CONRAD

Oilsands Water Usage Workshop 2004

Corrosion Control in Pipelines Using Oxygen Stripping
Champion Technologies
February 24, 2004
Agenda
Corrosion
- The economic impact of corrosion?
- What is it?
- Why does it occur?
- Types of Corrosion
Dissolved Gas Oxygen
- How does it accelerate the corrosion process?
- Why is it a problem?
Mechanical Treatment Options
Pros/Cons
Chemical Treatment Options
How do they work?
Pros/ Cons
Gas Scavenging
- Bisulfite chemistry
Metal Passivation
- Phosphate based chemistries
Zinc Orthophosphate
Phosphate Esters
Cost of Corrosion - Global Economic Impact
With new (evolving stricter) environmental guidelines the
requirements on industry to control effluent discharge has
increased.
Industry guidelines are evolving such that zero discharge is
the target.
Lost production and material replacement due to corrosion
mechanisms costs billions of dollars annually to industry.
These economic losses can be divided into two groups:
Direct losses
Indirect losses
Direct Losses Increased Costs
Cots of replacement of machinery or their components
Costs of maintenance/ servicing like repainting
Costs of rebuilding/ construction
Equipment capital
Environmental regulations
Chemical expenses
Safety considerations
Indirect Losses Decreased Revenue
Costs due to shut down
Lost production
Costs due to loss of efficiency
Costs resulting from catastrophes
Economic Impact - Profitability
Increased
Costs
Decreased
Revenue
Decreased
Profits
Mitigating corrosion is necessary to save costs, time, the environment.
Cost of Corrosion Local Economic Impact
EUB Statistics - 2002
Alberta has approximately 320 000 km of energy related pipeline
EUB conducted 516 inspections on failures/hits in 2002
563 corrosion incidents, up from 503 in 2001
Higher incidents and unsatisfactory inspections due to implementation of Guide-
66: Pipeline Inspection Manual
Failure frequency of 2.5/1000km down from benchmark 5.0/1000km in 1998
EUB statistics from 2002 show:
Facility suspensions by EUB down from 142 in 2001 to 128 in 2002
Cost was greater however, 25.8 million in 2002 compared to 16.3 million
in 2001
All Pipeline Failures by Cause
Industry Benchmarks - Alberta Pipeline Information - EUB
50% +
What is Corrosion?
The Electrochemical Corrosion Process
It involves the flow of ions and electrons through liquids and metals,
and their interaction across liquid-solid interfaces such as where water
and metal meet.
Corrosion occurs in a corrosion cell. It consists of:
A metal conductor
The anode, where metal goes into solution
The cathode, which is the reaction site for the electrons
Electrolyte, which completes the electrical circuit
Water must be present for electrochemical corrosion to occur. If
theres no water, its not corrosion.
The Corrosion Cell
Metal Metal
2H 2H
+ +
+ 2e H + 2e H
2 2
Fe Fe Fe Fe
++ ++
+ 2e + 2e
Electrolyte Electrolyte
Anode
Anode
Cathode
Cathode
e
e
e
e
Electron
Flow
Electron
Flow
Metal Structure
Metals used for construction and pipeline are inherently inhomogeneous materials.
Refined metals have a grain structure made up of microscopic metal crystals. They
always contain inclusions, precipitants and sometimes consist of different metallurgical
phases. Potential differences on the metal surface are a natural result. These
differences are one of the primary causes of corrosion.
Sometimes there can be no visible change in weight or appearance
Uniform corrosion, or overall general attack, occurs when anodic and cathodic areas
keep shifting. Corrosion then takes place more or less uniformly over the entire
exposed surface. The metal becomes thinner and eventually fails. In case of uniform
corrosion service life can often be quite accurately estimated on the basis of relatively
simple corrosion tests.
Some corrosion is sudden and unexpected
Pitting is readily recognised because of pits or holes. This is one of the most vicious
forms of corrosion and among the hardest to predict.
