EBS. esr itp .vab.org Reproduction in whale or in part anly with prior permission of he publishers, VES Powerlech Guideline Guidelines for Feed Water, Boiler Water and Steam Quality for Power Plants / Industrial Plants VGB-R 450 Le Second Edition 2004 Published by VGB PowerTech e.V. Obtainable from: VGB PowerTech Service GmbH Publisher of techno-scientitic papers P.O. Box 10 39 32, D-45039 Essen Phone +49 0201 8128-200 Fax +49 0201 8128-329 E-mail: mark@vgb.orgVGoB 3 Preface EPPSA, FDBR and VGB PowerTech hereby present a European Guideline for Feed Water, Boiler Water and Steam of Steam Generators. This new guideline replaces the former "VGB Guidelines for Boiler Feed Water, Boiler Water and of Steam Generators with a Permissible Operating Pressure > 68 bar, October 1988 Edition". The present Guideline is the work of a joint European Technical Committee with epresentatives of EPPSA, FDBR and VGB from most EU countries. The Technical Committees of these organisations have discussed and agreed this guideline. The following co-workers were involved in preparing this new Guideline: P. Colman, ESB K. Daucik, Elsam Engineering M, de Wispelaere, Laborelec D. Foussat, Alstom Power Boilers C. Fraikin, C.M.I. Utility Boilers B. Hausmann, FDBR M. Herberg, Alstom Power Boiler L. Héhenberger, TUV Siddeutschland B. Hughes, px limited Teesside Power Station Dr. S. Kemppinen, Foster Wheeler Energia T. Ruohola, Kvaerner Power Dr. U. Staudt, VGB PowerTech Dr. R. Svoboda, Alstom Power U. Teutenberg, Babcock Hitachi Europe Dr. R. Truppat, VGB PowerTech Dr. U. Vogt, TUV Suddeutschland R. Wulf, Siemens Power Generation The reader should be aware, that this guideline covers all pressure ranges applied to boilers generating heat, steam and/or electricity. In general the guideline covers steady state / full load operation of those boilers as well as start up operation mode by using action levels for the first time. This concept allows a quite flexible approach to combine requirements of the materials used throughout the steamiwater cycle with economical needs of the plant operator. It should be pointed out that this guideline does not deliver absolute limiting values of chemical parameters but prefers to demonstrate reasonable areas of permissible operation ranges in respect to a minimal corrosion within the steam/water cycle to reach an optimised lifetime of the plant. Plant specific agreements on various parameters may supplement these guidelines. Use it cum grano salis and as well respice finem! Essen, December 2004 VGB PowerTech e.V.Contents 1 Scope... 2 Definitions . 3 Steamiwater cycle system 34 Feed system 3.2 Steam generator 3.3 Turbine 3.3.1 Condensing Turbines. 3.3.2 Backpressure Turbines 3.4 Condensing system .. 4 Interaction between plant design, materials and water chemistry 44 Plant design 4.1.1 Onee through boiler 44.2 Drum boiler . 4.1.3 Combined cycle heat recovery boile 4.1.4 Waste Heat Boiler and Process Gas Cooler / Quench Boiler. 44.5 Boilers with gaps 42 Materials . 5 Treatment of stearn/water cycles. 54 Purification ...ccseseseeen 5.1.1. Make up water treatment. 5.1.2 Condensate treatment .. 5.1.3 Other methods of water/steam cycle purification.. 52 Deaeration and oxygen scavenging.. 521 Deaeration.... 5.2.2 — Oxygen scavenging... 53 Conditioning. i 5.3.1. Feed water conditioning... 5.3.1.1 Feed water conditioning with alkalizing agents (AVT) 5.3.1.2 Feed water conditioning only with oxidizing agents... 5.3.1.3 Feed water conditioning with alkalizing and oxidizing agents (OT) 5.3.2 Boiler water conditioning 5.32.1 Caustic or phosphate treatment (solid alkalizing)..sss 7.10 8.1 8.2 8.3 84 85 8.6 87 All volatile treat men Special conditioning agents Chemical specification . Action level control syste! Operation with demineralized feed water Requirements on feed water for once-through boilers Requirements on feed water for drum boilers Requirements on boller water for drum boilers Requirements on steam for condensing turbines. Operation with teed water non-demineralized. General . Feasibility study Raw water / treated water parameters. Condensate percentage return Concentration factor... Explanation of chemical specifications. PH value, acid capacity, alkalinity . Conductivity Oxygen Hardness Phosphate .. Sllica. Iron and copper. Sodium / Sodium hydroxide ... Carbon dioxide . Organic substances ... Analytical control of operation... ‘Sampling of Water and Steam... Measurement .. Monitoring .. Control. Maintenance and Calibration ... On-line measurements......... Manual controlsAnnex... Internal cleaning and preservation. Internal cleaning. Preservation. Physical-chemical processes... Basics of material protection Deposition... Deposition from water Deposition from steat COrrOSION «eee General... Oxygen corrosiorvidle corrosion .. Acid corrosion Caustic Corrosion Hydrogen Corrosio Stress Corrosion Cracking... Flow-Accelerated Corrosion. Corrosion Fatigue ; Economical consideration Assessment of water/steam chemistry by quality indice: Operation above Action level 3 Bibliography8 VGB 2 Definitions For the purpose of this guideline the following definitions apply: conductivity Direct measured conductivity of water. acid conductivity Conductivity of water measured downstream of a strongly acidie sampling cation exchanger. all volatile treatment (AVT) Conditioning concept where only volatile alkalizing agents are used mainly ammonia. ‘oxygenated treatment (OT) Conditioning concept where alkalizing agents and oxygen are added. caustic treatment (CT) Under this treatment boiler water pH is maintained with sodium hydroxide. phosphate treatment (PT) Under this treatment boiler water pH is maintained with tr- sodium phosphate. demineralized feed water — Water with an electrolyte content according to an acid conductivity of < 0.2 1.S/em and a silica content (SiOz) of < 0.02 mg/l [1, 2] non-demineralised feed Water which contains dissolved solids/matter and which water doesn't meet the requirements of demineralized feed water. make-up water Water which compensates for losses of water and steam from the system feed water Mixture of returned condensate and/or make up water supplied to the boiler inlet. boiler water Water within a natural or assisted circulation boiler. attemperator spray water Water for injection to contro! steam temperature. drum boiler Water tube boiler in which the water to be evaporated circulates due to the differences in density (natural circulation) or by means of pumps (forced or assisted circulation). once-through boiler Water tube boiler in which the water flow is effected by the feed pump. In such the water is evaporated completely or in a major portion during one single stage./ ——— VG 9 3 Steam/water cycle system A process diagram of a steam/water cycle system is shown in Figure 1. Blow down Steam i L i generator |—>| Turbine }——»| Condenser | .___ Make-up | 7 water ¥ | i | Solid | : Bevo conditioning * | || Fitration + { High | | | Gohdensing || pressure || I | “svatem | heater idee / + | exchanger * eee Volatile | | k= conditioning i | | | Feed Feed i Low | | water | water [gi | pressure | | i pump tank T heater | L | Feed systoni * optional Make-up water Figure 1: Example for a process diagram of a steam/water cycle system. 34 Feed system The basic approach to feed-water conditioning is maintenance of sufficient water purity to limit corrosion of feed train material and to minimise the transport of corrosion products and corrosive contaminants to the boiler. For once through boilers the only conditioning applied will generally be to the feed-water. In this cases the quality of the steam, is directly determined by the quality of the feed-water. For drum boiler circuits, although further contro! measures may be applied in the evaporator, it remains good practice for modern power units to have the same target with respect to feed-water and steam. Corrosion rarely threatens the integrity of the feed system as such. Erosion-corrosion of mild steel components, where water velocities and turbulence are high and oxygen levels are low, can cause damage and will also lead to enhanced iron levels which are ted forward to the boiler. Considerable contribution to corrosion product transport to the boiler comes from steam side of heaters, where partial condensation cause local pH10. VGB perturbations. Corrosion of copper alloys can be stimulated by the combined effect of dissolved oxygen and ammonia; this can cause copper to be transported from the feed system into the boiler and turbine. Traditionally the chemical systems for conditioning feed-water fall into two groups: — The reducing (ammonia or an amine with hydrazine) all volatile treatment, (AVT), where the protection steel is based on low solubility of iron oxides at elevated pH. — The oxidising (oxygen with a low concentration of ammonia) treatment, (OT) with very low anion concentrations (low acid conductivity), where the protection of steel is based on low solubility of iron oxides at elevated oxidation-reduction potential. Although individual national and company guidelines generally specify limited concentration ranges, overall experience indicates that these two protection mechanisms act simultaneously and there are no distinguished border lines between these types of conditioning. On the contrary, there is seen to be a continuum of suitable operation conditions in a broad range with high pH and low oxygen concentration at one end, and low pH and high oxygen concentration at the other. Achievable purity of feed-water determines the degree of freedom available to operators within this range (high oxygen concentrations are incompatible with chloride and sulphate contamination). Choice of the optimal chemical conditions within this broad range will be influenced by the boiler type, operational conditions, design and materials of construction. The presence of the following materials is particularly important: — Carbon steels are particularly compatible with mildly oxidising conditions in the absence of contamination anions (chloride, sulphate, etc.). — Copper and copper alloys may suffer oxide transport problems in oxidising regimes in some plants and are vulnerable to attack by high levels of ammonia. Other materials, such as titanium, high chromium steel and chromium nickel steel are relatively indifferent to the conditioning regime. 