17.

Boiler and Feed-water Treatment

Introduction

The explicit aims of boiler and feed-water treatment are to minimise corrosion, deposit formation, and carryover of boiler water solutes in steam. Corrosion control is sought primarily by adjustment of the pH and dissolved oxygen concentrations. Thus, the cathodic half-cell reactions of the two common corrosion processes are hindered. The pH is brought to a compromise value, usually just above 9 (at 250C), so that the tendency for metal dissolution is at a practical minimum for both steel and copper alloys. Similarly, by the removal of dissolved oxygen, by a combination of mechanical and chemical means, the scope for the reduction of oxygen to hydroxyl is severely constrained. Deposit control is important because porous deposits, under the influence of heat flux, can induce the development of high concentrations of boiler water solutes far above their normally beneficial bulk values with correspondingly increased corrosion rates. This becomes an increasingly important feature with increase in boiler saturation temperature. In addition, deposits can cause overheating owing to loss of heat transfer. Finally, carryover of boiler water solutes, which can be either mechanical or chemical, can lead to consequential corrosion in the circuit, either on-load or off-load. Material so transported can result in corrosion reactions far from its point of origin, with costly penalties. It is therefore preferably dealt with by a policy of prevention rather than cure. All of these factors need to be taken into account when defining a tolerable boiler and feedwater regime for any given plant. This has been done, for example, in BS 2486 (BSI, 1968) and by various other bodies (see Section 5.5). With increasing boiler operating pressure, considerations of purity become even more important. High-pressure utility boilers, whilst in the main operating at a few percent make-up, are extremely sensitive to contaminant ingress, so that high-purity feed-water is essential. Above about 40 bar, complete demineralisation is therefore virtually mandatory, with the result that scaling due to hardness salts is impossible, barring inadvertent cooling water ingress due to, for example, condenser leakage, rotary air pump

suckback, or water treatment plant malfunction. However, carryover of solutes in steam becomes increasingly important. This can occur either mechanically (in its worst form as priming) or chemically. In the latter case, substances become distributed between steam and water in a ratio determined by the temperature. Material carried over and subsequently deposited may cause a number of problems elsewhere in the steam/ water circuit. Assuming however, that appropriate water treatment has been arranged, the treated water, although unlikely to form scale, and with a greatly diminished tendency to carryover, nevertheless may still cause corrosion unless the quality is further adjusted. This is done by additions and/or removals of substances.

Fundamental Considerations Water Quality

The raw water available for any given installation will be of acceptable quality only rarely, and some degree of purification and adjustment will usually be needed. Following widely accepted usage we shall refer to the purification, i.e. the removal of undesirable constituents, as 'treatment' and the adjustment of quality or suitability, by, for example, alkalisation or deoxygenation, as 'conditioning'. Whilst a detailed consideration of methods of water treatment would be out of place here, nevertheless some brief discussion will be given as an aid to understanding the scope for corrosion control. Raw waters can be generally divided into four categories as follows: 1 . Well ^ater. This is rain water which has percolated through various strata until it enters an underground aquifer. Well water usually contains dissolved calcium and magnesium salts, but is low in organic matter owing to natural filtration. 2. Upland surface water. This is low in hardness salts having run over impervious rocks but will often be high in organic matter, i.e. fulvic and humic acids. 3. Clean rivers. These originate from upland surface waters, but contain more organic matter and also silt. 4. Industrial rivers. These are essentially re-used waters and contain, in addition to those constituents originally present, sewage and industrial wastes. A typical analysis of each of these water categories in presented in Table 17.2.
Table 17.2 Constituent Well Alkalinity (mg kg"1 CaCO3) Calcium (mg kg"1 CaCO3) Magnesium (mg kg" 1 CaCO3 Sodium (mg kg" 1 CaCO3 Chloride (mg kg "1CaCO3) Sulphate (mg kg" 1 CaCO3 Total organic carbon (mg kg 11C)
200 90 120 20 10 20 0-2

Typical analysis of water categories Water category Upland surface

10 12 5 8 10 5 5

Clear river
100 100 50 50 50 50 8

Industrial river
150 250 100 160 130 230 15

Treatment of waters for boiler feed For most boilers, then, raw water from any of the above sources will require treatment followed by appropriate conditioning. In simple, low pressure plants, precipitation of the hardness salts, e.g. by lime or lime/soda, will be adequate. For a wide range of low and intermediate pressure plant, base-exchange is applied. In this process, the potential scale-forming salts of calcium and magnesium are replaced by the equivalent sodium salts. This is achieved by passing the raw water through a bed-originally of a naturally occurring zeolite but now of a synthetic substitute-in which the exchange of unwanted for acceptable ions occurs. Periodic regeneration is necessary by passing brine through the bed. Whilst softened, i.e. rendered non-scaling, by this process, the water is corrosive owing to the presence of carbon dioxide, and in addition the solids content is undiminished. The corrosivity may be alleviated by conditioning, but the solids content becomes a constraining factor with increasing boiler pressure. Some means of lowering the solids content is therefore needed in many instances. Distillation was formerly extensively practised and is still viable in many situations. Increasingly, however, ion exchange is used. Ion exchange is analogous to base exchange and can be used for the removal of either cations or anions. Cations are replaced by hydrogen ions and anions by hydroxyl ions. Again, regeneration is required, this being most conveniently achieved in the UK with sulphuric acid for cation resins and sodium hydroxide for anion resins. For most modern high-pressure boiler plants ion exchange forms the basis of the water treatment plant. As many natural waters are coloured and turbid, and contain suspended solids (silt, clay etc) as well as organic matter, some pretreatment is necessary before ion-exchange as these impurities adversely affect resin performance and lead to lower water quality and higher operating costs. Pretreatment usually comprises coagulation/flocculation followed by settlement and filtration. Coagulation is often achieved by adding aluminium sulphate and, after subsequent flocculation etc, the suspended solids content of the water leaving the pretreatment plant should be less than 2 mg/kg. The water is then usually filtered through deep sand to provide an effluent of <0- 2 mg/kg which is then fed to the ion-exchange plant proper. This, typically, would comprise a cation unit, a scrubbing tower for carbon dioxide removal, an anion unit, and a mixed bed (see Fig. 17.1). Cation units usually contain a sulphonic acid resin whilst anion resins fall into the two main categories of strongly basic, with quaternary ammonium groupings and weakly basic, with tertiary amine groups. The final unit is the mixed bed in which, by a mixture of cation and anion resins in the same vessel, the effect is achieved of a multiplicity of separate cation and anion units. Resin separation is necessary for regeneration purposes. Considerable improvements in water quality are obtainable by these means. The major chemical problem met in ion-exchange practice is the fouling or poisoning of the anion resins by organic matter. The various counter measures deployed include: pre-flocculation, oxidation of the organic material, the use of specially developed resins, and treatment of the fouled resins by brine and/or hypochlorite.

Raw water storage

Cation exchangers

Degasser tower Air blown to tower base Pumps

Degassed water sump

Mixed bed plant

Fig. 17.1

Treated water outlet

Diagram of demineralisation plant

Condensate purification In some boiler systems the condensate returning is retreated using ion exchange to minimise corrosion and deposit accumulation. This particularly applies to once-through boilers (mainly nuclear) where there may be no water/steam separator and perhaps limited facilities for blow-down. Additionally, some high heat-flux boilers (oil-fired) have been fitted with condensate polishing plant (CPP). The quality of water demanded from a CPP depends on the power plant which it services. An indication of the qualities demanded are given in Table 17.3.
Table 17.3 Water qualities demanded from condensate polishing for power plant AGR Sodium (jug/kg Na) Chloride 0*g/kg Cl) Sulphate (pig/kg SO4) Conductivity (/xS/cm at 250C)
AGR, advanced gas-cooled reactor PWR, pressurised water reactor

