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ISGEC John Thompson

SECTION-14 WATER CHEMISTRY

ISGEC John Thompson

SECTION - 14 CHEMICAL CONDITIONING OF FEED & BOILER WATER 14.1 GENERAL The treatment of water utilized in steam generating plant requires the oversight of a qualified chemist trained in this specialized work. Boiler design needs a close look at the limiting conditions like heat transfer, heat exchanger metal temperature, circulation etc. The entire exercise of water treatment (both internal and external treatments) is aimed at (1) corrosion control and (2) steam quality. The cost of corrosion and deposition to parts is very high due to repairs and loss of production (shutdowns). Poor steam quality leads to deposition on turbine blades causing efficiency loss and failures. Thus the successful operation of boilers and turbine units require a strict vigil on the Water treatment practices and controls. MAKE UP WATER TREATMENT Trouble free continuous operations of boiler call for very stringent feed water quality. Total solids and silica, other than corrosion products, being the main constituents are responsible for carry-over and deposition reducing the units efficiency. Make up water is required to be controlled and maintained at low levels. Silica in particular, is CARRIED OVER in the form of VAPOUR at high pressures, needs to be controlled at low levels. Feed water is used for desuperheating spray and any contamination of feed water (either from steam condensate or from make up water) directly enters the superheated steam. IMPURE FEED WATER increases BLOW DOWN making the operation un-economical. Hence feed water is required to be very pure for make up water. NOTE : As soon as the plant is commissioned for service, a routine for the treatment of raw water and the conditioning of boiler water must be established. BOILER WATER CHEMISTRY Water, occurring in nature, cannot be used for any industrial purpose, as such without treatment. But it can be treated in different ways, to suit the application. Hardness and similar hard deposit forming elements like silica in water are desirable to be removed for any application. For highpressure boilers, in addition to this, almost all impurities from Section # 14 Page 1 of 10

ISGEC John Thompson

water are to be removed, as high-pressure units are almost designed to their limits for economy and compactness of size and hence they can tolerate very little deposits and corrosion. Moreover, modern steam turbines need stringent steam purity for trouble free operation. Water is required to be demineralised for high-pressure units, to minimize problems in boilers due to deposits and corrosion and to maintain steam purity desirable for turbines.

INTERNAL CORROSION Internal corrosion of tubes is the major problem in boilers. If the water is acidic or vary alkaline, both are harmful. Boiler tubes are protected from corrosion, by the presence of the thin layer of iron oxide (magnetite) coating inside the tube. The magnetite itself is a product of corrosion, as given below, but once if it is formed, it will stop further corrosion. 3Fe + 4 H2O ------ Fe3 O4 + 4 H2 This protective coating will be dissolved, if the water is too acidic or alkaline. It has been established that water at a pH of 10.0 to 11.0 is least corrosive. All treatment practices are aimed to achieve this. ACIDIC CORROSION i) CO2 corrosion

The presence of CO2 can make the water acidic. There are plenty of chances for this contamination. Raw water contains large amounts of carbonates and bi-carbonates. This carbonate alkalinity of water, if it is not removed, will disassociate into CO2 at high temperature. Treated water, if it gets exposed to atmosphere, can absorb CO2. In a power plant, chances for such absorption exist in a storage tank, where treated make up water is stored. Condensers work under vacuum. At start up and low load conditions, L.P. heaters may also be under vacuum. If they are not air tight, there will be ingress of air into water. Feed water for pressure boilers should be completely free from CO2. To achieve this: a) The degasser of the demineralisation plant should be working well to ensure D.M. water, free of CO2. Section # 14 Page 2 of 10

