Damage Mechanisms Which Affect Refinery Equipment

Presented By: Thomas D. Farraro Houston, TX Houston, Texas August 24 and 25, 2003
STRESS ENGINEERING SERVICES, INC.
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A Damage Mechanism is defined as:

A mechanism or process which results in deterioration of a material or its properties because of a reaction with or in response to the environment to which it is exposed.

Failure to Understand Damage Mechanisms May Have Dire Consequences

8 Types of Damage Mechanisms

1. Uniform (General) Corrosion
Atmospheric Corrosion (external) Process Corrosion (internal )

2. Localized Corrosion
Pitting Crevice Corrosion Under Deposit/Coating Corrosion, Thinning, Cracking)

3. Galvanic Corrosion 4. Environmental Cracking (Stress Corrosion Cracking)

a) b) c) d) e) f) g) h) Chloride Stress Corrosion Cracking Alkaline Stress Cracking (caustic, amines, carbonates) Ammonia Stress Corrosion Cracking Hydrofluoric Acid Stress Corrosion Cracking Polythionic Acid Stress Corrosion Cracking Sulfide stress Corrosion Cracking Hydrogen Induced Cracking Stress Oriented Hydrogen induced Cracking (ClSCC) (ASCC) (Ammonia SCC) (HFSCC) (PTASCC) (SSC) (HIC) (SOHIC)
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8 Types of Damage Mechanisms (Cont.)

5. 6. 7. Intergranular Corrosion Dealloying (Dezincification, Graphitization) High Temperature Corrosion
a) b) c) d) e) f) Oxidation Sulfidation Organic Acid Corrosion Carburization Metal Dusting Decarburization

8 Types of Damage Mechanisms (Cont.)

8. Mechanical/Metallurgical Assisted Degradation
a) b) c) d) e) Erosion Corrosion Cavitation Fatigue Fretting Metallurgical Effects
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. Grain Growth Graphitization Hardening Sensitization Sigma Phase Embrittlement 885 Embrittlement Temper Embrittlement Liquid Metal Embrittlement Brittle Fracture Creep Stress Rupture
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90% of Corrosion Problems Are Caused by One of the Following 12 Chemical Types
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. Oxygen Carbon Dioxide Hydrogen Sulfide Sulfur Dioxide Inorganic Acids Inorganic Alkali Halide Salts Organic Acids Organic Chlorides Organic Sulfides Organic Amines Water
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Distribution of Damage Mechanisms Types

30% of all corrosion failures are caused by general thinning (uniform corrosion). 70% of all corrosion failures are caused by local corrosion mechanisms (pitting, stress corrosion cracking, crevice corrosion etc.)

Wet vs. Dry Corrosion

Corrosion can be divided into to distinct processes. Wet Corrosion
Electrochemical reactions which require an electrolyte to be present - usually water.

Dry corrosion
Chemical reactions which occur in the absence of any electrolyte.
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Why do Materials Corrode?

The driving force behind corrosion is entropy; the tendency, in nature , for all things to return to the lowest possible energy state. Iron ore (rust) + Heat Corrosion
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Steel

Wet (Electrolytic) Corrosion

4 Essential Elements of an Electrolytic Corrosion Cell

Anode (-) Cathode (+) Electrolyte External circuit

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Anodic Polarization and Passivity

Anodic surfaces can be polarized by the formation of a thin impervious layer of corrosion products. When corrosion reactions are completely polarized the metal is said to be Passivated. At this point there is no potential difference between the anodes and cathodes and the corrosion ceases.
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Damage to the Passive Layer

When the passive layer is dissolved or disrupted at a given point a very active anodic site is set up which causes accelerated corrosion.
Reduction of ions or oxygen Metal Ions Fe++

Cathode
Elec t Migr ron ation

Cathode Anode
tron Elec tion a Migr

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Chemistry of Wet Corrosion

Electrolytic (Wet) Corrosion of Steel
Oxidation (Rusting)
4Fe + 6H2O + 3O 2 4Fe(OH)3 6H2O + 2Fe2O3

Hydrochloric Acid Attack

Fe + 2HCl FeCl 2 +H0

Sulfur Acid Attack

Fe + 2HSO3 Fe + H2SO4 Fe(SO3) + H0 FeSO4 + 2H0

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Primary Factors Which Effect Wet Corrosion Rates

pH Concentration of Dissolved ionic species (salts, gases) Temperature Pressure Velocity of the fluid

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Other Factors Which Affect Wet Corrosion

Heat Transfer Conditions Localized boiling/condensation, uneven heating causing galvanic corrosion

Amount of Suspended Solids

coke, catalyst particles, mud, sand, silt etc.

Presence of Microorganisms
sulfate reducing bacteria, sulfate oxidizing bacteria

Dissimilar Metals
Can lead to galvanic corrosion cells and accelerated corrosion due relative size of anodic and cathodic areas

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Dew/Boiling Point Corrosion

The inorganic salts and acids are typically vaporized or absorbed by saturated steam and carried with light hydrocarbons into the overhead systems of fractionation columns and separators. These inorganic salts and acids have very high solubility in water, consequently the first drops of water which condense or the last drops to vaporize will have a high concentration of salts and/or low acid pH which results in rapid localized corrosion, pitting and salt deposition. This is known as Dew Point or Boiling Point Corrosion
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Dew/Boiling Point Corrosion

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Wet or Dry ?
Saturated Steam Pressure vs. Temperature
3000

2500

Pressure (psig).......

2000

1500

Wet Dry

1000

500

0 200

250

300

350

400

450

500

550

600

650

700

750

Temperature (F)

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Effect of pH on Corrosion Rate for Different Metals

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Effect of pH on Corrosion of Mild Steel

Corrosion Rate in/yr

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Effect of Dissolved Salts on Corrosion Rate

The dissolved salts increase the conductivity of water (electrolyte).

Increasing the concentration of dissolved salts accelerates corrosion.

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SALTS

Saltwater vs Carbon Steel and Alloys 90 80

Corrosion Rate (mpy)..

70 60 50 40 30 20 10 0 0 50 100 150 Temperature F Adm. Brass 70-30 Cu-Ni 200 250

CS

Titanium
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Effect of Oxygen Concentration & Temperature on Corrosion Rate of Carbon Steel in Tap Water

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High Flow Velocities Can Erode Passive Layers and Accelerate Corrosion
Fluid Flow

Metal

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Effect of Velocity on Sulfuric Acid Carbon Steel Corrosion Rates

98 wt% Sulfuric Acid vs Carbon Steel
250

Corrosion Rate (mpy).

200

150

100

50

0 0 1 2 3 4 5 6 7 8 9 10 11 12 Acid Velocity ft/sec 40F 70F 100F 130F

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Corrosion Control Methods

Design and Fabrication Methods to Avoid Corrosion Operating Process Parameter Control Use of Corrosion Resistant Materials
Metals Non Metals

Create Barriers to Corrosion

Inhibitors Coatings and Linings

ElectroChemical Corrosion Control

Cathodic Protection
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Uniform (General) Corrosion

Atmospheric Corrosion Requires Humidity levels >60% Significant problem for facilities located in coastal zones or heavily industrialized areas. Salt and atmospheric pollutants (SO2, SO3, H2S, etc.) combine with moisture in air to form corrosive salts and acids.
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Atmospheric Corrosion Rates for Carbon and Low Alloy Steels

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Corrosion Rate (mpy)...

10 8 6 4 2 0 0 50 100 150 200 250 300

Metal Temperature Marine / Cooling Tower Drift Area Temperate

Arid / Dry
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Corrosion Under insulation

Occurs in carbon and low alloy steel which is insulated if insulation becomes wet. Localized corrosion can occur at penetrations in insulation jacketing at pipe supports, leaking steam tracing where moisture penetrates the insulation. Corrosion rates are similar to atmospheric corrosion rates
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Corrosion Under Insulation

Oxidation (Rusting)
4Fe + 6H2O + 3O 2 4Fe(OH)3 6H2O + 2Fe2O3

Salt Attack
Fe + NaCl +H2O FeCl 2 + NaOH + H0

Sulfur Acid Attack

Fe + 2HSO3 Fe + H2SO4 Fe(SO3) + H0 FeSO4 + 2H0

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Localized Corrosion

Corrosion limited to a specific relatively small area; while the remaining area is largely unattacked

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Types of Localized Corrosion

Pitting Corrosion Crevice Corrosion Under Deposit Corrosion

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PITTING CORROSION - Causes & Mechanisms

Pitting corrosion occurs when a passive film or another protective surface layer breaks down locally. After this initiation (local breakdown of the film) an anode forms where the film has broken, while the unbroken film (or protective layer) acts as a cathode. This will accelerate localized attack and pits will develop at the anodic spots. The electrolyte inside the growing pit may become very aggressive (acidification) which will further accelerate corrosion.
ILLUSTRATION '` Chlorides ... Pitting is most commonly induced by chloride ions. Like other halides, these are very potent agents for destroying otherwise protective passive surface films (e.g., on stainless steels, nickel alloys. etc.). In the case of chloride-induced pitting the corrosion mechanism also involves strong chloride concentrating effects in a growing pit. This will accelerate the rate of pit development (autocatalytic growth process).