PWR

<2 <2 <2 < 0-08

<0-5 < 0-5 <0-5 < 0-07

Basis of pH control Essentially, the pH is controlled to suppress the hydrogen evolution cathodic reaction- The Pourbaix Diagram for iron indicates that high pH values as well as low values may lead to corrosion. The construction of these diagrams for higher than ambient temperatures1'2 shows how the area of the alkaline zones increases considerably under boiler conditions, so that the risk of corrosion is correspondingly higher. Many feed systems contain copper alloys,

as well as steel and, as the optimum pH values for the two materials differ, a compromise value has to be selected, values in the range 8-8-9-2 being suitable. Some waters tend to become acidic owing, for example, to the hydrolysis of magnesium salts at elevated temperatures. Additions of alkali are needed to control the pH, and these may be required at more than one location in the system. As we have seen, initial design/economic considerations will show which quality of water to use as feed. Then, initially, some feed-line dosage will be required-solid alkalis for low-pressure plant, volatile alkalis for higher pressure boiler systems. Additional dosing to the boiler will also be desirable in some cases. However, once the system has done its work, e.g. by passing through a turbine, it becomes 'condensate return' and goes to supplement the feed-water. The amount of condensate return can range from nil to >99-5%, depending upon the type of plant. Solid alkalis Solid alkalis may be used, in principle, for the corrosion control of drum boilers at all pressures but other factors, e.g. carryover or 'hideout' a (reversible disappearance from solution on-load), may preclude them in some cases. However, they are used for feed-line treatment only in lower pressure plant where the boiler has increased tolerance to the higher solids burden which their use entails. Sodium hydroxide or, at very low pressures, sodium carbonate, (which is hydrolysed to the hydroxide at boiler temperatures) have been used, as have potassium and lithium hydroxides and various phosphate mixtures. (For a comparison of various alkalis for this purpose see References.) The extent of feed-line dosage, and to some extent, its type, is influenced by the amount of make-up water required by the plant. This is the quantity of water which has to be added to the feed-water to replace that either taken from, or lost in, the cycle. The amount of make-up varies with the type of plant from 100% to less than 1%. With 100% make-up, solid alkali dosing would lead to the need for heavy and costly blow-down-increasingly so with the higher pressures owing to the greater amount of heat in the water. In contrast, in the boiler, as opposed to the feed system, solid alkalis are suitable for pH adjustment as long as they are properly controlled. Thus, on the one hand, if the concentration is too high (e.g. above 5 mg/kg NaOH at 160 bar), the sodium hydroxide carried over with the steam presents some risk to the circuit. On the other hand, in some boilers, solid chemicals are subject to hide-out. If kept within proper limits, however, solid alkalis have the advantage over volatile agents when strong acids are present in the boiler. Organic bases Whilst for low-pressure situations, solid alkalis are acceptable for feed-line dosage, these become increasingly less desirable with higher pressures as boiler water requirements become increasingly stringent. An important control parameter is the dissolved solids content of the feed and boiler water (measured in terms of the electrical conductivity). If this is too great, blow-down requirements will be expensively high or the concentrations of sodium hydroxide and other solutes may increase to unacceptable levels with the risk of corrosion. This risk may to some extent be avoided by the use of organic bases for pH control. Their volatility prevents the development of high concentrations in the boiler and extends their protective effect

Table 17.4

Properties of amines pKb values 5O C

4-7 3-4 5-5 4-3
0

Steam water partition JOO C Ammonia Cyclohexylamine Morpholine AMP a

a

20O C
7-0 25 1-5 0-9

JOO0C
4.9 3-8 5-2 4-3

20O0C
5-0 4-7 5-6 5.0

14 2-0 0-4 0-4

2-amino-2-methyl-l-propanol. From Title and Kingerley

throughout the steam/water circuit. At the same time, their weakly basic nature means that excessively high alkalinities cannot be achieved. Various amines find application for pH control. The most commonly used are: ammonia, morpholine, cyclohexylamine, and, more recently AMP (2-amino-2-methyl-l-propanol). The amount of each needed to produce a given pH depends upon the basicity constant, Kb and values of this are given in Table 17.4. The volatility also influences their utility and their selection for any particular application. Like other substances, amines tend towards equilibrium concentrations in each phase of the steam/water mixture, the equilibrium being temperature dependent. Values of the distribution coefficient, Kp, are also given in Table 17.4. These factors need to be taken into account when estimating the pH attainable at any given point in a circuit so as to provide appropriate protection for each location. As feed systems usually contain copper alloys, the use of amines for their protection may seem somewhat strange as copper is prone to attack in ammonia/carbon dioxide/oxygen environments, with the formation of complex cupric or cuprous compounds. The requisite degree of protection can be achieved, however, by maintaining the concentrations strictly within the acceptable target range. In some systems where condensate returns form part of the feed-water, the returned condensate may be considerably contaminated by, for example, air, carbon dioxide, possibly by process liquors, cooling water, perhaps by oil, as well as by products of corrosion of the system. Corrosion control in such systems can be difficult in view of the varying pattern and nature of the impurity ingress. For example, this can pose problems in providing suitable dosage to cope with the varying quantities of air ingress which accompany unplanned load changes on a plant throughout the day. Filming amines In such situations, one approach is to use the filming type of amine, of which octadecylamine is the most common example. This, and related substances, forms a barrier on the internal surfaces of the feed system offering some protection against corrosive attack. Filming amines are of a wax-like consistency and require dispersion before introduction to the system. Particular care is needed when starting the dosage in case agglomerates formed from the amine, and debris (crud), cause blockage. An advantage of filming amines over neutralising amines is their relative independence of the concentration of corrosive substances. About l-2mg/kg of filming amine are usually adequate. This non-stoichiometric

behaviour is therefore of particular benefit is condensate return lines where large ingress of contaminant can occur. Deoxygenation Basis of deoxygenation The predominant cathodic reactions accompanying corrosion processes in aqueous solution are hydrogen evolution and dissolved oxygen reduction. With increasing pH, particularly above about 3 relative to 250C the latter plays an increasingly important part, provided that sufficient oxygen is present. Deoxygenation therefore offers an important means of corrosion control. The solubility of oxygen in water is influenced by several factors but, generally, most waters contain, at equilibrium, about 8mg/kg at 250C, although supersaturation may increase this considerably. Some indication of the amount of dissolved oxygen relevant in different situations is shown, on the one hand, by the value of O-1 mg/kg found in central heating systems5 and, on the other hand, by the value of 0-005 mg/kg specified by most users of large boilers as the upper limit at the economiser inlet (see Section 5.5). Deoxygenation can be achieved by mechanical and/or chemical means. Both methods are commonly used on conjunction, the chemical reagents being employed as 'scavengers' for the residual amount of oxygen left after mechanical treatment. Mechanical/thermal deoxygenation A substantial amount of deoxygenation can be achieved by mechanical or thermal means. At 1 bar, for example, whilst the equilibrium concentration of dissolved oxygen in water is 8 mg/kg at 250C, the figure is nearly zero at 10O0C. Merely heating, therefore will decrease the oxygen content of the water by expelling it into the vapour phase. In practice, vapour, along with its oxygen burden has to be removed to prevent the reverse reaction. Early types of equipment for this purpose include the vacuum deaerator, in which the water to be treated was introduced at high temperature into an evacuated atmosphere with a steam ejector operating in the vapour space. The residuals of oxygen attainable with the vacuum deaerator were limited to about 0-03 mg/kg, owing to the prevalent partial pressure of oxygen in the vapour phase. Lower residuals can be achieved by introducing another gas into the vapour phase and in boiler practice, this is conveniently provided by steam. By these means, the equipment can be operated at above ambient pressure, with concomitant advantages in respect of the lower solubility of oxygen in the liquid phase. Pressure deaerators also serve as additional feed-water heaters. These are located in the pre-boiler system of a power plant between the low- and high-pressure heater trains. Residual oxygen concentrations of as low as 0-005 mg/kg O2 are achievable by their use. The requirements for deaeration vary widely and are dependent upon the type of installation they are designed to serve. In central heating systems, make-up is minimal, provided that 'good housekeeping' limits the extent of leakage from the system and its consequential replacement by aerated make-up. Usually, therefore, no deaeration is applied. With low-pressure plant, either there may be no specific deaeration stage, or, perhaps, a vacuum deaerator. With