Pitting often starts because of concentration cell effects such as under a permeable
deposit. The environment under the deposit becomes exhausted of oxygen, or
increases in ion concentration, whereas the surrounding metal away from the deposit
is exposed to essentially a constant concentration of oxygen or ions.
The rate of penetration often accelerates because the pit acts as a crevice and
thereby increases the concentration cell effect. An unfavourable ratio of cathode to
anode also exists.
Forms of Corrosion?
Localized Pitting
General corrosion is not a major concern to corrosion risk. Typically flowlines can
produce for 15-20 sometime 30 years without failing. However in cases where pitting
corrosion is present we can sometimes see failure after 30-days.
Pitting Corrosion
Location of Corrosion Initiation
Corrosion cells may occur at:
Points where dissimilar metals connect
Points of internal stress
Places where there are differences in corroded ion concentration
On either side of the bending axis on pieces of bent metal
Stresses from the manufacturing process, or even wrench marks
Places where there are dings, scratches, stress, or other
imperfections have disrupted the uniformity of the metal surface
Places where there are differences in oxygen concentration
Factors Accelerate the Corrosion Process
Wherever water and metal meet, corrosion will occur. However, certain
factors speed up the rate at which corrosion occurs. These factors
include:
The pH of the water
The presence of dissolved acid gases (CO
2
, H
2
S)
Temperature (affects solubility)
Pressure (affects solubility)
Dissolved solids
Velocity of fluid through flowlines
Metallurgy (type of metal)
Dissolved oxygen (O
2
)
Suspended solids
Suspended Solids
Suspended solids (slurry/ hydro-transport process), including bacteria, may accelerate
corrosion in several ways:
Solids that settle on metal surfaces can act as cathodes causing concentrated under
deposit corrosion
Layers of deposited solids may also shelter bacteria, some of which produce acid
Solids flowing through tubing can act like a sandblaster, stripping away protective
coatings of corrosion by-product (iron carbonate and iron sulfide) as well as corrosion
inhibitor from the metal.
Flow Modeling/ Velocity Effects?
Flow Modeling - Importance
Flow modeling has an impact because we can determine the probability of solids
deposition, water hold up areas (high risk/ high consequence). It also has a direct
impact on the chemical selection/ dispersibility of the products for adequate
treatment.
Unified Flow Pattern Map
24" (610 mm) Line
Gas Velocity (VSG) m/sec
0.01 0.1 1 10 100
L
i
q
u
i
d

V
e
l
o
c
i
t
y

(
V
S
L
)

m
/
s
e
c
0.01
0.1
1
10
100
Stratified Wavy Flow
Annular
Flow
Slug Flow
Dispersed Bubble Flow
Stratified Smooth
Flow
Line Conditions
How does oxygen impact corrosion?
How does oxygen impact corrosion?
Of the three dissolved gases, oxygen is by far the most aggressive of the
group. If either or both of the other two gases are dissolved in the water, it
drastically increases their corrosivity.
The higher the concentration of dissolved gases in solution the higher the
corrosion tendency.
Oxygen accelerates the corrosion process in two ways:
First it acts as a depolarizer. This means that it will easily combine with
hydrogen atoms at the cathode and allow the corrosion reaction to proceed at a
rate limited primarily by the rate oxygen can diffuse to the cathode. Without
oxygen, the energy it takes to evolve hydrogen gas from the cathode is a major
bottleneck in the corrosion reaction and keeps it slowed down.
Second, the oxygen oxidizes the ferrous ions to ferric ions, which forms the
insoluble ferric hydroxide (above pH=3).
Any time there is a difference in the oxygen content of water in two areas of a system,
attack will take place preferentially in the area exposed to the lowest oxygen
concentration. An oxygen concentration cell. Therefore even solids, scale, corrosion
by-product which may cause areas of low oxygen concentration, can cause pitting.
Dissolved O
2
can cause severe corrosion at concentrations of 40 ppb (parts per
billion); most operations try to limit the oxygen content to 20-30 ppb in water sources.
