new - 02 classes of alloys in refinery use
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RE Alloys/2-1
Classes of Alloys in Refinery Use
RE Alloys/2-2
Outcomes
Recall alloy types which are commonly used in refineriesRecall specific examples of each alloy typeRecall factors (advantages/disadvantages) which govern the use of the alloy
RE Alloys/2-3
Classes of Refinery Metallurgy
Carbon and killed carbon steelsLow alloy (Cr-Mo) SteelsStainless steelsNickel alloysCopper alloysTitanium alloysAluminum alloys
RE Alloys/2-4
Carbon Steels
Alloy of Fe and C– Carbon content affects mechanical properties
— High CHigh strengthLow ductility
– Processing conditions also affect mechanical properties— Too many details for this course
– Harden when quenched from above 1333oF
RE Alloys/2-5
Refinery Metallurgy
Carbon steel is the default material of construction used in refineries– Inexpensive– Easy to work with– Normally economically satisfactory
— Cost vs. life expectancyOther materials used only when carbon steel is unsatisfactory
RE Alloys/2-6
Carbon Steels
Carbon steel processed in two forms– “Ordinary” Carbon steel
— Proper designation would be rimmed or semi killed carbon steel
– Killed carbon steel— Killing is a refining process— Affects
Mechanical properties“Cleanliness” of steel
RE Alloys/2-7
Carbon Steels
Killed Steel used– H2S, HF, CN- service
— Lack of inclusion helps prevent blisters– High temperature hydrogen service
— Lack of inclusion helps prevent blisters– Low temperature service
— Minimum temperatures as low as -50oF (-45oC)“Ordinary” carbon steel– Use in all other services
RE Alloys/2-8
Low Alloy (Cr-Mo) Steels
1 Cr-½Mo; 1¼ Cr-½Mo2¼ Cr-½Mo5 Cr-½Mo9 Cr-½Mo
RE Alloys/2-9
1 Cr-½Mo; 1¼ Cr-½Mo
Used where improved properties over carbon steel are required– Design temperature 1200oF vs. 1000oF– High temperature strength– Resistance to high temp hydrogen attack– High temperature sulfur
— Contradictory data existSimilar properties to carbon steel – Resistance to high temperature H2S/H2
RE Alloys/2-10
1 Cr-½Mo; 1¼ Cr-½Mo
Primary uses– Reactor shells for high temperature processes– Heater tubes– Piping– Exchangers
RE Alloys/2-11
1 Cr-½Mo; 1¼ Cr-½Mo
Primary cautions– High hardenability – weld cracking– Creep embrittlement
— Discussed later
RE Alloys/2-12
2¼ Cr-1 Mo
Used where improved properties over 1¼ Cr-½Mo are required– High temperature strength– Resistance to high temp hydrogen attack– High temperature sulfur
— Contradictory data existSimilar properties to 1¼ Cr-½Mo – Design temperature– Resistance to high temperature H2S/H2
RE Alloys/2-13
2¼ Cr-1 Mo
Primary uses– Reactor shells for high temperature processes– Heater tubes– Piping– Exchangers
RE Alloys/2-14
2¼ Cr-1 Mo
Primary cautions– High hardenability – weld cracking– Temper embrittlement
— Discussed later
RE Alloys/2-15
5 Cr-½Mo
Used where improved properties over 2¼ Cr-1 Mo are required– High temperature strength– Resistance to high temperature hydrogen attack– High temperature sulfur
Similar properties to 2¼ Cr-1 Mo – Design temperature– Resistance to high temperature H2S/H2
RE Alloys/2-16
5 Cr-½Mo
Primary uses– Piping– Exchangers
Primary cautions– High hardenability – weld cracking
RE Alloys/2-17
9 Cr-1 Mo
Used where improved properties over 5 Cr-½Mo are required– High temperature strength– Resistance to high temperature hydrogen attack– High temperature sulfur– Resistance to high temperature H2S/H2