high-pressure plant, preliminary thermal/mechanical deaeration is essential, and a pressure deaerator is advisable. In power generating practice, during steady-load operation, the scope for ingress of air is limited to leakage into those parts of the plant working at less than ambient pressure, i.e. the low pressure turbine and condenser, along with the air present in the small amount (about 1 %) of make-up water. However, in variable-load operation, air ingress during shutdown periods, together with the large amounts of water used during run-ups, necessitate the use of auxiliary deaerating equipment, e.g. immersion heaters in the off-load plant and, perhaps, nitrogen sparging etc (see Section 4.7). With lower pressure plant, when thermal deaeration may be rudimentary or even absent, reliance is placed on chemical means which, for higher pressure plant, play a complementary, but none the less important, role. Chemical deoxygenation Tannins have been used traditionally for chemical deoxygenation and are still fairly effective for low-pressure plant. Sodium sulphite is also still used extensively in the same range. This reacts with oxygen to form the sulphate. Where sulphate is required in solution for other purposes, e.g. as a palliative against caustic cracking (see Section 4.2), the treatment clearly has some additional value, but, otherwise, the increase in dissolved solids content of the water due to its use may be undesirable. In addition, depending upon the boiler operating pressure and make-up rate, there may be some formation of acidic compounds, e.g. sulphur dioxide and hydrogen sulphide, which may cause corrosion (particularly) of the copper alloys of the circuit as well as introducing some imbalance into the chemical control6. Hydrazine has the advantage that its use does not increase the dissolved solids content of the boiler water. The products both of its reaction with dissolved oxygen and of its decomposition are gaseous or liquid: N 2 H 4 + O2 -> N2 + 2H2O 3N2 H 4 -> 4NH3 + N2 or, higher temperatures: 2N2 H4 -> 2NH3 + N2 + H2 As a base, hydrazine will tend to increase the pH of the system. At ambient temperatures, the basicity of hydrazine is about one-tenth of that of ammonia, but with increasing temperature the disparity diminishes. Hydrazine is conventionally added in an amount equivalent to at least 100% of the dissolved oxygen content. In principle, additions should be made after thermal deaeration to economise on reagent usage, but in practice in some cases more thorough scavenging is found to result if hydrazine is added before the deaerator. This may reflect the kinetic aspects of the reaction with oxygen. Catalysis plays an important part in the hydrazine/oxygen reaction. Copper salts were formerly added for this purpose, but in recent years certain organic substances, e.g. quinhydrone, have been employed and a number of proprietary 'activated hydrazines' have been available. These are useful at low temperatures; above 15O0C scavenging rates with normal hydrazine are such that no great benefit is achieved by their use.

In recent years, possible alternatives to hydrazine have been suggested, and some have been used on plant. These include: carbohydrazide (NH 2 NHCONHNH 2 ), derivatives of hydroxylamine, e.g. diethyl hydroxylamine (HON(C2H5)2), ketoximes, and erythrobic acid (isoascorbic acid). These are usually faster scavengers than hydrazine or activated hydrazine7. NOLC In certain special circumstances, rather than removing oxygen, deliberate additions of it have been found to be beneficial for combating corrosion provided that adequate control is maintained. In particular, the conductivity of the feed-water must be kept below 0-2/uS/cm at 250C8. The conditions are 'neutral water with oxygen and low conductivity'-hence the term 4NOLC'. The low conductivity requirement effectively limits the use of the method to once-through boilers. Oxygen is added either directly as such, or as hydrogen peroxide, and either at the economiser or, depending upon circumstances, earlier in the circuit. With oxygenated regimes, the preferred oxide formed is haematite, instead of magnetite, and in addition thinner layers are found. Mixed conditioning has also been used. In this, one part of the circuit (usually the low-pressure system) is dosed conventionally, e.g. with hydrazine/ammonia, whilst the high-pressure system is subjected to oxygenated conditions.
Boiler Corrosion: Laboratory Studies

The prime reaction in boiler corrosion is the formation of magnetite and hydrogen from iron and water: 3Fe + 4H2O -> Fe3O4 + 4H2 This is considered, however, to proceed in two stages, i.e. the initial production of ferrous hydroxide: Fe2+ + 2OH- -> Fe(OH) 2 and is subsequent decomposition to magnetite and hydrogen (the Schikorr reaction): 3Fe(OH) 2 -> Fe3O4 + 2H2O + H2 Studies by Sweeton and Baes9 showed that this can be generalised into the reaction: Fe304 + 3 ( 2 - f c ) H + + H2 -> 3Fe(OHK 2 '^ + (4 - 3fc)H 2 O This implies that, given an adequate concentration of hydrogen, magnetite can be redissolved, and Berge etal.10 demonstrated that this is indeed so. In the absence of sufficient hydrogen, the solubility of magnetite is markedly temperature dependent, which provides an explanation for some of the problems in high-temperature circuits. Most studies in boilers relate to high temperatures. Thus the work of Bloom11 and of Potter and Mann 12 has reproduced the types of corrosion found in high-pressure boilers. The relationship between corrosion rates and iron solubility and pH are given in Fig. 17.2. Note that the pH range about the neutral point (relative to 30O0C

Fe (OH)J" Solubility (mmol/kg) (2) Corrosion (mm/year) (1)

Fe2+

Fe (OH)3-

FeOH+

Corrosion

Fe (OH)2
pH 30O0C NaOH Neutral Rapid acid chloride attack with hydrogen damage Normal bulk boilerwater operating region Rapid caustic attack

HCI

Fig. 17.2 Correlation between mild steel corrosion and magnetite solubility (by permission of G. M. W. Mann)

in the Figure), corresponding to the target ranges for good boiler-water practice, indicates modest corrosion rates. Excursions from neutral in either direction lead to increasingly severe attack, so that typical tube-wall thicknesses will be consumed in drastically short times, and faster in acids (10Os of hours) than in alkalis (months). It should be noted that (in terms of tube integrity) acidic become more hazardous than alkaline solutions at lower concentration factors*-about 103 for acids and 104 to 105 for alkalis. In addition, Fig. 17.2 shows that with increasing acidity, the risk of hydrogen damage increases. By this mechanism, hydrogen generated by the corrosion process, attacks iron carbide in the steel:

TeC' + 2H2 -> Fe + CH4 and so transforms it into a material that does not possess the hightemperature strength required for boiler tube integrity. In addition, at high
* Concentration factor: the ratio of concentration locally to that in the bulk solution.

corrosion rates, the methane produced cannot diffuse out of the steel and high internal stresses develop which blow the steel apart. The rate of hydrogen damage is far higher than that of the corrosion process at boiler temperatures so that tubes with, say, O-5 mm of corrosion damage may surfer hydrogen damage to the extent of, say, 5 mm and, in consequence, fail by brittle fracture. Mechanistically, in approximately neutral solutions, solid state diffusion is dominant. At higher or lower pH values, iron becomes increasingly soluble and the corrosion rate increases with the kinetics approaching linearity, ultimately being limited by the rate of diffusion of iron species through the pores in the oxide layer. In more concentrated solutions, e.g. pH values of less than 3 or greater than 12 (relative to 250C) the oxide becomes detached from the metal and therefore unprotective13. It may be noted that similar Arrhenius factors have been found at 750C14 to those given by extrapolation of Potter and Mann's data from 30O0C. On plant there is significant transport of corrosion product oxide ('crud') from the feed and return lines. This can be the dominant factor, and overall the accumulation rate is effectively linear. It should be emphasised that corrosion of the type found in operating plant can only be reproduced in the laboratory by employing far higher concentrations (1 000 to 100000 times) than those existing in bulk solution in practice. Interpretations therefore invoke the concept of concentration mechanisms.
Concentration Mechanisms

