BOILER WATER TREATMENT

Introduction
A boiler in basic terms is nothing more than a container in which heat can be transferred from one media through the walls of the container to water. Because thermal energy transport is directly related to cross-sectional area, boilers are designed to contain the maximum amount of surface area to volume ratio which will enable structural rigidity and reasonably controllable operation. With the ever increasing cost of materials and fuel, design engineers are continuously challenged to produce higher efficiency boilers and optimize the materials of construction whilst maintaining structural rigidity. This trend in turn challenges the Water Treatment Company to provide chemical treatment programs and technical back up service which will allow the boiler plant to operate at maximum efficiency while ensuring extended equipment operating life. Why water treatment so important? Water treatment goes beyond keeping steel looking new. Water contains all sorts of additional things that we don't see when it comes out of our taps. Water can contain: nitrates, nitrites, calcium, iron, and a lot of other things that we never see. Many of the "invisible" additives of water become visible in your home- maybe you can see rust in your bathtub from iron deposits, or maybe your dishwasher or hot water heater becomes clogged with calcium from hard water lime scale. All of things that you can see happen in your home from your water also happen to your boiler from your water...you just can't see them as easily until a problem develops. When you heat the water in your stove it can cause lime scale buildup in the bottom of the boiler. This causes a condition called under deposit corrosion, where the steel begins to oxidize from under the lime deposit.

Water Impurities Impurities may be classified into three types: i. ii. iii. Dissolved solids. Dissolved gasses. Suspended solids

Pure water does not exist in nature and impurities vary widely. While one may consider rain water to be pure, before the water has reached the earth's surface it has absorbed pollutants, oxygen and carbon dioxide. Due to the high solvency of water, additional impurities are dissolved from the land surface. A few examples include: Calcium Carbonate (limestone) Magnesium Carbonate (dolomite) Calcium Sulphate (gypsum) Magnesium Sulphate (Epsom salts) Silica (sand) Sodium Chloride (common salt) Iron

If all waters carried the same impurities, treatment could zero in on a nearly standard programmed for each use. Boiler System Throughout the boiler system including the treatment of raw water to the steam condensate: Carifier Filter Softener Deaerator system, increasing the chemical steam boilers steam condensate

Figure 1: Boiler system Boiler Feedwater Boiler feedwater is water used to supply a boiler to generate steam or hot water. At thermal power stations the feedwater is usually stored, pre-heated and conditioned in a feedwater tank and forwarded into the boiler by a boiler feedwater pump.

External and Internal feed water treatment External treatment Treatment of water that is done outside of the boiler is called pre-boiler or external treatment. The main physical methods for improving quality of water for boiler include flocculation, clarification, deaeration, oil removal, color removal, suspended solids removal and blow down.

Internal treatment There are number of treatments that are made within the boiler to minimize the adverse effects of small concentration of components that remain in the feed water after the external treatment. Chemical treatment or internal treatment of water inside the boiler is essential to take care of various impurities entering into the boiler such as hardness, dissolved solids, oxygen, and silica.

Softener Water softening is the reduction of the concentration of calcium, magnesium, and certain other metal captions in hard water. These "hardness ions" can cause a variety of undesired effects including interfering with the action of soaps, the buildup of limescale, which can foul plumbing, and galvanic corrosion. Conventional water-softening appliances intended for household use depend on an ion-exchange resin in which hardness ions are exchanged for sodium ions. Water softening may be desirable where the source of water is hard. However, hard water also conveys some benefits to health by providing dietary calcium and magnesium and reducing the solubility of potentially toxic metal ions such as lead and copper. Methods for water softening: Water softening methods mainly rely on the removal of Ca2+ and Mg2+ from a solution or the sequestration of these ions. binding them to a molecule that removes their ability to form scale or interfere with soaps. Removal is achieved by ion exchange and by precipitation methods. Sequestration entails the addition of chemical compounds called sequestration (or chelating) agents.

Figure 2: Softener pH The water content of acid or alkaline. H20 for hydrogen ion, OH for hydroxyl ion. Acid pH 0-6, acidic pH 8-14 & the pH of 7 is normal. Acid or alkali will affect the rising conductivity of water.