3.2 Steam generator Two general classes of water tube boilers are in use: — Once through boilers in which water is evaporated to a high steam content. These are intolerant of non-volatile dosing chemicals and generally operate without further dosing of the feed-water. — Drum boilers in which steam separation takes place in an unheated vessel. Boiling occurs in tubes through which water from the drum is re-circulated, preventing dry out at the boiling surfaces. Such boilers may be tolerant of addition of low levels of non- volatile alkalis to prevent any risk of acidic corrosion. ‘The major objectives of boiler water treatment are to minimise deposition and corrosion of the boiler and to ensure that steam is of the appropriate quality. From the very first start of, the operation and all the way through the lifetime the boiler steel reacts with the water and steam to produce a protective film of iron oxides. The rate of reaction decreases with time as the thickness of the protective oxide film increases. The rate of transport of iron oxides through the system is at its most rapid during the initial operational period, _ Boiler integrity can be harmed by a number of corrosion mechanisms or by overheating due to excessive thickness of oxide layer. The protective properties of the oxide layer are dependent on the chemical conditions in surrounding water as well as the chemical¥ ' VGB 44 conditions during its build up. The optimal chemical conditions are characterised by minimum solubility of the oxide. Generally the highest possible purity, slightly alkaline pH and appropriate redox potential are the basic parameters for integrity of the protective oxide layer. Non-volatile impurities concentrate in boilers and can increase the risk of corrosion, A number of factors influence this. The build up of porous oxides by deposition onto heat transfer surfaces is particularly detrimental. Other important factors include details of design, construction and operating regime. The optimum boiler water condition is mildly alkaline. Deviation either to acidic or to highly alkaline conditions carries a risk of damage. — Acid forming species (particularly chlorides, but also sulphates and organic anions) if present and able to concentrate at boiler tube surfaces can result in very rapid rates of general corrosion. This type of corrosion is often accompanied by hydrogen damage in mild steels, which can lead to large sudden tube failures. Acids can be generated from neutral salts particularly under oxidising conditions, and so it is particularly important to minimise ingress of chlorides and sulphates when using oxidising treatments and during oxygen transients at start-up for reducing treatments. ~ If strong alkalis concentrate at surfaces, corrosion at unacceptable rates can also occur. This type of attack does not normally cause hydrogen damage, but some alloys are vulnerable to stress corrosion cracking and grooving in very high pH environments. The required benign boiler water, which is mildly alkaline at operating temperatures and pressures, is achieved using either an AVT or solid alkali treatment. The choice of regime may be limited by heat flux considerations, since this has a strong effect on concentration of non-volatile materials at boiling surfaces. Furthermore all substances that are added to control boiler water corrosion will inevitably impact upon steam quality. Ideally the aim is to have a zero concentration of impurities, but this is impractical and realistic targets for both acceptable operation and limited out of specification operation are needed 3.3 Turbine 3.3.1 Condensing Turbines Normally direct conditioning of steam is not applied, and hence the chemical quality of steam derives from the measures applied to control feed water and boiler water. Thus, one of the objectives of feed water and boiler water conditioning is to avoid deposition and corrosion in the steam path, e.g. pipes, valves and turbine. Steam purity must be high and actual quality is determined by: = Vaporous carry over (volatility) of boiler water constituents. The volatility is a function of pressure, temperature and secondary influences of other chemical components. -> Mechanical carry over of droplets of boiler water. — Injection of feed water into steam for attemperation. The interaction of steam impurities with turbine materials is basically. determined by deposition and by condensation of these impurities. Deposition can take place when the solubility limit has decreased -with steam expansion- below the actual impurity concentration. Condensation can take place when steam expansion forms water droplets12 VGB or water films, in which the impurities can partition in relation to their distribution coefficients. Due to the rapid expansion of steam in the turbine, these processes may however be too slow to reach equilibrium conditions. The early condensation zone of the turbine is particularly sensitive to low volatiity contaminants, These impurities can concentrate on surfaces and in the very first droplets of condensate to form an aggressive environment. Enrichment of impurities can also occur when wet steams is locally dried up on turbine components. Enrichment of acidic impurities leads to a decrease in local pH on turbine components, which in turn enhances corrosion fatigue and stress corrosion cracking. Sodium hydroxide and chlorides at certain concentrations present a particular stress corrosion cracking risk to steels with non-heat treated welds or with austenitic structures. On the other hand, sodium phosphates from boiler water treatment are not considered as being aggressive to the steam turbine. They may however form salt deposits that can impair essential turbine control (e.g. function of the turbine inlet valves). Decomposition products of organic impurities (organic and carbonate anions) may be implicated in turbine damage. Silica is the most soluble of the common boiler water contaminants in high pressure steam and has a high volatility. It can become supersaturated during expansion in the turbine. This results in deposition on the blades causing loss of turbine efficiency, and in severe cases, loss of output. Salts deposited in steam pipe-work on-load can result in the development of concentrated solutions off-load following introduction of moist air or condensation of residual steam. This effect is particularly significant for re-heaters, turbines and some types of feed heaters. In the turbine, it may cause pitting. Besides causing mechanical degradation, pits may also initiate other forms of corrosion like stress corrosion cracking during the following turbine operation. The limits described for steam in the IEC Technical Specification TS 61 370 “Steam turbines - steam purity" [3] are specifically designed to protect the steam turbine. This specification is designed for new plants, but may be adapted for use on existing plant. 3.3.2 Backpressure Turbines Wf the steam data (pressure, temperature) at the turbine exhaust are sufficiently high, neither condensation nor salt deposition will take place in the turbine. Some of the steam purity requirements for condensing turbines may therefore be exceeded in backpressure turbines. However, this is only permitted if the composition of the steam is known and in accordance with the steam data at the turbine exhaust. These values must be defined plant-specifically, 3.4 Condensing system Because condenser leakage is the major source of impurities in circuits, monitoring of condensate is particularly important as an early indicator of the need for action. As station circuits vary, consideration for each plant on an individual basis is necessary to ensure that contaminated condensate is not fed to vulnerable components (such as attemporator sprays, etc.)Vos 13 Units with once through boiler are always equipped with condensate polishing plant (CPP) to take care of this problem. CPP should be designed, maintained and operated on a standard which is able to cope with condenser leakages. Drum boiler units are often without CPP and in case of condenser leakage precautions must be taken to avoid damages. 4 Interaction between plant design, materials and water chemistry 41 Plant design 4.44 Once through boiler Once through boilers are steam generators where the feed water evaporates completely within the tubes and the rest of electrolytes would be deposited on the tube walls. Therefore once through boilers need demineralised feed water which has to be only conditioned with volatile agents (AVT/OT). 4.1.2 Drum boiler Drum boilers are steam generators with natural or assisted circulation of the boiler water. The standard procedure of boiler water conditioning is the application of solid alkalizing agents. In this connection, particular reference must be made to the water for spray type desuper-heaters for steam temperature control (attemperators), The spray water must be of the same quality as demineralized feed water and must not contain solid alkalizing agents, which would deposit in the super-heater or turbine. Operation with contaminated feed water results as well in deposition of contaminants with setious risk of corrosion as a consequence. 4.1.3 Combined cycle heat recovery boiler Combined cycle power plants (CCPP) use the energy of a gas turbine exhaust for steam production in an adjacent heat recovery steam generator (HRSG) and operation of a steam turbine. This combination of gas and steam turbine cycles allows high efficiency power generation. Including district heating into the cycle further increases the efficiency. The development of combined cycle power plants started with single pressure drum-type heat recovery steam generators and reached the state of today with triple pressure drum- type and reheat or with a combination of once-through steam generators (OTSG) and drum steam generators. These arrangements require thoroughly considerations regarding the chemical treatment of low (LP), intermediate (IP) and high pressure (HP) boilers, depending on the design and the operational conditions. Drum steam generators may be operated with all volatile (AVT), phosphate (PT) or caustic treatment (CT). For once through steam generators the oxygenated treatment (OT) is recommended. Otherwise all volatile treatment has to be applied. All volatile treatment for low pressure drum steam generators is only suitable with an adequate high pH in the boiler feed water or with higher grade materials in the evaporator circuit, which are resistant against flow accelerated corrosion (FAC) attack. Flow accelerated corrosion is classified as the main cause for boiler tube failures in low pressure14 VGB evaporators, because the operating temperature is in that range where flow accelerated corrosion is most likely. The required high pH in the feed water may not always be applicable, e.g. restriction of pH in export steam for industrial processes, and an upgrade of the material not possible. In such case a solid alkalization of the low pressure boiler water is needed. High pressure evaporator circuits under phosphate or caustic treatment may suffer from under deposit corrosion (acid, caustic and hydrogen corrosion). Heat recovery steam generators with supplementary duct firing may not be suitable for phosphate or caustic treatment. The operation of the duct firing not-seldom results in at least temporary local dry out of evaporator tubes, concentration of the solid alkalizing agent and subsequent corrosion attack. Besides efficiency flexible operation with daily or weekly shutdowns and short start-up times as well as additional operating cost reduction (man power reduction) are actual requirements for most combined cycle power plants. Frequent start/stop and operation under phosphate or caustic treatment needs well skilled chemical operators. If this cannot be assured, the chemical treatment should be as simple as possible. The best approach in this regard is an operation with all volatile treatment. Combined cycle power plants are also in use for cogeneration purposes, at which steam is exported for industrial processes. A wide range of make-up water demand and return condensate flow is possible. Special attention should be directed to the quality of the return condensate, which might be contaminated by the process. Monitoring of the total organic carbon (TOC) is recommended, if there is a potential for pollution with organic chemicals or oil 100% make-up demand or return condensate flow or a mixture of both is possible at combined cycle power plants with back pressure turbines and at pure cogeneration plants without steam turbine. 