The three principal concentration mechanisms postulated as being responsible for on-load corrosion processes by Mann 3 are dry-out, concentration in crevices, and concentration in porous deposits. (Clean boiler tube surfaces on which high-pressure water is boiled under forced convection do not develop concentration factors of more than about two.) Baum15 has reviewed the theory and the laboratory, rig, and plant experience which has led to the current views on concentration mechanisms. Essentially, interpretation is based on the difference between heat transfer at certain localised sites of the tube and that at the free surface. In normal boiling, the removal of steam from the surface leads to its direct replacement by liquid, so that accumulation of solutes does not occur to any appreciable extent. However, in certain cases, principally those three listed above, where there is an inadequate supply of water to the surface for boiling to be maintained, steam preferentially forms. Consequently, solute is deposited and accumulates with the formation of highly concentrated solution (103-105 that in the bulk). In the dry-out mode of concentration, the steam blanket causes the tube to become superheated, so that the temperature rises in proportion. In the second mode of concentration, i.e. at crevices, it arises initially because the confined space impedes coolant ingress so that the liquid component is impoverished, and insoluble species are precipitated. The deposit causes a rise in temperature and steam blanketing follows, as described above. In the third common mode, wick-boiling occurs in the pores of the water-side deposit and produces increasingly concentrated solutions at the

deposit/tube interface owing to the relative impoverishment of the supply of liquid, and its resultant inability to exert sufficient cooling of the surface. In these ways, then, concentration factors of up to five orders of magnitude may be developed, depending upon the circumstances. Despite much work in this area, theory has not yet developed to the stage where accurate predictions can be made reliably, but the state of the art is such that semiquantitative assessments can be of considerable value in interpreting occurrences.
Feed-System Corrosion General

Feed system problems may become apparent by failures at the immediate site of corrosion or indirectly, for example by the appearance of corrosion products in the form of deposits either in the feed or even the boiler system, leading to the blockage of instrument tapping points, sampling lines, blowdown lines etc., by the falling off in efficiency of the feed-heating plant, or by the removal of unduly large amounts of material on chemical cleaning. These may, be due to corrosion and/or scaling. Whilst operational needs may dictate that the immediate requirements are to remove the deposit and repair the failure, in the longer term it is equally important to identify and eradicate the root cause. This may prove to be, for example a water treatment plant malfunction, or ingress of air, or a temporary inadequacy of conditioning chemicals. Any of these would call for an increased degree of scrutiny in the monitoring procedures. In more chronic cases, a decision to upgrade the purity of the feed-water may be required, to use a different alloy or to change an operational procedure. Both iron- and copper-based alloys are corroded more easily on either side of the neutral pH band. In low pH conditions e.g. due to carbon dioxide, the acidic environments attack the alloys readily, causing damage both at the points of initial corrosion and perhaps, consequentially, further along the system, by screening the surface with corrosion products and permitting the development of differential aeration cells. A similarly undesirable situation is brought about in unduly alkaline solutions caused by the indiscriminate use of amines which may lead to high dissolution rates of copper from its alloys owing to complex formation. The standards discussed in Section 5.5 are aimed at avoiding these undesirable situations.
Erosion-Corrosion

There has been renewed interest over the last few years in erosion-corrosion, i.e. essentially 'velocity-assisted corrosion' since it appeared in the feed systems of certain nuclear plant. This prompted extensive experimental investigations16. Erosion-corrosion is influenced by many factors-chemistry, flow, temperature, heat flux, and whether one or two phases exist. It also varies with the material, resistance increasing from mild steel, through 1% Cr-Mo to 2% Cr-Mo.

Geometric factors, as might be expected, also influence the situation. High turbulence exerts an adverse effect, whilst a pH increase in the range 8-5 to 9-5 is beneficial. Dissolved oxygen concentration is also important, protection increasing with increasing oxygen content, in contrast with most forms of corrosion. The 'phase' stripping of dissolved gases has been claimed to be harmful. Temperatures of 140-15O0C are the peak of bad conditions on a logarithmic wastage scale.
Boiler Waters General Considerations

In boiler water practice the three main aims that must always be borne in mind are to minimise corrosion, deposition, and the carryover of boiler water solutes in steam. Increasing operating pressure of a boiler greatly affects the relative importance of these three aspects. For example, in a domestic central heating system, raw water may be acceptable, depending upon its source. From the initial charge of water, a small amount of scale will form and some slight corrosion will occur as the dissolved oxygen content of the water is consumed. If there is not an unduly large amount of make-up, there may be little more corrosion after this initial period. However, systems requiring substantial quantities of make-up generate more magnetite, and chemical dosage to decrease this may be desirable, perhaps in conjunction with water treatment if scaling is also a problem. Industrial low-pressure boilers, particularly if they are of the steam generating type, rather than hot-water boilers, owing to their large make-up requirements, and also because of their mode of operation, may perform more satisfactorily with a softened water than with untreated supply. However, as many softened waters are intrinsically corrosive, some dosage to control pH and dissolved oxygen concentration will probably also be desirable (after base-exchange treatment, for example). With increasing boiler pressure, the use of treated water and supplementary dosage become increasingly desirable, as the carry-over of boiler-water solutes in steam becomes more pronounced, and the plant is less tolerant of scaling. A high degree of purity is therefore essential for the feed-water to lessen the risks of carry-over and scaling and to provide a basis for effective anti-corrosion measures. Deposit formation, due either to 'crud' (suspended matter-mostly metallic oxides) transported into the boiler or to the products of corrosion in situ, is undesirable as, in many parts of the system, quite apart from the risk of overheating which they present, deposits are able to participate in a mechanism for concentrating solutes to unacceptably high corrosive levels, and are particularly dangerous in high-pressure plant (see Section 4.5). It is particularly important to avoid waters which are inherently acidic or those which might become so in operation, e.g. those containing the chlorides of magnesium or, to a lesser extent, calcium, which undergo hydrolysis at elevated temperatures. This can be done either by removing such salts externally in a softener or by dosing enough alkali into the system to neutralise the acidity produced.

Boiler Corrosion: Low-Pressure Plant

The primary reaction in the corrosion of boiler steel is the formation of ferrous hydroxide and its subsequent decomposition to magnetite and hydrogen - the Schikorr reaction (Section 4.4). This is demonstrated by the products of corrosion encountered throughout the whole range of boiler operating pressures, but the details are influenced by other factors, i.e. the water quality, heat flux, and the boiler operating conditions. Thus, in domestic central heating systems, the three main causes of trouble are: blockages, hydrogen generation, and the pitting of radiators. Reaction in the radiators leads to the accumulation of deposits of iron oxide which may lead to partial blockages with some parts of the circuit becoming cool, and sometimes to complete blockage, with the resultant choking of the circulation pump. Hydrogen produced by the Schikorr reaction tends to accumulate at the tops of the radiators, which then require 'bleeding' to restore circulation. Deposits of magnetite result in the attack being concentrated beneath them (occluded cell) with increased risk of local failure. Studies by Smith17 show that 'chimneys' of magnetite tend to grow in flowing conditions on grey cast iron at 5O0C in water containing oxygen. Overheating leads to failure. This can result from scaling*, and the consequential impedance to heat transfer. A mild-steel tube, for example, which at 4480C will last for 30 years will, at 6240C, fail by creep in 9 h (see Table 17.5). Depending upon the rate of scale build-up, and the resulting rise in temperature, some associated corrosion, due to salt concentration, may also occur. Qualitatively, the control of scale in boilers is achieved by additions of sodium carbonate or phosphate. These precipitate the calcium as the carbonate or hydroxyapatite, respectively (the latter being the equilibrium form of calcium phosphate at boiler pH values). The aim is to add sufficient excess of the conditioning chemical to cause precipitation in the bulk of the solution, otherwise, nucleation may occur on the heat transfer surfaces and cause scaling. Hamer etal.19 suggest that the less soluble reaction products are more likely to produce the desired effect. Thus, in relatively untreated waters, calcium sulphate, which is fairly soluble, tends to form scale. The carbonate of calcium is less soluble than the sulphate, and hydroxyapatite still less so. This would account for phosphate conditioning tending to form a 'sludge', i.e. a precipitate, in the bulk solution, rather than the scale, which is often associated with inadequate carbonate dosage. In addition to carbonates and/or phosphates, a variety of substances have also been used to act as 'sludge conditioners'e.g. starches, lignins, polyacrylates etc. Other substances, such as nitrites and sulphates are claimed to have some value in the suppression of caustic cracking (see Section 5.1). Apart from caustic cracking, the main forms of corrosion in low-pressure plant are oxygen pitting and scab formation. The residence of oxygen at sensitive locations on-load, possibly following off-load initiation, means that
*Although the presence of oil in the boiler water, or water starvation may also cause overheating.

