Shell Global Solutions

Boiler Corrosion Issues

Harmen Bouwman

Steam system a thin layer of magnetite

HP steam t Superheater Turbine Attemporator Condensate Steam drum

Economiser Evaporator Deaerator Steam

Condensate
Mud tap

Stack

Polishing

Shell Global Solutions

Magnetite formation
Steel is o idi ed b (p re) water oxidized by (pure) At high temperature

layer of magnetite = Fe3O4

Protective barrier against further oxidation g Black Thin with little reduction of thermal conductivity

Shell Global Solutions

Magnetite formation reactions

at elevated temperature - passivation: p p 3 Fe + 4 H2O Fe3O4 + 4 H2, protective !
at l / d low/moderate temperature: 2 Fe + O2 + 2 H2O 2 Fe(OH)2 + O2 + H2O

2 Fe(OH)2 FeO 2 Fe(OH)3 Fe2O3

ensure proper formation & prevent damage !

Shell Global Solutions

Magnetite Damage
Damage to protective film by oxygen yg high alkalinity acidity idi corrosion fatigue/mechanical stress

Shell Global Solutions

Improper magnetite
Visible after1 day ambient exposure as brown stains

Shell Global Solutions

A boiler should
generate steam in a clean circuit controlled nucleate boiling efficient heat transfer

Shell Global Solutions

A boiler might
generate steam in a circuit with heavy deposits (water side) large steam b bbl l bubbles less efficient heat transfer higher tube temperatures

Shell Global Solutions

Scales and deposits

scale: relatively selective l ti l l ti precipitation, hard glassy material t i l deposit: precipitated elsewhere, transported and deposited

Shell Global Solutions

Impact of scales and deposits

Shell Global Solutions

10

Failure causes
mechanical nature

81% 15 % 66 % 19%
corrosion 19%

failure f il causes
long term overheating g 15%

long term overheating short term overheating h ti

corrosion of which d to f h h due feed water 37 %

short t h t term overheating 66%

Shell Global Solutions

11

Three major problems in Boilers

Deposits Corrosion C i Carry over In order to avoid these problems BFW and BW must comply to certain specifications, depending on the pressure and the design of the boiler boiler. BFW/BW impurities are usually controlled by a combination of External treatment, i.e. purification Internal treatment, i.e. counter measures to reduce or eliminate objectionable effects of contaminants bj i bl ff f i

Shell Global Solutions

12

Typical Boiler Feed Water IOWs l l d

Oxygen < 20 ppb Conductivity < 0.2 S/cm pH between 9.5 and 11 Iron < 50 ppb Silica < 20 ppb
Non-volatile Volatile

Conditioned with volatile alkalies or phosphates C diti d ith l til lk li h h t : Sodium-phosphate & Caustic p p : Ammonia, Morpholine & Hydrazine

Shell Global Solutions

13

Boiler Feed Water

Quality requirements for BFW, BW and steam are specified in different countries by internationally known standardization committees and/or organizations e.g.: British Standards Institute (BSI) (BSI), Vereinigung der Technische berwachungs Vereine (VdTUV ) < 68 bar Vereinigung Grosskraftswerk Betreiber (VGB) > 64 bar Shell Global Solutions uses the latest recommendations published by EN 12952.

Shell Global Solutions

14

BFW spec: EN 12952-12 12952-

15

Shell Global Solutions

Main Boiler Corrosion Issues

pH Oxygen Corrosion Caustic corrosion Caustic Cracking Flow Assisted Corrosion Erosion/Corrosion-Erosion Chelant Corrosion Scaling Corrosion fatigue g Overheating & Stress Rupture Creep Fire-Side Corrosion Flue Gas Corrosion (cold-end corrosion) Condensate Corrosion
Shell Global Solutions

16

Causes of corrosion
poor pH control
inadequate blowdown control poor boiler p feedwater quality poor chemical feed control

oxygen pitting
mechanical de-aerator performance downtime corrosion

poor condensate external contamination treatment poor boiler feedwater quality condensate poor contamination external treatment inadequate blowdown control

oxygen in leakage downtime in-leakage corrosion scavenger underfeed

boiler corrosion
concentrating mechanism poor chemical feed/control stressed area embrittling water characteristics

deposition

stress corrosion cracking

Shell Global Solutions

17

Corrosion vs pH vs.
Corrosion rate

Safe range
8.5 12.7

10

12

pH at 25C
18

Shell Global Solutions

pH
The pH is an important factor influencing either scale formation and corrosion t d i of th water. i tendencies f the t Water with a low pH will result in corrosion of the feed water lines, boiler materials and heat exchangers (Acid corrosion) corrosion). A high pH may lead to excessive scaling. Boiler feed water : Boiler water : pH controlled to around 9 - IOW pH between 9.5 and 11- IOW

pH Control: Non volatile Non-volatile - Sodium phosphate & Caustic for BFW and BW Volatile - Ammonia, Morpholine, Hydrazine for BFW mainly

