CORROSION INHIBITION

Definition

Inhibition is corrosion control by the addition of small quantities of chemical to the

environment

Inhibitor Efficiency
CRuninhib - CRinhib
E = x 100%
CRuninhib

E efficiency (%)

CRuninhib uninhibited corrosion rate

CRinhib inhibited corrosion rate

- a useful concept for the laboratory testing of inhibitors; but inhibitor availability
(see later) is a more relevant concept for corrosion management.

Approaches to Inhibition

inhibition

negative positive

cathodic anodic mixed

film formers film repairers

NEGATIVE INHIBITION

Remove corrosive agent by chemical treatment.

Examples in hydrocarbon production:
o neutralizing of acids (pH control)
pH control in tri-ethylene glycol (TEG) regeneration systems.
TEG contactors used to dry gas
TEG regenerated by thermally distilling off the water
(some) decomposition of TEG low mol wt. organic acids
need to monitor and adjust pH in glycol circuit.
case history (UAE):
failure to manage pH
failure of carbon steel heat exchanger
replaced with a Ti unit.

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CORROSION INHIBITION

o control of carbonic acid corrosion:

Elf (1970s)
NaOH, Na2CO3, NaHCO3, NaMBT (sodium
mercaptobenzothiazole), MDEA (methyl diethanol amine)
works by promoting FeCO3 scale deposition
need to shift pH by +1.5 units (H+ activity reduced ~ 30-fold)
only works in presence of condensed water (not formation water)
best if injected with hydrate suppressant (MEG or MeOH)
no experience in sour systems
case history: Statoil (Troll)
22% NaOH added with MEG
pH 6 7.4
corrosion rate 0.1 mm/year

o oxygen scavenging:

2 (NH4)2SO3 + O2 (NH4)2SO4

Application: treatment of seawater for reservoir injection

N2 H4 + O2 N2 + 2H2O (at higher temperatures)

Application: treatment of boiler feed water.

o H2S scavenging (gas):

removal of H2S for product quality and/or corrosion reasons:

R R

N N

H2C CH2 H2S H2C CH2

N N N S

CH2 R CH2 R

Triazine Thiadiazine
(liquid) (liquid)

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CORROSION INHIBITION

POSITIVE INHIBITION

Anodic Inhibitors

not common in hydrocarbon production

also referred to as passivating inhibitors
mainly employed in near-neutral/alkaline environments
only used in small, closed or recirculating systems
very high efficiencies (>99%)
concentrations: relatively high (0.01 to 1%)
mechanisms:
o film formers (e.g. acid phosphate)

3Fe + 2H3PO4 Fe3(PO4)2 + 6H+ + 6e-

o film repairers (e.g. nitrite)

2Fe + NaNO2 + 2H2O -Fe2O3 + NaOH + NH3

unsafe: can cause severe localized corrosion (pitting) if under-dosed

performance sensitive to:
o aggressive ion concentration (Cl-)
o pH
o temperature

Cathodic Inhibitors

not common in hydrocarbon production

moderate efficiencies (~70%)
normally function by precipitating metal hydroxides at cathodic sites:

Zn2+ + 2OH- Zn(OH)2

(inhibitor) (cathodically generated) (insoluble)

not suitable for acid solutions (precipitate dissolves)

effective for a wide range of metals
not greatly affected by aggressive ions
safe: under-dosing does not result in localized corrosion

Neither cathodic nor anodic inhibitors are much used in hydrocarbon production

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CORROSION INHIBITION

Mixed Inhibitors

Schematic representation

polar group non-polar hydrocarbon chain

hydrophilic hydrophobic

adsorbs on metal oleophilic

Operation:

inhibitor film

water (displaced)
metal surface

Characteristics

widely used in hydrocarbon production (neutral and acidic environments)

efficiencies >90% at dose rates: 2-100 ppm
very wide range of proprietary products (usually mixtures of compounds)
formulations are tailored to individual fluid chemistries and circumstances
optimum performance on clean metal surfaces (pre-corroded surfaces are
more difficult to inhibit)
surface active: may cause process upsets (foaming, emulsion formation), so
blends often also include components to counter-act side effects.

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 CORROSION INHIBITION

Some Inhibitors for Oil and Gas Systems

Primary amine

R CH2 NH2

Amide

R1 CH2 C NH R2

Polyethoxylated amines

(O CH2 CH2 )n OH
R N
(O CH2 CH2 )n OH

Quaternary ammonium ion

CH3
+
N CH2 R

CH3

Imidazoline

Phosphate Ester
N
O N
R CH2 CH2 CH2 NH2
O P OH
R1
O

R2

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CORROSION INHIBITION

Inhibitor Blends

Active components (N, P or S Compound) 10 25%

Co-active compound <10%
Surfactant <5%
Carrier/Solvent balance

Note: when an inhibitor supplier refers to a dose rate (e.g. 50 ppm) they are referring
to the dosing of the product blend. (The active component may be as little as
5 ppm).

