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CanmetMATERIALS

Standard and Non-Standard Methodologies to Evaluate


Crude Oil Corrosivity Under Pipeline Operating
Conditions

Canadas Natural Resources Now and for the Future


Outline
Introduction
Internal Corrosion Control
Crude Oil Corrosivity under Pipeline
Transportation Conditions
Oil-Water Emulsion
Oil-Wet-Water-Wet Condition
Influence of Oil Phase on Water Phase
Recommendations for Consideration
Introduction
CANMET laboratories spread across Canada
CanmetMATERIALS is the largest research
centre in Canada dedicated to metals and
materials fabrication, processing and
evaluation
CANMET laboratories have studied crude oil
corrosivity under pipeline operating conditions
since 1993
Over the past two decades about 100 crude
oils have been used to understand their
corrosivity under pipeline operating conditions
CanmetMATERIALS research contributed to
the development of a new ASTM International
Standard Guide (ASTM G205), which
describes methodologies for determining the
corrosivity of crude oil under pipeline
operating conditions
Internal Corrosion Control
Modeling
Prediction, mechanism,
mechanistic models, and
guidelines
Mitigation
Cleaning, corrosion inhibitors,
biocides, and internal liners
Monitoring
Intrusive, non-intrusive, and
inline Inspection
Maintenance
Equipment, workforce, data,
and communication
Management
Risk
Most Corrosion Occurs by Electrochemical
Mechanism

Four things are needed Electrolyte


Anode: Sites where metal
Ionic path
is lost and electrons and
ions are produced Anode Cathode
Cathode: Sites where Metallic path
electrons are consumed
Metallic path: Conducts
electrons from anodes to
cathodes
Electrolytic path:
Conducts ions or source
for reactants
Characteristics of Electrolyte

A liquid (sometimes a solid) that conducts


electricity by the flow of ions
The more ions the electrolyte has the higher its
conductivity and the higher the probability it
sustains corrosion
Seawater is conductive sustains corrosion
Pure water is non-conductive does not
sustain corrosion
Crude oil is non-conductive does not sustain
corrosion
Internal Corrosion

Stage 1 Stage 2 Stage 3 Stage 4

Water
Metal

Oil Surface layer Repassivation


Metal
Oil Transmission Pipeline
99.5% Oil and 0.5% Water and Solid

Water droplets
Oil Phase
Prediction of Corrosion in an Oil
Transmission Pipeline

Identification of locations susceptible to corrosion


Water accumulation
Oil phase water phase interactions in those
locations
Locations for Water Accumulation
(Standard Methods)
NACE SP0208 - Internal
Corrosion Direct
Assessment Methodology
for Liquid Petroleum
Pipelines
Lists several models to
predict locations where
water may accumulate
NACE TG 447
To develop a state-of-the-
art report on flow and
corrosion modeling and to
provide guidelines for
selecting appropriate
models
Locations for Water Accumulation
(Non-Standard Method)

Water deposition in heavy (a)


oil transmission pipeline
modelled
Computational fluid (b)
dynamics (CFD)
Near-wall velocity of flow
in heavy oil is significantly (c)
lower than in light oil

(a) Light oil turbulence model


X.Landry, A. Runstedler, S.Papavinasam, and T. Place, (b) Heavy oil turbulence model
Corrosion Journal (2012), Computational Fluid Dynamics (c) Heavy oil laminar model
Study of Solids Deposition in Heavy Oil Transmission
Pipeline Available online
Oil phase water phase interactions

Emulsion
Liquid-liquid physical interaction
Wettability
Liquid-liquid-solid interaction
Corrosiveness of the Aqueous Phase
Liquid-liquid chemical interaction
Influence of oil phase on water
phase corrosivity
Water Droplets Emulsion
Oil Droplets

Low conductivity High conductivity


(Non-corrosive (Corrosive
electrolyte) electrolyte)

Inversion Point

Oil-Phase Water-Phase
Water-in-Oil Emulsion Oil-in-Water Emulsion
Emulsion Inversion Point Determination
Non-Standard Methods
Electrical
Microwave
Radiation Scattering
Spectroscopic
Ultrasonic
Density-based techniques
Viscosity-based techniques
Emulsion Inversion Point Determination
(Standard Method: ASTM G205)

Electrical method
Emulsion Inversion Point
250

Inversion Point
200
Resistance (K-Ohms)

0
1
150
2
3
100
4
5
50

0
0% 10% 20% 30% 40% 50% 60% 70%
Water cut
Wettability Contact Angle Method
(Standard Method: ASTM G205)
Wettability Contact Angle Method
(ASTM G205)

Metal surface
Wettability Spreading Method
(ASTM G205)
Wettability Spreading Method
(ASTM G205)

Pins More than 15 5 to 15 of 20 Less than 5


exhibiting of 20 pins pins of 20 pins
high
conductivity
Wettability Water-wet Mixed-wet Oil-wet
Effect of Crude Oil on the
Corrosiveness of Aqueous Phase

99.5% Oil and 0.5% Water and Solid

What is the influence


of crude oil on this
water phase?

