Metallurgy and corrosion in ammonia plants

Anette Nrgaard Hansson

Tensile test

Stress

Plastic deformation

Elastic deformation

Strain

Elastic deformation
The atomic bonding is stretched
but not broken

Plastic deformation
The atomic bonding is broken

Mechanical properties

Stress
Tensile Strength
Stress to fracture
Yield Strength
Area: toughness

ductility
Slope: E-modulus

Fracture strain

0,2%

elongation

Strain

Metal bonding and crystal structure

Strong order of the positive cores is observed in metals

Metal cores arrange in 3-dimensional crystal lattices

The positive cores consist of protons and non-valence electrons

Valence electrons move freely in crystal lattice

This results in excellent electrical- and heat conductivity

Metal ions

Electrons

A sea of electrons
Valence electrons

Crystal structure
bcc-structure (i.e. a-Fe, a-Cr)

fcc-structure (i.e. g-Fe, Cu, b-Ni)

Close packed planes important for plastic

deformation behaviour

They act as slip planes during deformation

Slip planes are preferred directions of latice

movement

Crystals with few slip planes typically stronger

Atomic distortion defects

Point defects

vacancy
Line defects

Edge dislocation:
extra plane of atoms

Interstialcy

substitutional
Grain boundaries

Cross section of a metal (90x)

Strengthening / hardening mechanisms

Movement of dislocation

Hinder dislocation movement

Solid solution hardening: Lattice distortion.
Precipitation hardening: Dislocation movement by cutting or bypassing.
- Dispersion hardening: Precipitates insoluble at all temperatures
- Age-hardening: Precipitates soluble at high T, insoluble at low T.
Deformation hardening: By plastic deformation
- Increase of hardness, tensile strength and yield strength
Grain refining: By increase in amount of grain boundaries.
- Produced by controlled heat-treatment / micro-alloying (V, Nb, Ti).
- Example: HSLA-steels (High Strength Low Alloy)

Tensile test

Low alloy steel

Austenite = g

Fe-C phase diagram

Ferrite = a

Pearlite

a
725 C

Low alloy steel: Heat Treatments

Change of properties

Restitution

: Same deformation hardness but higher ductility

Recrystallization

: Removes deformation hardness, increases ductility

Spherodizing

: Softens the steel, increase machinability, forgability

Normalizing

: Improve yield strength, recover toughness

Low alloy steel: Heat Treatments

Hardness

Normalising

~ 200 BHV

Coarse perlite
~ 400 BHV
Fine perlite

~ 700 BHV

CCT-diagram for Ck35 steel

(0.35 %C, 0.25 % Si, 0.65 % Mn)

Martensite

Classification of steels

- Carbon Steel: Max 2 % Mn (ferritic)

- Low Alloy Steel:

< 12% Cr + Mo, additional Ni, V and others (ferritic)

- Stainless Steel:

> 12 %Cr, additional Mo, Ti (ferritic)

> 17 % Cr and 8% Ni, additional Mo, Ti, Nb (austenitic)
> 18 - 25% Cr, 4 - 7% Ni, additional Mo (duplex SS)

- Nickel Alloys: Min. 30 % Ni, Cr, additional Mo, V, W, Ti, Zr (austenitic)

Process layout
Ammonia
CO2

Air

Steam

Natural Gas

Desulphurization

Raw
Shift

Reforming
Synthesis Gas

Desulphurization unit: Hydrogen embrittlement

Reformer: Creep
Carburization
Oxidation
Metal dusting
CO2 removal unit: Amine SCC
Carbonic acid corrosion
Annomia converter: Nitridation
Hydrogen embrittlement
Temper embrittlement

CO2
Removal

Methanation

Ammonia
Loop

NH3

Hydrogen embrittlement
Low-Temperature Hydrogen Attack (T < 200C)
Hydrogen Embrittlement (HE)
Hydrogen Induced Cracking (HIC)
Sulfide Stress Corrosion Cracking (SSCC)

H
H

H H

Mechanism:
1.
Adsorption of hydrogen molecules to the metal surface.
2.
Dissociation of the adsorbed hydrogen molecules into hydrogen atoms and
permeation of hydrogen atoms in the metal.
3.
Hydrogen atoms diffuse in the steel
The amount of hydrogen depends on the solubility in steel and the hydrogen diffusion
coefficient (both parameters are alloy type dependent (carbon & low alloy / stainless / nickel
alloys)
4.
Degradation
A)
Hydrogen blistering: H + H H2 blisters/cracks (dirty steels)
The concentration of hydrogen in void increases, and the pressure thus created
increases cracking
B)
Hydrogen embrittlement: after penetration, atomic hydrogen reacts to form brittle
compounds (hydrides), which increase cracking.
Mechanical properties influenced:

Strength, ductility, toughness

Hydrogen embrittlement

High-Temperature Hydrogen Attack (T > 200C)

Gas with high p(H2)

C + 4H CH4 blisters/cracks and decarburization

Nelson diagram

Creep
Degradation due to exposure at high temperatures under pressurised conditions
Strengthening:

Weakening:

Dislocation movement
inhibited by obstacles dispersions
precipitates

Vacancies move by stress directed diffusion

Dislocation climb
Dislocations travel to grain boundaries
Voids are created
Alignment
Coalescence to fissures and cracks

primary

secondary

tertiary

Creep classification of damage

class 2b/3a

class 2b

class 4

class 3a/3b

Carburization/ nitridation
Nitridation: NH3 Nads + 3/2 H2
Carburization: CO + H2 Cads + H2O
N/ C diffuses into the alloy forming nitrides
or carbides.