4.1.4 Waste Heat Boiler and Process Gas Cooler / Quench Boiler Many waste heat boiler with operation pressure < 30 bars and common heat flux are shell type boiler with hot gas or process medium within the tubes and boiler water around the tubes. Most process gas coolers e.g. of ammonia, methanol and ethylene plants (quench boiler) are shell type boiler but show both high heat transfer (local max. heat flux up to 700 kWim2) and operational pressure (up to 130 bars). They require particular boiler feed water and boiler water quality Shell type process gas coolers and tube in tube quench boilers should have gapless welds of the tube to tube sheet or header connection at least at the gas inlet (hot end), but same welds are recommended for the cold end, In case of gaps or weld voids, e.g. dissolved solids of “boiling out" solution or boiler water may be concentrated within the heated gaps and may cause corrosion. Demineralised boiler feed water is a presupposition for trouble free operation of these boilers and all volatile treatment (AVT) is very advantageous. Otherwise tri-sodium phosphate dosing according the highest pressure range of the boiler water recommendations is necessary. Completely flooded Salt Bath Cooler do not have excessive heat transfer and may be operated with feed water and boiler water depending of operation pressure like normali i | | i | VGB 15 steam generators. In case of a heated water/steam boundary (not completely flooded cooler) the feed water and the boiler water should meet the limits for all volatile treatment (av). 4.1.5 Boilers with gaps Heated gaps allow excessive concentration of non volatile boiler water constituents and may initiate corrosion, particularly caustic stress corrosion cracking. Boiler of such design operated with demineralised feed water must not use sodium hydroxide for basic pH adjustment, but appropriate phosphate treatment is recommended. AVT regime causes no problems in such boilers but needs demineralised feed water. 42 Materials Typical materials used in the steanwater cycle are carbon steel and stainless steel. For condensate respectively feed systems often copper or copper alloys are applied because of their good thermal conductivity. Copper is very sensitive to complex forming agents like ammonia and is subject to increasing corrosion rates and stress corrosion cracking in presence of ammonia or ammonium ions, particularly in presence of oxygen. Therefore the pH value has to be considered carefully in the presence of copper or copper alloys in the water/steam cycle. 5 Treatment of steam/water cycles 5A Purification 5.1.1. Make up water treatment The necessary type of make up water treatment for boilers depends on: ~ Raw water quality (e.g. hardness, alkalinity, conductivity, silica content, turbidity) - Amount and quality of condensate return to the boiler feed water. = Requirements on the boiler feed water and boiler water (depending on boiler type, boiler pressure, max. heat transfer). — Requirements on the steam produced (e.g. super-heater/turbine operation, high quality steam for production processes, corrosion in the steam and condensate system). — Economic and ecologic requirements (e.g. blow down rate, effluent requirements). Make up water treatment is a demineralization process most commonly done in ion exchanger units of different design or in case of surface water with reverse osmosis combined with a polishing filter like e.g. mixed bed filter, electro deionisation (EDI) etc Before the demineralization it is often necessary to improve the raw water quality by ferent pre-treatment steps (especially for high contents of organic, iron or manganese) including chlorination, sedimentation, flocculation, filtration, oxidation, de-chlorination Softening Soitening is the minimum for make up water treatment, it exchanges the most important scale forming constituents of the raw water like calcium (Ca) and magnesium (Mg)16 VGB compounds for sodium (Na). Its application is mostly restricted to low pressure boilers (40 bars) with natural or forced circulation and low heat transfer rates, if there are no further requirements to boiler operation and steam quality. Optimised condensate return is advantageous in order to minimise the quantities of softened make-up. Decarbonisation Decarbonisation, in combination with softening is recommended if the raw water shows higher alkalinity, particularly if the total alkalinity of the boiler feed water exceeds ca. 1 mmol/l. Its application is mostly restricted to boiler pressures < 60 bars with natural or forced circulation and low heat transfer rates, if there are no further requirements to boiler operation and steam quality. Optimised condensate return is advantageous in order to minimise the quantities of decarbonised make-up. Partial Demineralization Partial demineralization by reverse osmosis (RO), electro dialysis (ED/EDR) or ion exchange reduce the content of raw water contaminants significantly (e.g. direct conductivity < 20 uS/cm, silica content mostly < 0.2 mgf). Partially demineralized water is usually further polished to demineralized water. Demineralization Demineralization in ion exchanger plants, consisting at least of cation, anion and/or mixed bed filters, or one of the above mentioned partial demineralisation steps in combination with a mixed bed filter or one of the modern membrane processes driven by electrical field (EDI), leads to demineralised water ("Demin” water). This “Demin” water is sufficient for the operation of all steam generators and is a presupposition for safe operation of a unit with injection spray water for steam attemperation or once through boiler [4]. 5.1.2 Condensate treatment The necessary type of condensate treatment for boilers depends on: — Condensate quality (e.g. conductivity, corrosion products, hardness, silica content, hydrocarbons, pollutants due to ingresses of product). — Amount and quality of condensate return in the boiler feed water. — Requirements to the boiler feed water and boiler water (depending e.g. on boiler type, boiler pressure, max. heat transfer). — Requirements on the steam produced (e.g. super-heater/turbine operation, high quality steam for production processes). — Economic and ecologic requirements (e.g. blow down rate, effluent requirements). Condensate treatment consists most commonly of mechanical filtration and/or ion exchanger units of different design Additional features are indicated for process return condensate. Potential presence of e.g. hydrocarbons (oil, grease, fat) may require pre-treatment steps like skimmers or activated carbon filters. In case of possible ingress of high risk matter, e.g. heavy fuel oil, acids or free caustic in high concentration, separate condensate return combined should be considered. Controlled by on-line monitoring, this condensate can then automatically be recycled or put to waste. Sac apemiacayVB 17 Overview on methods and recommendations for condensate polishing are detailed in VGB guideline VGB-M 412 L [5]. Filtration Filtration is highly recommended if the condensate return is continuously or frequently contaminated with higher (approximately > 0.03 mg/l) amounts of corrosion products e.g. Iron Oxides or non-dissolved matter. Common methods for filtration are: - Gravel or charcoal filters. It has to be assured that the filter material does not pollute the condensate with e.g. hardness, silica or organics. ~ Cartridge fiters. — Pre-coat fiters. - Electromagnetic filters. Demineralization Demineralization is required if the condensate has to have high ionic purity, For condensate polishing, ion exchange resins are used: — Deep bed filters. - Powdered resin pre-coat filters. Resins for condensate demineralization (condensate polishing) must have higher thermal resistance and higher mechanical strength than resins for make up water treatment: — Above 60°C the retention of silica decreases, and the resin starts to decompose, causing loss in capacity as well as release of decomposition products (leachables) that decompose to ionic contaminants if entering the boiler. Even the decomposition of cation exchange resin is modest its decomposition products give serious problems by producing strong acids (sulphuric acid) by further decomposition in the boiler. The decomposition of anion exchange resin is substantial above 80°C and lead to loss of capacity and fouling of cation exchange resin by decomposition products (amines). = Resin fines and chips of resin affect the quality of both boiler water and steam. Macro- porous resins have better mechanical stability than gel-type resins. Deep bed filters can be carried out as mixed-bed filters, either by themselves or with upstream cation exchanger or mechanical filters. Other combinations, like cation-/anion-/ cation-exchange beds have also proven to be of benefit. Powdered resin pre-coat filters can be carried out by use of pre-coat mixed-bed resin, optionally with a topping of inert filtration material. 5.1.3 Other methods of water/steam cycle purification Even with use of the best purification technology for make-up water and condensate polishing, some impurities will enter the water/steam cycle. These contaminants will accumulate at certain places, where the physical-chemical conditions cause deposition due to solubility relations. This paragraph describes possible methods to eliminate the concentrated contaminants from time to time.18 VGB Blowdown Blowdown is a well-known and generally used method to divert low volatility contaminants accumulated in the boiler water. Blowdown is the primary tool for control of the contaminants in the boiler water. ‘At commissioning and start-up continuous blowdown is necessary to reach the specified purity of the boiler water as soon as possible. During the operation many units change to periodic blowdown depending on the concentration of contaminants in the boiler water. The common parameters used for blowdown are silica and acid conductivity or chloride/sulphate (expressed by specific conductivity). Strictly speaking blowdown is applicable on drum boilers only. However, most of the once- through boilers have a separation vessel, which is acting at low load operation similarly to a drum. Diversion of the “boiler water” from the separation vessel at the right time is a useful method to eliminate the contamination accumulated in the evaporator during high load operation. The separation vessel is dry during high load operation. The main part of the ionic contamination accumulated in the evaporator will enter the separation vessel with the very first water at the transition to low load. It is recommended to divert this water out from the cycle and start the recirculation when the water from separation vessel reaches appropriate purity. Heaters Steam is often used for heating purposes both internally (feed water heaters, air heaters) or externally (district heating, industrial heating). Drain from indirect heat exchangers of this type is usually returned into the cycle, often without any polishing. if the steam is superheated, deposition of contaminants appears on the dry parts, where desuperheating occurs. When wetting the dry surfaces the deposits dissolve and contaminate the condensate drain. Washing of deposits in a heater can be performed during operation. The procedure starts with diversion of drain, as it is expected to pick up the deposited contamination, The closing of the steam supply for 5 ~ 10 minutes results in a cooling of the heat exchange surfaces to the temperature of the cooling medium. At the re-opening of the steam supply the deposits dissolve in condensate appearing on the dry surface, When the contamination is washed out, the recycling of the drain can be re-established. Periodical washing of the deposits is recommended, particularly up to an off-load period. ‘The removal of the ionic deposits improves the conservation during standstill Re-heaters and super-heaters Deposition of low volatile ionic contaminants from steam occurs also in re-heaters and super-heaters, particularly at their cold ends. These deposits can be removed by washing with saturated steam during by-pass operation of the turbine. The contaminated condensate from this washing must be polished before reuse. The operation is quite complicated and expensive. It can only be recommended if serious corrosion problems appear during off-load periods due to insufficient conservationVos 19 52 Deaeration and oxygen scavenging 5.2.1 Deaeration ‘As mentioned in other chapters, the presence of oxygen and other gases plays a major role in steam and water chemistry cycle. Even though oxygen properties are better known and even used in specific treatments, it remains mandatory to control its level and discard other deleterious gases such as carbonic acid, as well. Deaeration is therefore a key word for proper reliable chemistry management. Its action is applicable for condensates, make-up and feed water where gas may exist up to saturated level due to long contact with ambient air or, at lower concentrations from leakages through the balance of plant train. The condenser and the deaerator/feed water tank are specific items of pant where deaeration takes place. The presence of non reactive gas in liquids is governed by their solubllity, which is a function of the temperature and partial pressure of the gas in the vapour-phase Deaeration principle is therefore based on the closest contact between the liquid-phase and vapour-phase of which, said gas concentration, is lowered down to its reachable minimum. Deaeration key parameters are: ~The best spray available to offer the greatest surface to volume ratio and speed the transfer of the dissolved gas from the liquid phase to the vapour-phase. — The lowest concentration of the gas in the vapour-phase performed by air extraction and/or steam ventilation. Dearation equipment is working close to saturation conditions depending on the temperature characteristics of their place in the thermodynamics cycle. 