Problem that usually happen in Boiler system 1- Corrosion Corrosion is the loss of metal as it oxidises back to the ore form, for example iron reverts to iron oxide. The corrosion mechanisms involved are extremely complex electrochemical reactions and as such will not be dealt with in this paper. Of importance, however, is that corrosion can be uniform over the metal surface or localised, resulting in deep pits in the metal. Pitting corrosion caused mainly by dissolved oxygen is severe and can result in premature replacement of boiler tubes, feedwater lines and condensate return lines. Corrosion can be experienced in four areas: Feedwater System: Operating Boilers: Caused by low pH, dissolved oxygen and carbon dioxide Caused by high or low alkalinity, dissolved oxygen and deposits in the boiler. The corrosion process is accelerated by high temperatures and stresses in the boiler. Corrosion of boilers during out of service periods can be severe when correct lay-up procedures are not followed. The major causes of corrosion are oxygen pitting and low alkalinity.

Standby Boilers:

Steam / Condensate System: Caused by carbon dioxide / carbonic acid, oxygen and process contaminants. The cost of corrosion is immense, resulting in production downtime and high costs for equipment replacement. A further problem associated with corrosion is the deposition of corrosion products (iron, copper) on the boiler tubes which results in increased fuel costs and further under deposit corrosion. The secret for preventing high corrosion rates in the boiler is through the formation and maintenance of a magnetite layer (Fe3O4) on the metal surface. The ability to use inexpensive carbon steel material for boiler construction, where the metal surface is in contact with water at high temperatures and pressures, is due to the reaction that takes place between iron an oxygen-free alkaline water to form magnetite. The maintenance of this corrosion resistant layer is the difference between success and failure. With this in mind, effective corrosion prevention can be achieved by: Removing dissolved oxygen from the feedwater Maintaining correct alkalinity levels in the boiler Keeping metal surfaces clean and deposit free Protecting boilers during standby periods Chemically treating corrosive gasses in the steam / condensate system.

2- Carryover Carryover describes the contamination of the steam with boiler water. It can be due to FOAMING when bubbles are formed on the surface and are carried out with the steam. High concentration of solids in the boiler water cause foaming, as well as soil and other contamination of the feed water. Carryover can also be due to PRIMING when slugs of boiler water are thrown over the steam. This is often caused by excessive steam demand or rapid increase in load. In severe cases of priming top tubes can be exposed and subject to overheating. The effects of carryover can be quite serious. The steam will be contaminated; water hammer may occur; slugs of boiler water can damage machinery; dissolved or suspended solids in the boiler water will deposit in the steam and condensate system. Prevention of carryover: Carryover can never be eliminated completely. Even the best boiler designs operating with well controlled water chemistry produce trace amounts (0.001-0.01 ppm total solids) of carryover. However, the primary consideration in the selection of a boiler and its operating conditions is the amount of carryover that can be tolerated. Whenever superheated steam is required for process use or turbines, steam purity as low as 10-30 ppb total solids may be necessary to prevent deposits. These limits apply to most industrial applications within a pressure range of 300-1500 psig, to ensure uninterrupted service of superheaters and turbines. Although boiler manufacturers do not ordinarily guarantee less than 0.03% carryover, purity levels well below this level are routinely achieved in many systems. To obtain the desired steam purity, both the boiler designer and the operator must carefully select system equipment and operating conditions. The methods used to achieve the required steam purity can be divided into mechanical and chemical means of carryover prevention.

Figure 3: Carryover in boiler tube

3- Deposition Common feedwater contaminants that can form boiler deposits include calcium, magnesium, iron, copper, aluminum, silica, and (to a lesser extent) silt and oil. Most deposits can be classified as one of two types Scale that crystallized directly onto tube surfaces. Sludge deposits that precipitated elsewhere and were transported to the metal surface by the flowing water

Scale is formed by salts that have limited solubility but are not totally insoluble in boiler water. These salts reach the deposit site in a soluble form and precipitate when concentrated by evaporation. The precipitates formed usually have a fairly homogeneous composition and crystal structure. High heat transfer rates cause high evaporation rates, which concentrate the remaining water in the area of evaporation. A number of different scale-forming compounds can precipitate from the concentrated water. The nature of the scale formed depends on the chemical composition of the concentrated water. Normal deposit constituents are calcium, magnesium, silica, aluminum, iron, and (in some cases) sodium.

