Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Teach-in
Coupons
Online Monitors
Inhibition programs
Any method be made more effective…
…When you understand the
effect of the corrosion
environment
pH
Determine the rate limiting redox processes
Passive region
Activation
controlled
Rate-limiting
cathodic
process
Determine pitting potential and max growth rate
No PittingÍ ÎPitting
Pro-active Analysis
¾Test Corrective Actions
• Determine optimum pH
• Screen alloys and inhibitors
• Assess process changes
¾ Corrosion mechanisms
¾ Rate -limiting partial processes for your operating
Rate-limiting
conditions
¾ Effects of process and materials changes
Therefore
¾ Focusing lab time
¾ Reducing risky plant/field
testing
¾ Managing design, operation,
and maintenance
Today’s seminar
““Hands-on”
Hands-on” and ““How-To”
How-To”
¾ Using example problems
¾Using
¾ Examining plots and
¾Examining
diagrams
¾ Understanding the basis of
¾Understanding
the predictions
Today’s Seminar
¾ Perform ““Single
Single point
point”” calculations
¾ Construct / interpret real solution Pourbaix Diagrams
¾ Calculate corrosion rates
¾ Evaluate the effects of pH, T, comp / flow
¾Evaluate
Acid Gas
Absorber liquor
regenerator
Acid Gas Concentrations
H2S(aq)= ½ H2 + HS- - e
HS-= ½ H2 + S2- - e
H+= ½ H2 - e
Mitigation
¾ Adjusting solution chemistry
¾ Temperature profiling
¾ Alloy screening
¾ Cathodic protection
Adjusting the Solution
Chemistry
¾ Changing operating pH
z Add acid or base
Application Time
Adjusting solution pH = 8.0
Screening Alloys
¾ Select an alloy that has a preferential
corrosion rate
z 13% chromium
z 304 Stainless
Application Time
13 % Cr Steel Corrosion @ Dew Point
H2CO3(aq)= ½ H+ + HCO3- - e
HS-= ½ H2 + S2- - e
304 Stainless Steel Corrosion @ Dew Point
White area is region of Elemental iron (gray region) corrodes in water to form one of several phases, depending on
pH. At ~9 pH and lower, water oxidizes Fe0 to Fe+2 which dissolves in water (white region of
iron corrosion the plot). As the oxidation potential increases (high dissolved O2) Fe+2 precipitates as FeOOH,
or rust (green region). The lower the pH, the thicker the white region and the greater driving
force for corrosion
At higher pH (10-11), Fe0 forms Fe3O4, a stable solid that precipitates on the iron surface,
protecting it from further attack.
H2 O is o
Fe(III)3+ is the xidized to
O2 and H +
dominant ion Fe(
II) o
H 2 O is stable
and aer a
Fe(II)2+ is the Fe xidi ted Water Ox
idation Lin
zes
2O and
e
3 red pre
dominant ion uce
s an cipi
dd tate
isso s as
lves Fe
in w 2O
3
at e
H2 O is s r
table an
d deaer FeO(OH), rust is stable in water at moderate to high pH’s
H2 O is re ated
duced to
H2 and O -
H
Water Re Fe3O4 coats the iron
duc tion Line surface, protecting it from
corrosion
Elemental iron, Fe(0) oxidizes to Fe(II) in the presence of water
H 2 O → 1 O2 + 2 H + + 2 e −
2
H2 O is o
xidized to
O2 and H +
H2 O is sta Water Ox
ble and a idation Lin
erated
e
H2 O is s
table an
Pure water is here…
d deaerate
d No air, no acid, no base
H 2O + e → 1 H 2 + OH +H O is red
−
2 2 uced to H
2 and OH -
Water Re
duc tion Line
3 ppb O2 0.1ppm H2
80 ppm H2
0.1 ppT O2
Iron and water react because they are not stable together
2 H 2O + 2e − → H 2 + 2OH +
Fe o → Fe + 2 + 2e −
Fe o + 2 H 2 O → Fe + 2 + H 2 + 2OH +
Region of instability
The reaction generates H2, which puts
the EH near the bottom line
Initial Conditions
DI water, no Feo
7pH, 0.4V
Final Conditions
1 ppm Feo added
9.38pH, 0.5V
0.9 ppb Feo
7.07pH, -0.27V
.0033 mm/yr @ 25 oC
Corrosion of 304 Stainless Steel in
Deaerated Sea Water
Repassivation Potential
Large difference
means that pits are Corrosion Potential
unlikely to form Difference = 0.05 V
Or if a pit forms,
then it will passivate
What’s on a Polarization Curve?