Combining Inhibitors

additive: inhibitors A and B do not interact

synergistic: small additions of A greatly improve the performance of B
antagonistic: A and B counteract each others inhibitive effect.

synergistic
Inhibitor efficiency

e
additiv

antagonistic

0% inhibitor A 100%
100% inhibitor B 0%

Never combine inhibitors without conducting tests first.

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CORROSION INHIBITION

APPLICATIONS: HYDROCARBON PRODUCTION AND PROCESSING

Downhole Piping/Process Pipelines

Batch gravity placement slug between pigs
pumped
displacement
coiled tubing

Semi- squeeze
Continuous annulus
displacement

Continuous capillary tubing wellhead export fluid

Injection via gas lift separators
off-gas
compression
gas lift

APPLICATIONS: WATER INJECTION SYSTEMS CONTINUOUS TREATMENT

Seawater Produced Water

O2 scavenger yes (sometimes)
biocide yes (sometimes)
filming inhibitor (only occasionally) carried through +
make-up

APPLICATIONS: HYDRO-TESTING & WET STORAGE (SEAWATER)

corrosion products
yes yes no
acceptable ?
exposure duration < 1 month 1 -24 months <24 months
biocide no yes yes
oxygen scavenger no no no

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CORROSION INHIBITION

INHIBITOR SELECTION

Inhibitor suppliers do not disclose formulation details. Even if they did, the
information would be of little value because there is insufficient knowledge to
translate known inhibitor chemistries into anticorrosion performance predictions in
complex hydrocarbon systems.

Oil and gas company corrosion engineers are therefore concerned with managing
the activities of their chemical supply and service companies.

Stages in inhibitor selection

select inhibitor supply/service company

draw up a short list of candidate inhibitors
conduct laboratory evaluations
conduct (limited) field tests
carry out field trials and final evaluation

Inhibitor Supplier

Selection needs to take account of numerous factors:

substantial well-funded and resourced business

technical support available to the project
o laboratory facilities
o technical staff
track record/experience
QA and HSE systems

Selection of Candidate Inhibitors

Examine suppliers responses to a performance specification detailing:

compositions of fluids to be inhibited
process flow conditions
required inhibitor performance (corrosion allowance/design life)
other treating chemicals
facilities available for managing the inhibition programme:
o handling and storage
o pumping, injection, diluents
o disposal

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CORROSION INHIBITION

Analyse available inhibitor data:

corrosion control performance (CO2, H2S)
solubility/miscibility characteristics
possible deleterious interactions:
o emulsion forming
o foaming
o gunking
film persistency data
treatment costs
o dose rate x unit volume price

Laboratory Screening Tests

Carried out in a simulated process environment

bubble test
wheel test
recirculating loop
high fluid velocity test (rotating cylinder specimen)
high pressure/high temperature (autoclave)
compatibility with other process chemicals
compatibility with other metals (if present)
compatibility with elastomer seals (if present)

Field Tests

(optional stage)
carried out on water stream from water separator
limited scope and duration
electrochemical measurements
o rapid response
o comparison of short-listed inhibitors.

Field Trials and Final Evaluation

may require system to be cleaned prior to trials

typical duration 3 6 months
scope of trial
o single well/flowline
o entire facility
inhibitor evaluation
o on-line corrosion monitoring
o chemical testing
iron counts
inhibitor carry-through
o NDT (e.g. calliper survey on tubulars)

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CORROSION INHIBITION

Note: The selection of an inhibitor (and dose rate) is not a once-and-for-all process.

process conditions are likely to change through field life

o temperatures, pressures, flow rates
o water cuts
o possibility of souring
o introduction of enhanced recovery techniques
o new reservoirs tied-in

INHIBITOR AVAILABILITY

The inhibitor efficiency (defined above) provides a handy means of comparing

laboratory test results on inhibitors. It is not, however, a particularly useful method
for making corrosion engineering decisions. However, it is widely recognized that, if
the right inhibitor is delivered at the right dose rate, then the corrosion rate is very
low. To a first approximation, this holds irrespective of the uninhibited corrosion
rate.

It is more useful to consider:

inhibitor availability = % of production period for which the inhibitor is injected

at (or above) the recommended dosage.

It reflects the operators performance in:

maintaining inhibitor injection equipment (pumps, nozzles etc.)

managing the procurement, transport, storage and handling of inhibitor
chemicals.

As a matter of experience, a well managed petroleum production facility should be

able to achiever inhibitor availabilities of >90% over the operating period.