Figure 4: Classifications of deposits

4- Scaling Boiler scale is caused by impurities being precipitated out of the water directly on heat transfer surfaces or by suspended matter in water settling out on the metal and becoming hard and adherent. Evaporation in a boiler causes impurities to concentrate. This interferes with heat transfers and may cause hot spots. Leading to local overheating. Scaling mechanism is the exceeding of the solubility limits of mineral substances due to elevated temperature and solids concentration at the tube/water interface. The deposition of crystalline precipitates on the walls of the boiler interferes with heat transfer and may cause hot spots, leading to local overheating. The less heat they conduct, the more dangerous they are. Common feed water contaminants that can form boiler deposits include calcium, magnesium, iron, aluminum, and silica. Scale is formed by salts that have limited solubility but are not totally insoluble in boiler water. These salts reach the deposit site in a soluble form and precipitate. Prevention of scaling: Always use a softener system on your make-up water. Chemicals should be used in conjunction with the softener. Chemicals are used as a polisher to remove the minimal calcium or otherwise referred to as hardness that has surpassed the softener. Perform daily hardness tests on the softener to ensure it is functioning properly. Perform daily hardness tests on the boiler water. Remember a water test is a snap shot of what is happening at that exact moment of time. There are a number of things that can go wrong causing the softener to malfunction between tests. Performing a test on the boiler water will provide a more general feedback on how the softener perform between tests. If you do have periodic hardness spikes on your boiler water test. Have the softener serviced or replaced. If you have a critical boiler system consider using a dual softener system. The dual system with two softeners in series, where the first softener is automatically regenerated and the second tank is manually regenerated once a month. This will greatly reduce the chance of boiler scale.

Figure 5: Scaling in boiler tube

Steam Quality Poor steam quality results from a combination of poor boiler water quality and poor boiler operation. The steam produced from the boiler should always be as dry as possible and contain minimal dissolved solids. Boiler water carryover results in poor quality steam and is caused through two problem areas: Foaming: Bubbles form on the boiler water surface and leave with the steam. Foaming is caused by high TDS, high suspended solids and contaminants such as oils, greases, fats and certain organics. Oil, in particular, can cause major problems due to the saponification process where it reacts with caustic in the boiler water to form soaps. Priming: This is a more severe form of carryover where a sudden surge of boiler water is drawn into the steam line. Priming can be caused by operating the boiler above its rating, sudden changes in steam demand and finally by operating the water level in the boiler too high.

Carryover results in dissolved solids entering the steam / condensate system and forming deposits. The deposits will have a negative effect on heat transfer and will increase corrosion in the system. Where live steam is used, carryover will result in process contamination and production losses food industry. Deaerator Oxygen is the main cause of corrosion in hotwell tanks, feedlines, feedpumps and boilers. If carbon dioxide is also present then the pH will be low, the water will tend to be acidic, and the rate of corrosion will be increased. Typically the corrosion is of the pitting type where, although the metal loss may not be great, deep penetration and perforation can occur in a short period. Elimination of the dissolved oxygen may be achieved by chemical or physical methods, but more usually by a combination of both. The essential requirements to reduce corrosion are to maintain the feedwater at a pH of not less than 8.5 to 9, the lowest level at which carbon dioxide is absent, and to remove all traces of oxygen. The return of condensate from the plant will have a significant impact on boiler feedwater treatment - condensate is hot and already chemically treated, consequently as more condensate is returned, less feedwater treatment is required. Water exposed to air can become saturated with oxygen, and the concentration will vary with temperature: the higher the temperature, the lower the oxygen content. The first step in feedwater treatment is to heat the water to drive off the oxygen. Typically a boiler feedtank should be operated at 85C to 90C. This leaves an oxygen content of around 2 mg / liter (ppm). Operation at higher temperatures than this at atmospheric pressure can be difficult due to the close proximity of saturation temperature and the probability of cavitation in the feedpump, unless the feedtank is installed at a very high level above the boiler feedpump.

The addition of an oxygen scavenging chemical (sodium sulphite, hydrazine or tannin) will remove the remaining oxygen and prevent corrosion.This is the normal treatment for industrial boiler plant in the UK. However, plants exist which, due to their size, special application or local standards, will need to either reduce or increase the amount of chemicals used. For plants that need to reduce the amount of chemical treatment, it is common practice to use a pressurised deaerator.

Figure 6: General arrangement of a pressure deaerator

Prevention of Problem Internal water treatment program The purpose of an internal water treatment program is: To react with incoming feedwater hardness and prevent it from precipitating on the boiler metal as scale To condition any suspended matter such as hardness sludge in the boiler and make it no adherent to the boiler metal To provide antifoam protection to permit a reasonable concentration of dissolved and suspended solids in the boiler water without foaming To eliminate oxygen from the feedwater To provide enough alkalinity to prevent boiler corrosion To prevent scaling and protect against corrosion in the steam-condensate systems.

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 equipment or processes. 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.

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.