Corrosion Inhibition

Issues associated with selection and deployment of corrosion inhibitors

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Organic Film Forming Inhibitor Mechanism

Process Stream
Oil molecule Hydrocarbon chain R Hydrocarbon Inhibitor molecule dispersed in process stream

H C H N

H N H C H HC H H C H HC H HC H H C H H C H H C H N N N N N N N N

Chemisorption & physical adsorption by polar amine group

Metal

Adsorption
1 0.9 coverage

coverage, corrosion rate

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 10 20 30 40 50 60 corrosion rate

Concentration

Oil Field Corrosion Inhibitors

Primary Amine Amide Imidazoline
R CH2

CH 2
O

NH 2

R1

CH2 C
N N

NH

R2

CH2 CH2 NH2

CH3
N

Quaternary Ammonium Ion Polyethoxylated Amines

O CH2
R N

CH2

CH3

CH2

OH

O CH2

CH2

OH

Typical Composition
Inhibitor Package
2/3 Solvents or additives 1/3 Active Ingredients

Inhibitor Selection Strategies

Decision Process leading to Corrosion Inhibitor Selection

Inhibitor Selection Strategies

Planning define the objectives of the inhibition programme. Corrosivity and Hydrodynamic Assessments use of field chemical data, corrosion prediction models, hydrodynamic modelling, guidelines and field experience. Inhibition Risks need to address issues concerned with high CO2 / H2S concentrations, high temperatures and unusual brines. Inhibitor Selection Process aim is to choose the best inhibitor, in terms of performance, economics, business needs, etc. Inhibitor System Design this includes design of the injection system, including secondary containment, identification of the monitoring needs and selection of the monitoring method(s). Operation and Maintenance Issues identification of personnel with responsibility for day-to-day operation of the inhibition system, training of personnel.

Corrosivity Assessments
Typical desktop studies aim to clarify major corrosion issues:

Fluid Chemistries Hydrodynamic Considerations Predictive Models Inhibition Risks

Operating Information needed for Facility Design Decisions

Parameter Total pressure Temperature maximum, range Flow rates: Oil Gas Water Sand production: Gas composition CO2, H2S, O2 Water composition: Full cation and anion Analysis PH Volatile organic acids Hydrocarbon phase oil or condensate viscosity Equipment to be protected Age and condition Corrosion allowance Estimated corrosion rate Environmental concerns Accessibility to area Pigging capabilities Business risk Bar C m /day 3 m /day 3 m /day Kg/day mole % mg/L Type and concentration ASTM boiling point CP or API Downhole, surface, pipelines, onshore, offshore New-old, clean-dirty Proposed or remaining (mm) mm/yr. Regulations, HSE policy Possibility of repairs and monitoring Only for pipelines and some gathering lines / flowlines Consequences of failure to business strategy
3

Common Units or Comments

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Hydrodynamic Considerations

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Typical Inhibitor Selection Process

Start
pressure, temperature flow other factors

determine test requirements

review corrosivity

past experience

identify candidates

suppliers recommended

select candidates for testing

compatibility

Data base

screening tests

Suppliers

final tests

Lab data

commercial, business issues

final selection

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Vendor Recommendations
Expected uninhibited and inhibited corrosion rate in the proposed application Recommended concentration and application method Laboratory test data Practical method for quantitative determination of the inhibitor in field fluids if required Physical and chemical properties of the product(s) Information on environmental acceptability, toxicity and biodegradability Oil/water partitioning data if appropriate Compatibility with non-metallic components such as elastomers

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Physical Property Tests

Main physical / chemical properties:
Solubility of corrosion inhibitor in the carrier media (oil, water, glycol) Partitioning / phase distribution between aqueous and hydrocarbon phases Emulsion tendency Foaming tendency

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Oil / Water Partitioning

60

Inhibitor Conc (ppm)

50 40 30 20 10 0 0 10 20 30 40 50

Conc in water Conc in oil

60

70

80

90

100

water cut %

Theoretical effect of water cut on inhibitor partitioning for a preferentially water soluble inhibitor (partitioning coefficient = 2) added at 28ppm on total fluids.