Morphology - Oxygen corrosion has a pitting effect on metal. These pits start small,
very deep, with sharp, ice-pick hole-like bottoms accelerate rapidly.
Oxygen Corrosion
Pitting Corrosion by Oxygen Concentration Cell
Fe Fe
++ ++
Pipe Wall Pipe Wall
Flow Flow
Cathodic Area Cathodic Area Anodic Area Anodic Area
Fe Fe
++ ++
Fe Fe
++ ++
Fe Fe
++ ++ Fe Fe
++ ++
H H
+ +
O O
2 2
O O
2 2
O O
2 2
O O
2 2
O O
2 2
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
First it acts as a depolarizer. This means that it will
easily combine with hydrogen atoms at the cathode
and allow the corrosion reaction to proceed at a rate
limited primarily by the rate oxygen can diffuse to the
cathode.
O
2
+ 4H
+
+4e
-
2H
2
O
Fe Fe
2+
+ 2e
-
Iron atom ferrous ion + electrons
Pitting Corrosion by Oxygen Concentration Cell
Fe Fe
++ ++
Pipe Wall Pipe Wall
Flow Flow
O O
2 2
Cathodic Area Cathodic Area Anodic Area Anodic Area
Fe Fe
++ ++
Fe Fe
++ ++
Fe Fe
++ ++ Fe Fe
++ ++
O O
2 2
H H
+ +
O O
2 2
O O
2 2
O O
2 2
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
Fe
2+
Fe
3+
+ 1e
-
ferrous ion ferric ion+ electron
Second, the oxygen oxidizes the ferrous ions to
ferric ions, which forms the insoluble ferric
hydroxide (above pH=3).
O
2
+ 2H
2
O + 4e
-
4OH
-
oxygen molecule + water molecules + electrons hydroxyl ions
O
2
+ 4H
+
+4e
-
2H
2
O
Pitting Corrosion by Oxygen Concentration Cell
Fe Fe
++ ++
Pipe Wall Pipe Wall
Flow Flow
O O
2 2
Cathodic Area Cathodic Area Anodic Area Anodic Area
Fe Fe
++ ++
Fe Fe
++ ++
Fe Fe
++ ++ Fe Fe
++ ++
O O
2 2
H H
+ +
O O
2 2
O O
2 2
O O
2 2
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
hydroxide ferric ions hydroxyl ion ferric
OH Fe OH Fe
+
+
+
3
3
) ( 3
Oxygen Corrosion
Prevention Options
Materials, Operations, Chemicals
Preventing Corrosion
Change the metal to corrosion-resistant or non-corroding material, such as a corrosion
resistant alloy (CRA) or to a chrome interior.
Physically treat the metal with a permanent barrier to corrosion, such as hot dip, glass,
ceramic, and organic coating or paint.
Electrochemical cathodic protection, which redirects the corrosion to a weaker
galvanic couple, which serves as a sacrificial anode.
Alter the corrosive environment by removing acid gases from the water or de-ionize
the water to eliminate its electrical conductivity. Better yet, dehydrate the system and
remove the water altogether. Remember, without water you cant have corrosion.
Chemicals (Oxygen Scavengers/ Passivators) - Corrosion inhibitors.
Need to determine the root cause of corrosion
Direct Losses Increased Costs
Cots of replacement of machinery or their components
Costs of maintenance/ servicing like repainting
Costs of rebuilding/ construction
Equipment capital
Environmental regulations
Chemical expenses
Safety considerations
Indirect Losses Decreased Revenue
Costs due to shut down
Lost production
Costs due to loss of efficiency
Costs resulting from catastrophes
Economic Impact - Profitability
Increased
Costs
Decreased
Revenue
Decreased
Profits
Increase
Profits
Prevention Options
Materials, Operations
The most common methods of removing oxygen from systems fall in to two
categories mechanical de-aeration (counter current gas stripping towers or
vacuum towers) and chemical treatment.