Use of the Inhibitor Availability Model

The model is used in predicting the average corrosion rate in an inhibited system:

CRa = CRi x inhibitor availability + CRu x (1 inhibitor availability)

Where: CRa, CR,i, & CRu are the average, inhibited and uninhibited
corrosion rates.

Example:

A materials selection decision has to be made between using a corrosion resistant

alloy or carbon steel (with a corrosion allowance) plus inhibition for a crude gas
pipeline. To make this decision it is required to determine whether the carbon steel
option is viable. The following hypothetical example illustrates the process.

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CORROSION INHIBITION

Parameter Value Comment

Design life 20 years
Corrosion allowance 6 mm
CRi 0.1 mm/y This is a conservative value often
used in such exercises. In reality,
well inhibited systems should
corrode at <0.5 mm/y
CRu 0.75mm/y This value would be calculated
using an appropriate model
Inhibitor availability 80% Conservative assumption

The aggregate life-time corrosion (CRa x Design Life) is calculated and compared to
the corrosion allowance.

CRa = (0.1 x 80%) + (0.75 x 20%) = 0.23 mm/y

Aggregate life-time corrosion = 4.6 mm (i.e. within the corrosion allowance)

INHIBITOR PERSISTENCY

This is a measure of the length of time the inhibitor remains effective. It is the time
taken for an inhibitor film to desorb from the metal surface under a given set of flow
conditions. It is a consideration when timing batch treatments.

INHIBITOR RISK CATEGORIES

EFC Publication No. 39 The Use of Corrosion Inhibitors in Oil and Gas Production
(ISBN 1-904350-33-X) 2004

Shell Approach

CR (mm/y) T (oC) Flow (m/s) Inhibitor Inhibitor

Dose (ppm) Quality

<10 <60 1 to 5 10 - 50 standard

10 - 50 60-120 5 - 15 50-200 state-of-the-

art
>50 <150 <20 >200 leading edge

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CORROSION INHIBITION

BP Approach

Category CR (mm/y) Max Comment

Required
Availability
1 0.4 0% Benign

2 0.7 50% Low

3 3 90% Medium

4 6 95% High

5 >6 >95% Unacceptable

Why Do Some Corrosion Inhibition Systems Fail to Deliver the Required

Availability?

Target
o Over-ambition inhibitor availability requirements set at the design stage (in
order to permit CAPEX savings by selection carbon steel instead of
corrosion resistant alloys.
Design, Specification, Installation and Commissioning.
o Tendency for the chemical injection equipment is rarely a high priority
during the design stage of a project
o Equipment invariable selected on the basis of price
o Installation and commissioning can be over-looked in the rush to bring
production on-stream. There is more immediate incentive to bring a
new well on-stream than to complete the installation and
commissioning of the inhibitor injection skid.
Maintenance.
o Corrosion inhibition is not usually classified as safety- or production-
critical. Where maintenance is trimmed for budgetary reasons the
chemical injection system (viewed as non-critical) tends to get over
looked.
o There are particular problems when injection equipment is in remote or
un-manned locations.
o Often on a fixed-when-broke maintenance regime: but how long
before we notice that it is broke?
Management and Training
o Lack of ownership of the inhibitor injection system.
o Lack of awareness of its importance.

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How Can Corrosion Inhibition Systems Achieve High Availability?

Improved design
o Ensure that design team is aware of the detailed requirements for
injecting inhibitors (implies that the inhibitor is defined before project
start-up).
quills/nozzles appropriate to the fluids handled
high reliability of pumps (pumps need to be sized so that they
are controllable at the required pumping rates)
back-up pumps with automatic/rapid switch-over
security of power supplies (for electrical pumps, consider
hooking-up via the emergency supply panel)
tanks sized so as to hold sufficient chemical in case of suppliers
logistical problems
o Maintenance.
frequent/automatic monitoring
spares in stock
o Management
assign a senior manager as Process Owner
rolls and responsibilities defined,
make the corrosion inhibition system safety- or production-
critical
delivery performance measured and reviewed
effective (performance related) chemical supply contracts
o Education
The importance of corrosion and its control is not always fully
appreciated by operations staff. (Case History: a facility failed to
inject any inhibitor one month, so attempted to remedy the
problem by delivering double the dose the following month!)

Environmental Issues

Inhibitors added to a crude stream will eventually find their way into the
environment (for example with produced water discharged offshore).
Previously inhibitor suppliers issued product data. Since 2004, they have
been required to submit component data.
For permissible discharge to the environment each component of the inhibitor
blend must be demonstrated to be:
o low toxicity (EC50 >10 ppm)
o highly biodegradable (.60% in 28 days)
o low bioaccumulation potential (log Po/w <3 or MW >600)
Development of green inhibitors is a major challenge for the inhibitor
manufacturers
Management of inhibitor change over to environmentally acceptable products
is a significant issue for operators.

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