ISGEC John Thompson

b) The vents of storage tanks should not be left open to atmosphere and they should be sealed. The sealing can be done by either soda-lime filters or by continuously flowing water seals. c) Chemicals like ammonia should be dozed into the feed water to raise the pH to about 9.0, to ensure that there is no CO2 present. Ammonia neutralises CO2 and then raises the pH. CO2 corrosion generally occurs in condensate and feed lines. The presence of iron in feed water is a measure of corrosion of the feed system. ii) Hydrogen damage: Hydrogen damage is another type of acidic corrosion. Water wall tubes of high-pressure units, using sea water for condenser cooling, are highly prone to this type of corrosion. Even small amounts of sea water leakage through condenser can cause this corrosion. The extent of corrosion will be severe and large portions of tubes will have to be replaced, if this type of attack takes place. There will be huge loss of availability of the units. Sea water contains large amounts of chlorides and sulphates of calcium and magnesium. These salts at high temperatures of boiler water hydrolyse to produce acids, as given below. The acids produced cause extensive corrosion. A gas (methane) is generated in the corrosion reaction, which penetrates into the metal and weakens it. The tube metal will become brittle and failures will take place. Mg Cl2 + H2O --------- Mg (OH)2 + HCl If this corrosion is to be prevented, condenser leakage should be avoided. There should be an on-line conductivity analyser to detect immediately any condenser leak. PO4 dosing should be increased during condenser leak to maintain excess residual. pH of drum water should never be allowed to fall below 8.0. There should be a constant watch on total solids concentration of boiler water which should be controlled within limits by increasing blow down to avoid carryover. There should be no hesitation to shut down the unit, if pH cannot be maintained above 8.0 to save the unit from extensive corrosion. ALKALINE CORROSION

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ISGEC John Thompson

Alkaline corrosion is mainly caused by caustic soda. Concentrated amounts of caustic soda eats away material. As caustic corrosion attack will look like welding gouging, this type of corrosion is known as caustic gouging. Water wall tubes are subjected to this corrosion, when caustic soda is used as a treatment chemical. It is recommended to use tri-sodium phosphate instead of caustic soda for boiler water treatment, to raise pH to the required level. Coordinated phosphate treatment recommended by us, prevents the presence of free caustic soda in boiler water and thus does not cause corrosion. Small amounts of caustic soda present in water are not harmful. But unfortunately, there are areas in boilers, for concentration of caustic to high values so as to cause corrosion. Under deposits in a dirty boiler, it can concentrate. The crown of roof and low sloped water wall tubes can be attacked due to segregation of steam and water flows, leading to concentration of this chemical. Heat transfer phenomenon in a water wall increases slightly the temperature of water close to the tube wall and this can largely increase concentration. It is not desirable to use caustic soda as a boiler water treatment chemical. It can be used in a limited way during condenser leak. Where it is used, it should be used in conjunction with tri-sodium or di-sodium phosphate to avoid the presence of free hydroxide, by satisfying the co-ordinated phosphate curve. OXYGEN CORROSION Oxygen is also another gas responsible to cause corrosion. The presence of O2 in water will cause pitting in tube internal surfaces. O2 present along with chlorides can also cause hydrogen damage. The principal sources of oxygen contamination are storage tanks and ingress of air into condensers and heaters, as in the case of CO2. Deaerator removes oxygen. Residual oxygen can be removed by hydrazine dozing. O2 in feed water should be maintained below 0.007 ppm. Any amount of hydrazine dozing will not reduce O2 to this limit, unless O2 is primarily removed by good dearation. The exclusion of oxygen in feed water is essential to avoid corrosion. Small quantities of dissolved oxygen are capable Section # 14 Page 4 of 10

ISGEC John Thompson

of causing severe corrosion pitting in boiler tubes. A combination of poor oxygen control and chlorides in boiler water can result in serious hydrogen damage type corrosion of water wall tubes. Power plants employee tight cycles to prevent oxygen infiltration and condenser leakage are generally free from corrosion problems. Continuous monitoring of oxygen is required in high pressure system. Too often, oxygen enters the system undetected during periods of operation, which are poorly monitored. Poor startup procedure is also responsible for oxygen ingress. A most common error is the use of undeaerated water. Feed water at a temperature less than 100 deg. C contains excessive quantities of dissolved oxygen and hence feed water should never be allowed into the boiler at any time below this temperature. Deaerator is the main equipment to control oxygen within 0.01 0.02 ppm. With the main oxygen removal by deaeration, residual oxygen in small quantities can be reduced further by reducing agents such as sodium sulphite or hydrazine. Hydrazine being a volatile chemical, should only be used for high pressure boilers. Hydrazine reacts with oxygen to from nitrogen and water. Hydrazine is decomposed rapidly to nitrogen, hydrogen and ammonia. Hence hydrazine dozing alone cannot control oxygen without effective deaeration. Since hydrazine has also the property of passiviting the metal surfaces of the pre-boiler cycle by reducing the oxidized from of iron and copper. , it is advantageous to add hydrazine to the cycle at the outlet of the condensate ATMOSPHERIC CORROSION Major oxygen corrosion occurs during idle periods of boilers. Boiler system without proper preservation during shutdown suffer major atmospheric corrosion, Corrosion of unprotected boiler system generates large amounts of oxides, which form deposits inside water wall tubes. These deposits are instrumental for severe acidic or caustic corrosion when there is contamination of water. CONTROL OF CORROSION a) Maintenance of pH of water in the desired range is required to control corrosion (for limits, refer our recommendations given in technical data sheet). b) O2 in feed water should be controlled within 0.007 ppm, primarily by good deaeration, supplemented by hydrazine dozing. Section # 14 Page 5 of 10