As a generality, stripping or vacuum towers are used when large quantities of
dissolved oxygen are to be removed. Ie. Can handle water flow rates of 10 m3/h.
Chemical scavengers are used to remove small amounts of oxygen and
sometimes for removing the residual after tower de-aeration.
The final decision is an economic-technical one. Weigh the initial costs of a
mechanical set up vs. the costs of a chemical program. The shear volume of
chemical required to scavenge or passivate may not be practical.
The most functional removal of oxygen from water systems uses a combination of
mechanical de-aeration to reduce dissolved oxygen to 20-500 ppb, depending on
efficiencies in addition to the application of a chemical oxygen scavenger to reduce
the dissolved oxygen to < 5 ppb.
Controlling Oxygen Corrosion
A typical 3-stage vacuum de-aeration tower is shown. Efficiently maintained 3-stage
vacuum de-aerators may reduce dissolved oxygen mechanically to <20-50 ppb.















Residual O
2
Issues surrounding mechanical treatment:
Effectively Remove Oxygen from the System
Good for High Volume Throughput Systems
Up-front Costs/ Maintenance Costs
One Time Set-Up
Gas Stripping: Packed columns/ tray type columns
Maintenance
Fouling with solids and bacteria
Vacuum De-aeration: Vacuum pumps:
De-foamer maybe necessary
Note: the removal of CO
2
with gas stripping may also help with the precipitation of
calcium scale within the flowlines. This may require the addition of a scale inhibitor.
Controlling Oxygen Corrosion
Mechanical Considerations
Prevention Options
Chemical
How do Corrosion Inhibitors Work?
Oilfield corrosion inhibitors are derivatives of nitrogen groups (amines) and
organic acids. Phosphorus and sulfur are also utilized in the synthesis of
inhibitors.
Each molecule of the inhibitor chemical resembles a tadpole, with a head
and a tail. These molecules are electrically charged: the head has a
positive charge and the taila negative charge.
The electrical polarity creates an affinity in the molecule for solids, such as
metal surfaces of pipelines. As a result, the inhibitor molecules seek out the
metal surface and attach themselves to form the protective film.
Corrosion inhibitors form a protective layer between the metal surface and
the water. Without the metal-to-water contact, corrosion cannot take place.
Corrosion Corrosion
Inhibitor Inhibitor
Fluid Fluid
Pipe Wall Pipe Wall
Hydrocarbon Hydrocarbon
How do Corrosion Inhibitors Work?
Unprotected Cleaned Pipe Surface
Leading pig, 4-5% Oversized
Filming pig
Protected Treated Pipe Surface
How do Corrosion Inhibitors Work?
Surface of Steel Pipe
Inhibitor Adsorbed
onto Surface
Residual Inhibitor in Water
PRODUCED WATER - FILTERED
Dispersibility Testing
PRODUCED WATER WITH PRODUCTS
IMMEDIATELY AFTER ADDITION OF PRODUCTS
Dispersibility Testing
PRODUCED WATER WITH PRODUCTS
AFTER SLIGHT AGITATION
Dispersibility Testing
PRODUCED WATER WITH PRODUCTS
AFTER I HOUR
Dispersibility Testing
Coupon Treatment
Copper
Plating
Protected
Surface
Chemical
Treatment
Prevention Options
Scavengers - Passivators
Prevention Options
Scavengers
Oxygen Scavengers - Bisulfite
Oxygen scavengers physically react with the dissolved oxygen.
Ammonium bisulfite is the most commonly used oxygen scavenger in the oil field. It
has good low temperature stability (< -10
0
C) and can be further winterized to < - 40
0
C. It is the most economical and logistically friendly form of sulfite used for de-
oxygenation in the oil field.
Oxygen scavenger chemicals react stoichiometrically with the dissolved oxygen.
Typical treating rates for the scavenger chemistry is 6-10 ppm of scavenger for each
ppm measured of dissolved oxygen. Water contains approximately 8 ppm of
dissolved oxygen at STP, which is very corrosive.