Shell Global Solutions

19

Oxygen corrosion
High Oxygen levels destroy the protective Magnetite (Fe3O4) by the formation of soft Fe2O3. Localized corrosion (pitting) occurs in oxygen corrosion cells. (p g) yg Oxygen corrosion can occur throughout the system. Oxygen corrosion is influenced by [O2] pH and temperature ], General strategy/approach to mitigate: gy pp g Decrease Oxygen levels by mechanical deaeration and chemical dosing (e.g. Hydrazine, Hydroquinone) IOW Oxygen llevels should b kept below 20 ppb - IOW O l h ld be k t b l b

20

Shell Global Solutions

Oxygen corrosion
Attack in FW and economizer sections where magnetite is damaged Under deposits By thermal cycling

O2 + 2 H2O + 4e - 4 OH OH
-

O2

Deposit + porous Fe-oxides

Fe F ++ F +++ + e Fe
Anode

Cathode

Fe Fe + + + 2e -

Shell Global Solutions

21

Oxygen corrosion
Too much oxygen (> 20 ppb dissolved) Reaction on magnetite: 4 Fe3O4 + O2 6 Fe2O3 Reaction on bare surface: 4 Fe + 2 n H2O + 3 O2 Hematite - not protective Pitting
Fe3O4 Fe O2 Fen+ anode
22

2 (Fe2O3.nH2O)

O2

cathode th d

Shell Global Solutions

Oxygen pitting corrosion

Corrosion product present removed

Shell Global Solutions

23

Oxygen corrosion

24

Shell Global Solutions

Oxygen removal
Mechanical de-aeration Chemical oxygen scavenging Sulphite sulphate Hydrazine ( 2H4) d (N N2, H2O s pports passivation supports NH3 (neutralisation of condensate) Carbohydrazides C b h d id hydrazine, CO2 Others Oh

Shell Global Solutions

25

High alkalinity attack

Caustic attack / Gouging Local concentration of caustic under deposits and in crevices g g pH. causing a high p Dissolution of protective magnetite layer and the steel below as ferrates. Caustic embrittlement

form of stress corrosion cracking, along grain boundaries in metal high alkalinity in crevice / deposit

Shell Global Solutions

26

Caustic Corrosion
Usually f d i hi h U ll found in high pressure b il boilers Problem mainly caused by deposits Localized corrosion Also known as crater attack or caustic gouging Conditions Presence of caustic soda in the boiler water Presence of a concentrating mechanism

Shell Global Solutions

27

Caustic Corrosion
Caustic corrosion can occur in the presence of
Porous metal oxide deposits Operation above rated capacity Excessive localized heat input Localized pressure differentials Restrictions in the steam generating tubes

Mitigation
Limit the presence of free caustic Coordinated phosphate treatments Congruent sodium phosphate Phosphate-low hydroxide
Shell Global Solutions

28

Caustic Corrosion
Boiler water
Na+ OHlocal increase of pH Steam Porous Iron Deposit

Magnetite

Caustic attacks iron

Steel

Fe 2+ + 4OH - FeO22 - + 2H 2 O Fe 3O4 + 4OH - 2FeO2- + FeO22- + 2H 2 O

Shell Global Solutions

29

Caustic Corrosion
Removal of magnetite film at high pH Fe3O4 + 4 NaOH 2 NaFeO2 + Na2FeO2 + 2 H2O, soluble products Attack of bare steel at high pH Fe + 2 NaOH Na2FeO2 + H2, soluble products p Attack of bare steel at moderately high pH 3 Fe + 4 H2O Fe3O4 + 4 H2, e e porous oxide layer

Shell Global Solutions

30

Co-ordinated phosphate effect

Buffer: HPO42- + OH- PO43- + H2O Phosphate hide-out i a risk Ph h hid is i k

Boiler water
Steam HPO42Na + Porous Iron Deposit OH Magnetite

Phospate p neutralises OH - No attack

Steel
Shell Global Solutions

31

Caustic Corrosion

Shell Global Solutions

32

Caustic gouging

ref: The NALCO Guide to Boiler Failure Analysis (ISBN 0-07-045873-1)