Table 17.5

Creep lives of mild steel tubes at various temperatures (By permission of M.T. Robinson) Temperature (0C)

Time to rupture

Minimum

Mean

Maximum

C-Mn Steel
9h 24 h 5 days 10 days 100 days (240Oh) 3 years (2400Oh) 30 years (240 000 h) 624 607 579 567 527 488 448

Mild steel
615 599 571 560 521 482 443

C-Mn Steel
650 631 602 589 546 504 461

Mild steel
640 622 593 581 539 498 456

C-Mn Steel
677 658 626 612 567 522 476

Mild steel
664 645 614 601 557 513 469

the cathodic half-cell reaction is available to complete the corrosion mechanism. The scab type of corrosion may develop at sites of initial oxygen pitting or in the vicinity of scale or other deposits. Its severity arises from the occluded nature and hence the increased concentration of the corrodant, which may be due to excursions in the boiler water chemistry. The presence of the deposit restricts diffusion away from the corroding site, so that corrosion propagates, and further deposits accumulate, thus aggravating the situation. Reaction is accelerated by temperature and heat flux, and, in sensitive areas, final failure may be by corrosion or by overheating. As has been noted, scaling due to inadequate water treatment may, in the short term, lead to efficiency losses but, eventually, could result in overheating and possibly to associated corrosion. Awareness of this has led to an increasing use of appropriate water treatment with increasing boiler pressure. Scaling due to hardness salts is therefore less common now than formerly, but deposits caused by other means may occur with similarly undesirable consequences. Boiler Corrosion, High-Pressure Plant In high-pressure boilers, there are three types of on-load corrosion: acidic chloride, neutral chloride/dissolved oxygen, and caustic attack. The first and second (once it becomes established) are brittle and thick-walled and are accompanied by hydrogen damage which can lead to failure within a few hundred hours. Caustic attack tends to produce a 'gouged' appearance of the metal due to extensive wastage. The morphology is fairly characteristic of the failure type. Acidic chloride forms hard, laminated oxide, whilst, with caustic attack, the oxide is often soft, and, as it is easily removed, may be absent. The rate of corrosion in any of these three modes is substantially higher than in normal circumstances. In the absence of off-load corrosion, rates of accumulation of magnetite on boiler tubes range from 1 to 2 /xm/1 000 h. In contrast, on-load corrosion rates are from 20 to 1 000 times these values. The oxide forms as a duplex layer, although both layers are not invariably present. In waterside deposits, the outer layer, nominally of magnetite, also

contains the oxides of, for example, copper and nickel, which derive from the metals of construction of the feed system, as well as traces of silica, calcium etc. which originate in the raw water and 'slip' through even highperformance water treatment plants. Acid chloride failures on plant are usually caused by ingress of cooling water into the feed-water. In the boiler, constituents of the cooling water, mainly calcium and magnesium salts may suffer hydrolysis to acidic products, given an appropriate water chemistry. Neutral chloride type corrosion occurs owing to the production of an acidic environment in occluded sites to complement the cathodic reduction of dissolved oxygen at the surface, e.g. around a pit. Caustic attack usually arises, not from contaminant ingress, but from excursions from target values of conditioning chemicals. All of these types of corrosion may be produced in the laboratory, but only at concentrations far greater than those employed on plant, showing that concentration mechanisms are operative in the real situation.
Corrosion Control Corrosion Control in Low-Pressure Boilers

In some cases, given a benign water supply and a system free from leaks (which if present would lead to high make-up requirements and a correspondingly high rate of oxygen ingress), untreated mains water is adequate for domestic central heating boilers. Where these conditions do not apply, then some conditioning of the feed-water is advisable. Whilst a number of failures in low-pressure plant are due to overheating, rather than corrosion, these should be avoided by suitable water treatment, conditioning and operation. As regards corrosion, deaeration is an effective counter-measure to oxygen pitting. Scab formation could arise from the presence of deposits or from the effects of excessive concentrations of chemicals (the former may well lead to the latter). Anti-scaling measures, together with effective control of dissolved oxygen (as discussed in Section 4.2) should largely eliminate deposits. The control of chemical conditions should be implemented according to the recommendations of BS 2486 and to the specific type and pressure class of the boiler. For the particular problem of caustic cracking remedial measures include19: 1. Restraining the sodium hydroxide concentration held in the bulk boiler water. 2. Adding other substances which are claimed to act as palliatives for this form of attack. These include: sodium sulphate, sodium nitrate and certain tannins. Experience indicates that the maintenance of certain ratios of chemicals is helpful to vulnerable boilers, e.g. sodium sulphate to sodium hydroxide a ratio of 2-50, and sodium nitrate to total alkalinity of 0.4.
Corrosion Control in High-Pressure Boilers

With high-pressure boilers operating above about 60 bar, the complete removal of hardness salts from the feed-water by one means or another is

highly advisable if inconvenience is to be avoided. This means that one form of scaling is therefore preempted. However, deposits due to the products of corrosion of the boiler or the feed system, subsequently transported into the boiler, are still possible and these may well lead to overheating and associated corrosion. As the extent of solute concentration depends (amongst other factors) upon the thickness of the deposit, then clearly the degree of concentration can be limited by chemical cleaning at intervals (see Section 5.6). In addition, the strength and corrosivity of the solutions developed is influenced both by the nature and the amount of the chemicals present. Thus, when sodium hydroxide is used as an alkalising agent, the aim is to achieve in the boiler a NaOH:NaCl ratio of 1:1 on a molar basis (equivalent to 1:1 5 on a weight basis). This, in turn, is linked to an upper limit on the chloride determined by the boiler operating pressure to minimise carry-over. Amines are the main alternative alkalising agents to the solid alkalis. Their weak basicity precludes the development of unduly high alkalinities. In addition, there is limited scope for increasing the concentration of amines to raise the pH of the boiler water as, owing to their fairly high volatility, they are carried over in steam and high concentrations would present a threat to the copper alloys in the condenser and feed system. A serious disadvantage of volatile alkalis becomes apparent when acidic conditions arise in the boiler due, for example, to cooling water ingress from leaks in the condenser. In the concentration situation at the boiler-tube surface which precedes severe corrosion, whilst the salt concentration increases to the extent determined by the concentration factor, the amine is prevented from matching this by its volatility. In addition to this loss of material into the steam phase, the amines are too weakly basic to be capable of effectively neutralising strong acids. In such circumstances, then, if the ingress of contaminant cannot be stopped, the type of conditioning should be changed from volatile to solid alkali. If, however, the design of the plant is such that only volatile alkalis are permitted for conditioning, then condensate polishing emerges as the only option if the plant is not be be taken off load every time contamination occurs. The third main type of alkalising agent is the alkali phosphate. Sodium mono-, di- and triphosphates in appropriate proportions may be used to achieve the desired conditions. In addition to their use to prevent scale phosphates have the advantage for corrosion control of being pH buffers so that they limit the attainable concentration of free hydroxide ion in solution and so restrain the scope for corrosion of the caustic type. This behaviour has been harnessed in certain specific modes of boilerwater control. Coordinated conditioning aims at maintaining essentially Na3PO4, i.e. a Na:PO4 ratio of 3:1. The concentration should be within the range 5-30 mg/kg PO4, the actual value decreasing with increasing boiler pressure. In this way, ingress of acidic material is coped with as hydroxide is produced by ionisation to exactly match it, but at the same time excess alkalinity, and so the risk of caustic attack, is less likely. It is found, however, that in sensitive situations this mode of conditioning may still lead to undesirably high amounts of acidicity or alkalinity. This is caused by the precipitation from solutions of tri-sodium phosphate of material with an excess of sodium so that the residual solute is

correspondingly depleted. This can be avoided by working at a Na:PO4 ratio of about 2-7:1 - termed 'congruent' phosphate. Concentrations of up to 20 mg/kg PO4 are maintained with this regime, depending upon boiler pressure. For both coordinated and congruent control, the pH depends upon the phosphate concentration and the sodium to phosphate ratio. Generally, however, phosphates are unsuitable for use at boiler pressures above 100 bar as their low solubility and high concentration factors developed lead to corrosive conditions.
Once-Through Boilers