Similar properties to 5 Cr-½Mo – Design temperature
RE Alloys/2-18
9 Cr-1 Mo
Primary uses– Heater tubes
Primary cautions– High hardenability – weld cracking
RE Alloys/2-19
Stainless Steels
FerriticAusteniticMartensitic
RE Alloys/2-20
Stainless Steels, Ferritic
405 11 – 13% Cr, aluminum410S 11 – 13% Cr, low carbon– Body center cubic (“ferrite”)– Just enough Cr to be stainless
RE Alloys/2-21
Stainless Steels, Ferritic
Used where improved properties over 9 Cr-1Mo are required– High temperature sulfur– Resistance to high temperature H2S/H2
Generally not used for– Pressure boundaries– Where welding is required– Naphthenic acids service
RE Alloys/2-22
Stainless Steels, Ferritic
Primary uses– Cladding over carbon or low Cr steels– Trays– Exchanger tubes
Primary cautions– 885 embrittlement (discussed later)– Potentially low toughness
— Weld HAZ
RE Alloys/2-23
Stainless Steels, Austenitic
Face center cubic (austenite)– 304 18% Cr, 8% Ni– 316 Approximately 304 + 2% Mo– 317 Approximately 304 + 3% Mo– 321 Approximately 304 + Ti– 347 Approximately 304 + Nb– High Ni, Mo Stainless
RE Alloys/2-24
Stainless Steels, Austenitic
Theoretically available grades– Normal and L grades often
double stamped– H grades difficult to find,
316H nearly unavailable– No L grade for 321 and 347
(chemically stabilized rather than low C
347H347
321H321
317H317317L
316H316316L
304H304304L
RE Alloys/2-25
Stainless Steels, Austenitic
Used where improved properties over low alloy steels are required– High temperature strength– Resistance to high temperature hydrogen
attack– High temperature sulfur– Resistance to high temperature H2S/H2
– Design temperature (for high carbon material)
RE Alloys/2-26
Stainless Steels, Austenitic
Carbon is important– Normal and low C material good to 1000oF– H grade materials good to 1500oF– L grades don’t sensitize during welding
— Discussed later
RE Alloys/2-27
Stainless Steels, Austenitic
Molybdenum is important (316, 317)– Resists pitting from Cl-
— May or may not resist cracking from Cl-
– Resists naphthenic acid corrosion— Normally need 2.5% Moly
316 may be okNormally want 317
RE Alloys/2-28
Stainless Steels, Austenitic
Titanium and niobium (columbium) are important (321, 347)– Chemically stabilize steels
— Don’t sensitize during welding
RE Alloys/2-29
Stainless Steels, Austenitic
Primary uses– Heater tubes (347H)
— Oxidation, sensitization resistance– Exchanger tubes (304)– Linings (304)
— Aqueous H2S service– High temperature components (304)
— Strength and code allowable temperatures– High pressure hydrotreating piping (321, 347)
RE Alloys/2-30
Stainless Steels, Austenitic
High Ni, Mo stainless– Alloy 20, 254SMO, Al-6XN– Used in reducing acids such as H2SO4
— Sulfuric acid alkylation units– Used when resistance to corrosion
intermediate between 300 series stainless and Hastelloy C-276 are required
RE Alloys/2-31
Stainless Steels, Austenitic
Primary cautions– Subject to sensitization
— May lead to corrosion– Subject to pitting and stress corrosion
cracking from Cl-
— Use care in cooling water applications– Liquid metal embrittlement by zinc
— Be careful of galvanized materials– All issues discussed later
RE Alloys/2-32
Stainless Steels, Martensitic
410 12% Cr (higher C than 410S)Not used as pressure boundaryUsed for– Aqueous corrosion resistance– Strength– Wear resistance
Used in– Shafts, pumps, turbine blades
