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Waterside Scaling, Deposition and Corrosion in Steam Generators


Ludwig Hoehenberger, TV SD, IS-ATW1, Munich
E-Mail: Ludwig.Hoehenberger@tuev-sued.de

Frequently waterside deposition and corrosion were seen as two different and independent incidents, but deposits at heated surfaces in steam generators particularly in combination with non-volatile constituents of the boiler water may lead to severe corrosion problems, chiefly if the boiler feedwater and boiler water doesnt meet their requirements. Critical are mostly spots with the highest heat transfer or heat flux respectively. Generals and Basics A well-designed steam generator achieves satisfying lifetime only if the boiler steel is able to develop and to maintain a thin protective layer of iron oxides (exactly composed of three different layers of oxides), with its main constituent magnetite (Fe3O4), see Figs. 1 a +2. A real protective magnetite layer must be compact, nearly free of pores and adherent to the metal surface. The thickness of a protective magnetite layer depends on the material, operation temperature and operation time and results for 100.000 hrs ( 12 years) - calculated for the water or steam side - on low alloyed steel (2 Cr 1 Mo) at wall temperatures about 350 C (= 125 bars) to 10 -15 m and for 500 C to about 350 m, see Fig. 3 and Photo 1. Similar conditions for carbon steel (e. g. St. 35.8) lead to 10 - 20 times thicker layers. A compact oxide layer of 300 m on the inner side of a evaporator tube increases the wall temperature for about 30-40 K. Dense protective layers (porosity < 5 %) doesnt affect the heat transfer significantly as far as their thickness do not exceed approx. 0.2 0.3 mm, depending on heat flux, but any higher porosity or stratified layer (scale) affects the wall temperature more and more, see Figs. 4. A thin magnetite protection layer with low porosity is an urgent necessary scale but must not be mixed up with deposit formation due to precipitates from the BW! Highly porous layers of corrosion iron products can be seen in Photo 2, stratified layers of magnetite in Photo 3. In practice, the best boiler feedwater (BFW) and boiler water (BW) contains always traces of not avoidable impurities like non-volatile water constituents and particularly circulating metal compounds (corrosion products) of iron and copper (and zinc) in form of undissolved (oxide particles) and/or dissolved solids. During start-up impurities shows much higher concentration, especially iron compounds. Normal specifications for boiler feedwater for high-pressure boiler beside others are: Acid-Conductivity at 25 C (= Cation Conductivity at 25 C Silica (silicon oxide) Iron total (dissolved + undissolved) optimal operation value Copper total (dissolved + undissolved) < 0.2 S/cm < 0.2 micro mho/cm) < 0.020 mg/l SiO2 < 0.020 mg/l Fe < 0.005 mg/l Fe < 0.003 mg/l Cu

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Conductivity The theoretic lowest conductivity of pure water at 25 C is about 0.055 S/cm, that means good quality BFW with an acid conductivity at 25 C of 0.15 S/cm contains still impurities of about 0.1 S/cm. These might be: Volatile carbon dioxide from: Carbohydrazide) Degraded organics Steam-volatile organic acids from: Steam-volatile amines: Non-volatile mineral acids from: Hydrolysed and oxidised organic amines Degraded organics Not 100 % hold back from the cation exchanger Salt-like matter (slipped through the make up-water demineralisation and/or through the condensate polishing plant) exchanged in the cation exchanger into acids. Air (equilibrium up to 0.6 S/cm) Decomposed oxygen scavenger

(e.

g.

Fig. 5 shows the specific conductivity of some chemicals at low concentrations. Silica in ppm-concentrations doesnt affect the conductivity. Non-volatile impurities of the BFW were concentrated in the BW depending on the concentration cycles, commonly in HP boilers around 50 to 200 times. This results to significant concentrations of impurities in the BW e.g. 20 g/l (ppb) chloride in the BFW were concentrated to 1000 or 4000 g/l or 1 or 4 mg/l respectively. In case of AVT conditioning of the steam-water-cycle it may lead to a too low pH in BW and to corrosion. Silica / Silicon oxide (SiO2) Silica is commonly present in BFW up to the limits but in the BW mostly below the limits and happens mostly from slippage through the demin plant and/or condensate polisher. Although silica is a solid mineral matter, it is steam soluble in considerable concentrations, see Fig. 6. The steam solubility depends on pressure and temperature and results to a steam-side or steam born blow down of the boiler, that means the number of concentration-cycles cannot be calculated from the silica concentrations of the BFW and BW. Consequently steam contains silica depending on pressure, temperature and concentration in the BW, see Fig. 7. Frequently is thought that silica limits in BFW and BW were defined only for turbine operation to avoid silica deposition in steam turbines, which is true on one hand but silica can also form problematic silicate scale together with hardness or aluminium with low heat transfer (silica scale shows only 10 % of the heat transfer of phosphate scale!) and can be removed with hydrofluoric acid only. Silicate scale may appear underneath oxide layers, see Photos 4 a-d.