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Pitting Corrosion
Pitting corrosion can be defined as an extreme case of localized attack which results in the development of cavities or pits in the metal surface

This phenomena is common in stainless steels and aluminum alloys which are exposed to chlorides.
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Crevice Corrosion
Crevice Corrosion is a form of localized corrosion which occurs in a crevice formed between 2 surfaces at least one of which is a metal.
2 types of crevice corrosion: (a) oxygen concentration cell

(b) metal ion concentration cell

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Crevice Corrosion at Pipe Support Point Carbon Steel - High Pressure Propane

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Crevice Corrosion (prevention)

Use weld joints without built in crevices
POOR

GOOD

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Crevice Corrosion (prevention)

Dont skip weld !

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Under Deposit Corrosion

Similar to crevice corrosion except the crevice is created by foreign material depositing on the metal surface. Corrosion is then caused by difference in oxygen or metal ion concentrations beneath the deposit and the adjacent bare metal. Deposits can be coatings, salts, mud, sand, algae or anything else which adheres or is held against the metal surface.
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Microbiologically Induced Corrosion (MIC)

MIC on Carbon Steel

MIC on Stainless Steel

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Microbiologically Induced Corrosion (MIC)

Bacteria can cause corrosion in cooling water systems, firewater systems, heat exchangers, pressure vessels, storage tanks, oil and gas pipelines, and wells. Two common effects of MIC are:
MIC directly corrodes structures like steel or concrete, seriously weakening them; MIC also causes thick growths -called tubercles which form on metal surfaces, and cause under deposit corrosion, fouling, and losses in thermal conductivity;

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Microbiologically Induced Corrosion (MIC) Types of Bacteria

Anaerobic Sulfate Reducing Bacteria (ASRB)
ASRB are responsible for extreme damage to piping and support equipment in many industries. They are probably the most destructive bacteria in the MIC group. ASRB reduce sulfates in the water, soil or oil, to H2S which corrodes the steel under the deposit.

Acid Producing Bacteria (APB)

APB is a major player in the MIC corrosion process. APB are capable of producing organic and inorganic acids as well as producing nutrients for ASRB. APB metabolize sulfur in the water, soil or oil, to sulfurous acid which corrodes the steel u nder the deposit.

Iron-related bacteria (IRB)

IRB are an important part of the MIC-causing group, because they are able to build tubercles and have many redox (reduction--oxidation) reactions that support SRB and other MIC bacteria. They are also responsible, in many cases, for the destructive corrosive process of iron and steel.

Slime-producing bacteria (SPB)

SPB live in conjunction with other MIC-producing bacteria such as APB, SRB, and IRB. They are an important part of the MIC process, often acting as the transient from aerobic to anaerobic conditions and as a support system for the corrosion process. 43

Microbiologically Induced Corrosion (MIC)

Damage caused by MIC may appear the same appearance as other corrosion mechanisms. To confirm MIC specific tests for the presence of bacteria must be performed.

Biological Activity Reaction Test (BART)

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Galvanic Corrosion
Galvanic corrosion is attack associated with the current created by direct contact of dissimilar metals or thermal gradients on the same metal in an electrolyte (wet corrosive environment)

This results in the preferential attack of the more active (anodic) metal, while corrosion on the other passive (cathodic) metal is stopped.

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Galvanic Corrosion

Electrolyte ( saltwater)

Electrolyte ( saltwater)

Brass

Steel

Cold

Hot

Bi-metallic Corrosion

Thermo - Galvanic Corrosion

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Corroded End

Anodic

Protected End

Cathodic
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Stress Corrosion Cracking (SCC)

The cracking of a material produced by the combined action of corrosion and tensile stress. This stress can be applied stress or residual stress in the metal (i.e. due to welding , heat treatment etc.

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Environmental Cracking Types Commonly Found in Refineries Chloride Stress Corrosion Cracking Alkaline Stress Cracking
Caustic Carbonate Amine

(ClSCC) (ASCC)

Wet H2S Cracking

Sulfide stress Corrosion Cracking Hydrogen Induced Cracking Stress Oriented Hydrogen induced Cracking (SSC) (HIC) (SOHIC)

Hydrofluoric Acid Stress Corrosion Cracking Polythionic Acid Stress Corrosion Cracking

(HFSCC) (PASCC)
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Stress Corrosion Cracking Prevention

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Chloride Stress Corrosion Cracking

Occurs in austenitic and duplex stainless steels when exposed to aqueous environments containing chlorides. Areas of high residual stress welds, cold formed bends, bellows, cold expanded tubes are most susceptible. May occur externally due to chlorides in atmosphere or present in insulating materials.
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Chloride Stress Corrosion Cracking

Chloride Cracking is presents as surface initiated cracking which propagates perpendicular to the orientation of greatest tensile stress.

Cracking is transgranular passing through the grains of the material.

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Chloride Stress Corrosion Cracking Critical Parameters

Limited to austenitic and duplex alloys with <35% nickel. Must have liquid water present Chloride concentration >50 ppm Temperature >140F pH 2-8 Tensile stresses >25% of yield strength of the material
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Chloride Stress Corrosion Cracking

Effect of Temperature and Concentration

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Chloride Stress Corrosion Cracking Prevention

Avoid use of austenitic stainless steels or other susceptible alloys in neutral to acidic environments containing chlorides. Coatings are effective for prevention of external Chloride SCC. PWHT is not effective in preventing Chloride SCC

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Alkaline Stress Corrosion Cracking (ASCC)

ASCC is presents as surface initiated deposit filled cracking which propagates perpendicular to the orientation of greatest tensile stress.

Caustic Cracking Carbon Steel

Caustic Cracking 316SS Steel

Cracking is intergranular following the grain boundaries of the material.

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Alkaline Stress Corrosion Cracking (ASCC)

Caustic Cracking
Fe + NaOH Na2FeO 2 + H2

Carbonate Cracking
Fe + 2(HCO 3) -2 Fe(HCO 3) 2 + H2

Amine CrackingNot caused by pure amine but by carbon dioxide in the amine so it is similar to carbonate cracking.
CO2 + H2O 2HCO3-2 Fe(HCO 3) 2 + H2
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Fe + 2H+ + 2(HCO 3)-2

Caustic Cracking (Caustic Embrittlement)

Caustic cracking is caused by surface initiating cracks which occur primarily in and adjacent to Non-Post Weld Heat Treated Welds or other areas of high tensile stress.

Caustic in boiler carbon steel tubesheet

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Caustic Stress Corrosion Cracking Critical Parameters

Most steels and nickel alloys are susceptible to caustic cracking including carbon steels, low alloy steels, stainless and duplex steels and nickel alloys Must have liquid water present Caustic concentration >50 ppm Temperature >120F pH 8-14 Tensile stresses >25% of yield strength of the material. Non PWHTd welds are especially susceptible.
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Caustic Cracking Carbon Steel

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Caustic Cracking of Austenitic Stainless Steels

Caustic SCC of austenitic stainless steels occurs between 105 and 205 C (220 and 400 F), depending on caustic concentration. Cracking of austenitic stainless steels is often difficult to distinguish from cracking by chlorides, particularly because common grades of caustic also contain some sodium chloride. As a general rule, however, SCC by chlorides is usually, but not always, in the form of transgranular cracking, while caustic causes intergranular cracking, sometimes accompanied by transgranular cracking due to the presence of chlorides.
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Caustic Cracking of Nickel Alloys

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Caustic Cracking Prevention

Most effective method of preventing caustic cracking is
Post Weld Heat Treatment Post Cold Working Heat treatment

To relieve residual tensile stresses.

