Classes of Alloys in Refinery Use

EDS 2004/Metallurgy 2-1

Outcomes

Recall alloy types which are commonly used

in refineries
Recall specific examples of each alloy type
Recall factors (advantages/disadvantages)
which govern the use of the alloy

EDS 2004/Metallurgy 2-2

Classes of Refinery Metallurgy

Carbon and killed carbon steels

Low alloy (Cr-Mo) Steels
Stainless steels
Nickel alloys
Copper alloys
Titanium alloys
Aluminum alloys

EDS 2004/Metallurgy 2-3

Carbon Steels

Alloy of Fe and C
Carbon content affects mechanical properties
High C
y High strength
y Low ductility
Processing conditions also affect mechanical
properties
Too many details for this course
Harden when quenched from above 1333oF

EDS 2004/Metallurgy 2-4

Refinery Metallurgy

Carbon steel is the default material of

construction used in refineries
Inexpensive
Easy to work with
Normally economically satisfactory
Cost vs. life expectancy

Other materials used only when carbon steel

is unsatisfactory

EDS 2004/Metallurgy 2-5

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
y Mechanical properties
y Cleanliness of steel

EDS 2004/Metallurgy 2-6

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

EDS 2004/Metallurgy 2-7

Low Alloy (Cr-Mo) Steels

1 Cr- Mo; 1 Cr- Mo

2 Cr- Mo
5 Cr- Mo
9 Cr- Mo

EDS 2004/Metallurgy 2-8

1 Cr- Mo; 1 Cr- Mo

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 exist

Similar properties to carbon steel

Resistance to high temperature H2S/H2

EDS 2004/Metallurgy 2-9

1 Cr- Mo; 1 Cr- Mo

Primary uses
Reactor shells for high temperature processes
Heater tubes
Piping
Exchangers

EDS 2004/Metallurgy 2-10

1 Cr- Mo; 1 Cr- Mo

Primary cautions
High hardenability weld cracking
Creep embrittlement
Discussed later

EDS 2004/Metallurgy 2-11

2 Cr-1 Mo

Used where improved properties over 1 Cr- Mo

are required
High temperature strength
Resistance to high temp hydrogen attack
High temperature sulfur
Contradictory data exist

Similar properties to 1 Cr- Mo

Design temperature
Resistance to high temperature H2S/H2

EDS 2004/Metallurgy 2-12

2 Cr-1 Mo

Primary uses
Reactor shells for high temperature processes
Heater tubes
Piping
Exchangers

EDS 2004/Metallurgy 2-13

2 Cr-1 Mo

Primary cautions
High hardenability weld cracking
Temper embrittlement
Discussed later

EDS 2004/Metallurgy 2-14

5 Cr- Mo

Used where improved properties over 2 Cr-1 Mo

are required
High temperature strength
Resistance to high temperature hydrogen attack
High temperature sulfur

Similar properties to 2 Cr-1 Mo

Design temperature
Resistance to high temperature H2S/H2

EDS 2004/Metallurgy 2-15

5 Cr- Mo

Primary uses
Piping
Exchangers

Primary cautions

High hardenability weld cracking

EDS 2004/Metallurgy 2-16

9 Cr-1 Mo

Used where improved properties over 5 Cr- Mo

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- Mo

Design temperature

EDS 2004/Metallurgy 2-17

9 Cr-1 Mo

Primary uses

Heater tubes

Primary cautions

High hardenability weld cracking

EDS 2004/Metallurgy 2-18

Stainless Steels

Ferritic
Austenitic
Martensitic

EDS 2004/Metallurgy 2-19

Stainless Steels, Ferritic

405
410S

11 13% Cr, aluminum

11 13% Cr, low carbon

Body center cubic (ferrite)

Just enough Cr to be stainless

EDS 2004/Metallurgy 2-20

Stainless Steels, Ferritic

Used where improved properties over 9 Cr-1

Mo are required
High temperature sulfur
Resistance to high temperature H2S/H2

Generally not used for

Pressure boundaries
Where welding is required
Naphthenic acids service

EDS 2004/Metallurgy 2-21

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

EDS 2004/Metallurgy 2-22

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

EDS 2004/Metallurgy 2-23

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

304L

304

304H

316L

316

316H

317L

317

317H

321

321H

347

347H

EDS 2004/Metallurgy 2-24

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)

