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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.
The thickness of a protective magnetite layer depends on the material, operation tempera-
ture 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 < 0.2 S/cm
( = Cation Conductivity at 25 C < 0.2 micro mho/cm)
Silica (silicon oxide) < 0.020 mg/l SiO2
Iron total (dissolved + undissolved) < 0.020 mg/l Fe
optimal operation value < 0.005 mg/l Fe
Copper total (dissolved + undissolved) < 0.003 mg/l Cu
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:
Fig. 5 shows the specific conductivity of some chemicals at low concentrations. Silica in
ppm-concentrations doesnt affect the conductivity.
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 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.)
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
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.
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).
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!
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.
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.
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.
Hydrogen Damage
Hydrogen damage covers different material defects due to hydrogen influence, like
hydrogen embrittlement, decarburisation, fissure and crack formation on carbon and low-
alloyed steels. Affecting is atomic hydrogen only, developed by corrosion effects as well
as by thermal
formation from molecular hydrogen depending of its partial pressure.
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. manga-
nese 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.
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.
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.
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.
As far as the contamination of the steam is not severe, deposition in super-heaters or re-
heaters 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
Photo 2
Photo 3
Photo 4 a
Photo 4 b
Photo 4c
Photo 4d
Photo 5
Photo 6 a
Photo 6 b
Photo 6 c
Photo 7
Figures
Fig. 1
Fig. 2
Fig. 3
Figs. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12