rs oem p aD. lyadleep alae Se Cn . NTPC, NE WATER TECHNOLOGY FOR HIGH PRESSURE BOILERS 1) INTRODUCTION: ‘Water has been vital to man and nature since the beginning of time. Water technology as applied to steam generators is an interdiscipliniary professional field comprising of the elements of basic chemistry as well as chemical and mechanical engineering, Developments in the field of raw water treatment technology” to produce ultrapure water ( conductivity of 0.1 microsiemens/ em and 0.01 ppm silica ) and conditioning methodologies of feedwater and boiler water have made possible the use of more efficient steam cycles in very high pressure ranges. In spite of technological advancements , deposition of contaminants and corrosion of boiler metal are the prime cause of many forced outages of boilers through water wall tube failures. Material damage , lost power generation and product output , eventually etid up in huge financial losses to utilities and industries IL) WATER TREATMENT OBJECTIVES : The three main objectives of water treatment are to : ‘* Prevent formation of deposits + Reduce corrosion of metals * Prevent boiler water carryover Ill) PRE- COMMISIONING ‘FUNCTIONS : Before anew unit is put into service ; the internal surfaces of the heat exchanger tubes are chemically cleaned to remove oil, grease , siliceous materials , mill scale , rust , and other debris. The condensate and feedwater systems are mechanically cleaned and then given an alkaline flush. The economizer and boiler are given an alkali boilout followed by &n acid cleaning. Finally a very thin coating of protective magnetite layer ( FesO, ) is given ,which binds itself tightly to water wall surfaces and protects the surface from further corrosion by forming a physical barrier between the metal and the water. In simple terms , the function of water regime control is to maintain a chemical environment in which the oxide film is stable and hence protective. The superheater , steam piping and reheater are cleaned by scavenging with steam. IV) FEEDWATER / CONDENSATE CHEMISTRY : The main source of corrosion and deposition in modem high pressure boilers is through the feed water ( make-up water plus condensate ). Advanced raw water treatment plants with automated operational facilities ensure that the treated water ( used as make-up water ) produced is of the expected quality. Hence the potential for contaminant introduction to a steam generating plant is greatest in the condensate from the preboiler system a The preboiler system of steam generating units includes a steam surface condenser , several closed tube-in-shell feedwater heaters , and a deaerator el TRAIVa) CONDENSATE CHEMISTRY ‘A variety of materials are used for condenser and feed water heaters. Copper alloys are mainly used for their excellent heat transfer properties. During the initial operation of the boiler , copper from the preboiler material gets coated with layers of tightly bound , protective oxide ( cuprous oxide ). 2Cu.+ H20,. Cuz + Ha However , during subsequent operation of the unit with more than the recommended quantity of oxygen , ( during start ups , condenser leakage , low load ‘operation , etc ) the protective layer is further: ‘oxidized to cupric state . 2Cw0.+-O2, > 4.Cu0 Unlike the cuprous oxide , the cupric oxide , CuO is much less adherent, comes off the parent metal easily and hence is not prot to ‘Nodules of corrosion products and pits at the metal surface are formed at the corrosion sites. The corrosion products are ultimately transported to boiler and get deposited on the highest heat transfer zones. In the case of copper , the oxidized product , CuO will be transported and get deposited . The deposit formed will be porous , in contrast to the protective film. aie : “Additionally in situations where excess of ammonia is present along with dissolved oxygen , the oxidized copper gets complexed (i.e. dissolved) , removed from the parent metal and goes into solution in the condensate. CuO + 4NH3 + H20 > —Cu(NHo)s (OH)2 (insoluble ) (soluble ) The cupro-ammonium complex travels along with the feed water in the form of solution. However, the complex starts decomposing. at about 150°C , thus releasing “ free” copper at elevated temperatures, The released copper gets deposited on the heat transfer tubes in the boiler section. Thus copper may precipitate as either cupric oxide or finely divided metallic copper . Sometimes copper plates out in a continuous layer on the cold side of the tube . In the case of iron , just like copper , a protective layer of the oxide is formed during the initial stages of operation of the unit . 3 Fe + 4H20 + FeO, + 4H2 However , during subsequent operation of the unit and in situations where the quantity of oxygen is more than the recommended amount , the protective magnetic oxide is oxidized to the nonprotective ferric oxode, 4 Fes04 + O2 — 6 Fe20s Comparison between FesOz and Fe,0s ‘Magnetite , FeO. Ferric oxide , Fe,Ox 1) colour dark (black) brownish red 2) binding nature to tightly binds flakes off easily the base metal to the base metal 3 ) nature of binding dense loosely held 4) significance from protects the unprotective corrosion point of view base metal xThus the corrosion products ,namely , copper and oxides of copper and iron are transported to the boiler and get deposited in the highest heat transfer zones generally in alternating layers . Sometimes trace amounts of zinc and nickel from the preboiler side also get deposited