MONTHLY TECHNICAL ARTICLE

AMCO-TA-12
MAY 2016

Deposition and Corrosion in Fossil

Fired Boiler Tubes

FOREWORD
AMCO Saudi Arabia is an autonomous and independent Consulting Company with the objectives of best Metallurgical
and Lifting Equipment Services to Saudi Arabian Oil and Gas, Petrochemical, Power Generations, Fertilizers,
Refineries, Manufacturing, Construction, Manufacturing, Defense and Automobile Industries.

Our specialization is: Plant Life Assessment /Extension, Failure Investigation, Asset Integrity Management, Boiler
Inspection, Boiler Tube Condition Assessment, Tube Failure Analysis, RCM Studies, RAM Studies, Single Point of
Failure(SPOF) Studies, Plant Cycling, Cost Analysis, Plant Benchmarking, Crack Assessment, Risk Based
Inspection/Maintenance, Probabilistic Assessment, Fitness-for-Service Assessment, Conditional Assessment, Plan
Reliability Studies, Vibration Analysis, Condition Monitoring, Stress Analysis, Support and guidance in Plant Operation
and Maintenance, Advice in weld repairs, Support with Materials, Inspection and Monitoring; Corrosion and oxidation
issues, Technology Development, Finite Element Analysis, Stress Analysis, P91 Steel Assessment, Metallography,
SEM/EDS Analysis, Contamination Analysis, Plant Mechanical Improvement Studies with years’ experience around the
globe. The AMCO Monthly Article area offered within the following areas:

i. Plant Life Management

ii. Lifting Inspection
iii. Fitness for Service
iv. Risk Based Inspection/ Maintenance
v. Advance Materials
vi. Reliability Engineering
vii. Qualification, Quality and Safety Methodology
viii. Materials Technology
ix. Pipelines and Risers
x. Asset Operation
xi. Quality Control/Assurance
xii. Corrosion and Erosion
xiii. Inspection and NDT testing
xiv. Microstructures and damage mechanisms
xv. Operations and Maintenance
xvi. Vibration and Condition Monitoring

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About the Authors

Engr. Mohammad Hussain Turi

Lead strategist and authority figure in charge of asset integrity & reliability
management, life assessment, inspection activities, failure investigation, risk
management, and continuous process improvement studies for plant operators. In
order to achieve client requirements, my team works on undertaking
improvement initiatives in terms of technology, strategies, and other initiatives
with regards to material selection, RBI, corrosion monitoring and control
activities amongst others in the Operations and maintenance side of business.
Mentor, direct and lead a team of 50 direct and indirect reports. Have a deep
understanding of mechanical issues in a plant and can discuss and agree on solutions to prevent re-
occurrence in the future. He has actively participated in ongoing improvement of equipment health and
extension of component lives through the use of engineered solutions, current and developing
technologies and integrated computerized maintenance systems

Engr. Owais Manzoor Malik

Engr. Owais Manzoor is a graduate Engineer in Metallurgy & Materials,

encompassing more than 6 years of experience. He has served in upstream and
downstream sector (oil & gas) in Pakistan and Middle East. Owais specializes in
microstructural characterization of materials, Lab analysis, damage assessment
and corrosion failure investigations. He possesses substantial and demonstrable
Oil & Gas materials knowledge and intrinsic expertise including macro and micro
examination and fractographic analysis. He has performed several failure analysis
of the in service components in Petrochemical, Power generation and Oil and Gas
sector. His interest lies in determining the root cause of the failed components with special emphasis on
their metallurgical properties.

He has hands-on experience in performing innumerable site (In-situ) metallography to evaluate

nondestructively the conformity of microstructure of equipments. The ability to determine the detrimental
phases in the microstructural analysis of carbon steels, duplex stainless steels and Inconel material are his
trade mark. He has been the part of corrosion monitoring and testing team, working in the field and
Laboratory. These technical traits enable him to conduct the fitness for service studies of varied
equipment.

Deposition and Corrosion in Fossil Fired Boilers

INTRODUCTION

Deposition of low-solubility solids and corrosion products in steam generators is as old as thesteam
generating process itself. The low-solubility solids are formed either from impurities introduced into the
plant cycle via cooling water or makeup water or because of reactions between the impurities and the
boiler water treatment chemicals. Corrosion products participating in the deposition process within the
boiler originate in the low-temperature part of the cycle (condenser, LP and HP feedwater heaters,
deaerator and feedwater storage tank).

Corrosion products from the pre-boiler areas are the source of most suspended solids that are transported
into the boiler. For all-ferrous feedwater systems (no copper alloys in the feedwater and possibly copper-
based condenser tubing), the generation of corrosion products (magnetite, hematite and ferric oxide
hydrate) occurs mainly due to corrosion and flow-accelerated corrosion (FAC) of low-pressure and high-
pressure feedwater heaters, deaerators, economizer inlet tubing and piping, feedwater piping and drain
lines.