ISGEC John Thompson

c) Condenser leak should be immediately detected and acted upon. d) DM water storage tank should be properly sealed. e) Condensers & heaters should be air-tight. f) Proper wet lay-up of units during shut downs. MAKE-UP WATER QUALITY Make-up water for pressure boilers should be demineralised. Demineralisation removes almost all dissolved impurities. Conductivity is a measure of dissolved impurities in water. D.M. water should have conductivity less than 0.5 mmho/cm. Silica should be removed to less than 0.02 ppm. D.M.water will not contain any hardness. D.M. water is neutral with pH of 7.0 + 0.2. The boiler make-up should also be free from all suspended impurities, like organics, colloidal silica etc. Organics are not only harmful to boiler but also to the D.M.plant. The resins can be fouled by organics and the output and quality of treated water will suffer. With the complete removal of dissolved and suspended impurities, D.M.water is free from potential, for causing deposits in boiler tubes. Consistent quality of D.M.water depends on care and control during operation. Seasonal variations can take place in the composition of raw water. The turbidity of river water can increase very much during rainy season. Colloidal silica problems can become acute during some seasons. Unknown discharges and pollution ahead of the stream can alter the quality. All these are to be continuously watched and the water treatment plant, including the pre treatment section should be operated suitably. FEED WATER TREATMENT Feed water is treated for raising the pH and controlling residual oxygen. Ammonia is used for raising the pH. Ammonia also neutralises any CO2 present. Other amines like morpholine or cyclohexylamine are not preferred for this purpose for high pressure boilers, as they decompose at high temperatures into ammonia and by the use of these chemicals, ammonia concentration will increase in feed water. Excess ammonia present in feed water is corrosive to copper Section # 14 Page 6 of 10

ISGEC John Thompson

alloy materials used in condensers, L.P. heaters etc., desirable to maintain ammonia less than 1.0 ppm in water. Ammonia less than 0.5 ppm can raise pH of water to the desired level of 9.0, if there is no contamination of feed water.

It is feed feed CO2

Hydrazine is dozed for scavenging O2. As hydrazine is slow acting, unless dissolved O2 is already removed by good deaeration to less than 0.01 ppm, residual O2 cannot be controlled within 0.005 0.007 ppm by hydrazine dosing alone. Normally ammonia and hydrazine are doses at feed pump section. It is more desirable to doze hydrazine at condensate extraction pump outlet as hydrazine has the property of passivating copper surfaces of condensers and heaters. But ammonia dosing should be more carefully done at this point. BOILER WATER TREATMENT Tri-sodium phosphate is generally used for boiler water treatment. Tri-sodium phosphate is preferred over the other chemicals, as it is safer to use Tri-sodium phosphate. Trisodium phosphate is also a useful chemical during condenser leakage. Condenser leak brings in hardness and hardness is turned into a sludge, Trisodium phosphate help in not allowing it to form hard deposits. Sludge is easily removed by blowdown. Boiler feed water, Boiler drum water parameters are to be strictly maintained in limits for longer life of pressure parts and trouble free operation. Recommended values are given in technical data sheet in section 1. Effect of pH The reaction of feed water on steel is spontaneous and rapid at high temperature. The only reason that boiler steel can survive normal operating conditions is that the passivated layer of magnetite / hydrated iron oxide forms a protective layer on the steel surface preventing corrosion. The whole exercise of maintaining alkalinity control is to maintain an environment in which the oxide film is stable and protective. One of the objectives of Water Treatment in boiler is to protect this film against the aggressive of impurities introduced into the boiler with the feed water.