5.2.2 Oxygen scavenging During stable operation, the outlet of condensate pumps indicates dissolved oxygen content < 15 jig/kg and outlet of deaerator < 5 g/kg. When a reducing medium is chosen, it may worthwhile injecting some additional conditioning chemical to implement the oxygen removal and ensure a reducing medium’. The most commonly used scavenger is hydrazine whose properties match all the high pressure chemistry requirements, since it does not decompose into troublesome by products. Safety precautions must be taken since itis classed as a category 2 carcinogen in the European Union. Some hydrazine substitutes have proven to be effective but add carbon dioxide to the fluid which is detrimental to the chemistry management. For low pressure specific steam generators’, sodium sulphites may be used, noting its salinity contribution to boiler water and potential acidic decomposition. "Strong reducing medium may enhance erosion-corrosion phenomenon. Taken apart protection during outages, high hydrazine content is not advieable, nor a way to palliate a poor deaeraton. lis usual excess content in the feed water is ranging irom 5 to 10 wok. * Glactrode boilers with demineralized make-up water supply20 Vos 53 Conc Corrosion of plant components in contact with water and steam in a water/steam cycle can be minimized by chemical measures. A common feature of the standard conditioning methods described here is the requirement that a minimum pH and other conditions are adhered to and that the addition of various chemicals promotes the formation of a highly corrosion-resistant layer on metal surfaces. joning The dissolution of iron in pure, virtually oxygen-free water involves a hydrogen reaction, i.e. the formation of iron(ll) hydroxide and hydrogen. The oxidation of Fe(ll) to Fe(l) and the subsequent condensation to oxides which can form a protective layer are not possible with water as the oxidizing agent at temperatures of < 180°C. Condensate and feed water always contain traces of oxygen, which pro-mote these reactions at the phase boundary, thereby facilitating layer formation, albeit slowly, if the low oxygen level is matched by correspondingly low concentrations of iron(ll) hydroxide. This condition can be satisfied by raising the pH above the saturation pH of Fe(OH)2 (pH = 9.25 at 25°C) in order to suppress the solubility of the iron(ll) hydroxide and thus the iron dissolution itself (conditioning with alkalizing agents, see section 5.3.1 and 5.3.2). Oxidation of Fe(ll) to Fe(Itl), the limiting stage of the Schikorr reaction with water as the oxidizing agent, can be brought above by addition of oxygen. This greatly reduces the solubility of the corrosion product and makes possible the formation of an oxide protective layer, if oxidation occurs near the metal surface. The oxide layer inhibits the metal dissolution which is determined by the solubility of the iron(II) hydroxide, which is in turn dependent on pH, insofar as it reduces the area where water comes into contact with metal. Transport of corrosion products persists to a small extent through pore diffusion. If the ratio between Fe(Il) and the oxygen concentration shifts, when a film is present, which is caused by initial oxidation, for example, the catalyzed oxidation of Fe(\l) produced by hydrated Fe(lll) oxide leads to a growth in the oxide layer and reduces the corrosion product carryover to the feed water. This is the underlying principle of conditioning with oxidizing agents. 5.3.1. Feed water conditioning 5.3.1.1. Feed water conditioning with alkalizing agents (AVT) ‘Ammonia is the most common volatile alkalizing agent. In demineralized water at low temperature pH around 9.5 is necessary to achieve the minimum solubility of iron, and thus corrosion product take-up. Correspondingly high ammonia concentration levels are usually not permitted with brass-tubed condensers, as copper dissolution is caused by concentrations of ammonia resulting from the design characteristics, particularly in the air extraction zone. The alkaline conditioning thus necessitates a compromise. Because of the iron materials, the recommended pH in the feed water is 9 or above. If copper materials are present in the water/steam cycle the upper limit must be set according to the design characteristics and the materials of the condenser and is generally kept below 9.4. The upper limit to ammonia concenirations with tubing made from steel, chromium-nickel steel or'titanium is given by limits on condensate polishing plant load if any available. Air-cooled condensers made of aluminium only permit a pH of no more than 8. The optimum pH level for the whole plant must be established in the condensate/teed water train upstream of the low pressure heaters to ensure maximum corrosion protection for these heaters. Where a condensate polishing plant is installed, ammonia must therefore be dosed upstream of the low pressure heaters. In cycles without a condensateVGB 21 Polishing plant the ammonia only escapes from the water/steam cycle via vent in condenser and deaerator. The addition of ammonia in accordance with the make-up water quantity can also happen at other points, for example in the make-up water on the suction side of the feed water pump. The latter alternative is not feasible, if large quantities of make-up water are fed into the condenser, Hydrazine is also sometimes used to increase pH. It is a reagent, which affect both pH and redox potential through its reaction with oxygen. 5.3.1.2 Feed water conditioning only with oxidizing agents tron take-up by the feed water is reduced by dosing with gaseous oxygen, if the purity of feed water is high. This makes it possible to dispense with alkalizing in the condensate and feed water zone, if ammonia-free steam is desired or, if ammonia must not be present in the water/steam cycle for any reason. The solubility of iron is greatly reduced by oxidizing the primary corrosion product, iron (Il) hydroxide, which creates the conditions necessary for protective oxide layer formation. Conditioning with oxidizing agents is generally used in plants with once through boilers. Dosing with gaseous oxygen must take place upstream of the low pressure heaters. The oxidizing agent concentration must be adjusted so as to minimize dissolved divalent iron in the feed water upstream of the boiler inlet. A successful application of this conditioning is based on good control of feed water purity. Generally it requires condensate polishing plant to ensure the purity. 5.3.1.3 Feed water conditioning with alkalizing and oxidizing agents (OT) The concentration of iron in the feed water is reduced by adding both gaseous oxygen and ammonia. The alkalising agent promotes the oxidation process of Fe (Il) to Fe (Ill) in water containing oxygen and also offers a certain amount of protection against the harmful effect of anions on the protective laver in the event of salt penetrations. Oxygenated treatment is limited, with some exceptions, to plants with once-through boilers having condensate polishing. Ammonia and molecular oxygen must be fed separately into the feed water upstream of the low pressure heaters in concentrations, which ensure that the conditions stipulated in Table 6.3 are fulfilled in the feed water upstream of the boiler inlet. The small increase in pH encourages protective film formation on steel in water containing oxygen without the ammonia reaching concentration levels harmful to copper materials, even in the air extraction zone of a condenser. In comparison with alkaline conditioning, the ammonia concentration of the steam condensate with combined conditioning is so much lower that the run length of the condensate polishing plants until ammonia ion breakthrough is considerable extended. 5.3.2 Boiler water conditioning In drum-type boilers operating at the pressures above 1 MPa, the temperatures in the boiler water circulating system are such that a protective layer is produced by spontaneous magnetite formation. The solubility of magnetite depends on the pH, with a minimum at around pH 10 (measured at 25°C). At much lower pH values, the magnetite solubility increases considerably, likewise in the highly alkaline range. In principle, a solution balance is established in the circulating system, which, however, is disturbed by the evaporation process. This results in supersaturation leading 10 carry-over of corrosion22 VGB products and the depositing of corrosion products on the heated side of the evaporator tubes. 5.3.2.1 Caustic or phosphate treatment (solid alkalizing) The pH of the boiler water must be maintained within a specific range in order to minimize the solubility of the magnetite and to counteract the effect of contaminants, which reduce the pH and can be carried over with the feed water and concentrated in the boiler. This cannot be achieved using volatile alkalising agents, because in the boiler water circulating system they play virtually no part in increasing the pH due to their equal distribution between water and steam in the drum and their dissociation behaviour at high temperatures. The recommended standard procedure for drum-type boilers operating at less than 160 bar is the application of volatile and solid alkalising agents. The aim is for the volatile alkalising agents to maintain a pH above 9 in the condensate/feed water area and for the solid alkalising agents to achieve satisfactory boiler water alkalinity and pH. In order to ensure thorough mixing, the solid alkalising agent -usually sodium hydroxide or possibly tri-sodium phosphate -must be added to the feed water downstream of the spray water tapping point. Alternatively, the solid alkalising agents can be dosed into downcomers or to the boiler drum, if the dosing points are designed to ensure good distribution and avoid local overdosing. 