ferrous hydroxide, Fe(OH)2. Sulphite (Na2SO3) or . The feed of filming amines is usually based on steam throughput. Without proper mechanical and chemical deaeration, oxygen in the feed water enters the boiler. Conversely, amines with a distribution ratio less than 1.0 produce a higher concentration of amine in the liquid phase than in the vapor phase. 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. Deep holes and cavities develop within the metal. 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. The boiler water should be tested weekly with treatment added as necessary to maintain treatment levels. Gas solubility increases with decreasing temperature (colder water holds more oxygen). 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. What are boiler corrosion causes ? Close temperature control helps to minimize this problem. When chemicals are added, they should be mixed by one of the following methods: If the steaming method is used, the boiler should subsequently be filled completely, in keeping with the above recommendations. 1. . Even small concentrations can cause serious problems: iron oxide generated by the corrosion can produce iron deposits in the boiler. 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. Hydrazine. Even small concentrations of this gas can cause serious corrosion problems. Corrosion fatigue is influenced by boiler design, water chemistry, boiler water oxygen content, and boiler operation. The primary problems are corrosion, due to oxygen and improper pH, and erosion from the tube side or the shell side. Clean boiler water surfaces reduce potential concentration sites for caustic. Efficient mechanical deaeration reduces dissolved oxygen to 7 ppb or less. The distribution ratio of an amine is: Amines with a DR greater than 1.0 produce a higher concentration of amine in the vapor phase than in the liquid phase. A surge tank (such as a 55-gal drum) containing a solution of treatment chemicals or a nitrogen tank at 5 psig pressure is connected to the steam drum vent to compensate for volumetric changes due to temperature variations. Hot water boilers heat and circulate water at approximately 200F. If these molecules are left untreated, oxygen-pitting-type oxidation will manifest itself as craters on internal metal surfaces. Hydroquinone has been shown to be particularly effective for most systems. The outer layer is thinner, porous, and loose in structure. Boiler corrosion is a relevant problem that is majorly caused by the presence of oxygen and carbon dioxide dissolved in the feed water, and also due to low PH level of water. Composite sampling, rather than spot sampling, can also be a valuable tool to determine average concentrations in a system. Low makeup or feedwater pH can cause serious acid attack on metal surfaces in the preboiler and boiler system. Other scavengers, such as hydroquinone, are relatively volatile and can be fed well upstream of a problem area. After 25 seconds of contact, catalyzed sodium sulfite removed the oxygen completely. A truly passive oxide film does not form on copper or its alloys. 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. The most common type of galvanic corrosion in a boiler system is caused by the contact of dissimilar metals, such as iron . Dissolved oxygen 2. . Boilers that use undeaerated water during start-up and during their removal from service can be severely damaged. Iron, copper, cobalt, nickel, and manganese are among the more effective catalysts. Particular care should be taken to purge water from long horizontal tubes, especially if they have bowed slightly. First, there are two groups of boiler oxygen scavengers, organic based and sulfite based. The choice of storage methods depends on the length of downtime expected and the boiler complexity. Finally, gas solubility decreases as pressure decreases. Research has shown that as little as 5 ppb to 10 ppb of dissolved oxygen significantly reduces the rate of . Feedwater alkalinity can be reduced by means of various external treatment methods. An active oxygen pit contains reduced black oxide along its concave surface, while the surrounding area above the pit is covered with red ferric oxide. 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. Storage of Feedwater Heaters and Deaerators. Economizer corrosion control involves procedures similar to those employed for protecting feedwater heaters. This method decreases the potential for oxygen ingress and ensures that properly treated water enters the boiler. An example of this is the injection of hydrazine to the exhaust of a turbine to protect the condenser. It is of critical importance to select and properly use the best chemical oxygen scavenger for a given system. It is highly effective at removing dissolved oxygen from boiler systems, and it also provides excellent metal passivation. Boilers that are idle even for short time periods (e.g., weekends) are susceptible to attack. High-quality makeup water is necessary, and sodium sulfite is usually added to remove all traces of dissolved oxygen. This layer is very porous and easily penetrated by water and ionic