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ISGEC John Thompson

It was found that the protective layer is getting dissolved at pH values below 5.0 and above 13.0 Minimum corrosion is indicated at pH of 9.0 to 11.0 Although corrosion is low over a wide band of pH values, unfortunately, corrosion occurs by localized concentration of alkaline chemicals on tube metal due to starvation, localized over heating etc. Rather than the concentrations existing in the bulk boiler water. Local concentration changes the pH drastically and corrosion takes place. Due to limitations of chemicals used, an optimum pH of 8.8 to 9.2 is recommended for feed water, which can be achieved by use of not more than 0.5 ppm of ammonia. Any excess presence of ammonia (indicated by higher pH values) will cause copper corrosion in the pre-boiler system. Another parameter, which affects rate, is the temperature inside the reaction vessel. Hence different temperature ranges or the pressure ranges call for different pH values to be maintained in order to minimize corrosion. Accordingly boiler water pH requirements are higher than the feed water limits and different pressure ranges. Boiler water pH is elevated to the recommended levels using Trisodium phosphate. The use of caustic soda is not recommended for this purpose as it has the danger of concentration and destruction of protective oxide film to cause corrosion. 14.2 WATER LOSSES Economical operation of the boiler plant requires maintaining water losses to a minimum. Certain losses are unavoidable i.e. a) Steam used in condensate. process work and not received as

b) Steam vented through superheater drain valves during pressure raising. c) Steam used in warming through pipe lines. d) Water blown down either as routine or in emergency. e) Water may also be lost in other preventable, such as , i) ii) Section # 14 ways which are

Leaking valve glands and pipe joints. Leaking feed pumps glands . Page 8 of 10

ISGEC John Thompson

iii) iv) v)

Valves not shutting off effectively. Leaking safety valves/vent valves. Leaking steam traps.

These losses should be looked out for and kept to an absolute minimum. Any loss detected, which cannot be immediately rectified, must be reported and logged for attention to the next maintenance period. Other wastage may be incurred by inefficient operation of the boiler, which may result in the water level becoming too high, necessitating a wasteful blowdown to reduce it to normal. This is most likely to occur when initially filling the boiler on start-up or addition of water at shut-down to compensate for shrinkage. Experience gained with operating the plant will enable a routine to be established which will reduce these avoidable loses and increase running economy. 14.3 BLOWING DOWN The object of blowing down a boiler is to maintain the concentration of dissolved and suspended solids within the specified limits to avoid priming and carry over. Except in emergency the frequency and duration of blowing down must be to the instructions of a chemist or other responsible persons, and will be based on the prevailing conditions, and experience gained in using the plant. Blowing down to control the condition of the boiler water must ALWAYS be from the steam drum and NEVER from the water wall manifolds. If a chemist or other responsible persons considers it necessary to blowdown the manifolds for any reason this must be done ONLY during a low load period and then ONLY for a period of 5-10 seconds. Normally the only reason to blow down a manifold would be to remove precipitated sludge, which may be formed by the addition of Trisodium Phosphate in the water to remove hardness. 14.4 PRECAUTIONS WHEN BLOWING DOWN

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ISGEC John Thompson

The duration of any blow down must be kept to an absolute minimum since it interferes with boiler circulation. Positive circulation MUST be maintained at all times in a heat exchanger of this type if overheating and subsequent damage to heating elements is to be avoided. Steam drum water level must be closely monitored during any blowing down operation and maintained as nearly as possible normal. When opening blowdown or drain valves to admit steam or hot water into relatively cold pipelines, open slowly so as to avoid sudden shocks or water hammering which may cause serious damage. 14.5 CARRY OVER This is a general term, which embraces all types of steam contamination, which occurs when there is inadequate separation of steam and water in the steam drum. Under normal steaming conditions the amount of carry over may be neglible, but may become excessive under conditions where priming occurs i.e., the sudden surging which causes large volumes of water to become mixed with steam. Factors affecting carry over are:a) The concentration and condition dissolved solids in the boiler water. b) Water level above normal. c) Rapid changes of water level. d) Fluctuating load e) Leaking internal baffle seals. f) Foaming. Foaming is responsible for the majority of carry over problems in boilers and is usually the result of too high a concentration of solids in the boiler water. 14.6 CONTINUOUS BLOWDOWN This is operated in order to regulate and maintain the boiler water concentration at a constant level. of suspended and

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ISGEC John Thompson

The percentage of blowdown should be controlled to a minimum necessary to achieve this. Excessive blowdown will serve only to dissipate the chemical constituents of the boiler water to less than the required value. This in turn will require the introduction of more chemical than is strictly necessary. 14.7 INTERMITTENT BLOWDOWN This is resorted to only when the water analysis shows it to be necessary, or when an immediate change in Boiler total dissolved solids concentration is required, and then too only on the instructions of a chemist or a responsible person.

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