5.3.2.2 Allvolatile treatment Volatile alkalising agents can be used by themselves in the water/steam cycle of drum-type boilers when operating with demineralised feed water on condition that the conductivity of the boiler water can be maintained at a very low level, i.e. the ingress of trace contaminants can be virtually eliminated. When drum-type boilers use only feed water conditioned with oxidizing agents in accordance with section 5.3.1.2 or alkalising and oxidizing agents in accordance with section 5.3.1.3 (oxygenated treatment), the oxygen content should be maintained at the lower limit of the recommended range. The boiler water should then be conditioned with a solid alkalising agent. 5.3.3 Special conditioning agents The treatment chemicals described in chapter 5.3.1 and 5.3.2 are typical for power plants and also for industrial plants. Besides those “basic” chemicals numerous organic treatment chemicals are offered and in use, mainly in industrial plants. The chemicals can be classified as follows: — Neutralising/alkalising amines. = Film-forming amines. — Alternative oxygen scavengers ("hydrazine substitutes"). - Dispersants. Nearly all of these chemicals are subject to thermal degradation under boiler operating coniitions, resulting in formation of organic acids and/or carbon dioxide. The breakdown products increase the acid conductivity in the entire steam water cycle and possible ingress of contaminants from ather sources are masked. Concentration of the breakdown products in the first condensate of a condensing steam turbine may result in corrosion attack.VGBS 23 Acidic breakdown products decrease the pH of the boiler water and require the application of solid alkalising agents. Plants using organic treatment chemicals should thoroughly reconsider the actual chemical regime and investigate, if the applied chemicals are really indispensable or if a reduction in the number of chemicals is feasible. Single substances should be preferred, rather than proprietary chemical blends. A redesign of systems may be a worthwhile challenge to reduce the number and dosing concentrations of organic treatment chemicals or even enable a chemical treatment according to chapter 5.3.1 and 5.3.2 and save operating costs. Plants with long-term good operational experience without any damages or upsets related to the use of organic treatment chemicals may continue with the proven chemical regime, but take the above mentioned into account. The design of new plants should enable a chemical treatment according to chapter 5.3.1 and 5. The application of alternative treatment chemicals requires the agreement of the boiler and steam turbine manufacturer. 6 Chemical specification 6.1 Action level control system The chemical control is based on specifications of normal operating values and 3 action levels for concentrations of chemical species. The most significant parameters are defined as key parameters and stringent control of them is required, if possible continuous monitoring. Other chemical measurements will frequently provide valuable diagnostic data. Laboratory support is required for periodical extended analysis and check of monitors. The action levels are defined which allow the operator to use the same set of limits for continuous operation and for start-up. The detailed definitions of action levels are specified separately for these situations in table 6.1. Action levels are time related and the combination of concentration and time are set to minimise damage to feed, boiler and turbine components from corrosion and deposition processes. The limits for action levels are defined as a function of pressure. This is a simplified approach; there are other parameters which affect the “true” limits (e.g. heat flux) Nevertheless, pressure has been chosen as the most convenient parameter for operators. Boilers with extraordinary high heat flux (some designs of oil fired boilers) may require more stringent limits particularly in regard of boiler water quality Itis the aim of the guidelines to avoid the shut-down requirement as long as there is any realistic chance to eliminate the source of trouble. This should be managed by such actions as load reduction to reduce heat flux (i.e. reducing the risk of damage whilst remedial actions are being undertaken) before action level 3 limits are exceeded. Load reductions may also be essential when feed-water contamination is encountered in order to allow the flow of this water to attemporator sprays to be terminated’ without risk of overheating.24 VGB When a drum boiler on AVT dosing is exposed to high levels of impurities, it can be temporarily conditioned with solid alkali (giving it higher tolerance of impurities) and thus delaying or avoiding action level 3.25 Tena] 49ybjy Si4) We pauyep S| Jojewesed Bulpuad ou)! ‘seydde Ty JoyS1y rou oU) syumy ow O43 BuIpesaxe Ag “2 ‘sjuewea! 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Table 6.6: Drum Boilers with copper in condensate / feed water system Vos FEED WATER and Allempersior Spray Water pH N 89-91 ALT 88 93 AL2 85 9.4 ‘ALS 82 35 Conductivity pSiem [N’ 22-34 {only valid for ammonia ACT 7 55 dosing) AL2 08 7.0 ALS 0.4 85 Acid Conductivity uSiem [N) <0.10 ALT 0.20 AL2 0.30 ‘AL3 1 ‘Oxygen (02) ha/kg LN 5 ‘Alt 10 AL2 50 ALS 100 Silica (Si0,) uolkg LN 25 ACT 20 AL2 50 ‘ALS 7 Tron (Fe), total hows [IN =10 ALT 20 AL2 30 ALS = Copper (Cu), total ugikg[N 50 AL2 100 ALS 200) Phosphate (PO,) N <6 Silica (SiO,) N 0.25% ALT ALi according to figure 4 respectively § AL2 2xALt ALS = Organics: see chapter 7.10 N: Normal Level AL 1 (2,3): Action Level Table 6.9: Drum Boilers with AVT (Alkaline) Treatment ‘BOILER WATER ‘Steam Pressure (MPa) <8 8-16 316 1H N H is controlled by pH of the feed water" ‘Acid Conductivity Siem [IN <5 <3 <1 ALY 5 3 1 AL2 10 6 25 ALS. 20 12 Silica (SiO) N 0.25 xALt ALT ‘according to figure 4 respectively 5 AL2 2xALT ALS) = Organics ‘see chapier 7.10 N: Normal Level AL1 (2,3): Action Level {pH feed water > 9.5VGB 6.2.4 Requirements on steam for condensing turbines Table 6.10: Steam ‘STEAM for steam turbines ‘Acid Conductivity Silica (Si0,) Sodium (Na} N ALT AL2 ALS Tron (Fe), total N ALT AL2 AL3 Copper (Gu), total N ALA AL2 ALS N: Normal Level AL 1 (2,3): Action Level o Boiler Water Treatment AVT or Caustic <2 5 10 20 33 Boiler Water Treatment Phosphate <5 10 20, 40 Higher action values may be defined if the increase of acid conductivity can be attributed to carbon dioxide trom air inleakage and organic decomposition products can be excluded. 6.3 Operation with feed water non-demineralized 6.3.1 General For economical reasons, non-demineralised water may be used in some specific cases‘ Non-demineralised water is a water which still contains dissolved solids such as decarbonisated water or/and softened water. This water is used when the make-up rate to water cycle is low. This may be the case for process steam supply to industry or town power cycle. Then, the feed water is composed of condensates return mainly, mixed with a slight proportion of “non-demineralised” make- up. “dustry, low pressure unit34 VGB The feasibility of this kind of make-up is directly linked to the raw water characteristics, water treatment, ratio of make-up/condensates and main design/characteristics' of the steam generator. Each case must be specifically studied to estimate its feasibility and compliance with these recommendations. 6.3.2 Feasibility study 6.3.2.1 Raw water / treated water parameters Considering non-demineralised water make-up, several parameters have to be checked since the water treatment removes them partly or not. These parameters are mainly silica, chlorides and salinity. Total alkalinity is a key parameter for softened water, namely.? In any case, hardness must be fully eliminated. 63.22 Condensate percentage return To assess the feed water quality, it is necessary to know both amount and quality of the Condensate return’. In closed cycle (either from process or with a condenser) this quality will improve in time, due to the purification achieved in the boiler, through the blow-down. 6.3.2.3 Concentration factor The mineral species are concentrated in the boiler water. Alkalinity is decomposed in the boiler to give caustic. Since a maximum concentration is given in the boiler water®, blow- down is necessary to keep the water within the limits. This is particularly true for conductivity, silica, alkalinity and strong acid salts. The boiler blow-down rate is the decision parameter to judge on the feasibility. In some case, blow-down recovery can be considered after thermodynamic balance calculus. However, in other cases, due to the low condensates return - or poor quality - or high salinity of raw water, this kind of water is not suitable and demineralized water only is the issue. * None of these water qualities are suitable for allemperator spray water! * Total organic carbon must always been checked * Steam quality (silica, hardness) and water consitioning are to be assessedVGB 35 Table 6.11: Feed water for drum boilers FEED WATER. ‘Steam Pressure (MPa) <2 2-4 34 pHi N 9.2-9.5 0) 9.2-9.5 7 92-957 Aur fo2"T 95 [e247 95 | a2" | 95 AL2 | ee" | 10.0 [ea [100 | 387 | 100 AL3 | 80° 105 | 807 [405 | a0 | 105 Conductivity Siem Tot specified ~ consider boiler water Total Hardness (Ca + Mg) | mmobkg [ N = 0.005, 0.005 <0.005 ALT 0.02 0.01 0.005 AL2 0.05 0.02 0.0% ALS 02 02 ot Silica (SiO,) Loko not specified ~ consider boiler water Iron (Fe), total hgkg [NW =30 <20 <0 ALA 50 30 20 ALZ 200 100 50 ALS = = = Copper {Cu}, total ugk [N <3 <3 <3 ALT 20 10 3 AL2 50 25 10 ALS = = = ‘Oxygen (02 pokg TN 5 5 5 ALT 20 20 20 AL2 50 50 50 ALS 100 100 100 Oil Grease / Organics See chapter 7.10 N: Normal Level AL1 (2,3): Action Level with copper alloys in the system the pH value shail be maintained in the range 8.7 to 9.2 with softened make-up water (pH > 7) the pH value of boiler water according to table 6.12 - 6.14 should be considered @36. VES Table 6.12: Boiler water for drum boilers with saturated steam design Conductivity ‘Alkalinity (As) Silica (SiO2) ‘Steam Pressure (MPa) N ALI AL2 ALS N ALY AL2 ALS N ALT AL2 ALS N ALY AL2 AL3 Phosphate (POz) " N Organics ALA AL2 ALS N: Normal Level AL1 (2,3): Action Level © ifused BOILER WATER. <2 2-4 34 10.8 11.5, 10.8 = 11.5 10.5— 14.0 705 | 120 | 105 [ 118 | 10.3 7 115 100 | 122 | 10.0 12 10.0 | 11.8 95 | 125 | 95 | 123 | 90 | 120 < ALT ressure dependent according to figure 2 1.2K AL1 15x ALT 2-5 1 ALi ressure and alkalinity dependent according to figure 4 1.25% AL4 16 10 20, 30. 