Iron (Fe) and Copper (Cu)

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Iron compounds in alkaline BFW may be dissolved (e.g. in case of corrosion or erosion corrosion [FAC] in the BFW-line) and undissolved in form of fine oxide particles. In alkaline hot BW iron compounds were mostly present in form of undissolved oxide particles because of the water circulation (agitation) and pH and temperature above BFW conditions. Contrary to iron, copper compounds are mostly soluble in water, particularly in presence of ammonia and amines. Limitations for both are expressed for BFW only because it is very difficult to take really representative water samples including undissolved particles. Results for BW fluctuating strongly, which depends particularly on boiler load or pressure changes and sampling conditions (e.g. material for pipe-work, flow rate, vibrations, water hammer etc.)

Evaporation conditions and steam production Steam generation in boilers and evaporation of water seems to be very simple and people mainly think they are wasting time if they try to understand the proceedings of boiling water at a heated surface in a steam generator. The literature offers catch-words like under-cooled boiling, nucleate boiling, film boiling, steam blanketing etc. and suddenly boiling of water becomes a very complex process if one will understand the conditions directly at the heated surface. This paper will not explain all these effects but focuses on the deposition and corrosion related effects during steam production. If one wants to understand these localised conditions regarding deposition and corrosion it is necessary to realise that exactly the interface between metal surface and boiler water is the most important one because it is the location: Where heat from the furnace heats the fireside of the evaporator surface and creates there a metal temperature T1 Where the energy from the furnace passes through the evaporator wall to the BW and creates on the waterside a metal temperature T2. T1 is always higher than T2, see example Photo 5. Waterside scale increases T2! Where the protective magnetite and other layer on the BW side are built Where the wall material must be cooled to avoid over-heating Where BW evaporates, that means - BW must be transported to the surface (mass flow), - pure water evaporates to pure steam and - water with dissolved and undissolved impurities becomes locally concentrated to conditions far away from that of the circulating BW Cooling effects and heat extraction from evaporator surfaces Very important is the fact, that the best cooling effect to evaporator surfaces shows liquid water under boiling (saturated) conditions in equilibrium between pressure and temperature because the (latent) evaporation energy extracts most energy from the surface. For example the evaporation energy at 120 bars (325 C) is about 1.200 kJ/kg.

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Water below saturated conditions must be heated first to mentioned conditions and during heating of hot water to boiling conditions liquid water extracts for a temperature difference of e.g. 20 K at 120 bar only around 130 kJ/kg from the surface, see enthalpy tables. These conditions may lead also to under-cooled boiling. Even superheating of steam shows low cooling effect because superheating to about 20 C or 120 C above saturated conditions at 120 bar extracts only about 150 kJ/kg or 520 kJ/kg from the surface. Erosion Corrosion / Flow assisted Corrosion (FAC) Erosion corrosion or flow assisted (accelerated) corrosion (FAC) results if an aqueous medium or gas (e.g. air, flue gas, steam) with high flow rate removes an existing or freshly built protection layer faster than it can be newly built. Media with two phases e.g. gas & ash, water & sand, steam & water droplets, water & steam bubbles are more dangerous. The latter both may also cause additional impingement or cavitation attack. Steel may be affected at a flow rate > 8 - 10 m/s in weak alkaline medium (pH < 8.5 9), particularly at temperatures around 150 C in absence of oxygen. An increasing pH and little of oxygen (about 15-30 ppb) are reducing the risk of FAC, see Fig. 8. Also material with increased Cr-content reduces the risk of FAC, see Fig. 9. Particularly susceptible for erosion corrosion are metals with relatively soft protective layers, like copper and aluminium. For copper and aluminium the local maximal flow velocity of a non-corrosive medium should not exceed 1.6 - 1.8 m/s. Eroded surfaces are mostly metallic shiny without corrosion product and appear a smooth surface (structure like sand dunes). Hot Water Oxidation (Steam Side Burning) This corrosion phenomenon was formerly called inexactly Steam Splitting Corrosion and describes an excessive reaction of carbon steel or low alloyed steel and hot water or steam forming oxide layers and hydrogen. At temperatures below 570 C iron and hot water or steam react slowly to little wustite (FeO), major magnetite (Fe3O4) and again little hematite (Fe2O3), see Fig. 1 a. The reaction rises with increasing temperature, but is acceptable low below 450 C! [1] Simplified: 3 Fe + 4 H2O Fe3O4 + 4 H2