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Partitioning Tests
Equilibrium
Allow HC and aqueous phase to equilibrate test in aqueous phase

Dynamic
Study rate of inhibitor transfer from HC to aqueous phase

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Effects of Parameters on Corrosivity and Inhibitor Efficiency

Parameter
pp CO2 Temperature Flow pH Oxygen H2S Calcium, Mg etc Organic Acids Brine components Metallurgy Pre-corrosion Hydrocarbon

Corrosivity
Large Large Medium Medium Small Large Small Possibly Large Small Small ? Small / Medium Medium

Inhibition
Medium Large Small - Large Large Large Large Possibly Large Small ? Possibly Large Possibly Large Possibly Large Possibly Large

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Test Environments
As close to real as possible
Brine composition pp gases Temperature Flow rate Metallurgy

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Bubble Tests

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Standard Rotating Cylinder Cell

Shaft Gas in Gas out

Thermocouple pocket Glass vessel

Luggin

Counter electrode Specimen

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Jet Impingement
Luggin capillary QVF Flange Pt Electrode QVF Flange

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Inhibitor Persistency

What happens if inhibitor supply is interrupted? How quickly does rate return to uninhibited rate?

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Loss of Performance after Depletion

Quaternary Amine at 20 ppm
1.000

Corrosion rate (mm/y)

Inhibitor Addition

0.100

Depletion

0.010 0 5 10 15 20 25 30 35 40 45 50 55 60 65

Time (h)

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Example of Good Persistency

Carboxylate - Amine at 20 ppm
1.0000

Corrosion rate (mm/y)

Inhibitor Addition
0.1000

Depletion
0.0100

0.0010 0 10 20 30 40 50 60 70 80 90

Time (h)

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Preferential Weld Corrosion (PWC)

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Cause of Preferential Weld Corrosion

Complex issue influenced by many factors
Differences in weld / parent material composition. Weld procedure Microstructure Corrosion product film formation Flow Environment conductivity Inhibitors

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Effect of Inhibitor on PWC

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Weldment Sectioning
3mm 10mm 10mm P1 H1 W H2 P2

Flange or pipe

Flange Pipe or pipe HAZ Weld HAZ metal

Pipe

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Consequences of Inadequate Dosing

P1 H1
1.9 Corrosion rate (mm/year)

W H2 P2

1.4

0.9

0.4

-0.1

10 Inhibitor Concentration

25

50

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Inhibitor Deployment re PWC

Early deployment of CI is essential where there is a risk of PWC
Overdosing in the early weeks of operation is recommended

For systems already suffering PWC:

Increased dose rates recommended Inhibitor availability extremely important

Inhibitor optimisation should be carried out using a weldment probe

ER probe with weld metal element Segmented probe with appropriate measurement technique

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Compatibility
Compatibility of the corrosion inhibitor with:
The production fluids Other chemicals Downstream processing of produced fluids (e.g. oil/water separation) All materials in the injection and production systems (such as elastomers, seals, liners) The environment (environmental "friendliness" on disposal/export)

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Key Points Testing

Lab tests tend to use simulated brine but it is important to use real hydrocarbon samples. Use representative grade of steel Use two corrosion rate methods, typically linear polarisation or impedance Use CO2 / N2 or CO2 / H2S / N2 mixtures to simulate the gas phase Use wall shear stress to simulate flow conditions

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Key Points Selection

Develop a clearly defined inhibitor selection strategy for use in various production environments. Test protocols for screening should address the required key performance parameters. Check on compatibility with components and other chemicals / fluids. Optimise dose rates in the field

Deployment of Inhibitors

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Typical Field Concentrations of Corrosion Inhibitor

Location Oil Well Gas production Corrosion inhibitor dose based on total Fluids (ppm) 20 50 10- 20 l/m3 of gas (100 based on total water) 20 50 (100/300 in high vel water) 15 30 2 pint/MMSCF 2000 1000 >300

Infield oil line Short oil transport line Long oil transport line Long gas transport line Extreme Cases Hot, deep gas well 50% H2S gas line V high velocity, high water oil line

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Corrosion Risk Category (BP)