50, ‘see chapter 7.10VGB 37 Table 6.13: Boiler water for drum boilers with superheated steam design ‘Steam Pressure (MPa) N ALG AL2 ALS Conductivity N ALi AL2 ‘ALS ‘Alkalinity (An) N ALT AL2 ALS Silica (SiO) N ALA AL2 ALS Phosphate (PO,) N ALI AL2 ALS Organics N: Normal Level AL1 (2,3): Action Level *) ifused BOWLER WATER <2 108-115 105 | 118 10.0 | 12.0 a0 | 126 2-4 40.8-11.5 105 | 17 10.0 | 118 90 | 125 7) reaction of liquids, particularly water samples of water steam-circuits. Because of the definition of the pH-value (negative decadic logarithm of the concentration of hydrogen ions) any step of a pH-unit is an actual change of the acidic or alkaline concentration for a factor of ten! For exact results the pH value must be measured electrochemically using pH-meter and electrodes, indicators give rough information only. The pH value changes significantly with the temperature and must be either noted together with the measuring temperature or corrected to a reference temperature of 25°C, see Figure 6. Corrosion of unalloyed and low-alloyed steels commonly used in boiler plants is affected considerably by the pH. The required pH can be established in boiler water by dosing (conditioning) with non-volatile alkalising agents (e.g. caustic soda and tri-sodium Phosphate, see Figure 7) and in feed water and condensate by conditioning with volatile alkalising agents (e.g. ammonia, amines, hydrazine, see Figure 8). As far as possible, their combined use, with continuous dosing, should be aimed for. The pH must be limited in the feed water, boiler water and condensate to prevent attack on certain metals, dissolution of iron protective layers and to avoid foaming of the boiler water. Due to the increasing solubility of the protective layers of iron oxide in acidic solutions aqueous samples of water-steam-circults should be basically alkaline, see Figure 9. Acid capacity Acid capacity is a titration method to measure and to calculate the amount of both ~ strong alkaline substances (acid capacity to pH 8.2) like caustic alkalis and ~ free caustics of alkali-carbonates, tri-alkali phosphates and di-alkali silicates as well as ~ _ strong alkaline volatile substances like ammonia or amines and ~ weak alkaline or neutral substances with hidden alkaline power (acid capacity to PH 4.3) like alkali or ammonia/amine bicarbonates and di-phosphates respectively, The unit of the acid capacity is mmol/l (measured with a single base acid like hydrochloric acid) or meq/l. 100 mg/kg CaCOs correspond an acid capacity of 2 mmol! or 2 meqil The correlation between pH and acid capacity can be seen in Figure 10 Alkalinity Alkalinity is similar to the acid capacity and divided into total alkalinity - comparable to acid capacity to pH 4.3 and caustic alkalinity - comparable to acid capacity to pH 8.2.i 42 VGB Significant difference to the latter is a particular treatment with barium chloride to obtain the real amount of free caustic alkali — without influence of carbonates, phosphates and silicates. pH-value | — pure water — 1.5 mg/kg ammonia — 10 mg/kg trisodium phosphate Figure 6: pH influence of 1.5 mg/kg ammonia (NHs) respectively 10 mg/kg tri-sodium phosphate (NasPO) to i ‘pure water depending of temperature pH-value — sodium hydroxid — trisodium phosphate Figure 7: Increase of pH value at 25°C in pure water by non volatile alkalising agents sodium hydroxide (NaOH) and trisodium phosphate (NasPO.)43 pH-value — ammonia — hydrazine Figure 8: Increase of pH value at 25°C in pure water by volatile alkalising agents ammonia (NH) and hydrazine (NeH,) 10 11 12 138° «14 HOH ha Ste He Ate aeettg pH-value (25 °C) Figure @: Magnetite (Fes0,) solubility at pH 3 to 1344 strongly __acicic weakly Figure 10: Interrelation between pH value and acid- (Ks) respectively base-capacity (Ka) 7.2 Conductivity The electrical conductivity is a measure for the sum of all dissociated substances (salts, acids, bases and some organic substances) in liquids and is the actual substitute for the value of total dissolved solids/matter (TDS), particularly for TDS < 1 mg/l. The unit for conductivity is Siemens (S) per metre (m) corresponding to 1/(Ohm - m) and is expressed in 1 S/m , 10* uS/em or 10° mS/m. The conductivity changes strongly by the temperature and must be either noted together with the measuring temperature or corrected to a reference temperature of 25°C. The temperature correction factor is not constant and depends on the type of electrical ‘conductive matter and the absolute value of the conductivity, particularly < 0.2 1S/cm. The conductivity of the purest water at 25°C is approximately 0.055 wS/em. Conduetivity is the direct measured specific conductivity of any liquid. Acid conductivity is the conductivity measured downstream of a strong acidic cation exchanger (sampling filter) which results in the elimination of any cation (like ammonia, sodium, potassium) and the emission of H'-cations. In that case, salts change to its free acids e.g. NaCl4H’-cation exchanger = > ~—- HCI + Na-cation exchanger. Bases, however, like ammonium or sodium hydroxide reacts to water e. g. NaOH +H*-cation exchanger > +~—-H0 + Na-cation exchanger. Acids, also carbonic acid, are passing the cation exchanger without any effect. This is an advantage for the indication of traces of salts (e.g. of condenser leaks) in water samples alkalised with ammonia, because acids have a significant (4 to 7 times) higher specific conductivity than its neutral salts. On the other hand it prevents the indication of leaks of e.g. caustic soda in water samples.VGB 45 Increasing conductivity in water samples promotes corrosion processes, particularly in presence of oxygen. Elevated conductivity in BW may lead to carry over and poor steam quality. 73 Oxygen Concentration of dissolved oxygen is generally used as a parameter to express the oxidation or reduction potential (redox potential) of an aquatic solution. This use is found to be the most appropriate for practical purposes, even though it is biased by insufficient equilibrium of the system. The solution can simultaneously contain oxygen, other oxidation agents and even reduction agents, which did not react so far. The assessments of oxygen concentration have to be made together with pH and purity of the system (acid conductivity). High purity of the water allows increased concentrations of ‘oxygen and decreased pH, resulting in better protection of steel. The improvement of the protection is caused by an oxidation of the surface of the magnetite protective layer to hematite. Hematite has lower solubility and much finer crystalline structure and seals the porous magnetite structure. If high purity of the water is not achievable, the protection must relay on increased pH at low oxygen concentrations. However, the extremely low oxygen concentration achievable by addition of strong reducing agents (oxygen scavengers) should be carefully considered, as the reduction of the magnetite layer result in increase of its solubility and tendency to flow assisted corrosion. 74 Hardness Hardness is a measure for the sum of all alkaline-earth elements, like calcium and magnesium (rarely also barium and strontium) compounds in water samples and an indicator for the risk of scale formation due to hardness (hardness scale). Deposition on heated surfaces leads to uneconomic operation and may lead to material over-heating and to corrosion underneath the scale due to concentration of dissolved solids. The Sl-unit for hardness is mmol. 1 mmol/l corresponds to 100 mg/l CaCOs. Hardness and silica together may lead to particular scale with very low heat transfer rate. 75 Phosphate Phosphate in form of alkali phosphates — mostly tri-sodium phosphate — is used for both -_alkalisation agent, see Figure 6 and - scale inhibitor to prevent hardness scale. Due to the particular solution behaviour of tri-sodium phosphate tri-sodium phosphate is an alkalisation agent for boilers with heated gaps or heated phase boundaries because of its significantly reduced solubility > 250°C. Due to the particular solution behaviour phosphate tends to local deposit formation so called ‘hide out" on surfaces with high heat transfer. In case of phosphate dosing therefore the specified concentration in boiler water must be reduced with increasing pressure. 76 Silica Silica concentrations in the feed water of once-through boilers and the boiler water of drum-lype boilers must not exceed certain values because of the requirement concerning46 VGB ‘steam purity for turbine operation. The solubility of silica in steam increases with pressure. When operating with fully demineralized make-up water, the silica concentration in the feed water and steam of once-through and drum- type boilers remains far below the specified values in Tables 6.3 and 6.6 and 6.10. Even when the specified values are complied with, silica deposits in the high pressure section of the turbine cannot be excluded under the most unfavourable conditions, especially in the presence of substances such as aluminium. If there are differences between the silica concentration in the feed water and in the steam or if the silica concentration in the boiler water is higher than the product of concentration coefficient and silica concentration of the feed water, then the raw water probably contains colloidal silica, which was not retained in the make- up water treatment plant and has hydrolysed to form soluble silica in the boiler. Ww tron and copper Iron and copper concentrations in feed water and steam are an indicator of the efficiency of conditioning. They supply information on the metal dissolution processes in the system and the metal take-up by the water as well as possible deposits in the boiler and turbine. Changes in iron and copper concentrations due to load fluctuations cannot be influenced by chemical measures. In respect of corrosion product absorption, we again refer to the requirement that condensates should not influence the characteristics of feed water or boiler water. 7.8 Sodium / Sodium hydroxide Sodium is used to condition the boiler water of drum-type boilers in the form of sodium hydroxide and trisodium phosphate, but it also occurs as a contaminant in the water/steam cycle through slippage from ion exchangers or heat exchanger leakage. Measuring the conductivity or the sodium level with an ion-sensitive (pNa) electrode is a sensitive indicator of impurity ingress, typically due to cooling water. In plants with drum-type boilers, whose water is conditioned with solid alkalizing agents, the sodium concentration in the steam complies with the normal operating value in Table 6.10, if the sodium hydroxide or tri-sodium phosphate concentrations are held within the pH and phosphate limits in Tables 6.7 and 6.8. Levels which exceed the specified values point to unfavourable water/steam separation in the drum and boiler water droplet entrainment. Carry-over of sodium compounds to the steam can result in super-heater and turbine deposits possibly also in corrosion. 79 Carbon dioxide Carbon dioxide is a common contaminant in the steam water cycle that leads to an increase of acid conductivity. Depending on the quantity of air entering the steam water cycle, as well as on cycle capabilities for degassing (condenser, deaerator) and demineralisation (condensate polishers), some residues will remain circulating through the systems. Another source is thermal decomposition of organic matter that has entered the cycle. Besides carbon dioxide, other decomposition products, e.g. organic acids may be formed.VGB AT Han increase in acid conductivity can be attributed to air in-leakage and organic decomposition products can be excluded, relaxed action levels and schedules on acid Conductivity can be defined, according to operator and turbine supplier's experience. 7.10 Organic substances Organic substances, which are carried over with the feed water into the steam generator, can, after being concentrated in the boiler water of drum-type boilers, increase its foaming tendency, cause carry-over of boiler water droplets and thus indirectly affect the steam quality. Decomposition products of organic substances formed under boiler conditions can directly affect the pH of boiler water and, if volatile, the steam quality [6]. Organic substances in the water are best detected by determining the dissolved organic carbon (DOC) content. The DOC content of demineralised make-up water should not exceed 0.2 mgll (the knowledge of the type of organics is very important and not the sum parameter DOC). It is recommended to strive for less than 0.1 mg/l. Even this value may be too high in special cases, depending on the nature of the organic matter and the make- up water demand. High make-up rates require a minimization of the DOC content. Where organic substances can enter the steam water cycle from other sources, e.g. return Of non-purified condensate in industrial power plants, continuous monitoring of the DOC content in the condensate or feed water is recommended. When operating with demineralised feed water, the effects of such ingresses usually can also be detected due to the shift of some other measured parameters, for example a decrease in the pH of the boiler water, an increase in the acid conductivity of steam or the occurrence of a difference in acid conductivity between feed water and steam as a result of the decomposition of organic substances. It is not possible to specify generally applicable specified values. Where necessary, assessment criteria must be established conceming the influence of oil, other organic substances or their decomposition products and concerning the maximum permissible DOC content based on specific operating experience and requirements. 