2
1.5
Standard Tafel Behavior
1
Transition to mass-transfer
Potential V(SHE)
0.5
limited current density
0
-0.5
-1
-1.5
-2
1.0E-09 1.0E-06 1.0E-03 1.0E+00 1.0E+03 1.0E+06 1.0E+09
-0.5
2 H 2O → H 2 + 2OH − − 2e −
Current density at corrosion
-1 potential also read at intersection
-1.5
-2
1.0E-09 1.0E-06 1.0E-03 1.0E+00 1.0E+03 1.0E+06 1.0E+09
0.5
-0.5
-1
Basic polarization curve with water
decomposition and corrosion
-1.5 reaction
-2
1.0E-09 1.0E-06 1.0E-03 1.0E+00 1.0E+03 1.0E+06 1.0E+09
-0.5
-1
-1.5
-2
1.0E-09 1.0E-06 1.0E-03 1.0E+00 1.0E+03 1.0E+06 1.0E+09
This is what is
Transpassive region
measured
experimentally
Passive region
Active Corrosion
0.5
Passive
0
-0.5
-1
Polarization curve demonstrating a galvonostatic sweep. Active
The arrows indicate
-1.5 how the potential is changing as
one moves along the line.
-2
0.001 0.1 10 1000 100000 10000000
2H2O=O2+4H++4e-
H2O + e- = ½ H2+OH-
H+ + e- = ½ H2
The Polarization Curve for 304
SS in Deaerated Water
Oxidation of water to O2
Measurable
polarization curve
Breakdown of water to H2
oxygen, etc.)
z Anodic reactions (e.g., oxidation of metals)
z Temperature
oxide layers
¾ Synthesis of the partial processes according to the mixed
potential theory
May 20, 1997 OLI Systems, Inc,
Application Time
Corrosion of 316 SS in
Deaerated Water
Much better
corrosion rate than
304 ss
Corrosion of 316 SS in
Deaerated Water
Difference = 0.086 V
Application Time
Corrosion of 254 SMO in
Deaerated Water
Difference = 2.7 V
Summary in Deaerated Water
(V)
304 0.0033 0.05
¾ The CorrosionAnalyzer
allows you to add a gas Species Partial
Pressure
phase based only on (atm)
partial pressures N2 0.7897
¾ You can set the O2 0.21
water/gas ratio CO2 0.0003
WGR 0.01 bbl/scf
Application Time
304 SS in Aerated Solutions
304 SS in Aerated Solution
The corrosion
potential is greater
than the passivation
potential = .37 V at
max O2
8 ppm O2
Corrosion potential
shifted anodically of
the repassivation
potential. 0 ppm O2
Pitting occurs at
higher oxygen
concentrations =
.21V at max O2
Application Time
S31254 Corrosion in Deaerated
Water
4 H + + O2 + 4e − → 2 H 2O
E = 1.23 − 0.059 pH
2 H + + 2e − → H 2
⎛ 1 ⎞
E = 0 − 0.059 Log ⎜⎜ + ⎟⎟ = −0.059 pH
[ ]
⎝ H ⎠
Water Stability – Natural Waters
Surface water
Ocean water
Bog water Organic rich lake
water
Organic rich
waterlogged soils
Oxidized Species
E Independent acid
and base chemistry
pH dependent redox
pH independent
redox
Predominant
species
Reduced Species
Copper Pourbaix Diagram
Equilibrium between
species in contact with a
solid
Natural pH
Equilibrium between speciesStability field for base metal
or alloy
Copper Pourbaix Diagram