At temperatures > 570 C (see Fig. 1b) iron and hot water or steam react very fast primarily to FeO (wustite), little Fe3O4 (magnetite) and again little Fe2O3 (hematite), see Photo 6 a+b. [2] Simplified: Fe + H2O FeO + H2

The hydrogen produced exists first in atomic status and recombines later into molecular hydrogen. Atomic hydrogen is able to migrate into the metal lattice and may cause hydrogen damage on carbon steel and low-alloyed steel, see Photo 6 c.

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The hot water oxidation rises exclusively in heated boiler tubes as a consequence of too high temperature at the tube walls due to unsatisfactory cooling of the tubes. This process can already be initiated at wall temperatures from ca. 500 C upwards. On-load Corrosion / Under-deposit Corrosion Localised corrosion at boiler evaporator areas with high heat transfer due to deposition of corrosion products - first of inert iron oxides precipitated from the BW - subsequently formed on site, in combination with boiler water not in accordance with the specification. At areas with high heat flux, first porous (sponge like) deposits of undissolved solids became formed. Soluble impurities of the BW penetrate into these porous deposits, accumulate and concentrate and remain there for longer time frequently in presence of an insulating steam phase within the pores. The result is a material attack either due to a low pH (by acidic acting boiler water remains, e.g. from cooling water ingress) or high pH (by caustic acting remains, caustic gouging). Hydrogen Damage Hydrogen damage covers different material defects due to hydrogen influence, like hydrogen embrittlement, decarburisation, fissure and crack formation on carbon and lowalloyed steels. Affecting is atomic hydrogen only, developed by corrosion effects as well as by thermal formation from molecular hydrogen depending of its partial pressure. In boilers, significant amount of hydrogen may be produced by an excessive reaction of iron with water or steam to iron oxide and hydrogen, particularly at temperatures > 570 C: [3a] [3b] Fe + H2O FeO + 2 {H} atomic 2 {H} H2 molecular.

Atomic hydrogen migrates into the lattice of the mentioned steels and leads to hydrogen embrittlement and after molecule formation at voids or inter-metallic phases (e.g. manganese sulfide) to inter-granular fissures, some times in the shape of a fish eye and to brittle ruptures (see Photo 6 c). Atomic hydrogen reacts additionally with carbon of the steel by developing methane that produces localised fissures and cracks too. Because of the reduction of the carbon content in the steel, in parallel its strength will be reduced. Statement Considering the very important formation of protective layers and the mentioned evaporation and operation conditions of boilers, scaling and deposition is a logical consequence of longer boiler operation and may lead to local corrosion, as far as scale is too thick, too porous or contains aggressive media. Whilst scale formation of protective layers in both boilers and super-heaters is essentially, in boilers additionally deposition of omnipresent iron corrosion product existing undissolved in the BW cant be avoided. Preferable locations for deposition are evaporator areas with the highest heat transfer (heat flux) and/or low mass flow (lack in BW flow due to boiler design and operational conditions like heavily fluctuating load and too fast start-up as well as deposition).

