Friday 11 May 2012

Deposits and scales found in boilers

Water formed and steam formed deposits

        May occur anywhere
        Wall and screen tubes most heavily fouled , superhtr has deposits formed elsewhere and carried with the steam or carryover. Economisers ( non-steaming) contain deposits moved from there original site.
        Tube orientation can influence location and amount of deposition.
        Deposits usually heaviest on the hot side of the steam generating tubes. Because of steam channelling, deposition is often heavier on the top portion of horizontal or slanting tubes
        Deposition occurs immediately downstream of horizontal backing rings.
        Water and steam drums can contain deposits, as these are readily accessed then inspection of the deposition can indicate types of corrosion. e.g. Sparkling black magnetite can precipitate in stm drums when iron is released by decomposition of organic complexing agents.
        Superhtr deposits ( normally associated with high water levels and foaming ) tend to concentrate near the inlet header or in nearby pendant U-tubes
        Contaminated attemperating spray water leads to deposits immediately down stream with the possibility of chip scale carried to the turbines.
        At high heat transfer rates a stable thin film boiling can occur, the surface is not washed ( as it is during bubble formation ) and deposits may form
        Thermal stressing can lead to oxide spalling ( the exfoliation of oxide layers in areas such as the suphtr). These chips can pass on to the turbine with severe results. Steam soluble forms can be deposited on the turbine blades , If chlorides and sulphates are present , Hydration can cause severe corrosion due to hydrolysis.
        As deposits form on the inside of waterwall the temperature increases. This leads to steam blanketing which in turn leads to reduced heat transfer rate , long term overheating and tube failure.

Effects on tube temperature of scale deposit

DEPOSITS
Iron oxides
Magnetite (Fe3O4)
A smooth black tenacious , dense magnetite layer normally grows on boiler water side surfaces.taken to indicate good corrosion protection as it forms in low oxygen levels and is susceptible to acidic attack

Heamatite (Fe2O3)

is favoured at low temperatures and high oxygen levels can be red and is a binding agent and tends to hold over materials in deposition. This is an indication of active corrosion occuring within the boiler/feed system

Other metals

Copper and Copper oxide is deposited by direct exchange with iron or by reduction of copper oxide by hydrogen evolved during corrosion . Reddish stains of copper are common at or near areas of caustic corrosion. Copper Oxide appears as a black depositi. It is considered very serious corrosion risk because of the initiation of galvanic corrosion mechanisms. Galvanic corrosion associated with copper deposition is very rare in a well passivated boiler. Zinc and nickel are very often found near copper deposition , nickel being a particularly tenacious binder
Rapid loss of boiler metals can occur. Copper can appear in various forms as a deposit in the boiler. As a copper coloured metallic deposit, usually in a corrosion pit, as a bright red/orange tubercules on the boiler metal surface or as a brown tear drop shaped formation.
Copper is generally an indicator of corrosion (or possible wear) occuring in the feed pump whether in the condensate lines or in the parts of a feed pump. A possoble cause of this is the excessive treatement of hydrazine which decompose to ammonia carrying over with the steam to attack suc areas as the air ejectors on condensers.

Copper oxide formed in boiler conditions is black and non- metallic.

SALTS

    The least soluble salts deposit first Calcium carbonate-effervesces when exposed to HCl acid
    Calcium sulphate-Slightly less friable then CaCO3
    Magnesium Phosphate-Tenacious binder, discoloured by contaminants
    Silicates-Insoluble except in hydroflouric acid E.G. Analcite

Water soluble deposits can only be retained if local concentration mechanism is severe. Prescence of NaOH , NaPO3 Na2SO3 should be considered proof of vapouration to dryness.
Calcium and magnessium salts exhibit inverse solubility. As the water temperature rises their solubility reduces, at a temperature of 70'C and above they come out of solution and begin to deposit. Feed water must be condition to remove the hardness salts before the water enters the boiler. The purity of the water is related to the steam conditions required of the boiler.