EDS 2004/Metallurgy 2-25

Stainless Steels, Austenitic

Carbon is important
Normal and low C material good to 1000oF
H grade materials good to 1500oF
L grades dont sensitize during welding
Discussed later

EDS 2004/Metallurgy 2-26

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
y 316 may be ok
y Normally want 317

EDS 2004/Metallurgy 2-27

Stainless Steels, Austenitic

Titanium and niobium (columbium) are

important (321, 347)

Chemically stabilize steels

Dont sensitize during welding

EDS 2004/Metallurgy 2-28

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)

EDS 2004/Metallurgy 2-29

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

EDS 2004/Metallurgy 2-30

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

EDS 2004/Metallurgy 2-31

Stainless Steels, Martensitic

410 12% Cr (higher C than 410S)

Not used as pressure boundary
Used for
Aqueous corrosion resistance
Strength
Wear resistance

Used in

Shafts, pumps, turbine blades

EDS 2004/Metallurgy 2-32

Nickel Alloys

Ni, Cr, Fe alloys Alloy 800 (series)

Ni, Cr, Mo alloys (C-276, alloy 625)
Monel

EDS 2004/Metallurgy 2-33

Ni, Cr, Fe Alloys

Face center cubic (austenite)

800, 800H, 800HT
Carbon, aluminum and titanium vary
825
Trade name of these alloys is Incoloy

EDS 2004/Metallurgy 2-34

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

EDS 2004/Metallurgy 2-35

Ni, Cr, Fe Alloys

Use 825 where improved properties over

austenitic stainless steels is required
Cl- SCC
Reducing acids
Ammonium bisulfide

EDS 2004/Metallurgy 2-36

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

EDS 2004/Metallurgy 2-37

Ni, Cr, Fe Alloys

Primary cautions
Some alloys subject to sensitization
Follow suppliers temperature
recommendations
Some alloys embrittle when operated
between 550750oC (10201380oF)

EDS 2004/Metallurgy 2-38

Ni, Cr, Mo Alloys

Alloy C-276

Alloy 625

Trade name Hastelloy

Trade name Inconel

Alloys C2000 and 59

Newer alloys which may be used in the future

EDS 2004/Metallurgy 2-39

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

EDS 2004/Metallurgy 2-40

Monel

Alloy 400
Monel or Monel 400 are trade names
70 Ni, 30 Cu

Resists
HCl
HF
Caustic cracking

EDS 2004/Metallurgy 2-41

Monel

Primary uses
HF Alkylation units
All areas where the corrosion rate exceeds
acceptable limits for carbon steel
y Mostly high temperature areas
Crude unit overheads
Linings, rings trays
Hot and or concentrated caustic applications

EDS 2004/Metallurgy 2-42

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

EDS 2004/Metallurgy 2-43

Copper Alloys

Cupronickels
70 Cu, 30 Ni
90 Cu, 10 Ni

Inhibited admiralty brass

Aluminum brass, arsenical

71 Cu, 28 Zn, 1 Sn, 0.04 As

77.5 Cu, 20.5 Zn, 2 Al, 0.1 As

Naval Brass

60 Cu, 39.25 Zn, 0.75 Sn

EDS 2004/Metallurgy 2-44

Copper Alloys

Primary uses

Heat exchangers
Use dictated by water side
Use for seawater
Use for untreated fresh water

EDS 2004/Metallurgy 2-45

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

EDS 2004/Metallurgy 2-46

Titanium

Several grades available

Highly reactive material

Oxide film makes highly corrosion resistant

Highly resistant to Cl-

EDS 2004/Metallurgy 2-47

Titanium

Primary uses

Exchangers
May be dictated by water or process

Primary caution

Subject to hydriding when coupled to steel at

temperatures above 80oC (176oF)
Hydriding makes titanium brittle

EDS 2004/Metallurgy 2-48

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

EDS 2004/Metallurgy 2-49