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Super-heaters facing different conditions because the medium steam is purer than BW and the temperatures are much higher. First the porosity of the protective magnetite layer but also from other deposits is important. As higher the porosity as lesser the heat transfer due to stagnant steam phase within the pores and as higher the wall temperature depending of the heat flux. In evaporators made of carbon steel with operational temperatures < 400 C the thickness of the real protective layer is very thin (<< 0.1 mm even after 20 years operation). Evaporators are mostly affected by deposition of at least iron corrosion product (mostly hematite), which builds a porous layer on top of the protective magnetite layer, see Photo 2. If the thickness of these deposits exceeds a specific value (depending on deposit composition, porosity, boiler design and heat transfer) localised too high wall temperatures are possible and corrosion will appear even if the BFW and BW quality meets the requirements. As mentioned the effect comes from an insulating steam phase within the porous deposits (similar to steam blanketing by stagnant steam phases on evaporator walls). Elevated wall temperatures in general lead to more and faster iron oxide production (see formula [1] and [2]), to thicker oxide layers and to reduced wall cooling again etc. etc. If the critical temperature of about 570 C is achieved the reaction becomes excessive and loss in wall thickness - may be in combination with hydrogen damage - leads to failures. Photos 6a-c show nearly horizontal installed riser tubes with heat input around the tube with damage because of water/steam separation and insufficient cooling of the tubes top part with the steam phase. Excessive iron oxide production leaded to corrosion in one case and additional to hydrogen damage on the second case. Consequences for boilers: Depending on the water quality (with really exceptional, not significant deviations from the requirements), operation conditions, heat flux and boiler design, steam generators should be preventively cleaned after an operation time of 3 to 10 years to remove deposits of porous iron oxide. Quench boiler of petrochemical plants with very high heat flux should be cleaned after about 3 years, well designed industrial boiler after about 6 years and well operated boilers of power plants after about 8 -10 years. In case of severe ingress of acidic acting (e.g. seawater, cooling water etc.) or alkaline acting (e.g. caustics, water glass etc.) impurities and porous deposits a proper chemical cleaning is urgently recommended, except the last cleaning was less then 6 - 8 months ago. In the latter situation in case of acidic acting ingress, treatment with solid alkalising agents (volatile agents are not sufficient!) and/or increased blow down (in case of alkaline chemicals) may be sufficient. In case of moderate ingress of the mentioned impurities and possible porous deposits a chemical cleaning must be recommended to avoid corrosion even if the BW later shows good values. Localised porous deposits keep remains of ingress for a long time without indication in the bulk of circulating BW. Consequences for super-heaters or re-heaters:

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Contrary to boilers, super-heaters and re-heaters show rarely porous deposits of iron oxide but mostly compact thicker protecting oxide layers due to the elevated temperatures. Temperatures above design (considering steam temperature and material) lead to too thick oxide layers, which chips away due to the increasing thermal expansion rate of oxide in comparison of that of steel, see Fig. 10 and Photo 1 & 7. Contamination of super-heaters or re-heaters is possible if the steam/water separation in the drum is insufficient or if particular operational conditions (like heavily load, pressure, and/or drum level fluctuations) lead to carry-over of BW. To the extent that the BW contains non-volatile substances, deposition of these substances at the inlet of the heaters is possible. Another reason for deposition is contaminated spray water for steam attemperation, which may also contain iron and copper compounds. As far as the contamination of the steam is not severe, deposition in super-heaters or reheaters must not be the logical consequence because many solids are more or less really soluble in steam. It is well known, that silica is highly steam soluble, see Fig. 6, even caustic soda (NaOH, see Figs. 11 & 12) shows a significant solubility in steam. The steam solubility for phosphates, chlorides, sulfates and metal oxides is much lesser. The steam solubility of solids is strongly depended of pressure and temperature, which conveys problems into turbines or steam lines for pack-pressure or extracting steam. However turbines are mostly affected by deposits and subsequent lower efficiency, in steam lines caustic stress corrosion cracking is not rare, particularly if superheated steam contains more than 10 ppb sodium hydroxide! Photographs: 1-7 Figures: 1-12

Photographs:

Photo 1

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Photo 2

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Photo 3

Photo 4 a

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Photo 4 b

Photo 4c

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Photo 4d

Photo 5

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Photo 6 a

Photo 6 b

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Photo 6 c

Photo 7

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Figures

Fig. 1

Fig. 2

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Fig. 3

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Figs. 4

Fig. 5

Fig. 6

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Fig. 7

Fig. 8

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Fig. 9

Fig. 10

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Fig. 11

Fig. 12

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