Cautions:
If the source water contains excessive amounts of dissolved barium the selection of
a scavenger may not be the wisest. The barium may react with the sulfate ion causing
the highly insoluble barite scale leads to other problems
2NH
4
HSO
3
+ O
2
= (NH4)
2
SO
4
+ H
2
SO
4
- May Lower pH values
Pitting Corrosion by Oxygen Concentration Cell
Fe Fe
++ ++
Pipe Wall Pipe Wall
Flow Flow
Cathodic Area Cathodic Area Anodic Area Anodic Area
Fe Fe
++ ++
Fe Fe
++ ++
Fe Fe
++ ++ Fe Fe
++ ++
H H
+ +
O O
2 2
O O
2 2
O O
2 2
O O
2 2
O O
2 2
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
First it acts as a depolarizer. This means that it will
easily combine with hydrogen atoms at the cathode
and allow the corrosion reaction to proceed at a rate
limited primarily by the rate oxygen can diffuse to the
cathode.
O
2
+ 4H
+
+4e
-
2H
2
O
Fe Fe
2+
+ 2e
-
Iron atom ferrous ion + electrons
Oxygen Scavengers
Fe Fe
++ ++
Pipe Wall Pipe Wall
Flow Flow
Cathodic Area Cathodic Area Anodic Area Anodic Area
Fe Fe
++ ++
Fe Fe
++ ++
Fe Fe
++ ++ Fe Fe
++ ++
H H
+ +
O O
2 2
O O
2 2
O O
2 2
O O
2 2
O O
2 2
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
H H
+ +
Fe Fe
2+
+ 2e
-
Iron atom ferrous ion + electrons
2NH
4
HSO
3
+ O
2
= (NH4)
2
SO
4
+ H
2
SO
4
Oxygen corrosion is normally
controlled by the use of oxygen
scavenger chemicals, which react
stoichiometrically with the
dissolved oxygen.
Oxygen Scavengers
Do Graphs: Work completed for Hydro-testing Sea Water; Assume a worst case
scenario of 8-ppm dissolved O
2
. Add 100-ppm of the 65% active scavenger package
OS2 Trend dissolved oxygen as a function of time. The method used to measure the
dissolved oxygen content was an orbisphere membrane that measure DO
2
.
Prevention Options
Passivators
Controlling Oxygen Corrosion
Passivators
Typical oilfield corrosion inhibitors (amines) are not designed to prevent
oxygen (O
2
) corrosion. Oxygen molecules are sometimes able to penetrate
the chemical film and attack the metal.
Cathodic inhibitors tend to form cations similar in charge to H+ ions. These
types of inhibitors adsorb strongly to the cathode surface. When this happens
the cathode is no longer in contact with the electrolyte and the corrosion
current stops.
Passivating (Anodic) inhibitors form a protective oxide film on the metal
surface. Examples of passivators include chromate, nitrate, molybdate, and
orthophosphate.
O
2
passivators, which render the metal surface passive
These chemicals require continuous application to be effective because the
oxygen is always in the water.
Oxygen Passivators - Phosphates
The basic difference between scavengers and passivators:
Scavengers effectively remove the corroding agent, oxygen, from the
electrolyte and by default reduce the corrosion potential on the metal
surface. The passivators basically transport the oxygen through the
system but reduce the overall corrosion rates by introducing a
passivation layer on the metal surface. In effect, corrosion rates are
minimized overall.
Fluid compatibility should also be determined to ensure that there is no
increase in the amount of solids precipitated with the addition of chemical.
We do not want to increase treatment problems downstream of the chemical
injection locations. These products are highly surface active.
Note: In adequate concentration of passivating inhibitors may actually
induce pitting on untreated segments.