Engineering considerations in some cases dictate that boilers should be of the once-through design rather than of the drum type, for both fossil- and nuclear-fuelled plant. For instance, the once-through design needs fewer penetrations of the pressure shell in its construction. It may be noted that the once-through type has been rendered practicable only by the availability of high purity water. In once-through boilers the water is converted into steam progressively in a process of continuous transition through the plant, each tube functioning along its length in turn as economiser, evaporator, superheater etc. There is thus no real distinction between feed and boiler water. There are no facilities for blowdown, and solutes entering the boiler must either be deposited, or leave with the steam (unless they undergo chemical change). Once-through boilers may be either sub- or super-critical. Sub-critical boilers are clearly at some potential risk of on-load corrosion owing to the presence of the evaporator zone. Measures aimed at avoiding on-load corrosion include keeping the overall solute concentration low, keeping the ionic balance matched, and maintaining the waterside oxide suitably thin. With super-critical plant, there is no chance of on-load corrosion whilst it is operating in the super-critical mode, as there is no phase boundary. The risk is present, however, when the plant is run in the sub-critical mode, as all super-critical plant must be at times. As for the turbines, no steam-purifying equipment of the type used on drum boilers is feasible, so that the steam from super-critical boilers tends to be of inferior quality. Deposits have been reported of cuprous oxide on the extra high-pressure turbines and of cupric oxide on some high-pressure turbines of sub-critical plant. These deposits may lead to a loss of efficiency and to some risk of corrosion. At intervals, slugs of solute are carried over in the steam, which is therefore of fluctuating quality. This is countered by periodic water-washing of the boilers. Overall, these features mean that chemical control standards are necessarily high. For example, supplementation of the water treatment plant by condensate polishing plant and periodic chemical cleaning are particularly important. In addition, before each period of operation, a clean-up of the cycle is applied to remove crud. Stringent attention must be paid to the feedwater conditioning. As an example of a standard for feed-water for a once-through boiler BS 2486 gives a maximum conductivity of 0-2/iS/cm at 250C and pH in the

range 8 5-9 2 or 9 2-9 5, depending upon whether or not copper alloys are present, with the following maximum quantities of impurities 50 /xg/kg total solids, 5 /xg/kg dissolved oxygen, 20 Atg/kg silica, 19 /-tg/kg iron and 2 ^g/kg copper nickel 2 jig/kg.
Nuclear Plant

It is not the intention here to consider in detail the subject of boiler feedwater conditioning and treatment for nuclear plant, but the general principles may be noted. Essentially, the same objectives apply as in fossilfuelled plant, embodied in the three aims to minimise corrosion, deposition and steam-carryover. Requirements are more stringent in nuclear plant because there is no possibility of repairing tubes which have failed, let alone those which have suffered either deposition or corrosion. Again, certain tubes in nuclear plant have very modest design corrosion allowances so that only minimal loss of thickness from any cause can be tolerated. The objectives are sought by much the same means as in conventional plant, although with higher standards of purity for any given pressure class. Thus, with deaerated feed-water, dosed with hydrazine and ammonia, sodium hydroxide and/or alkaline phosphate or 'all volatile treatment' are widely employed. In other cases, virtually the same principles apply, but with different reagents, e.g. alkaline borate (cf. alkaline phosphate) has been used. In nuclear practice, condensate polishing tends to be more commonly used than on fossil-fired plant. Water purity tends to be higher and the types of boiler and feed-water conditioning tend to be more sophisticated with increasing complexity of the plant.
Boiler and Feed-Water Standards

A number of authorities have issued standards for boiler and feed-water. These include boiler manufacturers, water treatment firms and the British Standards Institution, as well as other interested bodies. The authorities noted here to illustrate the scope for similarities and differences in this field are as follows: Central Electricity Generating Board (CEGB)3, Electric Power Research Institute (EPRI), as discussed by Smock20, British Standards Institution (BSI) Treatment of Water for Land Boilers' (BS 2486:1978), American Society of Mechanical Engineers (ASME), as discussed by Simon and Fynsk21 and the (VGB) Guidelines as noted by Smock20 and by Bolton and Ray22. All of these authorities emphasise that their standards are essentially guidelines and advise that in any given case the views of the boiler manufacturer should be sought and local circumstances taken into account. Certain general points emerge from these guidelines: 1. Softened water is recommended for boilers in the range 13-40 bar. 2. Demineralised water is recommended for boilers in the range 40-60 bar. 3. Increasingly pure demineralised water is recommended for those boilers operating above 60 bar.

The different specifications recognise the need to deal simultaneously with the three main aims of treating and conditioning of boiler water, i.e. to minimise corrosion, deposition and carryover. Thus, the increasing stringency of the water treatment, as indicated above, takes account of the need to diminish scaling. At the same time, the progressive increase in total dissolved solids content which this trend to higher purity water brings about also tends to compensate for the increased tendency to carryover with increasing pressure. In addition, between these last two requirements, which produce waters too soft to scale and too dilute to lead to significant carryover, is a range of waters which, in each specific case, have to be conditioned to restrain corrosion. The boiler-water standards for shell boilers, as given in BS2486:1978 for 2, 20 and 40 bar, respectively, indicate that some parameters are fairly insensitive to pressure, whilst others are not. Thus, sodium phosphate should fall within the range 50 to lOOmg/kg and sodium sulphite between 30 and 70mg/kg for each of these pressures. Total alkalinity should have a maximum value of 1 200 mg/kg at 2 bar and 700 mg/kg at both 20 and 40 bar, with the corresponding caustic alkalinity at 350 300 and 200 mg/kg. Silica should be less than 40% of the caustic alkalinity in each case. Total hardness should be undetectable in all cases. Dissolved solids maxima are given as 3 500, 3 000 and 2 000 mg/kg, again at 2, 20 and 40 bar. The inverse relationship between dissolved solids concentration and pressure is illustrated by the figures given for low-pressure boiler waters in Table 17.6. That there is room for different opinions is shown by contrasting the BSS and ASME recommendations. Whilst both of these authorities propose essentially similar figures for feed- water (Table 17.7), some of the ASME boiler-water figures are substantially below their BS equivalents. This is probably due to the increasing trend towards higher heat fluxes than formerly in some low-pressure plant, particularly waste-heat boilers.

Table 17.6 Feed- water standards for low- to intermediate-pressure boilers

BSS

ASMF

Issuing authority ASMF BSS

BSS

ASME

Pressure (bar) pH at 250C Total hardness (mg/kg) SiO2 (mg/kg) Total iron as Fe (mg/kg) Total copper as Cu (mg/kg) Oil (mg/kg) Total organic carbon (mg/kg)

20 60 60 40 40 20 8-5/9-5 7-5/10-0 8-5/9-5 7-5/10-0 8-5/9-5 7-5/10-0 10 0-1 2 0-2 0-5 0-3 NoteS <0-05 Note 3 <0-02 Note 3 <0-01 a NA 0-02 <0-02 NA <0-03) <0-10 <0-015 NA NA <0-02j <0-05 ND <1 ND <0-5 ND <0-5 <1 Note 4 Note 4 <0-5 Note 4 <0-5

In this Table, BSS refers to British Standard Specification 2468: 1978, and ASME refers to the American Society of Mechanical Engineers Industrial Boiler Sub-Committee of the Research Committee on water in Thermal power stations, 1986 NA, not applicable; ND, not detectable a -Sum of iron, copper and nickel. Note 1: Shell boiler feedwater specifications are usually limited to pH alone. Note 2: pH and ammonia limits depend on whether or not copper-based alloys as well as ferrous materials are present in the feed system. Note 3: The concentration should be such as not to require blowdown of boiler water in quantities exceeding either the design value or feedpump capacity. Note 4: Total organic carbon is not specified but it is stated that values for organic matter depend on circumstances.