Preventive Inhibitive Neutral Corrosive


Effect of Crude Oil on the
Corrosiveness of Aqueous Phase -
Non-standard methods
Chemical analysis of fluids
Acid number and water content were found
irrelevant to corrosivity
Optical spectroscopy
Iron concentration
pH, viscosity, and density
Could not be correlated with corrosivity
Electrochemical measurement
Unreliable
Microelectrodes
Conducting polymer method
Electrochemical quartz crystal microbalance
No Correlation between physical properties and crude corrosivity
(Non-Standard Methods)
5000 5

Only 4 crudes showed somewhat measurable corrosion rate


4000 .001 mpy 4
Water Content
Acid Number
Water content, ppm

Acid Number, , mg KOH/g


3000 .001 mpy 3

2000 .001 mpy 2

.001 mpy

1000 1

0 0
0 10 20 30 40 50 60 70
Crude Oil Number
Effect of Crude Oil on the
Corrosiveness of Aqueous Phase -
Standard methods
ASTM G170: Guide for evaluating and qualifying oilfield
and refinery corrosion inhibitors in the laboratory
ASTM G184: Practice for evaluating and qualifying oilfield
and refinery corrosion inhibitors using rotating cage
ASTM G185: Practice for evaluating and qualifying oilfield
and refinery corrosion inhibitors using rotating cylinder
electrode
ASTM G202: Test method for using atmospheric pressure
rotating cage
ASTM D665: Test method for rust-preventing
characteristics of inhibited mineral oil in the presence of
water
NACE TM0172: Standard Test Method of determining
corrosive properties of cargoes in petroleum product
pipelines
Hierarchy of ASTM Standards

Standard Guide
Provides general guide (ASTM G170)
Standard Practice
Rotating Cage
Prescribes procedure (ASTM
G184, G185, and G188)
Standard Test Method
Prescribes procedure and expected
results (ASTM G202)
Precision developed based on round
robin tests
Based on 225 data points produced by
10 different laboratories around the
world (Canada, India, USA, and
Venezuela)
Bench-mark aqueous phase corrosion
rate established by round robin tests:
23 + 2 mpy or 0.58 + 0.05 mm/y
Corrosivity of Aqueous Phase in the
Presence of Different Crude oils
30
Corrosive Crude Oil

25
23 + 2 mpy Neutral Crude Oil
Corrosion Rate (mpy)

20

15

Inhibitive Crude Oil


10

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Crude Oil Identification Number
ASTM G205: Standard Guide for Determining
Corrosivity of Crude Oils
W/O No Corrosion

Emulsion
O/W

Oil-Wet No Corrosion

Wettability Mixed-Wet

Water-Wet

Less then 0.01 mpy (Preventive


No Corrosion
Hydrocarbon)

Lower then Absence of Hydrocarbons


(Inhibitive Hydrocarbon) Reduced Corrosion
Corrosivity of Brine in
the Presence of
Hydrocarbon
No Change (Neutral Hydrocarbon) Aqueous Corrosion

Higher then Absence of Hydrocarbons


Accelerated Corrosion
(Corrosive Hydrocarbon)
Summary

No crude oil can sustain corrosion under pipeline


operating conditions
Absence of conductive electrolyte phase
Conductive water phase is required for corrosion to
occur
In the presence of water and oil phases three
properties should be evaluated
Emulsion
Wettability
Change in corrosivity of Aqueous phase by oil
phase
Recommendations

Crude oils should be tested as per ASTM G205


at the point of entry into the pipeline
Unless test shows that it is neutral or
corrosive, no new action is required with
respect to Dil-bit

Preventive Inhibitive Neutral Corrosive


crude oil crude oil crude oil crude oil
Contributions from
Jennifer Collier
Heather Dettman
Alex Doiron
Wally Friesen
Jean-Philippe Gravel
Xavier Landry
Sankara Papavinasam
Parviz Rahimi
Allan Runstedtler
Winston Revie
Bill Santos
Chao Shi