8 Analytical control of operation a4 Sampling of Water and Steam It cannot be emphasised enough, that: “Poor sampling gives poor results” Too often “chemists” cary out extremely sensitive and complex analysis which, undoubtedly area accurate but if the sample is flawed the results are meaningless. For example, leaking unions on sample coolers allowing air ingress prior to deaerator efficiency monitoring, or cooling water ingress, contaminating the cooled sample. These samples may show high oxygen or high acid conductivity — but is this a function of sanipling or a problem with plant conditions? Decisions and communication need to be clear as to WHAT is sampled and from where. Typical sample points should include, but not be limited to: - ~ demineralized or non-demineralized water make-up feed, ~ condensate returned to the make up,48 VGB - feed exit the deaerator, — recirculating boiler water, ~ saturated steam. The physical conditions of the process fluid e.g. temperature, pressure, rate of flow and the limitations of the analytical technique need to be considered and suitably designed sampiing facilities installed. There are standards for the sampling of key fluids e.g. superheated and saturated steam where iso-kinetic sampling is recommended as mandatory for meaningful results, It is vital to take a safe representative sample. Sample conditioning is equally as imperative e.g. temperature, pressure and flow of the final sample should be normalised and kept constant for the most accurate and reproducible results. Settlement of solids in the sample-line needs to be avoided whilst erosion-corrosion of the sample line must not ocour. The choice of materials for the sample line and cooler needs to be selected with care for the various duties. The length of run of a sample line should be kept as short as is practical to avoid complications from delays in changes in plant conditions to the arrival of samples at the analyser although short lag times can be accommodated in the process control loops. ‘Sample line residence time and materials choice become even more critical where “grab" samples are taken. Ideally all samples should be run continuously, at constant rate. Any change in rate (e.g. an operator opening the sample valve to get a quicker flow to fill 2 bottle more rapidly) may pick up material that has settled behind needle valves or in horizontal runs of pipe, leading to analytically correct, but process-wise, misleading values. The choice of the container for discrete samples is critical e.g. do not use glass bottles for sodium analyses or plastic containers for carbon dioxide. Sample-lines that are isolated need to be run until freshly removed fluid has completely filled the line and stable conditions have been established. There are arguments for On-line Analysis and for discrete samples, analysed and monitored on a much reduced frequency which, provided the above considerations are catered for, devolve to one of economics regarding cost of acquiring the data versus the hysteresis of the system for reliable control. Such decisions should be made on a case by case basis, subject to analysis of process capability. A closed loop control system can be used to regulated the process for the desired determinant set point in the operation e.g. pH in boiler water. 82 Measurement The choice of determinants needs to be made on a case by case basis, depending on the chosen chemistry of the station. Details of chemistries, levels, ranges and, by definition, the required parameters to monitor and control them, are given in Chapter 6. From this, analytical requirements can be selected However, accuracy, reproducibility, calibration and reliability should be taken into account. 83 Monitoring Parameters change on Power Plants and inter-relate with each other, often in predictable ways but occasionally with unexpected side effects. It is strongly recommended that an inter-active data base is operated with a facility to plot a minimum of any four parameters simultaneously over any time period to enable lateral thinking of chemical and temporal effects. This is often the case for plant based systems, through DCS technology, but it isVGB 49 strongly recommended that the same functionality and sophistication is applied to laboratory based measurements. 8.4 Control Process control is best maintained by selecting a single, primary determinant; analysing for that determinant in a sample of the process fiuid that needs to be controlled and altering the process accordingly. For example, in a phosphate/oxygen scavenger/alkalizing agent dosed boiler all three chemicals can have an impact on pH and conductivity but it is recommended that control is affected by three separate steps: 1. Inthefeed - measuring direct and acid conductivity for calculating pH and dosing alkalizing agent continuously and automatically to a set point which is in the middle of the “N" range. 2, Inthefeed - — measuring oxygen and dosing scavenger continuously to a set point which is in the middle of the “N" range. 3. Inthe boiler - — measuring pH and dosing phosphate to a set point which is in the middle of the "N" range. 8.5 Maintenance and Calibration Requirement for dedicated articifers on the plant is necessary to maintain and calibrate instruments on a daily basis if necessary. The laboratory results should plot deviations from norm over a long time periods and report accordingly. 8.6 On-line measurements (This chapter will be considered in the next revision.) 8.7 Manual controls (This chapter will be considered in the next revision.)50 VGB 9 Annex 94 Internal cleaning and preservation 9.1.1 Internal cleaning The topic of internal cleaning plays an important role in reaching the aim of this guideline, enabling boiler operation that is as trouble-free as possible as well as good steam quality for the operation of turbines. If the Water-Steam-System isn't cleaned properly and professionally problems for the operation of the plant will recur leading to poor availability and possible damage to the system. In the power plant industry there are numerous company-specific or proprietary guidelines and specifications for internal cleaning and steam blowing. Independent guidance can be found in VGB guideline, VGB R 513 “Internal Cleaning of Water-Tube Steam Generating Plants and Associated Pipe-work" [7] which is generally agreed upon by the power plant industry. This guideline is intended to give recommendations for: — Flushing, — alkaline boil-out, — _ preoperational acid cleaning of new plants, - chemical cleaning of plants under operation, = steam blowing of water-tube generating plants and associated pipe-work upstream to the turbine, where required. When selecting the type and performance of the cleaning procedures, agreement shall be reached between the (steam boiler/pipe-work/turbine) manufacturers and the plant user and be stipulated in writing. This agreement should be reached as early as possible in the design stage. 9.1.2 Preservation Preservation means any method to avoid corrosion on the waterside of boilers, parts of it or auxiliary components made of low-alloyed steel during shut down and stand-by. It also includes storage and transportation, erection and commissioning of plant. This can be realized by excluding either oxygen or water respectively. A sufficient present protective layer of iron oxides on the waterside of boilers (in operation for at least 1 month before shut down) can protect low-alloyed steel in presence of humidity or moisture and air for restricted time only. If non-demineralised BFW/BW is used the time without preservation is restricted to 1 week, in case of the use of demineralised BFW/BW the shut down time without preservation should not exceed 2 weeks. Exceeding times require preservation methods by either - wet preservation (in absence of air) eg. by replacing of air by nitrogen or complete kept filling of the boiler with alkaline water containing oxygen scavenger, or — dry preservation (in absence of moisture) by drying with desiccants, e.g. silica gel or regenerative circulating dryers.VGB 51 Details may be obtained from special papers (for example VGB A116 H ‘Preservation of Power Plant Systems”) (8). High-alloyed or stainless steel may require particular preservation methods to avoid chloride induced pitting or SCC in special cases during transport, storage and stand by. Preservation on the flue gas side of boilers may be necessary too, particularly on coal and oil fired boilers. 9.2 Physical-chemical processes 9.2.1 Basics of material protection The corrosive attack of water or steam on steel leading to the formation of iron oxides is naturally limited if a protective layer, i.e, a dense and uniform oxide layer forms on the surface of the steel. The only iron oxide, which can exist in direct contact with the metal, is magnetite, on which oxides of trivalent iron can grow, depending on the redox conditions. Such protective layers restrict the transport of corrosion products to pore diffusion and reduce the area available for reaction between steel and water or steam, thereby minimizing the material loss rate (surface layer passivity). The basic chemical reaction between iron (steel) and water involves iron dissolution through several reaction stages - a redox stage Fe({l) - Fe(\ll) and condensation stages (Schikorr reaction) - to the thermodynamically stable end product, magnetite. The kinetics, of the Schikorr reaction show marked temperature dependency which is characterized by inhibition of the redox stage. Oxidation of the divalent iron by water needs particular configurations and conditions, which only occur in exceptional cases at low temperatures (6.3). On the other hand, magnetite is spontaneously formed at temperatures, when condensation of iron(ll) hydroxide is possible. The steel is covered by a protective layer. 3 Fe + 4H20 + FesQq + 4 He (9.1) Based on these interactions, water/steam cycles in power plants can be divided into two areas: — the temperature range up to around 200°C, where an inhibited Schikorr reaction assures that the steel surface in contact with water remains active in respect of iron dissolution and - the hot water area from around 200°C, where the magnetite protective layer forms spontaneously. Iron dissolution is at maximum at around 150°C. In the condensate/feed water line, i.e, near the LP pre-heaters at low and medium water temperatures, the iron dissolution in pure water is normally diffusion controlled. It can change into erosion-corrosion under unfavourable local flow conditions. Conditioning is needed to reduce corrosion and corrosion product pick-up by the feed water. 9.2:2 Deposition 9.2.2.1 Deposition from water lron(ll) hydroxide as the dissolved corrosion product of iron, whose solubility decreases as the temperature increases, tends to form supersaturated solutions above 200°C. At points of high turbulence, e.g. around boiler control devices, or on heating faces subjected to high52 VGB heat fluxes, magnetite precipitates out from such solutions in crystalline form. This leads to reductions in cross-section or hampers the heat transfer in steam generation tubes and can cause damage to materials due to overheating, Undissolved, suspended corrosion products, which are carried with the feed water into the boiler or are produced in the boiler itself, can form deposits, especially on thermally stressed tube walls and these normally have a detrimental effect. On the one hand, such deposits can affect the heat transfer which causes the tube wall temperature to rise, leading to overheating and rupture of the tubes due to hydrogen damage from enhanced reaction between iron and water. On the other hand, electrolytes dissolved in the water can concentrate under deposits, thereby initiating a chemical attack on the tube material or protective layer. The concentration of electrolytes depends on the heat flux (evaporation intensity) and the electrolyte concentration in the bulk water. 