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Carbonate Cracking
Caustic cracking is by surface initiating cracks which occur primarily in and adjacent to Non-Post Weld Heat Treated Welds or other areas of high tensile stress. Only carbon and low alloy steels are susceptible. High strength steels used in underground pipelines are susceptible to external carbonate cracking when excessive cathodic protection current is applied. Primary cause of cracking in amine systems

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Carbonate Cracking
Critical Parameters
Only carbon or low alloy steels are susceptible Liquid Water must be present CO2> 2% Temperature >120F pH 8-10 Tensile stresses >25% of yield strength of the material. Not Post Weld Heat Treated

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Carbonate Cracking Prevention

Most cost effective method of preventing carbonate cracking is:
Post Weld Heat Treatment Post Cold Working Heat treatment Austenitic Stainless Steels are resistant to carbonate cracking

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Alkaline Stress Corrosion Cracking Special Precautions

Be careful with external welded attachments to equipment and piping in alkaline service (caustic, carbonate or amine). Residual stresses from welding external attachments without PWHT can result in internal ASCC due to residual stresses at the ID surface of the metal. All welds, pressure containing, internal attachment and external attachment welds must all be PWHTd to avoid ASCC.

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Wet H2S Cracking

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Chemistry of Wet H2S Cracking

Chloride and Bisulfide Corrosion Most refinery process streams contain both chlorides and bisulfides.
Alkaline Conditions Blistering/Cracking

Cl

Acidic Conditions -Corrosion

2H0 +FeS

-S-Fe-SH
HS
-

-S-Fe-Cl +SH-

FeCl2 + H2S

In acidic (low pH) conditions the right hand reaction dominates and will lead to formation of FeCl2 and H2S Increased Corrosion Rates In alkaline (high pH) conditions the left hand reaction dominates and will lead to formation of FeS and H2 Hydrogen Blistering and Wet H2S Cracking
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Chemistry of Wet H 2S Cracking

Effect of Cyanides and pH

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Chemistry of Wet H 2S Cracking

Effect of Cyanides

Atomic Hydrogen is formed as a result of corrosion

Fe++ +2HSFeS + S= + 2H+ Fe(CN)6-4 +6NH4 + S= + 6H+

FeS + 6NH4CN + 6H2O

When alkaline pH conditions are present, cyanide dissolves the protective iron sulfide layer on the surface of the metal and causes a 3 fold increase in atomic hydrogen generation.

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Where do the Cyanides and Ammonia Come From?

Organic Nitrogen compounds present in crude oil are converted to ammonia and cyanide during catalytic cracking or desulfurization. Cyanides will be found down stream of fluid catalytic cracking, hydrodesulfurization and hydrocracking units. The amount of ammonia and cyanides formed depends on the amount and type of nitrogen compounds found in the feed to these units.
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Forms of Wet H2S Cracking

Tensile Stress
Tensile Stress

Sulfide Stress Corrosion Cracking (SSC) Hard Weld Cracking

Stress Oriented Hydrogen Cracking (SOHIC)-

Hydrogen Blistering and (HIC)

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Hydrogen Blistering and Hydrogen Induced Cracking (HIC)

Hydrogen blisters may form as surface bulges on the ID, OD, or within the wall thickness of the steel. The blister results from hydrogen atoms that form on the surface of the steel during the wet sulfide corrosion process. The hydrogen atoms collect at discontinuities in the steel, laminations, inclusions etc.) where they recombine into molecular hydrogen which is to large a molecule to diffuse out of the steel.

HIC occurs when cracks form at the end of the blisters and grow to connect other blisters.

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Hydrogen Blistering

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Hydrogen Blistering

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Stress Oriented Hydrogen Induced Cracking (SOHIC)

SOHIC is HIC cracking which occurs in areas of high tensile stress. The tensile stresses cause the Hic cracking to orient itself perpendicular to the direction of the tensile stress. SOHIC can lead to through wall cracking.

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Sulfide Stress Corrosion Cracking (SSC)

SSC is also known as hard weld cracking Cracking typically initiates at the surface the weld metal or Heat Affected Zone (HAZ) base metal adjacent to the weld. Cracking can also occur in cold worked bends or other areas where high hardness exists. Cracking will be oriented perpendicular to the direction of the tensile stresses.

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Wet H2S Cracking

Critical Factors for Hydrogen Blistering, HIC, and SOHIC
Susceptibility is limited to carbon and low alloy steels Wet H2S Cracking requires the formation of atomic hydrogen as a result of a corrosion reaction. >50ppm H2S pH < 5 or >8 Liquid water must be present >20 ppm CN- will significantly increase the rate and severity of damage PWHT will not prevent Blistering or HIC but may improve resistance to SOHIC
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Sulfide Stress Corrosion Cracking (SSC)

Carbon steels, stainless steels, duplex steels, and nickel alloys are all susceptible to SSC. SSC requires the formation of atomic hydrogen as a result of a corrosion reaction. >50ppm H2S pH < 5 or >8 Liquid water must be present >20 ppm CN- will significantly increase the rate and severity of damage Sulfide Stress Cracking requires hardness of steel to be >237HB PWHT is effective in preventing SSC
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Hydrogen Embrittlement
Hydrogen embrittlement occurs when atomic hydrogen diffuses into the steel in sufficient quantity to cause a decrease in the fracture toughness (impact strength) of the steel without causing any cracking or blistering. The source of the hydrogen may be corrosion or atomic hydrogen created during a welding process. Hydrogen embrittlement is reversible by performing a Hydrogen Bake Out at 400-600F for 1-4 hours which allows trapped atomic hydrogen to diffuse out of the steel.
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Wet H2S Cracking Special Precautions

Steel that has suffered hydrogen blistering, HIC or SOHIC is irreversibly damaged. If repairs are to be made to hydrogen damaged steel remember that the steel is still saturated with atomic hydrogen and has possibly suffered hydrogen embrittlement. Prior to making any repairs on hydrogen damaged steel a Hydrogen Bake Out should be performed to avoid causing additional damage to the steel due to trapped atomic hydrogen.
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Hydrofluoric Acid HF - Hydrogen Cracking

Similar to SSC, Cracking typically initiates at the surface the weld metal or Heat Affected Zone (HAZ) base metal adjacent to the weld as a result of exposure to HF acid.

Monel 400 HF Cracking

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HF Hydrogen Cracking (HFSCC)

Carbon steels, stainless steels, duplex steels, and nickel alloys are all susceptible to HFSCC. SSC requires the formation of atomic hydrogen as a result of HF acid corrosion. Liquid water must be present Steels with Carbon Equivalent (CE)>.43 are highly susceptible. CE=%C+%Mn/6+%(Cr + Mo +V)/5+%(Cu+Ni)/15 HFSCC susceptibility increases with hardness of steel. Steels harder than 237HB are highly susceptible. PWHT is effective in preventing HFSCC

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Polythionic Acid Stress Corrosion Cracking (PTASCC)

Polythionic acids are formed when iron sulfide FeS on the ID surface of an austenitic stainless steel in sour service is exposed to moisture and oxygen.
Polythionic acid

FeS + O2 + H2O

HSxOy + FeOH

The polythionic acid attacks the sensitized grain boundaries of the austenitic stainless steel in the presence of residual tensile stresses which causes an intergranular stress corrosion crack to form.

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Polythionic Acid Stress Corrosion Cracking (PASCC) Critical Factors

Susceptibility is limited to sensitized austenitic stainless steels and nickel alloys A sensitized stainless steel is one that has been exposed to temperatures in the range of 750F 1500F for a duration sufficient to result in grain boundary segregation of carbides. PASCC requires the presence of a iron sulfide scale on the ID surface of the steel. The sulfide scale must be exposed to moisture and oxygen to form polythionic acids. This usually occurs during equipment outages and turnarounds. Liquid water must be present Tensile stresses >25% of the yield strength of the material. PWHT will not prevent PASCC

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Polythionic Acid Stress Corrosion Cracking (PASCC) Prevention

Use of stabilized grades of stainless steel ( 321SS, 347SS) which are not susceptible to sensitization at the operating temperatures. Prevent moisture or oxygen from entering the equipment during outages by utilizing positive pressure purge of inert gas (nitrogen). Wash the equipment with a dilute alkaline solution (soda ash) immediately upon opening to neutralize any polythionic acid which may form. Alkaline film must be maintained on the surface until equipment is returned to service. Note: Soda ash solutions always contain some chlorides. Ensure that all alkaline solution is completely drained from equipment before returning to service to avoid concentration of chlorides and subsequent chloride SCC.