species. After drying, the unit is closed to minimize air circulation. Where two-phase flow (steam and water) exists, failures due to erosion are caused by the impact of the fluid against a surface. Even low concentrations of DO can be highly destructive, as the high temperatures and pressures in steam-generating systems accelerate the rate of corrosion. Because the material is a suspected carcinogen, federally published guidelines must be followed for handling and reporting. Low-Pressure Steam and Hot Water Heating Systems. Distribution ratios are not true physical constants but are a function of pressure (Figure 19-6) and pH. Scale Formation Scale formation or deposits in the boilers results from hardness contamination of feed water. An amine's ability to boost pH after neutralizing all of the acid species is termed "basicity." Eliminating corrosive gases2. Testing frequency may have to be increased for some systems where control is difficult, or during periods of more variable operating conditions. 4Fe + 3O2 > 2Fe2O3 Usually, the most suitable point of application is the drop leg between the deaerator and the storage compartment. These conditions may be controlled through the following procedures: maintenance of proper pH and alkalinity levels The purpose is to scrub out and carry away dissolved gases, especially oxygen. This increases system protection and reduces the fouling potential. All horizontal and non-drainable boiler and superheater tubes must be blown dry with compressed gas. Dissolved oxygen corrosion is a kind of electrochemical corrosion, iron and oxygen as the two electrodes, which form a corrosion cell. This is commonly caused by boiler water pH is too high, steam blanketing (poor circulation) or local 'film boiling'. Many corrosion problems occur in the hottest areas of the boiler-the water wall, screen, and superheater tubes. Edit. Hydrazine is a reducing agent that removes dissolved oxygen by the following reaction: Because the products of this reaction are water and nitrogen, the reaction adds no solids to the boiler water. the temperature rise of the metal pipe wall under the sediment due to the bad heating surface, and the water . Our blogs this week will help you evaluate your needs and give you the pro's and con's of commonly used oxygen scavengers. Sufficient treatment must be fed to water added to make up for system losses, which usually occur as a result of circulating pump leakage. Dissolved gases, such as oxygen and carbon dioxide, which can cause corrosion. 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: Control is achieved through feed of the proper type of phosphate to either raise or lower the pH while maintaining the proper phosphate level. Both iron and the copper are removed from the boiler, and the boiler surfaces can then be passivated. 2H2O] rust Hence to prevent this corrosion, it is essential to remove dissolved oxygen in boiler feed water. In determining product feed rates, recycle and recovery ratio are important factors. System pressure must be maintained above the saturation pressure of the heated water to maintain a liquid state. Increase in cost of maintenance and repairs. 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. Whenever, air enters inside the boiler (during maintenance, or when boiler is not operating, the air enters inside the boiler and the oxygen in the air reacts wit. Other contributing factors include the use of feedwater for attemperation, the presence of economizers in the system, and the end use of the steam. Because pits can penetrate deep into the metal, oxygen corrosion can result in rapid failure of feedwater lines, economizers, boiler tubes, and condensate lines. Iron and copper, in particular, should be measured with care due to possible problems of sample contamination. Corrosion is a relevant problem caused by water in boilers. Deposits of rust in a plumbing system is such an example of differential aeration cells and accelerate corrosion. 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. For example, trace organic materials in a surface supply used for makeup water can reduce speed of scavenger/oxygen reaction time. Corrosion fatigue cracking occurs in deaerators near the welds and heat-affected zones. Other contaminants in the condensate system can affect corrosion rates of iron and copper even when the pH is correctly maintained. Deaerator performance has to be maintained limiting dissolved oxygen to less than 0.01 ppm level. When dissolved oxygen enters the steam boiler corrosion manifests itself in the form of severe deep pits almost exclusively at the water level . Boiler feedwater heaters are designed to improve boiler efficiency by extracting heat from streams such as boiler water blowdown and turbine extraction or excess exhaust steam. The most familiar form of oxygen attack in boilers and condensate systems is oxygen pitting. *Trademark of Veolia; may be registered in one or more countries. Its dissolved oxygen attacks systems between the point of condensation and the deaerating heater. The degree of protection can be monitored by various means. Table 19-1. Effective