Deposition of chemicals, contaminants and corrosion products in the boiler may result in a reduction in
boiler efficiency and may reduce the service of boiler parts, and may finally lead to boiler tube failures. A
few typical examples:

Rippled deposits formed in economizers or waterwalls of once-through steam generators

operating on reducing all-volatile treatment cause a pressure drop increase. This increase
deteriorates cycle efficiency, requiring additional feed pump work, and full-load
operation may no longer be possible.

Buildup of excessive deposits in waterwalls of supercritical once-through steam

generators may cause or be one of the major root causes of waterwall cracking.

Thick and porous deposits in boiler tubes of drum boilers are the primary root cause of
under-deposit corrosion and may lead to boiler tube failures due to hydrogen damage,
caustic gouging and acid phosphate corrosion.

Mechanical carryover of sodium sulfate in steam during operation leading to the buildup
of sodium sulfate deposits in superheaters and reheaters may lead to or intensify pitting
corrosion during shutdown if inadequate or no layup methods are applied.

Water-side deposits in boilers typically consist of two layers – a thin inner magnetite layer adjacent to the
metal (topotactic layer) and a more porous outer iron oxide deposit layer(epitactic layer).

Slagging and Fouling in Boilers

Different types of depositions accumulated in boiler. When the deposition of ash on furnace walls, mainly
in the radiant section, is in a highly viscous state and forms a liquid layer then it is called slagging, when
the deposit is built up by condensed materials, forming a dry deposit, generally in the convective section,
then it is called fouling, [4,5]. Slagging is mainly a molten deposit of ash particles. When the molten ash
contacts the boiler tube surface then it tends to solidify due to the lower temperature of the boiler tube.
For particles to fuse to the tube wall and not rebound from the inertia force, it is necessary that the
particles be sticky.

Fig 1.0 Schematic of coal ash deposition process in utility boilers

The particles require a certain amount of force to carry them from the centre of the boiler to the where
they impact the wall. This can be done in different ways. The most common process is inertial impaction
where the particle gains inertia from the flame and is thrown towards the wall [7]. Reference 8 defines the
term fouling as sintered or cemented deposits that form on convection surfaces. In general, slagging
occurs on the water walls near the high temperature region of a furnace, and fouling is most likely on the
preheated and superheater surfaces where the flue gas temperatures are much lower than in the
combustion zone [9]. Fouling and slagging phenomena are affected by different coals used in boilers. It
has been demonstrated that bituminous Scottish coal has a slightly higher fouling propensity compared to
the Colombian bituminous coal. It has been demonstrated that the Na2O content of coal ash and the
chlorine content of the coal, are indicators of likely fouling problems [9]. Deposition in a boiler depends
mainly on the amount and type of inorganic materials present in the coal being used. Porous deposits of
corrosion products transported from the pre-boiler sections into the waterwalls are particularly dangerous.
Within the deposits, many individual microsystems may develop that generate steam ("wick boiling,"
Figure 2.0). Within the deposits, circulation and evaporation lead to an additional concentration of boiler
water. Thus, a chemistry condition is established within or underneath the deposits which is totally
different from that in the bulk boiler water.

Figure 2.0 Steam Formations in Porous Waterside Deposits

Soot and slag generation

In any combustion process of a fuel there will be always some unburned carbon (soot) generated and
some ash carried with the stack gas stream. Soot, ash, and molten ash (slag) will accumulate at the tube
banks of the heat exchangers. Some ash will even melt down at the tube surface. The final result is a layer
insulating the tubes against the hot combustion gases. Soot generation has various causes such as

Insufficient atomization of fuel oil

Low oil line pressure and lack of turbulence will result in poor atomization of fuel oil, resulting in
larger droplets leaving the flame envelope partially unburned. Major causes are low oil line
pressure, lack of primary combustion air, or low fuel oil preheating temperature.

High moisture content in the fuel

Too much water in a fuel leads to a “cold” fire causing excessive smoke generation because there
is not enough fuel energy available to generate a sufficiently high flame temperature. However
some water helps to speed up kinetic reaction. It also shortens the flame length. Major cause of
this type of soot generation is a combination of high moisture content and too much excess air .

Dripping burner
 Occasionally liquid oil drips directly from the burner down into the fire tube and forms a pile of
soot. This soot burns up and generates smoke.

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 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. 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:

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 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.

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. Also material with increased Cr-content reduces
the risk of FAC. Particularly susceptible for erosion corrosion is 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).

Measuring the amount of total deposit respect the surface and deposit thickness.

The measure of the total deposit weight amount per unit of surface is called Deposit Weight Density
(DWD), and it gives an indication on whether the surface has too much deposit and risk to have problems
due to overheating. For determination of deposit-weight-density (DWD), a tube section is weighed before
and after removal of the internal/external deposit. Dimensional measurements before and after the deposit
removal are performed to determine the deposit thickness. The deposits are carefully removed from the
surfaces for further deposit analysis. The surfaces are subsequently cleaned using a sandblasting unit
The value for DWD that can be acceptable for a safe operation depend on three main aspects: 1) The
heat flux in the area where the deposit is located 2) The composition of the deposit and 3) Porosity of
the deposit.
Analysis of the deposit bulk composition and analysis of deposits located in different
positions respect the tube.