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Intergranular Corrosion
Intergranular corrosion is a highly localized corrosion which occurs a and adjacent to grain boundaries. Typically intergranular attack is caused by the actions of a specific chemical environment. For example, the corrosion which initiates PASCC in stainless steels is intergranular corrosion by polythionic acid. Sulfuric acid and Hydrofluoric acid are other refinery services that can cause intergranular corrosion.

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Dealloying
Dealloying is a corrosion process in which specific elements are corroded away leaving the remainder of the alloy intact.

In refineries, dealloying corrosion is usually associated with

Cast iron (graphitization, actually deironification) Brass (dezincification)

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Liquid Metal Cracking (LMC)

LME is a form of catastrophic brittle failure of a normally ductile metal caused when it is exposed to another liquid metal and is stressed in tension. In refineries, LMC has occurred when
Copper alloys were exposed to liquid mercury (mercury is a common contaminate in produced gas and crude oil) Austenitic stainless steels were exposed to molten zinc or aluminum (usually as a result of a fire).

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High Temperature (Dry) Corrosion

Oxidation Sulfidation Carburization/Metal Dusting Decarburization
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High Temperature (Dry)Corrosion

Oxidation

3Fe + 2O2 Fe + H2O Fe + H2S

Fe3O4 Fe3O4 + H2 FeS + H2 Fe(COOH)2 +C6 H16

Sulfidation

Organic Acid (Napthenic)

Fe +C6H15COOH 2Fe + 2CO

Carburization (Metal Dusting)

2Fe3C + O2

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Oxidation
The reaction of a metal with oxygen at dry high temperature > 700F conditions. Uniform metal loss, corrosion rate increases with metal temperature. Cr addition to steels is effective in reducing high-temperature corrosion
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High Temperature Oxidation Rates of Various Alloys

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Corrosion Rate (mpy)

60

40

20

0 800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800

1900

2000

2100

2200

2300

2400

2500

Temperature F CS 309 SS 1-3% Cr 310 SS/HK 5% Cr Incoloy 9Cr/410SS Inconel/Hastelloy 304/316SS

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Carburization
Carburization is caused by the carbon diffusion into the steel at elevated temperatures >1100F in a carburizing environment. Carburizing environments are those which are chemically reducing (deficient in oxygen) and contain carbon compounds ( CO, Coke etc.) The rate of carburization increases with temperature. Carbon steels, stainless steels, and nickel alloys are all susceptible to carburization. Carburization produces a carbon-rich surface layer on the material which is hard and brittle. Some alloys are intentionally carburized to improve hardness and wear resistance.

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Carburization
In refineries, typical areas to subject to carburization are: The ID of furnace tubes which are in services which produce coke deposits on the ID of the tubes. Cyclones and other internals of FCC unit regenerators which have uneven burning patterns can result in localized carburization in some areas.

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Metal Dusting
Metal dusting is a catastrophic form of carburization which occurs at temperatures > 1250F. Metal dusting can result in rapid localized loss of wall thickness do to intergranular carburization and grain drop out. The damage takes the form of severe localized metal loss with no surface deposits.

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Decarburization
Decarburization is caused by the removal of carbon from steel at elevated temperatures >1100F in a low carbon activity gas environment (i.e. hydrogen). The carbon reacts with the hydrogen to form methane and is removed from the surface of the steel. Surface decarburization is the first sign of high temperature hydrogen attack. The rate of decarburization increases with increasing temperature. Carbon steels, low alloy steels are susceptible Surface decarburization produces a carbon deficient pure iron surface layer on the material which is very soft and ductile. Internal decarburization can lead to the formation of micro fissures which result in loss of fracture toughness and intergranular cracking. (High Temperature Hydrogen Attack)
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High Temperature Hydrogen Attack (HTHA)

Hydrogen gas in contact with steel at high temperatures can result in decarburization and the subsequent formation of hydrocarbons
C(Fe) + 4H0 CH4

The formation of methane bubbles in the steel causes a loss of fracture toughness and can result in intergranular fissures and cracking.

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High Temperature Hydrogen Attack (HTHA)

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High Temperature Hydrogen Attack

Hydrogen Attack Formation of Microfissures 108

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API 941 Limits for Hydrogen Service

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High Temperature Hydrogen Attack (HTHA)

Prevention
Addition of Cr and Mo to steel improves resistance to HTHA. New equipment should be fabricated from materials known to be resistant to HTHA at their operating pressure and temperature using API 941 guidelines. Existing equipment which does not meet the current guidelines should be inspected if HTHA has occurred and to what extent. HTHA causes a loss in strength and fracture toughness of the base metal and can result in brittle fracture. If HTHA is found the equipment should be evaluated to determine fitness for continued service.

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Metallurgical Damage Mechanisms Embrittlement

Embrittlement occurs when an alloy suffers a loss of fracture toughness or ductility. The embrittlement may be limited to specific ranges of temperature with ductility returning when the material temperature is moved out of the embrittlement range. Embrittlement is usually measured by means of tensile tests ( reduction of area and elongation values) or impact tests which measure the force required to fracture the material.
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Metallurgical Damage Mechanisms

Embrittlement

Sigma Phase Embrittlement 885 Embrittlement Temper Embrittlement

113

Sigma Phase Embrittlement

Sigma Phase formation occurs when austenitic stainless steels with more than 17% Cr are held in the temperature range of 1000F 1500F. Sigma is a hard, brittle, non-magnetic phase which is formed by transformation of ferrite present in the austenitic stainless steel. Upon embrittlement there is an increase in the alloys room temperature tensile strength and hardness and severe loss of ductility. As a result cracking is likely to occur during cooling from operating temperatures, during handling, and during weld repair.

114

Sigma Phase Prevention

High nickel alloys are immune to sigma phase formation. Ductility may be restored to an embrittled material by solution annealing the material @ 1800F 2000F followed by rapid cooling. Since sigma phase is formed by transformation of ferrite, specifying a maximum ferrite content of 10% will the prevent the austenitic stainless steel from becoming embrittled.
115

885F Embrittlement
885F Embrittlement occurs after aging of duplex and ferritic stainless steels (i.e. 430, 446, 2205) at 650F 1000F and produces a loss of ambient temperature ductility. The loss of ductility involves the ferrite phase it self and is not related to sigma phase embrittlement Ductility can be restored by heating the embrittled component to 1200F followed by rapid cooling.
116

Temper Embrittlement
Temper embrittlement occurs in 2-1/4 Cr-1 Mo and 3 Cr -1 Mo steels when operating between 700F-1050F for long periods of time. In refineries these steels are typically utilized for Hydrotreating and Hydrocracking reactors which typically operate in this temperature range. Temper embrittlement is not apparent at operating temperature but rather results in a loss of ambient temperature ductility which can lead to brittle fracture during shut down or start up of the equipment. Temper Embrittlement is normally accommodated by limiting the allowable pressure on the equipment to 25% normal until the metal is above 250F. The susceptibility to temper embrittlement for new equipment can be reduced by limiting the J and X factor to 100 and 15 respectively using the formulas below :
J=(Si + Mn) x (P + Sn) x 104 = <100 {elements in wt%} for base metal X = (10P + 5Sb + 4Sn + As)/100 = <15 {elements in ppm} for weld metal
117

Metallurgical Damage Mechanisms

Creep

118

Metallurgical Damage Mechanisms

Creep
Creep is a high temperature mechanism wherein slow continuous deformation (strain) of the metal takes place under applied stresses that are below the normal yield strength of the material. Creep growth will eventually lead to brittle fracture of the material. The length of time required for a creep fracture to initiate (Creep Life) is determined by the magnitude of the applied stress and the metal temperature. Typically there is no visible evidence of creep damage until 70-80% of the total creep life is has been consumed. However microstrucural damage can be detected at ~ 40-50%. During the last 20% of the total creep life deformation is visible. Typically, failure occurs when creep growth has reached 5%-8%.

119

Creep - Prevention
The creep properties of most common steels and alloys have been determined by laboratory testing. Industry practices such as API 530 and API 579 provide information on expected creep life of materials as related to applied stress and temperature. Typically, alloys which will operate under conditions which will cause creep are designed for a 100,000 hr creep life. However exceeding the stress or temperature design levels can lead to premature failure.