Shell Global Solutions

33

Caustic cracking / embrittlement

Conditions required C diti i d
Concentrating mechanism Metal under high stresses Temperature (rare below 150 C)

Shell Global Solutions

34

Flow Assisted Corrosion

Thinning corrosion associated with high purity, low oxygen condensate (or ( boiler feed water) caused by the relative movement of a fluid against ) y g the metal surface. Metal loss results from the dissolution of the protective oxide film by localized turbulence Type of Corrosion-Erosion Feed water velocities above 2.1 m/s can remove oxide films Damage is aggravated by local turbulence Low oxygen concentration destabilizes the magnetite layer pH < 9.3 (note: pH or feed water controlled between 8.5 9.3) Maximum damage in o one-phase flow @140 deg C o two-phase flow @ 180 deg C Corrosion rates between 0.1 10 mm/year C i t b t 01 /
Shell Global Solutions

35

Flow Assisted Corrosion

Too low o yge co ce t at o s with too high liquid velocities oo o oxygen concentrations t g qu d e oc t es can lead to Flow Assisted Corrosion

Shell Global Solutions

36

Flow Assisted Corrosion

Feed water line inside a boiler drum Feed water contained <5 ppb O2.

Shell Global Solutions

37

Flow Assisted Corrosion

Mitigation g
Modification of the water chemistry (usually minimum changes allowed) Materials selection: - Resistance improves with small additions of Cr, Cu and Mo - Use of 1.25 Cr or 2.25 Cr steels - Use of 12Cr stainless steels provides best protection Change material at areas with high corrosion rates Ch i l i h hi h i

38

Shell Global Solutions

Carry-Over y
Carry-over is any contaminant in the solid-, liquid- or vapour form, which leaves the boiler with the steam due to incomplete separation of the steam in the steam drum. It is related to steam quality. Carry-over may lead to superheater failures, sticking govenor valves in turbines, erosion of turbine parts, reduced turbine efficiency. Causes for carry-over: y Mechanical Pressure or level surges, inadequate design, overloading, surges design overloading high drum level operation Chemical Foaming, formation of bubbles (accumulation of solids), vapour carry-over carry over (silica)
Shell Global Solutions

39

Cracking due to deposits from carry-over in superheater carry over

Shell Global Solutions

40

Erosion - Corrosion/Erosion
Combined action of corrosion and erosion Metal l M t l loss rates d t depend on d Velocity and concentration of impacting medium Size and hardness of impacting particles Hardness/corrosion resistance of material. Factors increasing corrosivity of the environment ( temperature, pH) can increase susceptibility to metal loss loss. Prevention Design i D i improvements modify shape/geometry/materials selection t dif h / t / t i l l ti

Shell Global Solutions

41

Erosion - Corrosion/Erosion
Major locations for Erosion Soot Blowers Steam cutting from adjacent tube failures Fly-Ash Erosion in eco, superheater, reheater & rooftubing (higher sensitivity for lower temperatures: harder particles) Erosion on water side is comparatively rare p y Locations with increased turbulence (internal surface discontinuities & tube ends: Corrosion-Erosion) Corrosion Erosion)

Shell Global Solutions

42

Corrosion/Erosion: tube end

Shell Global Solutions

43

Chelant Corrosion
Only when Feed Water is chelant controlled Attacks the protective magnatite layer of the boiler (drum, economizer, tubes economizer tubes, lines) Mechanism Fe3O4 + Fe + 8H+ 4Chelant Mitigation Close control of Chelant levels Control of dissolved Oxygen levels Reduce fluid velocity (turbulent flow)
Shell Global Solutions

4Fe(II)Chelant + 4H2O

44

Scaling
Silica The presence of Silica can promote the formation of Sodiumiron-silicates. The solubility of Silica is dependent of the alkalinity of the water. lk l f h The higher the alkalinity, the higher the solubility. For high pressure steam boilers the Silica content in the BFW boilers, should be limited to 20 ppb. Cycles of concentration raises the Silica concentration to y ppm levels e.g. 60 cycles x 20 ppb > 1.2 ppm

45

Shell Global Solutions

Scaling
Iron
Can form a scale in boiler tubes, particular in the presence of Silica thru the formation of Sodium iron silicate Iron levels should be limited to 50 ppb (co o y equ ed boiler a u actu e s) (commonly required by bo e manufacturers)

Copper pp
The presence of copper is thought to accelerate on-going corrosion processes Recovered condensate (unpolished) is the main source of copper
46