Hydrolyzable salts such as MgCl can concentrate in porous deposits and hydrolyze to hydrochloric acid
Scaling mechanism examples
Calcium Carbonate
Cacium Carbonate is formed by the thermal decomposition of Calcium BiCarbonate and apperas as a pale cream to yellow scale

Ca(HCO3)2 + Heat = CaCO3 + H2O + CO2

Magnessium Silicate

Tor form requires sufficient amounts of magnessium and silicate ions coupled with a deficiency in OH- alkalinity

Mg2+ + OH- = MgOH+

H2SiO3 = H+ + HSiO3-

MgOH- + HSiO3- = MgSiO3 + H2SO4

Thus this rough tan scale can be prevented by the maintenace of alkalinity levels

Calcium Phosphate (hydroxyapatite)

Ca10(PO4)6(OH)2

Found in biolers using the phosphate cycle treatment method this is a tan/cream deposit. This is generally associated with overdosing a boiler but can occur where insufficient disperseing agent reduces the effects of blow down.
In anouther form Ca3(PO4)2Ca(OH)2 it is associated with correct treatment control
Scales forming salts found in the boiler

    Calcium Bi-Carbonate 180ppm
        Slightly soluble
        >65oC breaks down to form CaCO3 +CO2, remaining Calcium carbonate insoluble in water
        Forms a soft white scale
    Magnesium BiCarbonate 150 ppm

        Soluble in water
        at more than 90oC breaks down to form MgCO3 and CO2 and then Mg(OH)2 and CO2
        Forms a soft scale
    Calcium Sulphate 1200 ppm

        Worst scale forming salt
        > 140oC (sat. press 2.5bar) or >96000ppm will precipitate out
        Forms a thin hard grey scale
    Magnesium Sulphate 1900ppm

        Precipitates at high temperatures and about 8 bar
        Forms sludge
    Magnesium Chloride 3200ppm

        Breaks down in boiler conditions to form MgOH and HCl
        forms a soft white scale Rapidly lowers pH in the event of sea water contamination of the boiler initiating rapid corrosion MgCl2 + 2H2O---> Mg(OH)2 + 2HCl HCl + Fe --->FeCl + H 2FeCl + Mg(OH)2 ---> MgCl2 + 2FeOH This series is then repeated. Effective feed treatment ensuring alkaline conditions controls this problem
    Sodium Chloride 32230 to 25600 ppm

        Soluble <225000ppm
        forms a soft encrustation
        Free irons promote galvanic action
    Other deposits-

        Amorphous Silicon dioxide (SiO2) - trace
        at high tempos and pressures (>40bar) silica can distill from the bioler as Silicic acid and can sublime and pass over into the steam system as a gas. Here it glazes surfaces with a smooth layer, which due to thermal expansion crack and roughen the surface. Troublesome on HP blading. Can be removed only by washing with Hydroflouric acid. Magnessium Silicate 3MgO.2SiO2.2H2O (Serpentine) is formed in water with proper treatment control

SCALE FORMATION

The roughness of the heated surface has a direct relationship to the deposit of scale. Each peak acts as a 'seed' for the scale to bind to.

Nucleate Boiling

normal ebulition
Scale built up as a series of rings forming multi layers of different combinations. Much increased by corrosion products or prescience of oil, even in very small quantities.
Oil also increases scale insulatory properties.
Departure form nucleate boiling (DNB) Under normal conditions steam bubbles are formed in discrete parts. Boiler water solids develop near the surface . However on departure of the bubble rinsing water flows in and redissolves the soluble solids normal ebulition However at increased rates the rate of bubble formation may exceed the flow of rinsing water , and at higher still rate, a stable film may occur with corrosion concentrations at the edge of this blanket.

Dissolved solids in fresh water

Hard water
   

-Calcium and magnesium salts

   

- Alkaline

   

-Scale forming

   

.

   

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Soft water
   

-Mainly sodium salts

   

- Acidic

   

- Causes corrosion rather than s

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