120

Short Term Overheating (Stress Rupture)

121

Short Term Overheating (Stress Rupture)

The yield strength of metal decreases with increasing temperature. A short term stress rupture occurs when a component is heated to a temperature where the applied tensile stress exceeds the yield strength of the material. Short term stress ruptures can be recognized by the fish mouth appearance of rupture and severe deformation (usually exceeding 15%). A short-term stress rupture indicates that the equipment has been operated well beyond its allowable design limits of temperature and pressure.

122

High Temperature Graphitization and Spheroidization

Carbon and carbon Mo steels are susceptible to spheroidization and graphitization respectively when heated in the 800F 1200F temperature range. In spheroidization the iron carbides which are normally a flat plate like structure dispersed throughout the steel segregate and form spherically shaped carbides. This results in a loss of tensile strength in the steel particularly at high temperatures. Ductility is not affected by spheroidization. In graphitization the iron carbides in the steel decompose and form graphite nodules. This results in a loss of high-temperature strength and ductility.

123

Fatigue Cracking
Fatigue Cracking is a mechanical form of degradation that occurs when a component is exposed to cyclic tensile stress for an extended period. If the cyclic stress results in cracking in less than <10,000 cycles then it is defined as Low cycle Fatigue. If the fatigue life is >10,000 cycles the cracking is due to high cycle. The fatigue life (#of cycles) is determined by the magnitude of the cyclic stress.
124

Fatigue Cracking
Typically the fatigue life of a component is divided into 3 stages
Damage Accumulation-80% of the total fatigue life is spent in this phase. There is no visible evidence or cracking or damage on the part during this stage. Crack Initiation starts occurs after ~80% the total fatigue life is consumed. The first evidence of visible cracking occurs at this stage. Crack Propagation and Failure this is the final 15% of the total fatigue life cycle.

125

Fatigue Life of Steel

0.80 0.70 Length of Crack in. 0.60 0.50 0.40 0.30 0.20 0.10 0.00 (0.10) 0 10 20 30 40 50 60 70 80 90 98

Fatigue Life Expended (% )

126

Applied Cyclic Stress psi..si...

ASME Section VIII Fatigue Design Curve

10,000,000

1,000,000

100,000

10,000

1,000 10 100 1,000 10,000 100,000 1,000,000

# of Cycles

127

Corrosion Fatigue
When cyclic loading occurs on a component which is exposed to corrosive environment the total fatigue life is significantly shortened. This is because the cyclic loading causes breakage of the passive layer on the surface of the component and results in accelerated corrosion at the fracture site. Corrosion fatigue cracks are easily identified because they are filled with corrosion product and tend to be round bottomed.

128

Corrosion Fatigue Comparison with Ordinary Fatigue

129

CAVITATION
Cavitation damage in general can be defined as damage of a material associated with collapse of cavities in the liquid at a solid / liquid interface under conditions of severe turbulent flow. The latter conditions may, for example, result from boiling phenomena.
130

131

Cavitation-Corrosion
Cavitation-Corrosion is a cavitation-enhanced corrosion reaction in which the cavitation process is responsible for the (mechanical) breakdown of the protective (passive) surface film on the metal. Upon this depassivation an accelerated corrosion will take place.

132

133

134

135

136

Fretting localized damage

137

138

Crude Oil Corrosion

Primary corrosive constituents in crude oil:
1. Inorganic Salts 2. Sulfur Compounds 3. Organic Acids

Secondary corrosive constituents:

1. Organic Nitrogen Compounds 2. Vanadium Compounds
139

Corrosive Compounds (cont.)

Chloride Compounds
Inorganic Chloride Salts Hydrochloric Acid Ammonium Chloride Amine Chlorides MgCl, NaCl, CaCl2 HCl NH4Cl (Cx-Hy)-NH2.HCl

Sulfur Compounds
Hydrogen Sulfide Ammonium Bisulfide Sulfur Dioxide Sulfurous/Sulfuric Acid Organic Sulfur Species H2S NH4HS SO2 HSO3/H2SO4 Mercaptans, Disulfides Thiophenes

140

Corrosive Compounds (cont.)

Oxygen Hydrogen Ammonia Amines Carbon Dioxide O2 H2 NH3 (C x-H y)-NH2 CO2

141

Desalting Removes Most Chloride Salts but Not All Most Salts in crude are removed prior to processing in the crude still by Water Washing and Electrical polarization
Usually removes salts down to 1-2 lbs /1000/bbl of crude

Sodium Hydroxide Injection

Used to reduce hydrochloric acid formation
142

Hydrolysis of Chloride Salts to Form Hydrochloric Acid

Magnesium Chloride Mg(OH)2 + HCl

Mg2Cl + H2O Calcium Chloride

CaCl2 + 2H2O Sodium Chloride

Ca(OH)2 + 2HCl

NaCl + H2O

NaCl + H2O
143

Hydrochloric Acid Corrosion

Hydrochloric acid corrosion occurs in the overhead systems of atmospheric crude distillation columns. The hydrochloric acid is formed as a result of hydrolysis of magnesium and calcium chloride salts commonly found in crude oils. Corrosion occurs at the top of the column when steam and acid starts to condense (dew point corrosion).

144

Atmospheric Fractionator Overhead System Carbon Steel Corrosion Rates due to (Hydrochloric and Other Acids)

400
Corrosion Rate (mpy)

350 300 250 200 150 100 50 0 0 2 4

pH of Condensed Water 100 F 150 F 200 F
145

304 SS vs. Hydrochloric Acid Corrosion Rates

500
Corrosion Rate (mpy)

400 300 200 100 0 0.5 1.5

SS@100F SS@250F

2.5

3.5
SS@150F Monel 400@ 200F

4.5

5.5

6.5

Hydrochloric Acid pH
SS@200F Hastelloy C276 @200F

146

Determination of pH from Cl- Concentration*

Cl- Concentration (wppm) 3,601 - 12,000 1,201 - 3600 361 - 1,200 121 - 360 36 - 120 16 - 35 6 - 15 3-5 1-2 <1 pH 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

*Assumes no alkaline agent present (NH3, neutralizing amines or caustic

147

148

Salt Corrosion
Chlorides and Bisulfides
Most refinery process streams contain both chlorides and bisulfides.
Cl
-

-S-Fe-SH
HS
-

-S-Fe-Cl +SH

In acidic (low pH) conditions the right hand reaction dominates and will lead to formation of FeCl2 and H2S Increased Corrosion Rates In alkaline (high pH) conditions the left hand reaction dominates and will lead to formation of FeS and H2 Hydrogen Blistering and Wet H2S Cracking
149

High Temperature Sulfur Corrosion (Sulfidation)

150

Sulfur Compounds in Crude Oil

Hydrogen Sulfide Mercaptans Disulfides Thiophenes

151

Chemistry of High Temperature Sulfur Corrosion

All high temperature sulfidation is caused by hydrogen sulfide. Fe + H2S FeS + H2S FeS + H2 FeS2 + H2

The degree to which the other sulfur compounds decompose to H2S determine the corrosivity of the crude.
152

Comparison of H 2S Evolution for Various Crude Oils

153

High Temperature Sulfidation Corrosion Rates

154

Corrosion Rates based on H2S Concentration

155

Effect of Hydrogen on Sulfidation Corrosion H2S/H2 Corrosion

Sulfidation in the presence of hydrogen occurs primarily in catalytic desulfurization and hydrocracking units. The presence of hydrogen results in an iron sulfide scale that is porous and not very adherent. In contrast to sulfidation- which occurs in non-hydrogen type processes and which peaks in the 700F-800F temperature rangethis type of corrosion has no apparent peak. Also the addition of Cr alone to the steel does not provide the same level of corrosion resistance as seen in non hydrogen units.

156

H2S/H2 Corrosion Rates

157

Organic Acid Corrosion

Organic Acids can cause corrosion in both wet environments and high temperature dry environments. Low-Temperature (wet) organic acid corrosion occurs at temperatures below <350F. High-Temperature dry organic acid corrosion occurs at temperatures above >350F.

158

Napthenic, Organic Acid and TAN

Napthenic acid is a collective name for organic acids found in crude oils The Total Acid Number (TAN) is a measure of the acidity of a given crude. TANs in crude oil and distillate streams can vary from 0.25 10.0. This number not only includes napthenic acids but also other organic acids and mineral acids which may be present in the crude/distillate.