Shell Global Solutions

Scaling

Mud drum scales

Riser tube

47

Shell Global Solutions

Corrosion fatigue/mechanical stress

Damage to protective Fe3O4 mechanical damage (hammer testing, etc.): rusting ti tube vibration or thermal cycling : cyclic stress with repetitive breakage/formation of Fe3O4 corrosion fatigue cracking water hammer at de-aerator inlet mixing of h t condensate steam with cold make-up water i i f hot d t t ith ld k t

Shell Global Solutions

48

De-aerator De aerator cracking

Cracking has been observed in de-aerator vessels g The root cause of failure is corrosion fatigue Since th cracks are very tight, it can usually only be Si the k ti ht ll l b found with (wet) fluorescent magnetic particle examination

49

Shell Global Solutions

Overheating & Stress Rupture

Localized overheating (short term/long term) causes permanent deformation (bulging) and eventual failure/rupture at normal operating stress levels p g Critical factors: Temperture & Time (stress) Loss in thickness reduces the time to failure Avoid overheating Burner management Prevent scaling Main sources of fouling in boiler tubes are silica, iron and copper

Shell Global Solutions

50

Creep
Time dependent deformation of stressed components under load at high temperatures Critical factors: Material, Load/Stress and Temperature Beyond threshold temperatures damage/cracking/failure is a concern Mitigation: Operate equipment within design limits, Inspect & Monitor

Shell Global Solutions

51

Creep damage

Shell Global Solutions

52

Failure from creep voids

Membrane tube from boiler Overheated at 750 C after voids had developed

Shell Global Solutions

53

Creep
Allowable stress

SS 321 CS time independent strength LA

time dependent creep strength 800H

200

400

600

800

Temperature in C T t i
Shell Global Solutions

54

Creep Threshold Temperatures

Carbon Steel C - Mo 1Cr Mo 1C - M 2Cr - 1Mo 5Cr - Mo 9Cr 1Mo 304H 347H : 410 C C : 490 C : 500 C : 480 C : 470 C : 515 C C : 580 C : 595 C

Shell Global Solutions

55

Fire-side Corrosion
Oxidation Firing with excess of Oxygen (1-2 %) (1 2 Oxide scale (protective)

Shell Global Solutions

56

Fire-side Corrosion
Oil-Ash Corrosion Metal temperature range: 593 816 C Presence of Vanadium and Sodium Compounds in Fuel Mechanism Formation of V2O5 & Na2O by oxidation (in flame) Ash particles stick to the metal surface (Na2O as binder) V2O5 + Na2O forms a liquid (eutectic) Liquid fluxes the protective oxide resulting in rapid corrosion Mitigation Metal temperature < 593 C Additive: Mg-compounds, when fuels with very low quantities of V and Na can not be specified

Shell Global Solutions

57

Flue Gas Corrosion (Cold-End Corrosion)

Sulfuric acid corrosion if Steel temperature is below 150C 1) AND Fuel contains sulphur

natural gas: oil:

[S] > 20 ppmv ( 30 mg/Nm3) (~30 [S] > ~ 0.1 %w

1)

or the actual acid dew point of the flue gas, calculated on the basis of the SO3 concentration, estimated from the radiant cell temperature and the excess air.

Shell Global Solutions

58

51

Condensate corrosion CO2

CO2 is formed by the dissociation y of carbonates in the boiler NaHCO3 NaOH + CO2 Mechanism: CO2 + H2O H+ + HCO3low pH at carbon steel large patches of attack with steep edges

Shell Global Solutions

59

Condensate corrosion O2
O2 corrosion sources: i Oxygen ingress De-aerator D Mechanism: Oxygen pitting Fe

Worse: CO2 & O2 combined

Shell Global Solutions

60

Condensate corrosion NH3

Sources: NH3 from boiler Mechanism: M h i Cu & alloys Stress Corrosion Cracking

Shell Global Solutions

61

Prevention Condensate Corrosion

Reduce
carbonates BFW oxygen ingress vacuum systems vents condensate pumps / traps / valves p p p intermittently operated systems ammonia

Shell Global Solutions

62

Condensate Treatment
De-oiling (oil from turbines) g
Oil removed by skimming tanks, clarifiers and filters. Alternatively by coalescers and absorbents y y

Condensate Polishing
Oil-free condensate is treated in a condensate polishing treater (ion exchangers)

Shell Global Solutions

63

Once a boiler ...

Shell Global Solutions

64

Thank you for your attention

Shell Global Solutions

65