Documentos de Académico
Documentos de Profesional
Documentos de Cultura
Presented By: Thomas D. Farraro Houston, TX Houston, Texas August 24 and 25, 2003
STRESS ENGINEERING SERVICES, INC.
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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.
2. Localized Corrosion
Pitting Crevice Corrosion Under Deposit/Coating Corrosion, Thinning, Cracking)
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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Dry corrosion
Chemical reactions which occur in the absence of any electrolyte.
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Steel
11
Cathode
Elec t Migr ron ation
Cathode Anode
tron Elec tion a Migr
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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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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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SALTS
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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200
150
100
50
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Arid / Dry
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Salt Attack
Fe + NaCl +H2O FeCl 2 + NaOH + H0
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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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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
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Crevice Corrosion at Pipe Support Point Carbon Steel - High Pressure Propane
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GOOD
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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
Corroded End
Anodic
Protected End
Cathodic
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Environmental Cracking Types Commonly Found in Refineries Chloride Stress Corrosion Cracking Alkaline Stress Cracking
Caustic Carbonate Amine
(ClSCC) (ASCC)
Hydrofluoric Acid Stress Corrosion Cracking Polythionic Acid Stress Corrosion Cracking
(HFSCC) (PASCC)
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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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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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Cl
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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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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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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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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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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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.
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Sulfidation
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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Corrosion Rate (mpy)
60
40
20
0 800
900
1000
1100
1200
1300
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1700
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2000
2100
2200
2300
2400
2500
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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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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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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.
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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
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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.
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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.
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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.
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1,000,000
100,000
10,000
# of Cycles
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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.
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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.
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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.
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Sulfur Compounds
Hydrogen Sulfide Ammonium Bisulfide Sulfur Dioxide Sulfurous/Sulfuric Acid Organic Sulfur Species H2S NH4HS SO2 HSO3/H2SO4 Mercaptans, Disulfides Thiophenes
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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
Ca(OH)2 + 2HCl
NaCl + H2O
NaCl + H2O
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Atmospheric Fractionator Overhead System Carbon Steel Corrosion Rates due to (Hydrochloric and Other Acids)
400
Corrosion Rate (mpy)
2.5
3.5
SS@150F Monel 400@ 200F
4.5
5.5
6.5
Hydrochloric Acid pH
SS@200F Hastelloy C276 @200F
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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
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The degree to which the other sulfur compounds decompose to H2S determine the corrosivity of the crude.
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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.
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Napthenic Acid
Catalytic Cracking
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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
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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.
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75
50
25
0 300
400
500
800
900
1000
CS
317SS
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150
125
100
75
50
25
0 300
400
500
600
700 Temperature F
800
900
1000
CS
5Cr
9Cr
304SS
317SS
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120 100 80 60 40 20 0 300 400 500 600 700 800 900 1000 Temperature F CS 5Cr 9Cr 304SS 317SS
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400
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800
900
1000
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140
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0 300
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Affected Materials:
Carbon steels Low alloy steels (<11.5%Cr)
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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,
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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
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Effect of CO2 Concentration and Flow Velocity on Carbon Steel Corrosion Rates
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This nomogram for predicting CO2 corrosion of carbon steel is based on the deWaard-Milliams equation .
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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)
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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.
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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.
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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
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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
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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
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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
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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
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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.
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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+
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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.
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<10ft/sec
10 - 20 ft/sec
21 - 30 ft/sec
>30 ft/sec
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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.
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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
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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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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
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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
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
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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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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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Uniform
Fair Poor Fair Good Good N/A N/A Fair N/A
Localized
Pitting, Crevice, Galvanic etc.)
Cracking
(SCC, Fatigue, Creep, Rupture etc.)
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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Ultrasonic Testing
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