55 h at 980 C in
Ar-5H2-5CO-5CH4
(aC=1.0, pO2=9x10-22atm)

Oxidation

Metal dusting
Reduction reaction:
CO + H2 C + H2O
Boudouard reaction:
2 CO C + CO2
Methane reaction:
CH4 C + 2 H2

a C = K1

PCO PH 2
PH 2O

2
PCO
a C = K2
PCO2

a C = K3

PCH4
PH2 2

19 bar

H2

35 %

H2O

40 %

CO

12 %

CO2

12 %

TB

738 C

TR

713 C

Metal dusting
a. Local defect in the oxide scale
b. C transfer from the carburizing
atmosphere to the metal formation
of carbides (M23C6)
c. aC > 1 disintegration of metal
d. Disintegration by:
- Low Ni alloys formation of
unstable cementite
- High Ni alloys direct inward,
internal growth of graphite
e. Disintegrated particles act as catalyst
for C deposition coke formation

Wet Corrosion
Neutral & basic environments
Oxidation
Fe Fe2+ + 2 eIron transforms in iron ions and electrons

Reduction
O2 + 2H2O + 4 e- 4 OH2 H2O + 2 e- H2 + 2OH-

Oxygen or water from hydroxydes

Overall reaction in neutral or basic

environments:
2Fe + O2 + 2 H2O 2Fe(OH)2
In total: iron transforms into hydroxydes)

Carbonic acid corrosion

CO2 is a weakly acidic gas and becomes corrosive when
dissolved in water a relatively slow reaction

CO 2 + H 2 O H 2 CO 3

H + + HCO 3-

Reduction
H+ + e- Hads
Hads Hbulk (Hydrogen embrittlement)
or
Hads + Hads H2 (g)
The result can be the formation of a protective layer of Fe-carbonate.
Whether or not corrosion in a CO2 system depends on the factors
governing the formation and retention of the protective Fe-carbonate
scale. Velocity effects are therefore very important to the CO2 system.
Excessive turbulence results in larger corrosion rates.

Stress corrosion cracking

Wet condition

SCC is the fracture of a metal that results

from the joint action of static tensile
stresses and a corrosive environment.

View of chloride stress corrosion

cracking in a 316 stainless steel
chemical processing piping system.
Mag: 300X

The stresses required for SCC are small, usually below the macroscopic yield
stress, static and tensile in nature. They can be external or residual.

The environments are usually aqueous.

Cracks can be intergranular or transgranular.

Stress corrosion cracking

Caustic or Alkaline stress corrosion cracking:
Aqueous alkaline environment containing H2S, CO2 and tensile stresses (residual
or applied), pH = 8-11. The cracking is branched and intergranular in nature, and
typically occurs in non-stress-relieved carbon steels.
Local anodic dissolution of iron at breaks in the normally protective corrosion
product film on the metal surface.
Hardness has no effect on susceptibility to ASCC.
Cracks start at localised stress raises (surface discontinuities adjacent to welds)
Ammine stress corrosion cracking:
Amine solutions are used to remove hydrogen sulphide and carbon dioxide from
refinery and petrochemical plant streams.
It is a form of intergranular alkaline SCC in otherwise ductile material, usually
without the formation of visible corrosion products.
Cracks are in most cases related to welded joints and propagate both parallel and
transverse to the weld, but cracking is not related to weld hardness.

Summary
Mechanical properties:
Yield strength
Tensile strength
Ductility
Toughness
Crystal structure:
Metal bonding
Unit cell
Defects
Steel:
Fe-C phase diagram
Microstructure
Strengthening mechanism
Heat treatment
Classification of steel

Degradation mechanism:
Hydrogen embrittlement
Creep
Carburization/ Nitriding
Oxidation
Metal dusting
Wet corrosion
Carbonic acid corrosion
Stress corrosion cracking

Mechanical properties
Elasticity

Property of a material by virtue of which deformation

caused by stress disappears upon removal of the stress.
Hookes low:

s E e

where s is the applied stress, e is the strain and E is the

modulus of elasticity.
Elastic deformation A change in dimensions directly proportional to and in phase
with an increase or decrease in applied force.
Elastic limit

The maximum stress that a material is capable of sustaining

without any permanent strain (deformation) remaining upon
complete release of stress.

Plasticity

The property that enables a material to undergo permanent

deformation without rupture.

Mechanical properties
Ductility

The ability of a material to deform plastically without

fracturing, measured by elongation or reduction of area
in a tensile test.

Toughness

The ability of a metal to absorb energy and deform

plastically before fracturing.

Plastic deformation The permanent (inelastic) distortion of metals under

applied stresses than strain the material beyond its
elastic limit.
Plastic deformation can take place by slip, twinning or a
combination of both.