159

Organic (carboxylic - COOH -) Acids Found in Crude Oils

The acidity of organic acids is measured using a pKa which is similar to pH scale used for inorganic acids. Using this scale, the acidity of acids typically found in crude oils can be compared: pKa 3.75 4.76 4.87 4.82 4.79

Formic Acid (HCOOH) Acetic Acid (CH3COOH) Propionic Acid (CH3CH2COOH) Butyric Acid (CH3CH2CH2COOH) Napthenic Acids(CH3CH2CH2CH2COOH)

Remember that the lower the value for pKa, the stronger the acid is.

160

Organic Acid Corrosion Reactions

Without iron sulfide present:
(CH3CH2CH2CH2COOH)2 + Fe (CH3CH2CH2CH2COO )2Fe + H2
-

With Iron Sulfide Present

(CH3CH2CH2CH2COOH)2 + FeS (CH3CH2CH2CH2 COO )2Fe + H2S
-

161

Decomposition of Organic Acids

Long chain organic acids tend to decompose into shorter chain acids in thermal cracking or catalytic cracking processes.
800 oF

Napthenic Acid
Catalytic Cracking

Butyric, Proprionic, Acetic acids

162

Effects of Interaction Between Sulfur and Organic Acids on Crude Oil Corrosivity
H2S may inhibit organic acid corrosion if acid levels are low Organic Acids may accelerate sulfidation corrosion due to sulfide scale removal. The combination of H2S and Organic acids may result in higher corrosion rates than either one alone. Blending crude oils to reduce sulfur or acid levels may actually result in higher corrosion rates then the unblended crude oils

163

Boiling Points of Organic Acids Present in Crude Oils and Distillates

Organic Acids (X-COOH)
Napthenic Acid Phenolic Acid Butryic Acid Carbonic Acid Acetic Acid Formic Acid Atm. B.P. oF 570 530 330 310 245 212

164

Orgainic Acid Corrosion - Locations

Napthenic Acid corrosion is most severe at locations where phase changes occur such as:
Condensation Flashing Turbulent Flow Pressure Drops i.e. across valves, pumps orifice flanges

Accelerated corrosion is caused at these locations due to a localized increase in acid concentration and erosion of protective scales in areas where these phenomenon occur.
165

Appearance of Napthenic Acid Corrosion

The appearance of napthenic acid corrosion is highly characteristic, varying with stream velocity from sharp edged crater-like holes to sharp edged streamlined grooves. The pits or grooves are usually free from deposits because the iron napthenate corrosion product is oil soluble.

166

Napthenic Acid Corrosion 304SS @ 400F-700F

167

168

Corrosion Curve 1 Sour / Napthenic Crude Oil vs. Steels

100

75

Corrosion Rate (mpy)

50

25

0 300

400

500

600 700 Temperature F 5Cr 9Cr 304SS

800

900

1000

CS

317SS

169

Curve 2 - Sour/Napthenic Reduced Crude vs Steel and Alloys

150

125

Corrosion Rate (mpy)

100

75

50

25

0 300

400

500

600

700 Temperature F

800

900

1000

CS

5Cr

9Cr

304SS

317SS

170

Curve 3 - Sour \ Napthenic Atmospheric HGO

160 140
Corrosion Rate (mpy)

120 100 80 60 40 20 0 300 400 500 600 700 800 900 1000 Temperature F CS 5Cr 9Cr 304SS 317SS

171

Curve 10 - Sour \ Napthenic VHGO

180 160
Corrosion Rate (mpy)

140 120 100 80 60 40 20 0 300

400

500

600

700

800

900

1000

Temperature F CS 5Cr 9Cr 304SS 317SS

172

Curve 11 - Sour \ Napthenic Vacuum Resid

160

140

120

Corrosion Rate (mpy)

100

80

60

40

20

0 300

400

500

600

700

800

900

1000

Temperature F CS 5Cr 9Cr 304SS 317SS

173

Carbon Dioxide (CO2) Corrosion

174

Carbon Dioxide (CO2) Corrosion

Description of Damage:
CO2 Corrosion can take the form of uniform thinning, localized and/or pitting type damage. General thinning or channeling generally occurs in areas where a separate liquid water phase is present. Localized weld corrosion is common in areas of high turbulence Pits caused by carbonic acid corrosion are characteristically sharp edged and free of deposits

Affected Materials:
Carbon steels Low alloy steels (<11.5%Cr)
175

Carbon Dioxide (CO2) Corrosion

Description of Mechanism:
Carbon Dioxide (CO2) is usally formed by the decomposition of of bicarbonate and carbonate alkalinity found in the boiler feed water. As indicated below: 2HCO 3- + Heat CO3-2 + CO 2 + H2O (1) (2)

CO3-2 + H2O + Heat

2OH- + CO2

The first (1) reaction usally achieves 100% completion. The second typically achieves 80% or more completion at pressures over 150 psig. Between 50 psig and 150 psig the percentage varies between 30-80% and between 10 psig and 50 psig the norm is 10 30%. Each ppm of bicarbonate alkalinity in the feed water as CaCO3 will generate approximately 0.79 ppm of CO2 Other sources of CO 2 are free carbon dioxide in the feed water and the use of soda ash as an internal treatment chemical,
176

Carbon Dioxide (CO2) Corrosion

In the water phase carbon dioxide combines with water to form carbonic acid: CO2 + H2O H2CO3

The formation of carbonic acid lowers the pH of the water . The carbonic acid reacts with the steel to form iron carbonate which is soluble at pH values of less than 5.9 (about 5ppm of CO 2 ). In addition carbonic acid leads to the formation of ferrous bicarbonate which is highly soluble and has no passivating effect Fe0 + 2H+ + 2HCO3-2 Fe(HCO3)2 + H2

177

Carbon Dioxide (CO2) Corrosion

Carbonic acid corrosion can be appreciable in turbulent areas at CO2 levels greater than 2 ppm particularly if oxygen is present. Above 5 ppm the corrosion rate is roughly proportional to the CO2 concentration.
When both oxygen and carbon dioxide are present, corrosion proceeds more rapidly. Unless stopped, the terminating reactions release CO 2 making the process self perpetuating. 4Fe (HCO3)2 + O2 2Fe2O3 + 8CO2 + H2O

178

Affected Units or Equipment

Boiler feedwater and steam condensate systems in all process units. Light Hydrocarbon (<C4) recovery units Hydrogen plants CO2 Removal Units

179

Critical Parameters for Corrosion Rate Prediction

Critical Parameters:
Partial Pressure of CO2 Concentration of Dissolved CO2 (pH) Fluid Temperature Fluid Velocity/Turbulent Flow

180

Effect of CO2 Concentration and Flow Velocity on Carbon Steel Corrosion Rates

181

This nomogram for predicting CO2 corrosion of carbon steel is based on the deWaard-Milliams equation .
182

CO2 Corrosion Prevention/Mitigation Chemical Treatments

Reduce alkalinity of boiler feed water and other process waters. Neutralizing amines or volatile amines are generally used to prevent steam/condensate corrosion caused by low pH. They neutralize carbonic acid and raise condensate pH. Filming amines represent an effective and economical approach to condensate system corrosion control. Protection by filming amines is through the formation of an adherent, nonwettable organic film on metal surfaces preventing contact between the metal surface and corrosive condensate. Volatile oxygen scavengers is effective in scavenging oxygen, passivating metal surfaces, and perhaps even raising condensate pH, it may properly be called a steam/condensate corrosion inhibitor and placed in the same category as neutralizing and filming amines.
183

CO2 Corrosion Prevention/Mitigation Materials Selection

300 series stainless steel (i.e. 304L/316L) is the most common ally upgrade to prevent CO2 corrosion. (Verify Chlorides levels are below 100 ppm to avoid problem with stress corrosion cracking of stainless steels.) 400 series stainless steels and duplex stainless steels are also resistant to CO2 corrosion and are less susceptible to chloride cracking problems. Copper based alloys (i.e. brass and bronze) are resistant to CO2 corrosion

184

CO2 Corrosion Inspection and Monitoring

Monitoring and controlling water chemistry analysis pH, Carbonate Alkalinity, Dissolved Fe & CO2, is most effective method of controlling CO2 corrosion. NDE methods UT, RT, and VT are effective in finding general metal loss. Special attention should be paid to piping downstream of steam condensers, condensing turbines, piping welds in areas of high turbulence and areas where liquid water condenses and collects.