Table 17.7

Water tube boilers - examples of low-pressure boiler water standards Pressure, bar

20
Parameter SiO2 mg/kg Total alkalinity as CuCO3 mg/kg Free hydroxide as CuCO3 mg/kg Electrical conductivity nS/cm@25C Total dissolved solids mg/kg

40
ASME

60
ASME

BSS
0.4CA 700

BSS
0.4CA 500

BSS
200 30

ASME

100 BSS ASME

100 10

150 350 NS
3500

40 250 NS
2500

20 150 NS

2 NS
ND 150

300

150

1500

3000

2000

1200

350

In this Table, BSS refers to British Standard Specification 2468: 1978, and ASME refers to the American Society of Mechanical Engineers Industrial Boiler Sub-Committee of the Research Committee on water in Thermal power stations, 1986 ND, not detectable NS, not specified.

Table 17.8

Feed-water standards for high-pressure boilers Issuing authority a CEGB

KGBb BSS

BSS
130

ASME

ASME

Boiler pressure (bar) Elect. Conductivity /iS/cm 25 degC pH at 250C Dissolved oxygen (/ig/kg) Iron as Fe (/xg/kg) Copper as Cu (/xg/kg) Silica as SiO2 , <>g/kg) Oil (/ig/kg)
a

100/165 8-8/9-3 c 15 (EP)d -N 5 (EF)

> 10e
< 100 0-3 20

100

100

130

8-5/9-5 5

9/9-6 7
10 10 < 200

30 > 5 20 < 500

10e

The full titles of the authorities issuing these standards are given in the text. VGB standard also includes upper limits of lug/kg for carbon dioxide and 5ug/kg for chemical oxygen demand. Secondary parameter. d 'EP' and 'EF denote 'extraction pump' and 'economiser inlet', repectively. e lron plus copper plus nickel.
c

At boiler pressures above about 85 bar, the tolerable level of total dissolved solids is so low that all the parameters specified are necessarily low in value. Several examples of recent specifications are given in Table 17.8 (feed) and 17.9 (boiler). Implementation of these standards depends upon a number of factors: 1 . Solid alkalis may hide-out in some boilers so that the operator has little choice but to apply 'all volatile treatment' (AVT) 2. Phosphate, if it does not hide out, may be difficult to control as the ratio Na: PO4 is affected by substances other than those added for alkalisation. 3. Whilst AVT cannot itself cause on-load corrosion, it provides only limited protection against acidic contamination. 4. In addition to the chemical requirements, a number of other factors affect the susceptibility of the system to on-load corrosion, particularly operation and design.

Table 17.9 Boiler-water standards for high-pressure boilers Issuing authoritya ASME Consensus Pressure (bar) Electrical conductivity at 250C GiS/cm) pH at 250C Caustic alkalinity as NaOH (mg/kg) Silica as SiO2 (mg/kg) Chloride as Cl (mg/kg) Phosphate as PO4 (mg/kg) Sulphate as SO4 (mg/kg) Total dissolved solids (mg/kg)
a

VGB

CEGB* Solid alkali A VT

EPRI* With reheat 60-200 Without reheat 60-200

BS 2486 BS 2486

100

133

60 <2 500 9-10-5f O- 25-8f

160 100 <50

165

100/165

60-80

100

<150
Not detectable <2

<100

Not a primary standard 1-5 x NaCl <2 <4 <0-2 <2-<0-2 0-2 (NaCl)

9.1-10.2d

9.1-10.2d
24 8

<1

<2 (NaCl)

0-1-3-5 0-5-4
<10C

0-2-7 1-8

20

<6

<20C
3-9

12

30

1-5-4-5

<1200

350

Authorities names given in full in the text. b EPRI values depend on pressure. c Depends on pH and sodium to phosphate ratio. Depending on pressure.

Depends on PO4 and ammonia. c CEGB also specified a minimum NaOH.

Variable-load operation may result in higher heat fluxes than on baseload, as well as unusual chemical conditions. If, however, after allowing for these, and remedying them as far as is practicable, a boiler persistently suffers from on-load corrosion, then the cure may lie in a design change. As regards steam purity, standards have not usually specified more than a few parameters. Thus, both CEGB and VGB put upper limits for sodium and silica of 10 and 20 jig/kg, respectively. In addition, VGB specify upper limits or conductivity of 0-3 /xS/cm at 250C, for iron of 20/xg/kg and for copper of 3 ptg/kg. There are indications that fuller specifications may be introduced for steam standards. EPRFs Consensus Guidelines suggest upper limits for sodium (5 jig/kg), chloride (3 /ig/kg), sulphate (3 /Kg/kg) and silica (10^g/kg) for drum boilers on phosphate treatment, and with reheat. For plant without reheat, the values are doubled. For drum boilers on AVT, the sodium level is slightly modified to 3 and 6 ng/kg for plant with and without reheat, respectively, chloride, sulphate and silica remaining unaltered. A common value of 100/xg/kg is proposed for 'total organic carbon'. Conductivity is given as 0-3 and 0-35/iS/cm for drum boilers with and without reheat on phosphate treatment. The implementation of feed- and boiler-water and steam standards should be linked to an appropriate scheme for sampling and analysis. Departures from target conditions should be responded to by instituting appropriate remedial measures and increasing monitoring until conditions are restored to normality. Some authorities assess the permissible degree of contamination on a cumulative basis, i.e. using a factor derived from the product of concentration and time in any given operational period.
Chemical Cleaning

At times it may be desirable to chemically clean various parts of the boiler plant and its auxiliaries. The reason may be curative or preventative. With low-pressure boilers and heat-exchange equipment, cleaning is carried out to restore heat transfer, and, for boilers, to prevent overheating. With higher pressure boilers, the restoration of heat transfer is trivial and, whilst some overheating may be avoided, the main reason for chemical cleaning is to prevent corrosion. In nuclear plant, an additional reason for cleaning is to remove radioactive material and improve safety. With heat exchangers, cleaning should be considered as an option when the efficiency has fallen off to some specific level e.g. a terminal temperature difference. With boilers, unless there has been some occurrence which may be alleviated by a particular clean, periodic cleaning to pre-empt corrosion by limiting deposit thickness should be considered23. Cleaning is usually carried out in several successive stages on the off-load plant e.g. flushing (to remove easily detached debris), degreasing (both to remove organic material and to permit easier access of the cleaning reagents to the metal surface), dissolution of hardness scale and/or metallic oxides (both grown and deposited), neutralisation, and, if necessary, passivation. Intermediate rinse stages also feature in the sequence. There may also be the need for ancillary stages such as, in boiler cleaning, copper removal. Degreasing is usually undertaken by means of alkaline and/or organic reagents. The dissolution of hardness scale and oxides is carried out with

acids and/or complexants. This requires the presence of an inhibitor to restrain attack on the substrate metal after descaling. Typical cleaning solutions are hydrochloric acid, citric acid (used in the form of the monoammonium salt), hydrofluoric acid, sodium or ammonium EDTA and, for certain specialised applications, LOMI (low oxidation-state metal ions) reagents24. Passivating formulations may be any of a variety of alkalis, sometimes used in conjunction with oxygen scavengers. Chemical monitoring is employed to follow the course of the clean and to identify the end of each stage. Boilers and certain new process plant may be subjected to a steam blow after chemically cleaning, but before commissioning.
Operational and Design Factors

Operational and design factors also influence on-load corrosion. Thus, as was noted in Section 4.5, the bulk boiler-water concentrations of a number of solutes can be transformed into those strengths which are capable of causing on-load corrosion. Heat flux influences the degree of concentration developed and this, in turn, may be affected by fluid flow, and by oxide thickness. Some operational factors may differ during variable load operation (e.g. two-shifting) from their value on base-load, as indeed may the boiler-water chemistry. Corrosion fatigue may occur25. The role of hydrodynamic parameters has been discussed by a number of workers. Gardner draws attention to the possible influence on on-load corrosion of: tubeinclination, surface condition, poor circulation, temperature elevation, sub-cooling, partial and final dry-out, particulate deposition, and parallel channel stability26. Klein considers temperature elevation for three conditions of boiling and relates this to overheating failures27. Low angle tubes, he suggests, are more susceptible to on-load corrosion owing more to preferential deposit accumulation than to heat adsorption. Klein also mentions weld backing-rings and tube (bore) mismatch as factors in deposition. It must be noted that heat fluxes can vary widely in boilers28. The trend to higher heat fluxes recently in lower pressure plant means, in effect, that standards of boiler-water quality need to be enhanced, conditions for a higher pressure boiler being adopted for a lower29.