During the start up of a boiler , chemical regime control becomes extremely difficult . Dissolved oxygen levels can be very much higher than the ‘recommended values. This can lead to severe corrosion with subsequent pick-up of high amounts of copper and iron in the feed water. The concentration of both iron and copper. have been practically found to peak up to 100 times their normal steadystate concentrations during the startup period. The corrosion products in such huge qu: is transported to the boiler and eventually get deposited on heat transfer tubes. Very little of the corrosion product is removed by blowdown , contrary to common conceptions. IVb) REMEDIAL ACTION : 1 Corrosion of metals depend on two factors , namely , pH and dissolved. oxygen, In the case ferrous based materials , minimum corrosion occurs at pH values of 9 to 11. Copper is mostly resistant to mild acidic and alkaline solutions , except to those containing ammonia. Hence , elimination of oxygen is the best way to prevent the attack ‘on copper and ferrous alloys . Ammonia ,not exceeding 0.5 ppm provides the necessary pil condition . Guidelines for feed water and boiler water given by the supplier have to be followed very strictly. 2) Corrosion and deposition can be enhanced during condenser leakage . Lot of dissolved oxygen can enter the boiler depending on the quantity of condenser leakage, Necessary steps have to be taken to control the condenser leakage and hence the dissolved oxygen. 3) ‘Since condenser is operating under vacuum, air in-leakage is very difficult to prevent . Prime spots for air leakage include the expansion joint between the turbine and condenser , turbine seals , diaphragms , and condensate pump seals. Necessary steps are to be taken to prevent the entry of dissolved oxygen from the ai. 4) Major part of the dissolved oxygen is removed mechanically by deaerating heaters. Since the solubility of gases decreases with increasing temperatures , oxygen is liberated from water at clevated temperatures . Steam at the required temperature , quantity and flow rate removes the oxygen from the feedwater falling as fine droplets. The removed oxygen is vented out through the top. Temperature oxygen concentration oF °C ce per litre 30 = 11 10.1 90 32 5.1 150 66 3.1 190 88 dS: 210 99 0.1 . Proper deaerator performance is dependent on several factors © Correct alignment of trays Evenly distributed condensate and steam flow * sufficient steam temperature, pressure and quantity + sufficient ventingThus the correct functioning of the deaerator must be ensured for proper ‘oxygen control ( down to lower than 20 ppb ) . Chemical reducing agents like sodium sulphite ( low pressure ) and hydrazine ( high pressure ) removes the last traces of oxygen. NoHs + O02 > 2H20 + No Additional benefit of hydrazine is that it will passivate oxidized arcas of piping and tube materials . Nos _ 6 Fe,03 > 4 Fe304 + No + 2120 Noy + 4Cu0 > 2CwO + N2+2H20 ~ Round the clock feed of hydrazine or alternate oxygen scavenger , along with proper deaeration is very important to properly protect feed water and boiler water components 5) Majority of corrosion in the pre-boiler section takes place during periods of stratup of the unit. Hence maximum care should be given to water regime control during such periods as per guidelines given by the manufacturer. Mechanical stresses imposed during load changes and startups and shutdown will fracture the copper oxide films on spalling, Oxygen corrosion of unprotected feedwater heaters an outage can cause severe corrosion and exfoliation of heater tubes. If the is found to be serious , the steam-side of the heater should be blanketed with steam or nitrogen during extended outages. Altematively , feed water heater tubes are ‘fabricated from stainless’ steel’ titanium , ete. 6) Monitoring of dissolved oxygen by plant chemists is the most important aspect water regime control . On-line monitoring of dissolved oxygen ( before and after dearator ) is the best preferred practice. Some of the important chemical parameters to be maintained in the feedwater are given below 2 FEED WATER CHEMISTRY GUIDELINES Feedwater Volatile treatment PO, treatment parameter (hydrazine - ammonia) ‘treatment mixed metallurgy all ferrous pH 88-91 92-96 88-92 Cation condueti= vity (uS/em) <02 <02 <03 Dissoived Oxygen , ppb <5 <10 <7 Iron, ppb <10 <5 <10 Copper , ppb <2 : <5 V) BOILER WATER CHEMISTRY : Boiler water chemistry is , to a partial extent , dependent on the effect on the steam purity along with corrosion and deposition control. Boiler water chemical control started with the use of sawdust or potato peels As boiler operating pressures increased , more advanced practices were introduced, Sodium phosphate ( NasPOs ) has been the most common chemical used for boiler water conditioning. The phosphate ion is effective because it conditions boiler water in an alkaline pH range, and reacts with scale — forming compounds to produce soft sludgesTrisodium phosphate provides the needed alkalinity as per the following equation : NasPO4 + H20 ‘ NagHPO; + NaOH Phosphate ions ( PO,” ) can exist in the mono, di, and tri hydrogen state in aqueous solution. Thus , it can give up or accept hydrogen buffering capacity inakes phosphate effective in preventing wide pH swings in water due to contaminant ingress. = The second major function of phosphate is to absorb contaminants that enter the boiler during abnormal conditions , for example , periods like condenser leakage . Phosphate reacts directly with calcium to produce calcium hydroxyapetite, 10 Ca? +6 POs? + 2OH- — —3.Cas(PO.)2. Ca (OH)2 | ~—~‘Magnesium and silica react with the alkalinity produced by phosphate to form the nonadherent sludge, serpentine, 3 Mg’? + 2Si0s?