185

Amine Corrosion
Description of Damage:
Lean Amine - general and localized metal loss (especially in the HAZ of welds) caused by amine degradation products organic acids, and heat stable salts (HSS). May also cause alkaline stress corrosion cracking in non-post weld heat treated equipment Rich Amine - Localized metal loss in high turbulence areas caused by flashing of acid gases (H2S and CO2). High acid gas loadings and high HSS levels can also lead to hydrogen blistering, hydrogen induced cracking. May also cause alkaline stress corrosion cracking and sulfide stress corrosion cracking in non-post weld heat treated equipment.

Affected Materials:
Carbon steels Low alloy steels (<11.5%Cr)
186

Amine Corrosion
Description of Mechanism:
Amines by themselves are only mildly corrosive. However amines are used to remove acid gases (H2S & CO2) from process gases and liquids. These acid gases are corrosive. Also, the treated streams may also contain corrosive contaminates. CO2, and amine degradation products can be highly corrosive.

Contaminants Contaminants are items that enter the process and pollute the amine. These items would generally include solids/particulates, hydrocarbon, process chemicals, strong cations (sodium), HSS (from their precursors entering with the gas or liquid stream being treated.

187

Amine Corrosion
Degradation Products Degradation Products are contaminants in solution that are derived from reactions with the base amine molecule itself, where the molecule is broken down or changes chemical form. Many of these compounds are the result of irreversible degradation of the base amine molecule; ethylenediamine derivatives (THEED in the case of DEA and HEEU in the case of MEA) would be examples of this. Some of these compounds are the results of a reversible reaction or chemical equilibrium with the base amine molecule; formamides in the case of primary and secondary amines and BHEEU in the case of DGA would be examples of this.
188

Critical Parameters for Corrosion Rate Prediction

Critical Parameters for Amine Corrosion:
Temperature Amine Concentration Acid Gas Loading (H2S, CO2 ) Heat stable salts (HSS) concentration in amine Fluid Velocity/Turbulent Flow
189

Carbon Steel Corrosion Rates for Lean 20% MEA or 30% DEA
130 120 110 100 90 80 70 60 50 40 30 20 10 0 180 200 220 240 260 280
Corrosion Rate (mpy)

Temperature F
Heat Stable Salt Content & Velocity of Amine Stream <2 wt% & <20ft/sec <2 wt% & >20ft/sec 2.1 - 4 wt% & <20ft/sec 2.1 - 4 wt% & >20ft/sec >4 wt% & <20ft/sec >4 wt% & >20ft/sec
190

Effect of Heat Stable Salts and Acid Gas Loading of Rich MEA Solutions on Carbon Steel Corrosion Rates
45.0 40.0
Corrosion Rate (mpy)

35.0 30.0 25.0 20.0 15.0 10.0 5.0 0.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Acid Gas Loading (mol/mol)

HSAS < 1 wt.%

HSAS < 2 wt.%

HSAS < 3 wt.%

HSAS < 4 wt.%

For velocities >5Ft/sec multiply corrosion rate by 2.0

For operating temperatures >220F multiply corrosion rates by 2.0

191

Carbon Steel Corrosion Rates for Rich <20% MEA or <30% DEA (*Velocity <5 ft/sec and **Acid Gas Loading < 0.5 mol / mol)
Corrosion Rate (mpy)
180 160 140 120 100 80 60 40 20 0 180 200 220 240 260 280

Temperature F

<2 wt%

2.1 - 4 wt%
Heat Stable Salt Content of Amine Stream

>4 wt%

*For Flow Velocities >5 Ft / sec multiply corrosion rate from chart by 3 **For Acid Gas Loading >0.5 mol / mol multiply corrosion rate from chart by 2

192

Corrosion Rate (mpy).

Carbon Steel Corrosion Rates for Rich <50% MDEA Acid Gas Loading (0.1 - 0.4 mol / mol)*
200 150 100 50 0 180 200 220 240 260 280

Temperature F

<.5 wt%

.51 - 4 wt%

>4 wt%

Heat Stable Salt Conc. of Amine Stream For flow velocities >5 ft / sec multiply corrosion rate shown on chart by 2.5 *For Acid Gas Loading >0.4 mol /mol multiply corrosion rate shown on chart by 1.5

193

Corrosion Rate (mpy)...

Carbon Steel Corrosion Rates for Lean <50% MDEA

70 60 50 40 30 20 10 0 180 200 220 240 260 280

Temperature F

<0.5 wt%

0.51 - 4 wt%

>4 wt%

Heat Stable Salt Conc. of Amine Stream For flow velocities >20 ft / sec multiply corrosion rate shown on chart by 2.5
194

Prevention/Mitigation
Process Control / Chemical Treatments
Monitoring and controlling the acid gas loading (H2S and CO2 , amine circulation rates and contaminate levels (HSS, organic acids, iron) in the circulating amine is the most effective method of controlling amine corrosion. Filming amines represent an effective and economical approach to condensate system corrosion control. Protection by filming amines is through the formation of an adherent, nonwettable organic film on metal surfaces preventing contact between the metal surface and corrosive condensate. Volatile oxygen scavengers is effective in scavenging oxygen, passivating metal surfaces, and perhaps even raising condensate pH. It may properly be called a steam/condensate corrosion inhibitor and placed in the same category as neutralizing and filming amines.

195

Amine Solvent Quality Guidelines

196

Amine Corrosion Prevention/Mitigation Materials Selection

300 series stainless steel (i.e. 304L/316L) is the most common alloy upgrade to prevent amine corrosion. (Verify Chlorides levels are below 100 ppm to avoid problem with stress corrosion cracking of stainless steels.) Duplex stainless steels are also resistant to amine corrosion and are less susceptible to chloride cracking problems.

197

Amine Corrosion Inspection and Monitoring

Corrosion Probes (ER and FSM), Hydrogen Flux Monitoring, and Corrosion Coupons are best methods for real time corrosion monitoring and control. NDE methods UT, RT, and VT are effective in finding general metal loss. Special attention should be paid to amine regenerator towers and reboilers and associated piping where temperatures are over 200F. Rich amine piping, high velocity, and turbulence lead to flashing of acid gases (i.e. down stream of let down valves, pump discharges).

198

Ammonium Bisulfide Corrosion (Alkaline Sour Water)

199

Ammonium Bisulfide Corrosion

Hydrotreater Reactor Effluent Air Cooler Corrosion (REAC) Ammonia and hydrogen sulfide in HDS/HC reactor effluent streams combine to form ammonium bisulfide
NH3 + H2S NH4HS

In the presence of water ammonium bisulfide ionizes and reacts with Iron Sulfide and then Iron.
2(NH4HS) + FeS + 2(H2O) 2(NH4HS) + Fe + 2(H2O) Fe(HS)2 + 2(NH4OH) + H2S Fe(HS)2 + 2(NH4OH) + 2H+

200

Ammonium Bisulfide Corrosion

No Flow Stagnant Conditions

201

Effect of Cyanides and pH on Ammonium Bisulfide Corrosion

202

Chemistry of Ammonium Bisulfide Corrosion

Effect of Cyanides

Atomic Hydrogen is formed as a result of corrosion

Fe++ +2HSFeS + S= + 2H+ Fe(CN)6-4 +6NH4 + S= + 6H+

FeS + 6NH4CN + 6H2O

When alkaline pH conditions are present cyanide dissolves the protective iron sulfide layer on the surface of the metal and causes a 3 fold increase atomic hydrogen generation.

203

Effect of Velocity on Ammonium Bisulfide Carbon Steel Corrosion Rates

Hydrotreator Reactor Effluent Air Cooler (REAC) Corrosion Rates
600
Corrosion Rate mpy...

500 400 300 200 100 0 0 2 4 6 8 10 12 NH4HS wt % 14 16 18 20

<10ft/sec

10 - 20 ft/sec

21 - 30 ft/sec

>30 ft/sec

204

Parameters Which Affect Ammonium Bisulfide Corrosion Rates

Basic Data NH4HS Concentration (wt.%) Comments Determine the NH 4HS concentration of the condensed water. It may be calculated from analyses of H 2S and NH3 as follows: If wt.% H2S < 2 X (wt% NH3), wt.% NH4HS =1.5 X (wt.% H 2S)
If wt.% H2S > 2 X (wt% NH3), wt.% NH4HS =3 X (wt.% NH3)

OR Kp factor Kp may be used where sour water analyses have not been conducted and is based on the vapor phase H2S and NH3: Kp = mole % H 2S x mole % NH3 (on dry basis) Stream Velocity (ft/s) The vapor phase velocity should be used in a two -phase system. The liquid phase velocity should be used in a liquid full system.