Risk Category Maximum Required Availability Max. Expected Uninihb. Corr. Rate (mm/yr) 0.4 Comment Proposed Category Name

0%

Benign fluids, corrosion inhibitor use not anticipated. Predicted metal loss may be accommodated by corrosion allowance. Corrosion inhibitor probably required but with expected corrosion rates there will be time to review the need for inhibition based on inspection data. Corrosion inhibition required for majority of field life but inhibitor facilities need not be available from day one. High reliance on inhibition for operational lifetime. Inhibitor facilities must be available from day one to ensure success. Carbon steel and inhibition is unlikely to provide integrity for full field life. Select corrosion resistant materials or plan for repairs and replacements.

Benign

50%

0.7

Low

90%

Medium

95%

High

>95%

>6

Unacceptable

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Summary of Monitoring & Inspection Requirements for Pipelines

Overall System Requirements
Does not rely on corrosion inhibition.

Corrosion Inhibition Risk Category 1

Inhibitor Injection System

No requirement

First Inspection Schedule

Inspection determined by previous operation of similar systems. As category 1

Monitoring of Subsea lines

Process monitoring of fluids.

Category 2

Inhibition not used in early life but is available when conditions change, i.e. increased water cuts Inhibition not available due to logistics problems but must be operated as soon as possible. Corrosion control working on day one. Inhibitor and dose rate pre-selected Assumes technical, SHE & financial factors answered satisfactorily Requirements as category 4

Commissioning without shutdown

Standard inspection techniques at accessible points. As category 1 plus weight loss coupons, ER / LPR probes and occasional intelligent pig runs. As category 2 plus FSM or UT mats system. Continual logging for all monitoring devices. As category 3 plus increased inspection frequency.

Category 3

Commissioned as soon as practical and incorporate level device and flow monitor into injection system. As category 3

Early inspection as determined by anticipated corrosion rates. As category 3

Category 4

Category 5

As category 3

As category 3

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Inhibitor Efficiency and Availability

Target acceptable corrosion rate to give required system life Inhibitor availability must also be taken into account

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Availability Approach
Assume a certain corrosion rate when inhibitor added (e.g. 0.1 or 0.05 mm/y) Assume uninhibited rate when inhibitor not added Emphasises that inhibitor downtime is critical

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Deployment Considerations

Injection System Requirements Storage and Injection System Monitoring and Data Acquisition Analysis and Information System Management of Inhibition Programmes

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Injection Location
B
C
W ELLHEA D F L O W L IN E S

E1

SLU G C ATC H ER

M A N IF O L D

CO2

D
T R U N K L IN E / P IP E L IN E

E2

H 2S

A
SAN D

SEPARATOR T R U N K L IN E / P IP E L IN E TANKAGE
O IL GAS H 2O

w a te r d isp o sa l

R E S E R V O IR

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Continuous Injection
Chemical reservoir Injection pump

Pipeline

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Main Disadvantages of Continuous Injection Downhole

Slugging of inhibitor Plugging of the valves Large inhibitor inventory Long residence time Risk of killing the well

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Squeeze Treatment
Casing

Displacing Fluid Tubing

Inhibitor mixture Packer Perforations Inhibitor

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Tubing Displacement Treating Method

Displacing fluid or nitrogen Inhibitor mixture

Oil

Perforations

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Storage and Injection System

Injection systems typically comprise: Storage tank Mixing tank, if product is to be diluted Injection pumps and connecting lines Injection ports, quills, valves Control equipment valves, gauges, instrumentation Secondary containment to capture leaks and spills

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Storage Tank
Chemical reservoir Injection pump

Pipeline

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Corrosion Inhibitor Pumping Problems

Corrosion inhibitor fluid problems: inhibitor viscosity compatibility of inhibitor with pump materials line blockages inhibitor storage tank empty abrasive particles in inhibitor

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Corrosion Inhibitor Pumping Problems

Pump and hardware problems : wrong dose rate pump wrongly sized air locks poor delivery system design/installation dosing downhole

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Quality Control of Corrosion Inhibitor Supplies