RE Alloys/2-33
Nickel Alloys
Ni, Cr, Fe alloys Alloy 800 (series)Ni, Cr, Mo alloys (C-276, alloy 625)Monel
RE Alloys/2-34
Ni, Cr, Fe Alloys
Face center cubic (austenite) – 800, 800H, 800HT
— Carbon, aluminum and titanium vary– 825– Trade name of these alloys is Incoloy
RE Alloys/2-35
Ni, Cr, Fe Alloys
Use 800 series where improved properties over austenitic stainless steel is required– High temperature strength– High temperature oxidation– Creep– High temperature sulfur– High temperature H2S/H2
– Design temperature
RE Alloys/2-36
Ni, Cr, Fe Alloys
Use 825 where improved properties over austenitic stainless steels is required– Cl- SCC– Reducing acids– Ammonium bisulfide
RE Alloys/2-37
Ni, Cr, Fe Alloys
Primary uses 800, 800H,800HT– Heater tubes– Pig tails for H2 reformers
Primary uses 825– Hydrotreater reactor effluent air coolers – Low point drains
RE Alloys/2-38
Ni, Cr, Fe Alloys
Primary cautions– Some alloys subject to sensitization– Follow suppliers temperature
recommendations— Some alloys embrittle when operated
between 550–750oC (1020–1380oF)
RE Alloys/2-39
Ni, Cr, Mo Alloys
Alloy C-276– Trade name Hastelloy
Alloy 625– Trade name Inconel
Alloys C2000 and 59– Newer alloys which may be used in the future
RE Alloys/2-40
Ni, Cr, Mo Alloys
Use when high resistance to aqueous corrosion is required– Acid chlorides (ammonium chloride)
— Immune to Cl- stress corrosion cracking– Reducing acids (sulfuric and hydrochloric)– Oxidizing acids (nitric acid)
— Lower resistance than with reducing acids– Ammonium bisulfide
RE Alloys/2-41
Monel
Alloy 400– Monel or Monel 400 are trade names– 70 Ni, 30 Cu
Resists– HCl– HF– Caustic cracking
RE Alloys/2-42
Monel
Primary uses– HF Alkylation units
— All areas where the corrosion rate exceeds acceptable limits for carbon steel
Mostly high temperature areas– Crude unit overheads
— Linings, rings trays– Hot and or concentrated caustic applications
RE Alloys/2-43
Monel
Primary cautions– Not resistant to oxidizing environments– Applications over 300oF (150oC) may not be
successful– Highly resistant to but not completely immune
from ammonia SCC
RE Alloys/2-44
Copper Alloys
Cupronickels– 70 Cu, 30 Ni– 90 Cu, 10 Ni
Inhibited admiralty brass– 71 Cu, 28 Zn, 1 Sn, 0.04 As
Aluminum brass, arsenical– 77.5 Cu, 20.5 Zn, 2 Al, 0.1 As
Naval Brass– 60 Cu, 39.25 Zn, 0.75 Sn
RE Alloys/2-45
Copper Alloys
Primary uses– Heat exchangers
— Use dictated by water side— Use for seawater— Use for untreated fresh water
RE Alloys/2-46
Copper Alloys
Primary cautions– Ammonia stress corrosion cracking
— Cu Ni less sensitive than brasses– Sulfur compounds
— May cause excessive corrosion– Water velocity
— High velocities, higher corrosion (varies by alloy)
– High concentrations of oxygen/oxidizers— May increase corrosion rates
RE Alloys/2-47
Titanium
Several grades availableHighly reactive material– Oxide film makes highly corrosion resistant– Highly resistant to Cl-
RE Alloys/2-48
Titanium
Primary uses– Exchangers
— May be dictated by water or processPrimary caution– Subject to hydriding when coupled to steel at
temperatures above 80oC (176oF)— Hydriding makes titanium brittle
RE Alloys/2-49
Aluminum Alloys
Many classes of alloys– Many alloys within each class– Mechanical and corrosion properties vary
Primary refinery uses– Fin Fans– Cold boxes– Rotating equipment– Not piping or vessels
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