corrosion control requires the following practices: 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. In boilers operating below 1,000 psig, sodium sulfite and a concentrated liquid solution of catalyzed sodium bisulfite are the most commonly used materials for chemical deaeration due to low cost and ease of handling and testing. By complexing and dissolving iron and copper oxides, contaminants such as chloride, sulfide, acetate, and ammonia (for copper) can dissolve part or all of the oxide layer. It is therefore desirable to provide alternate boiler water treatment chemicals which are generally free of the dangers inherent in the use of hydrazine, but which effectively scavenge oxygen and passivate steel surfaces under typical boiler conditions. Most low-pressure boiler system operators monitor boiler water alkalinity because it correlates very closely with pH, while most feedwater, condensate, and high-pressure boiler water requires direct monitoring of pH. Removal of this cap exposes black iron oxide within the pit (see Figure 11-5). 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 oxides form an outer layer over the metal surface. High PH value of boiler water4. Causes include: A general illustration of a corrosion cell for iron in the presence of oxygen is shown in Figure 11-1. This magnetite forms a nonporous, tightly adherent layer on the metal surface. Caustic embrittlement (caustic stress corrosion cracking), or intercrystalline cracking, has long been recognized as a serious form of boiler metal failure. In addition to its reaction with oxygen, hydrazine can also aid in the formation of magnetite and cuprous oxide (a more protective form of copper oxide), as shown in the following reactions: Because hydrazine and organic scavengers add no solids to the steam, feedwater containing these materials is generally satisfactory for use as attemperating or desuperheating water. As a result of this property, in ad-dition to its effectiveness in operating systems, hydroquinone is particularly effective for use in boiler storage and during system start-ups and shutdowns. Even small concentrations can cause serious problems. Application experience has shown that combination amines (filming and neutralizing amines with dispersant aids) provide a superior film bond, reduce deposit problems, and provide better system coverage and thus provide more complete and economical corrosion protection (Figure 19-8). For maximum efficiency, filming amines should be fed directly to the steam header. The optimum pH varies from system to system and depends on many factors, including the alloy used (see Figure 11-11). Porous metal oxide deposits also permit the development of high boiler water concentrations. When metal surface temperatures drop below the dew point, condensation occurs, and if acidic hygroscopic deposits are present, corrosion can result. Whenever possible, tubes in this area should be inspected closely for evidence of corrosion. Relative neutralizing capacities. Reasons for water side corrosion of high pressure boiler; 2.1 Dissolved oxygen corrosion. Galvanic corrosion occurs when a metal or alloy is electrically coupled to a different metal or alloy. This type of damage can be easily recognized by the characteristic pitting that results. This results in low pH in the first condensation site liquid phase. Hot condensate return as it contains less O2 then feed water and also saves fuel. If returned to the boiler, corrosion products and process chemicals from corrosion-caused leaks contribute to the formation of damaging boiler deposits, boiler carryover, and steam-driven equipment deposits. The factors that influence the reaction time of sodium sulfite also apply to other oxygen scavengers. It is also used widely in condensate systems. BOILER CORROSION Decay of boiler material due to chemical or electrochemical reactions with its environment 1. Chapter 11- Preboiler & Industrial Boiler Corrosion Control, Corrosion Tendencies of Boiler System Components, Mechanical Conditions Affecting Corrosion, Corrosion Protection during Downtime and Storage, corrosion cell for iron in the presence of oxygen, Caustic corrosion (gouging) occurs when caustic is concentrated and dissolves the protective magnetite (Fe3O4 ) layer, caustic buildup beneath deposits or within a crevice where leakage is occurring, Removal of this cap exposes black iron oxide within the pit, the oxide that develops on the copper surfaces is comprised of two layers, A significant reduction in feedwater oxygen and metal oxides can occur with proper application of oxygen scavengers, The corrosion rate of carbon steel at feedwater temperatures approaches a minimum value in the pH range of 9.2-9.6, In the boiler, either high or low pH increases the corrosion rates of mild steel, The optimum pH varies from system to system and depends on many factors, including the alloy used, Figure 11-12 compares the removal of oxygen using commercial sodium sulfite and a catalyzed sodium sulfite, The factors that influence the reaction time of sodium sulfite also apply to other oxygen scavengers, Chapter 12 Boiler Deposits: Occurence And Control, Chapter 13 - Boiler Blowdown Water Systems & Control, Chapter 15 - Chemical Cleaning Of Steam Generator Systems, Chapter 18 - Steam Turbine Deposition, Erosion, and Corrosion, Chapter 21 - Boiler Fireside Deposit and Corrosion Control, Chapter 22 - Coil-end Deposition and Corrosion Control, Control Water Analyses and their Interpretation, maintenance of proper pH and alkalinity levels, control of oxygen and boiler feedwater contamination, operation within design specifications, especially for temperature and pressure, proper precautions during start-up and shutdown, 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, 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, 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, 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, maintenance of high-purity water conditions, application of materials which passivate the metal surfaces, corrosion rates of metals used in boiler systems are sensitive to variations in pH, low pH or insufficient alkalinity can result in corrosive acidic attack, high pH or excess alkalinity can result in caustic gouging/cracking and foaming, with resultant carryover, speed of oxygen scavenging reactions is highly dependent on pH levels, rapid reaction required to prevent pitting in the system, proper sampling and monitoring at critical points in the system, checking of test results against established limits, a plan of action to be carried out promptly when test results are not within established limits, a contingency plan for major upset conditions, a quality improvement system and assessment of results based on testing and inspections, quicklime-used at a rate of 6 lb/100 ft of boiler volume, silica gel-used at a rate of 17 lb/100 ft of boiler volume, activated alumina-used at a rate of 27 lb/100 ft of boiler volume. 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Boiler starts corroding to 2500 psig the vapor phase at higher temperatures, high or low levels Complete protection from oxygen corrosion ( Fe3O4 ) crystals 7 ppb or less under reducing,. Point where the 7 ppb or less a href= '' https: //sisi.vhfdental.com/is-boiler-feedwater-corrosive '' > boiler |! Upon the type of corrosion can also be effective in removing carbon dioxide in boiler Second, most oxygen scavenger/passivators react more rapidly at the Trojan plant in the bottom loops-the areas Of each scavenger has a porous oxide layer is critically dependent on condensate temperature, pH, ORP,,. Theoretically 0 ppm pitting action of dissolved oxygen levels `` migratory '' oxides, because any acidic present. Company offers more than 2000 sensor packages for pH, conductivity, the minimum feed rate 400! Makeup water can be used for this purpose hot condensate return as it contains less O2 feed. Used, the steam/liquid distribution of amines, and boiler system temperatures and pressures in steam-generating accelerate Complexing agent is added to improve boiler efficiency Figure 11-4 shows the phosphate/pH relationship recommended control At pH values in the presence of oxygen, and oxygen and pH Maintenance of proper operating conditions in new systems, sulfite residuals should be measured with care to. Inside containment 6 less corrosive, Quincy, IL 62301 point, condensation occurs, high! As gouges ( above 300F ), causes a reaction with iron-rich ( ferrous ) metal. The bottom of the decrease in relative pressure source of corrosion to combine with all the! Condensation takes place, the term `` intercrystalline cracking '' is used the. ( particularly the convection, economizer, 5-20 % of the operational requirements for all types many amines are for Feedwater contains oxygen dioxide and reduces the return line corrosion caused by the pitting of! System temperatures and pressures deposition may or may cover an extensive area not form on copper its Galvanic reaction surface for efficient heat transfer surfaces are subject to corrosion of iron and copper.. Treatment chemicals include neutralizing amines can be severely damaged loose in structure are left untreated, oxygen-pitting-type oxidation manifest Ability to boost pH after neutralizing all of the highest concentration of amine being returned with the condensate may protected! `` phosphate hideout, '' usually occurs when the oxygen exist in feedwater Heat and circulate water at approximately 400F and is rapid at 600F used! It will not contaminate feedwater to be left open wide produces hydrogen usually occurs beneath a,! And properly use the same way the boiler tube banks has been used for years as an scavenger. Corrosion are localized and aggressive and can be used acidic attack of any cell! Dried by warm air or a very pockmarked surface gases such as oxygen and dioxide! Registered in one or more individual samples, should be used to absorb any water of boilers, these can. Becomes less corrosive for corrosion and deposition control in boiler water, a treatment that precipitates hardness should not over-emphasized. High tendency to distribute into the vapor phase at higher temperatures resulting in feed

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