205

Ammonium Chloride Salt Corrosion

206

Ammonium Chloride Salt Corrosion

207

Ammonium Chloride Salt Corrosion

208

Sulfuric Acid Corrosion

98 wt% Sulfuric Acid vs Carbon Steel

250
250

93 wt% Sulfuric Acid vs Carbon Steel

Corrosion Rate (mpy)...

Corrosion Rate (mpy)...

200

200

150

150

100

100

50

50

0 0 1 2 3 4 5 6 7 8 9 10 11 12 Acid Velocity ft/sec 40F 70F 100F 130F

0 0 1 2 3 4 5 6 7 8 9 10 Acid Velocity ft/sec 40F 70F 100F 130F

209

Sulfuric Acid Corrosion

89 wt% Sulfuric Acid vs Carbon Steel
250

Corrosion Rate (mpy)...

200

150

100

50

0 0 1 2 3 4 5 6 7 8 9 10 Acid Velocity ft/sec 40F 70F 100F 130F

210

6 Factors Which Influence Equipment Service Life

Selection of Materials of Construction Design Details Specification of Materials Fabrication and Inspection Process Operation Maintenance (Cost and Frequency)
211

Safety and Mechanical Integrity Issues in Materials Selection

Potential for injury of personnel as a consequence of failure. Potential for damage to the equipment itself as a result of a failure. Potential for collateral damage to equipment and the environment in the event of a failure. Toxicity of the process fluids.
212

Corrosion Considerations in Materials Selection

Corrosivity of the process fluids and external environment. Susceptibility of selected materials to corrosion mechanisms. Sensitivity of the corrosion resistance of the material to changes in process parameters.

213

Other Factors Affecting Material Selection

Expected Equipment Life Operational Reliability Maintainability. Cost

214

Material Properties
n

Mechanical Property Requirements - Tensile Strength, Fracture Toughness, Ductility, Fatigue Strength, High/Low Temperature Strength, Hardness, etc. Physical/Chemical Property Requirements - Melting Point, Thermal Conductivity, Electrical Conductivity, Density, Magnetism , Radiation Resistance, etc. Corrosion Resistance to process and atmospheric conditions.

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Practicality Factors

Availability in the Required Product Form

Ability to be Fabricated, Weldability, Formability, Castability, etc.

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Economic Factors

n n n

Design Life Expectancy Reliability (Mean Time Between Outages) Life Cycle Cost (i.e. $/year of life)

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Common Metallic Materials

Iron Base Irons 2-5%C Carbon Steels <1%C Low Alloy Steels Stainless Steels Cr- Mo Steels Nickel Steels Aluminum Alloys Non - Heat -Treatable Aluminum Alloys Heat -Treatable Aluminum Alloys Nickel Base Pure & Low Alloy Nickels Fe - Ni - Cr Alloys Ni - Cr - Fe alloys Ni - Cu Alloys Copper Base Copper >96% Cu Brass Cu - Zn Cupro- Nickel Cu - Ni Bronze Cu -Sn

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Iron Based Alloys

Irons 2-5%C Cast Irons White Gray Nodular Silicon Nickel Malleable Iron Carbon Steels <1%C Low Alloy Steels Cr-Mo Steels 1-3% Cr 5-9% Cr Nickel Steels 31/2%Ni 9% Ni

Low Carbon (0.1 - 0.3% C) Tool Steels Medium Carbon (0.3 - 0.6% C) HSLA High Carbon (0.6 -1.0% C) Machine Steels Cast Steels Speciality Steels 4140 4340 HIC Resistant Steels Low Temperature Steels

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Stainless Steels
. Stainless Steels Matensitic 11-13% Cr Type 410 Type 416 Austenitic 16-25% Cr & 7-35% Ni Types 304(L), 316(L),317(L) Types 347(H), 321(H) Types 309, 310(H) Alloy 20 Duplex Ferritic 11-30% Cr Type 405. 409, 410S (12%Cr) Type 430 (17%Cr) Type 446 ( 27% Cr) Precipitation Hardening

Martensitic - 17-4 PH Semi Austenitic - 15 -7PH, AM350 Austenitic 17-7 PH

Alloy 2205 3RE60

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Non-Ferrous Alloys
Nickel Base Pure & Low Alloy Nickels Nickel 200 Nickel 301 Fe - Ni - Cr Alloys ...............Aluminum Alloys.............. Non - Heat -Treatable Aluminum Alloys 1xxx pure Al 3xxx Al - Mn 5xxx Al - Mg Heat -Treatable Aluminum Alloys 2xxx Al - Cu -Mg 4xxx Al - Si 6xxx Al - Mg - Si 7xxx Al - Zn - Mg - Cu Copper Base Copper >96% Cu ETP, FRTP(electrical) Coppers Beryllium Copper Leaded Copper Brass Cu - Zn

Alloy 800 Alloy 825 Alloy 556 Ni - Cr - Fe alloys

Admiralty Brass
(28Zn - 1%Sn) As, Sb, or P inhibited

Naval Brass
(39%Zn - 1%Sn) As, Sb, or P inhibited

Bronze Cu -Sn Alloy 600 Alloy 625 Alloy C-22 Alloy C-276 Alloy X-750 Ni - Cu Alloys

Phosphor Bronze Aluminuim Bronze Silicon Bronze Cupro- Nickel Cu - Ni

Alloy 400 Alloy R-405 Alloy K-500

90-10 Cupro - Nickel 80-20 Cupro - Nickel 70-30 Cupro - Nickel

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Common Plastic Materials

Plastics Composites Thermoplastic Resins Thermosetting Resins Phenolics Polyesters Epoxies Silicone Polyurethanes Vinyl Esters

Thermoplastic Matrix Composites Glass Fibers Carbon Fibers Aramid Fibers Themoset Matrix Composites Glass Fibers Carbon Fibers Aramid Fibers

Polyethylenes (PE, HDPE,UHMWPE) Polypropylene (PP) Nylon Polyvinyl Chlorides (PVC,CPVC) Fluropolymers (TFE, PTFE) Acrylonitrile-Butadiene-Styrene (ABS) Polyaryletherketones (PEEK)

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Common Refractory Materials

Refractories Clay Based Fire Clay (Al2O3-2SiO2-2H2O) High (50-87%) Alumina (Al2O3) Non-Clay Based Dolomite (CaO) Chromite (Cr2 O3) Sintered Alumina (Al2O3) Magnesia (MgO) Mullite (3Al2O3-2SiO2) Silica (SiO2) Silicon Carbide (SiC) Zircon (ZrO2-SiO2) Available Forms Bricks and Fired Shapes Castables Gunning Mixes Ramming Mixes Plastics Mortars Fiberboard or Blankets
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Specialty Metal Materials

Cobalt Base Alloys
Stellite, Colomonoy

Refractory Metal Alloys

Titanium, Zirconium

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U.S. Standards Organizations

Abbreviation
AA AISI ANSI API ASME ASTM AWS AWWA CDA CMA MTI NACE SAE TEMA

Organization Name
Aluminum Association American Iron and Steel Institute American National Standards Institute American Petroleum Institute American Society of Mechanical Engineers American Society for Testing Materials American Welding Society American Water Works Association Copper Development Association American Cast Metal Association Materials Technology Institute NACE International Society of Automotive Engineers Tubular Exchanger Manufacturers Association
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Detection of Corrosion Damage

There are a number of inspection methods that are used to detect corrosion. Each inspection method has its strengths and weaknesses The inspection method(s) must be capable of detecting the type of corrosion damage which is occurring.
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Selection of Inspection Methods Based on Corrosion Type

Corrosion Type Inspection Method
Visual Examination (VT) Leak Testing (Hydro,
Pneumatic, Vacuum, Soap)

Uniform
Fair Poor Fair Good Good N/A N/A Fair N/A

Localized
Pitting, Crevice, Galvanic etc.)

Cracking
(SCC, Fatigue, Creep, Rupture etc.)

Good Fair Good Poor Good N/A N/A N/A N/A

Poor Fair Fair Fair Good Good (Surface Breaking Only) Good Good Good

Radiography (RT) Manual Ultrasonics (UT) Auto Ultrasonics (AUT) Liquid Penetrant (PT) Magnetic Particle (MT) Eddy Current (ET) Acoustic Emission (AET)

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Detection Of Corrosion

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Magnetic Particle Inspection

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Liquid Dye Penetrant Method

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Ultrasonic Testing

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Eddy Current Testing

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Caustic Cracks Found with Dye Penetrant Test

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