Comparison of NMR Spectra for Two Samples of a Corrosion Inhibitor

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Injection Quill in a Pipeline

ACCESS FITTING PUMP QUILL PIPE

FLOW

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Monitoring and Data Acquisition

Data collected to aid system performance evaluation: Inhibitor injection data Corrosion monitoring data Inhibitor residuals Condition monitoring Production rates and conditions System upsets Financial data Maintenance data Water chemistry Inspection data

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Corrosion Inhibitor Dose Record

Failure to meet target of injection rate limited the pipeline life

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Typical Monitored Process Parameters

Parameter
Flow rates (oil/gas/water) Water cut

Effect
+ or -

Action
Alter corrosion inhibitor delivery rate to maintain concentration Could increase or decrease inhibitor delivery depending on the oil/water partitioning properties Increase [CI] but scope to reduce [CI] if protective carbonate films occur Scope to reduce [CI] or increase [CI], may need to reselect Reselect CI and/or increase [CI], reduce velocity, install downhole sand screen

+ or -

Temperature

pH

+ or -

Sand

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Inhibition System - Data Storage, Analysis and Information System

Inhibited corrosion rates on-line data is compared with
operational data on fluid chemistry/bio-chemistry, inhibitor residuals and inspection data (check out initial predictions of corrosion rates and changes with time)

Changes in wall thickness obtained through inspection

records

Inhibitor consumption obtained through injection data Impact on operations obtained through feedback from
operations and downstream experience

Mechanical/maintenance performance obtained through

maintenance feedback of records/costs

On-line availability obtained through on-line monitoring and

maintenance inspection records

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Water chemistry
Trending of chemical analysis data can often: Identify potential problems Compliment on-line corrosion monitoring data Analyses include: pH Iron counts Compositions SRB counts Inhibitor residuals

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Monitoring methods used in corrosion inhibition

Iron counts (regular chemical analysis to provide trends) Coupons (weight loss & detection of pitting/scales/bio-films) Insert probes
electrical resistance/modern versions electrochemical - linear polarisation resistance / electrochemical impedance / electrochemical noise / galvanic coupling)

Hydrogen patches/probes (electrochemical, beta foils) FSM (field signature method) Ultrasonic strips (UT Mats) Erosion/sand probes Radiochemical

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Data Storage, Analysis and Information System

Inhibited corrosion rates Changes in wall thickness Inhibitor consumption Impact on operations Mechanical/maintenance performance On-line availability Human factors

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Effective Management for Corrosion Inhibition Programmes

Stated aims to include:
Agreed strategies/policies Procedures for activities from design to abandonment Assessments of risks & management of mitigation procedures Agreement of responsibilities and identification of personnel authorised to carryout actions Development of appropriate organisational structures, teams and reporting routes Effective deployment of resources, including budgets, inhouse/alliance personnel and contractors Procedures for the management of change - change in process conditions and personnel Use of key performance indicators for all activities Defined and regular updates based on reviews and audits and Personnel to be nominated as procedure owners

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Independent Audit Scheme that Ensures Improvement

No leaks or emissions 20% annual reductions Reduce/elimivate emissions

Health & Safety, Integrity & Corrosion Issues

Getting it Right

Clear Policies & Objectives Reports used to achieve improvements

Assess skills and competence Define roles & responsibilities Ensure co-operation & communication

Organisational Structure & Responsibilities

Identify hazards & assess risks Agree targets, processes & systems Set standards for measuring performance

Planning, Procedures & Implementation

Reviews used to provide correction

Proactive measurement using regular checks to show controls are working Reactive measurement identifies why performance was substandard

Measure Performance
Yes No

Review activities & trends Check for compliance Learn from experience & make changes

Review of Data & Performance

Meeting the control criteria? Independent Audit

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Inhibitor Review Meetings

Information to be reviewed at Corrosion Team meetings:
oil, water, gas production rates; inhibitor consumption and expenses; inhibitor performance results; inspection results, if available; operational upsets, related to chemical usage; safety and environmental incidents, concerns and results, related to chemical usage; maintenance and reliability issues; ideas for improvements: how to reduce costs, improve HSE performance.