Filming Mechanism
Zinc - orthophosphate
Zn
3
(PO4)
2
Metal
Surface
P O
-
O
-
O
-
O
Fe
Fe
Fe
Fe
Fe
Zn
2+
Zn
2+
Zinc Orthophosphate:
Advantages
Highly effective corrosion control
Cost effective
Limitations
Cannot be used above pH 8.1 due to premature zinc
precipitation.
Divalent zinc ions may help to stabilize interface pads.
Depending on discharge techniques, zinc loading is highly
toxic to fish and other aquatic organisms.
Zinc to phosphate ratios can be adjusted to avoid zinc
loading.
P O
-
O
-
O
-
O
Di- phosphate ester single binding site to Metal Surface
Fe
Fe
Metal
Surface
Fe
P O
O
O
O
P O
O
O
O
P O
O
O
O
P O
O
O
O
Filming Mechanism
Metal Surface
Hydrocarbon Film
Produced Water
Inhibitor
Molecules
Apolar
Polar
Formation of " Double Layer" Protective Film
- Corrosion Inhibitor plus Condensate
Metal Surface
Hydrocarbon Film
Produced Water
Inhibitor
Molecules
Apolar
Polar
Formation of " Double Layer" Protective Film
- Corrosion Inhibitor plus Condensate
K
+
K
+
Phosphate Esters
Advantages
Hydrocarbon Chain Improved Effectiveness
Surface Activity may Reduce Friction
Cost effective
May Reduce Emulsion Stability (Ethoxylation)
Mono phosphate ester two binding sites to Metal Surface
New processes enriched mono-phosphate ester
double binding site to Metal Surface
Improved film persistency
P
O
O
O
O
Fe
Metal
Surface
Fe
P
O
O
O
O
Fe
Filming Mechanism
Metal Surface
Hydrocarbon Film
Produced Water
Inhibitor
Molecules
Apolar
Polar
Formation of " Double Layer" Protective Film
- Corrosion Inhibitor plus Condensate
Metal Surface
Hydrocarbon Film
Produced Water
Inhibitor
Molecules
Apolar
Polar
Formation of " Double Layer" Protective Film
- Corrosion Inhibitor plus Condensate
K
+
K
+
No Inhibitor
28 days
Inhibited
28 days
Pictures of an untreated LPR electrodes. Electrodes were exposed to surface
water without corrosion inhibitor. The left picture shows the edge of the electrode
with clear sign of crevice attack. The right picture shows the surface with pitting
attack
Pictures of an treated LPR electrodes. Electrodes were exposed to surface water dosed
with 50 ppm oxygen passivator/ corrosion inhibitor. The left picture shows the edge of
the electrode, the right picture shows the surface; no signs of significant corrosion were
found.
Oxygen Passivators
Advantages of a Chemical Program
The basic advantage of a phosphate ester program versus a simple
scavenger program or mechanical de-aeration is that we get the benefit of
an inhibitor presence to help mitigate corrosion of other types other than O
2
.
One other advantage is that the upfront costs are considerably less than
setting up a mechanical de-aeration system. The performance can be
measured quite quickly with the use of appropriate monitoring tools. Rates
can be adjusted easily. All you need is a storage tank/secondary
containment, a chemical pump.
Corrosion Control Using Oxygen Stripping
Important Guidelines
Keep the System Clean
Keep the Water Moving
Eliminate Oxygen
Acknowledgments - References
1. Pipeline Treatment School Corrosion Fundamentals
Champion Technologies.
2. Common Problems In Oilfield Water Systems
Champion Technologies.
3. Corrosion Inhibitor for Treatment of Carbon Steel
Pipelines Transporting Oilfield Waters. W. Veneman.
Champion Servo Europe BV. 2002
4. Corrosion Principles, Introduction. J anet Schepers.
Champion Servo BV Champion Technologies.
5. Module 8 Corrosion. Champion University.
Champion Technologies.
Open Forum/ Questions???
CONRAD
Oilsands Water Usage Workshop 2004
Corrosion Control in Pipelines Using Oxygen Stripping
Champion Technologies
February 24, 2004