9.2.2.2 Deposition from steam Impurities in steam can deposit on super-heaters, control devices and turbine blades and lead to corrosion and a decrease of the turbine efficiency. Dissolved solids enter the steam by physical or chemical carry-over. The physical carry- over of boiler water droplets is typical for drum boilers only. Satisfactory water/steam separation in drum should be ensured by appropriate design measures. However, operational conditions have significant effect on mechanical carry-over. Disturbance of the control of boiler water level in the drum is the most common cause of an increased steam contamination. Foaming due to contamination of boiler water, sudden change in pressure of load are typical disturbances. The chemical carry-over is due to the solubility of water-soluble solids in steam. The solubility in steam is primarily dependent on density of steam. As density of steam rise with pressure and fall with temperature, will the solubility follow the same pattern. The highest solubility at a given pressure is in saturated steam. Dissolved solids in steam can therefore precipitate in super-heaters because of density decrease due to temperature rise and on turbine blades because of density decrease due to pressure drop. The deposits - where electrolytes are involved -cause corrosion in the presence of water or as a molten material. Commonly observed corrosion at the place of early condensation at the last turbine rows is connected with deposition of contaminants decreasing pH of early condensate. Elfect of weak acidic contaminants is therefore moderated comparing to strong acidic contaminants. ‘The effect may be even more moderated by condensing alkalising agent. Non electrolytic deposits (i. silica) may change the roughness of turbine blades resulting in decrease of turbine efficiency. 9.2.3 Corrosion 9.2.3.1 General Corrosion is the interaction between a material and its environment. Many different types of corrosion occur in steam water cycles. The mechanisms and the influence of material properties, chemical and operational conditions and system design on the corrosion processes are known today. Avoidance of corrosion processes and its impact on plant availability and costs should be a main target of a plant management. This includes an optimized chemical treatment of the cycles according to this guideline as well. | |VGB 53 9.2.3.2 — Oxygen corrosion/idle corrosion Damages due to oxygen corrosion are often a result of missing or inadequate lay-up measures during shutdown periods. Systems or components filled with aerated water or left drained with moisture and air in it suffer from this type of corrosion. Pits from oxygen corrosion may act as start location for stress corrosion cracking. Oxygen corrosion is also a known trouble with the operation of condensate return lines including atmospheric open condensate collecting tanks or basins. 9.2.3.3 Acid corrosion Acid corrosion results in an uniform removal of the protective layer and attack on the metal. This process requires concentration of an acidic contaminant, which source may be condenser leakages, regeneration chemicals or the boiler water treatment with Phosphates. Most commonly the damage occurs in regions with high heat flux, excessive deposits and/or flow disturbances. Acid attack on system materials during acid cleaning can be excluded, if standard practices for chemical cleaning are used [7]. 9.2.3.4 Caustic Corrosion Caustic corrosion (caustic gouging) during operation shows the same effect and needs similar preconditions as the acid corrosion, but with the localized concentration of sodium hydroxide, e. g. from caustic treatment of the boiler water. 9.2.3.5 — Hydrogen Corrosion This type of corrosion requires the liberation of atomic hydrogen, which may occur under acid corrosion processes. Atomic hydrogen diffuses into the steel, reacts to molecular hydrogen and/or methane and results in formation of cracks and damage. 9.2.3.6 — Stress Corrosion Cracking Stress corrosion cracking is probable, it metal with sufficiently high tensile stresses, prone to this type of corrosion and a specific corrodent are present. Typical corrodents are sodium hydroxide for carbon steel and sodium hydroxide and chloride for stainless steel. 9.2.3.7 Flow-Accelerated Corrosion Flow-accelerated corrosion prevents the building-up of protective layers on carbon steel. The process is influenced by velocity, geometry, temperature, steam quality, water chemistry and material. The resistance increases with chromium, copper, and molybdenum content of the material. The maximum of this corrosion attack occurs around 150°C. Beyond approx. 250°C or a pH-value of > 9.5 an attack is unlikely. Oxygen in high purity water prevents flow-accelerated corrosion. 9.2.3.8 Corrosion Fatigue The causes for corrosion fatigue cracking are cyclic stresses/strains of sufficient order, produced by pressure fluctuations and/or by rapid temperature changes. Frequent start. ups and shutdowns promote the start and growth of cracks until penetration or rupture of the metal.BA ves 93 - Economical considerations Evaluation of economical consequences of operation outside the recommended range is an extremely difficult task. Even after decades and decades operation experience it was not possible to estimate the standard costs of operation and maintenance associated to chemistry, because of great variations of boundary conditions and difficulties in estimation of the chemical share in long term wear and damages. However, some guide is required to be able to manage the operation outside the chemically optimal range on an economically convenient way. Up to date time limits are used for each exceeding of an Action level. But this system has no relation to the economy, as the price of power varies with time in the open marked, the price of an alternative production varies as well and remaining value of the unit varies from place to place. The true economical evaluation is only possible if we are able to express the life time consumption as a function of operational chemical parameters. And this is the difficult part of the task. The first attempt is based on quality index expressing the life time consumption factor relative to reference lifetime consumption (normal operation). There is no doubt that system will need some adjustments to make more convenient application possible 9.3.1 Assessment of water/steam chemistry by quality indices The quality index | for any control parameter p is in general terms defined as a ratio of lifetime consumption (Tp) of a component effected by the control parameter at the actual operating value and the lifetime consumption (Ti1p) of this component operating at the reference conditions, which means at the limit between target and action level 1 (Lip). lp=dTe/dTup (3.3.1) The index expresses the relative rate of lifetime consumption and will then be 1 at the operation at the limit for Action level 1, which is considered as conditions with reference life time consumption: AtP = Lip Ip = lo = ATup/dT ip (9.3.2) The lifetime consumption at actual conditions Tp of a particular component during any operation period t is then calculated from the formula: ' Tp= fle: dt (9.3.3) ° Operating at action level 1 (P > Lup) the index will have value above 1 and operating below the action level 1 limit (target area), the index will have value less then 1. Thus the lifetime consumption will be faster or slower comparing to the operation at reference conditions. Itis extremely difficult to establish a scientifically or statistically based model for the lifetime consumption deviations from reference conditions. A pragmatic way was chosen , based on the following concept: ~The lifetime consumption should be evaluated separately for each main component of water/steam circuit using parameters significant for component in question. - The rate of lifetime consumption (Index |) is an exponential function of the relevant parameter. — The exponential function is normalized for action level limits defining: ALP =Lip l= 1 (9.3.4)a] | | i VGB 55 AtP = Lap I= 10 ALP = Lop T= 100 ALP =3°Lap 1= 1000 The justification of these values is based on some experience from units operating with good chemical practice and also from units where less attention is paid to chemistry; however, the data basis is limited. The index is mathematically related to action levels by the following equations: bb b= 1085 for P< Le (9.3.8) Poke Ip=tobebe forleLs (9.3.10) where Ip __is the index for parameter p P is the monitored value of parameter p L, is the threshold tor action level 4 Lo is the threshold for action level 2 Ls is the threshold for action level 3 The index can be used for relative evaluation of the chemical performance with respect to the lifetime consumption of components for which the parameter p is the key parameter. It has to be emphasized, that it is an evaluation relative to reference conditions and if more than one key parameter is relevant for the component in question, a combination of indices as described should be used. 9.3.2 Operation above Action level 3 If the chemistry in an operating unit come out of control and a key parameter exceed the Action level 3, a continued operation will result in damage. An assessment based on the system described in paragraph 9.3.1 of a continued operation of an unit with once through boiler is shown in Figure 11. It illustrates the lifetime consumption for every hour operation with acid conductivity of feed water in between 1 and 500 uS/cm. Operation time lo expect collapse is also indicated. This is an example only and uncertainty of the evaluation is quite big. However, it ilustrates the order of magnitude of damage.(u) saeyoo 0} aun BuNE10e— VGB 1000 100 0 1 ° 400 00 0 100 Acid conductivity in feed water of once through boiler (Siem) 1 peepee 1000000 (4) vonduuneuce suo woreants Figure 11: Example of lifetime consumption at operation above Action level 3 limit. Fe) i)VGB 57 10 Bibliography [1] DIN EN 1295212, Ausgabe:2003-12, Wasserrohrkessel und Anlagenkomponenten - Teil 12: Anforderungen an die Speisowasser- und Kessehwasserqualtal; Deutsche Fassung EN 12952-12:2003 [2] BSEN 1295212, Edition: 2005-10-03, Water Tube Bollers and Plant Components - Demands on Feed Water and Boiler Water Quality {91 International Electrotechnical Commission (IEC) Technical Specification TS 61370 “Steam turbines - steam putty”, Ed. 1.0 b:2002 (hip:/mebstore.ansiorg/ensidocstore/}. [4] VGB Instruction Sheet M407 G “Conception, Specification and Efficiency Statement for We Pants. VGB PowerTech Service GmbH, Essen, {51 VGB Instruction Sheet M 412 L “Tasks and Methods of Condensate Polishing’. VGB PowerTech Service GmbH, Essen, [6] VGB Instruction Sheet M418 Le “Organic Matter and Dissiolved Carbon Dioxide in the Steam Waler Circuit of Power Plant”. VGB Powerlech Service GmbH, Essen. M7] VGB Guideline R 819 ¢ “intemal Cleaning of Water-Tube Steam Generating Plants and Associated Pipe-Work" VGB PowerTech Service GmbH, Essen [8] _VGE Guideline A 116 He “Preservation of Power Plant Systems", VGB PowerTech Service GmbH, Essen. 1 Deminaralization