The technique used Scanning Electron Microscopy - Energy Dispersive X-ray Analysis (SEM-EDXA) is
used to identify the elemental composition of the internal corrosion products/deposit and of the base alloy
material of the tube sections. Elemental determination with the SEM-EDXA system is based on analysis
of X-rays produced via electron beam excitation of a sample area. This technique allows analysis of a
sample in selective areas. The limited depth of analysis (typically a few microns), and the possibility to
select the area of interest under the electron beam, allows for local analysis to reveal differences in
composition. Representative (bulk) analysis of a deposit sample is performed by grinding a representative
sample to a fine, homogeneous powder. The identification and measurement of individual peak intensities
in the X-ray spectrum is done with a computerized multichannel analyzer. With this system, the range of
detectable elements is from carbon to uranium. With the current light element detector using an ultra thin
window, the light elements down to Carbon can be detected (atomic number = 6). However, the light
elements cannot be accurately quantified by SEM-EDXA. Based on the X-ray intensities, the
concentration of the elements with atomic number >10 can be calculated. Sensitivity approaches 0.5
weight percent. The semi-quantitative analysis is reported as weight percents, and only elemental
constituents are reported. For the elements with atomic number >10, elements not reported are not
present, or are below detection limit. The analysis can be additionally completed with the WDXRF
(Wavelength Dispersive X-ray Analysis by X-ray Fluorescence) to have the composition of crystalline
structure of the deposit. It is a technique similar to SEM-EDXA, is used for determination of elements
based on analysis of X-rays produced. However, instead of electron beam excitation, an X-ray Cathode
tube is used for excitation of the sample area. Besides, the Wavelength Dispersive method identifies the
elements on basis of the wavelength of their X-radiation instead of the Energy Dispersive method that
discriminates on basis of the energy of the detected photons.

Figure 4.0 SEM images of the deposits

DEPOSITION IN SUPERHEATERS AND REHEATERS

Deposit formation is possible in superheaters, reheaters and steam piping. Deposition in these areas can
be caused by
Contamination in feedwater and steam,
Contamination in attemperation water,
Boiler mechanical and vaporous carryover,
Contamination from layup practices and/or
Contamination from chemical cleaning practices

Deposits in superheaters, reheaters and steam piping can be controlled by:

Maintenance of proper water and steam chemistry,

Maintenance of designed boiler scrubber efficiency (drum units),
Elimination of high boiler water levels and foaming (drum units) and/or
Adoption of proper layup and chemical cleaning procedures.

Methods to Control or Prevent Deposition

Changing the cycle design and piping where necessary,

Retrofitting condensate polishers,
Minimizing mechanical carryover,
Minimizing cycle air inleakage,
Mimimizing oxygen in cycle makeup,
Nitrogen blanketing boiler and heaters,
Optimizing feedwater heater options, and
References:

1. Cycle Chemistry Corrosion and Deposition: Correction, Prevention, and Control, EPRI, Palo Alto, CA:
2. State-of-Knowledge of Copper in Fossil Plant Cycles, EPRI, Palo Alto, CA: 1997.TR-108460.
3. Deposition of Corrosive Salts from Steam, EPRI, Palo Alto, CA: 1983. NP-3002.
4. Guidelines for Chemical Cleaning of Fossil-Fueled Steam-Generating Equipment, EPRI, Palo Alto, CA:
5. O. Jonas, W. Steltz and R. B. Dooley, “Steam Turbine Efficiency and Corrosion: Effects ofSurface Finish,
Deposits, and Moisture,” Sixth International Conference on Fossil Plant Cycle Chemistry EPRI, Palo Alto,
CA: 2001. 1001363.
6. Guidelines for Chemical Cleaning of Conventional Fossil Plant Equipment, EPRI, Palo Alto, CA: 2001.
1003994.
7. 22. Steam Turbine Efficiency and Corrosion: Effects of Surface Finish, Deposits, and Moisture, EPRI, Palo
Alto, CA: 2001. 1003997. 23. Cycling, Startup, Shutdown, and Layup Fossil Plant Cycle Chemistry
Guidelines for Operators and Chemists, EPRI, Palo Alto, CA: 1998. TR-107754.
8. 24. M. Ball, A. Bursik, R. B. Dooley, M. Gruszkiewicz, D. A. Palmer, K. J. Shields and J. M. Simonson,
“The New Approach to the Volatility of Impurities in Water/Steam Cycles,” Sixth
9. International Conference on Fossil Plant Cycle Chemistry, EPRI, Palo Alto, CA: 2001. 1001363.
10. G. Couch, 1994, “Understanding slagging and fouling during pf combustion” Fuel and energy vol.36

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