+ 20H — 3MgO.2Si02.2H20 | ‘Hydroxyapetite and serpentine are more benign and easy to remove via blowdown than the hard scale or corrosive products which would otherwise form. Va) BOILER WATER CONTAMINATION : 1) EFFECT OF DISSOLVED OXYGEN : ‘The most familiar form of attack by dissolved oxygen on boiler metals is pitting. Feo + Fe + 2e .... Anode Oo + 2k2O + 4e + 40H... . Cathode Fe? + 2OH- = Fe(OH)2{ 4 Fe(OH )2 + 02+ 2HxO > 4Fe(OH)s | 2Fe(OH)}s > Fe203| + 3H20 Pitting is common to all steam generating systems regardless of type , size , ‘or pressure, Since the extent pitting corrosion increases with temperature , units operating at higher pressures and temperatures will experience more corrosion. 2) CAUSTIC ATTACK : Although mild alkaline condition ( pH 9 to 11 ) is desirable for steel surfaces , corrosion resulting from excess caustic can take place in boilers. As discussed already , the boiler waterside tube walls develop a tightly bound layer of magnetite when the unit is placed in operation. Over the passage of time , the protective film becomes overlaid with porous deposits , mainly transported from the preboiler side, This porous deposit serves as a trap for other chemical species such as phosphate , chlorides , and sulphates etc. As steam bubbles form within the porous deposits , the concentration of the contaminant in the boiler water increases by several orders of magnitude in the film surrounding the bubble. These corrodent concentrations can reach 10,000 times the bulk boiler water concentration. The combined effects of the corrosion product and the concentrated corrodent deposits can lead to several type of.tube failures. Some of the mechanisms of boiler tube failures include hydrogen damage , caustic gouging ete. Water entering the porous deposit through some openings will boil off through other channels , leaving the salts behind . One of the salts is sodium hydroxide , which gets concentrated and starts attacking the protective magnetite film and finally the parent metal itself. 5Fes0; + 4NaOQH + 2NaFeOz + NagFeO2 + 2H20 Fe + 2 NaOH > NasFeO2 + Hot The localized attack may cause tube damage within a relatively short period of time 3) ACIDIC ATTACK : Deposition ( porous ) can also cause the concentration of acid species like chlorides , which enter the boiler, specially during periods like condenser leakage. MgCl + 2H20 — Mg(OH)2 | + 2HCI Not only does the acid corrode the boiler metal , but the reaction generates hydrogen , which can lead to hydrogen damage of the tubes. In this mechanism , hydrogen gas molecules , which are very small , penetrate into the metal wall where they react with the carbon atoms at the grain boundaries in the steel structure to generate methane . 2H. + FesC — 3Fe + CHst Formation of the very voluminous methane molecules causes cracking in the steel , ‘greatly Weakening its strength , A portion of the weakened tube is blown away , mostly without thinning of the edges. Hydrogen damage is very troublesome because it cannot be easily detected . After replacement of the failed tube , the other affected tubes will start failing leading to stoppage of the unit.. Vb) REMEDIAL ACTIONS : 1) Since , the boiler steel is attacked by high acidity or alkalinity, boiler water conditions must be carefully maintained ( in a mild alkaline pH range of 9 to 11) as per the recommended guidelines . 2) Though bulk water chemistry can be alright as per the sample analysis , localized concentrations can be very high , as under deposit evaporation . Water wall tube samples have to be cut from high heat transfer zones ( usually 2 to 3 metres above the top most bumer ) and assessed for cleanliness“ . If found high the unit has to be chemically cleaned to remove the deposits , thus closing down the chances for under deposit evaporation and concentration of harmful species. 3) Condenser tube leakage results in the entry of many unwanted contaminants into the boiler . Early detection of condenser leak by measurement (on-line) of feed water conductivity is a must for the well being of the unit. Condensate polishing units are set up for very high pressure units to mitigate the problem. In spite of the actions taken by the station , it may be observed , in rare instances, that the pH of boiler water is getting lowered during the entry of acidic contaminants . If the pH is going below 8 , then the unit has to be taken out of service , till the problem is solved, 4) ‘More corrosion occurs during an outage than at any other time . This is due to the entry of oxygen and subsequent corrosion. During such periods the boiler and the feedwater system must be laid up properly or severe corrosion will result . The boiler should be filled with condensate ( or equivalent water ) containing about 200 ppm of hydrazine and enough ammonia to bring the pH to 10. A nitrogen blanket (about 5 psig) should be introduced to the druni and superheater through the vent lines. In the feedwater section , the standard operating concentrations of oxygen scavenger and pH conditioner can remain. If not , a solution containing 50 ppb of oxygen scavenger at a pH of 10 must be introduced into the system The steam side of the heaters should be blanketed with steam or nitrogen . The deaerator