Steam Purity

Steam needs to be of an acceptable degree of purity for any given plant because: 1. Deposition and corrosion can cause loss of turbine efficiency. 2. Material deposited on-load may, when conditions become wet in the off-load plant, cause corrosion. , 3. If the steam is used in certain manufacturing processes, contamination may be undesirable, e.g. in food plant. Solutes are carried over in steam in two ways - mechanical and chemical. Attempts are made to control mechanical carryover by steam washing, e.g. cyclones and chevron washers etc. Mechanical carryover increases with

pressure, and at 160 bar is about O- 1%. Chemical carryover occurs because of the intrinsic solubility in steam of solutes30, boiler operating pressure determining the degree of partition between steam and water. The most commonly experienced problems with steam solubility occur with silica, and boilers, when necessary, are run at reduced pressure to minimise carryover of silica and its subsequent deposition on turbine blades, which would lead to a consequent loss of efficiency. Silica is soluble in steam under the conditions obtaining in the low pressure turbine to the extent of about 0-02 mg/kg. For boilers operating at 65,100 and 165 bar, the permissible boiler water concentrations of silica to avoid carryover are about 20, 2 and 0-2 mg/kg, respectively. Some other solutes exhibit a greater dependency on pressure than silica so that trouble may be experienced at, for example, 165 bar, but not at lower pressures. This is found with copper oxide in some (but not all) supercritical turbines, and even in some subcritical high-pressure turbines. Again, sodium sulphate is deposited in the primary reheaters of some 165 bar boilers, but rarely to any extent in those in lower pressure plant. In general, the concentration of any impurity in steam should not exceed the amount present at the location of minimum solubility in the circuit31.
Corrosion in the Steam/Water Circuit Due to Solute Carryover

There is extensive literature dealing with the consequential corrosion in steam/water circuits after solute carryover. It is not the intention to discuss it here at any great length, but two examples are given to illustrate some aspects of the subject. Superheaters Service conditions often dictate the choice of austenitic materials for part (the secondary stage) of the superheater. These materials are susceptible to stress-corrosion cracking, the principal corrodants being chloride and caustic alkali. As these feature in many boiler-water chemistry regimes, there is clearly a need to minimise their entry into the superheater. On-load, sodium concentrations in steam are limited to less than O-005 mg/kg Na (twice this for ferritic superheaters). Before service, care should be taken to prevent the ingress of adventitious impurities, either solid, e.g. pulverised fuel ash, or in solution. Thus, in chemical cleaning, for example, 'low chloride' citric acid should be used and demineralised water used both for making up the solution and for any flushing, rinsing, etc. Reheater Corrosion In certain large steam generating units, a reheat stage is included in the cycle. Briefly, steam from the boiler is first passed through the superheaters and then through the high-pressure turbine. It is then taken through the reheaters before being passed through the intermediate-pressure and low-pressure turbines. If any solids are carried over in the steam, their solubility is determined by the temperature and pressure, and a point of low solubility in the cycle is the primary reheater. Any material so deposited presents no problem during operation, as dry conditions prevail. However, off-load, condensation may occur and lead to the formation of corrosive solutions from the deposited material. Sodium sulphate is the substance most prone to deposition in reheaters, although in some cases this may be accompanied by sodium hydroxide. The form of reheater corrosion is different for ferritic and austenitic steels. In ferritic steels, typically in this context, 1% or 2% chromium-

molybdenum, the corrosion occurs as saucer-shaped pits, at rates up to 2 mm/104 off-load hours. In austenitic steels, the corrosion is inter granular, with similar rates. Remedial measures include: stringent attention to chemical control, drying, and/or nitrogen blanketing of the reheater during off-load periods, periodic water-washing to remove the deposits (although unless the plant is thoroughly dried out afterwards this may lead to enhanced corrosion) and, possibly, if necessary, changing the material of construction of the primary reheater.
Off-Load Protection General

Protection from corrosion during off-load periods is an essential supplement to on-load control measures. Such corrosion may assume a number of forms. Off-load corrosion, e.g. rusting, may occur at rates of up to 1 5 mm/year and may take place under atmospheric or immersed conditions. Sites so attacked may propagate further when the plant is on-load. When plant is taken out of service, ingress of air and water, together with acidic gases, possibly carbon dioxide and sulphur oxides, may transform a previously benign environment into one which is undesirably aggressive. Offload corrosion may occur both before initial operation and in the intervals between periods of service.
Before Commissioning

The periods before commissioning include fabrication at works, storage, transport, perhaps storage on site, and then further storage after construction. The means of protection employed are also influenced by the nature of the plant item in question. Tubes, for example, which form the greater part of the internal surface of many industrial installations, may be chemically cleaned at works, rinsed, dried by means of warm air blowing before beingtreated with vapour-phase inhibitors and sealed with plastic closures either caps or plugs. The external surfaces of tubes should also be protected. This may be done by any of a number of protective coatings available for this purpose. The protected items should then be stored under cover, away from the effects of direct weathering, and preferably on racks which themselves stand on a concrete floor. Partly fabricated components, e.g. feedheaters, may be cleaned at works and then 'cocooned' in the presence of vapour-phase inhibitors or desiccant until they are welded into the system. The inhibitors are usually a mixture of two substances, one with a high volatility, the other with a low volatility, e.g. cyclohexylamine carbonate and dicyclohexylamine nitrite, to provide more effective all-round protection in varying seasonal and diurnal conditions. A high degree of dryness is essential for an acceptable standard of performance of vapour-phase inhibitors. Boiler drums may be partly cleaned at works but, in many cases, still require some further degree of cleaning before commissioning, e.g. prior mechanical cleaning followed by chemical cleaning on site when construction is complete.

Condensers and turbines are not generally cleaned on-site in the same way as boilers etc. but may require treatment to remove the protective coating employed between fabrication and commissioning. These coatings are classified as 'removable' or 'non-removable' depending upon whether a specific removable stage is necessary or whether the coating can be left to wear off during operation. Turbine lubricating systems receive particular attention, being invariably subjected to a flush with oil and, if necessary, chemically cleaned. The condition of stored plant should be monitored and, if and when necessary, the protective measures reinstated after any cleaning which may be required. If the degree of deterioration in storage of any component exceeds certain criteria, that component should be rejected.
After Service

After service, either wet or dry methods may be used for storage32. The period of storage is fixed by operational or maintenance requirements. For example, if a boiler is likely to be required for service at a few hours notice, then it can neither be drained nor dosed with any substance which is incompatible with its operational chemistry. Short-term storage of up to, say, three days, may be achieved by 'nitrogen capping' over the boiler water. Longer term storage may be started by blowing the boiler empty at a pressure of a few bars so that, at least initially, the relative humidity is too low for corrosion to occur. However, in time (days or weeks depending upon the prevailing conditions) the humidity will increase so that additional protective measures will be necessary. Long-term wet storage is sometimes employed. For this purpose, alkaline solutions, in some cases with added oxygen scavengers are used. For high-pressure plant, volatile reagents are preferred even for storage in case any chemical is inadvertently left in during subsequent operation. As with on-load protection, ammonia and hydrazine are used. With ammonia alone, a pH value of greater than about 10-5 is desirable, whilst with ammonia and hydrazine together, about 50 mg/kg of each, giving a pH value of about 10-0, is adequate. Mixtures of sodium borate and nitrite have been used to store plant. The solution may either be left in. If this is impracticable, for instance if the plant needs to be drained for maintenance purposes, then the solution may be drained from the plant after initial dosing so as to leave locations which are difficult to drain containing a residue of inhibitive solution33.
A ckno w/edgemen ts

Acknowledgements are made to Mr N. J. Ray for providing material on the water treatment aspects of this subject and to Dr A. Rantell for helpful discussions. D. G. KINGERLEY

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