FILMING CORROSION INHIBITOR

FOR OIL AND GAS FIELD REV.01

BONY BUDIMAN
NOVEMBER 2021

https://www.linkedin.com/in/bony-budiman-39886031/
COMMON QUESTIONS

• What is corrosion especially in the oil and gas field ?

• How Corrosion Inhibitor works to inhibit corrosion rate ?
• How to select the suitable corrosion inhibitor ?
• How to apply the corrosion inhibitor in the field ?
• How to monitor the performance of corrosion inhibitor ?
• Lesson learnt from field cases !
OUTLINE

• OBJECTIVE
• INTRODUCTION
• INTERNAL CORROSION MITIGATION
• FILM FORMING CORROSION INHIBITOR
• SELECTION
• FIELD APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
OBJECTIVE, SCOPE AND DISCLAIMER

• The objective is to share the use of FILMING CORROSION

INHIBITOR to control corrosion rate in the oil and gas field
• Corrosion in this topic limited to internal corrosion in carbon
steel (CS) caused by chemical corrosion agents such as CO2,
H2S, O2, and bacteria. I exclude corrosion caused by
environmental (external corrosion).
OUTLINE

• OBJECTIVE
• INTRODUCTION
• INTERNAL CORROSION MITIGATION
• FILM FORMING CORROSION INHIBITOR
• SELECTION
• FIELD APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
CYCLE OF IRON
+ C, Ni, Mn, Cr, V etc

Fe3C.”X”
FexOy

+ H2O, Acid, Bacteria, Cl-, etc

 CORROSION : DEFINITION

• In a very simple words, corrosion is a

degradation of material (mostly refer to
carbon steel)
• Corrosion product known as rust
• Corrosion causes CS to lose its main
function
• Corrosion is natural process, cannot be
stopped but can be inhibited.

Picture courtesy : https://www.pipingengineer.org/pipeline-internal-corrosion-protection-and-monitoring/

 CORROSION IN OIL AND GAS FIELD

• Internal corrosion occurred in any location of

carbon steel as long as water and corrosive
agent exist.
• Corrosion in oil and gas field may start at
production tubing then continue at wellhead,
flowline, topside facilities, discharge pipe and gas-
crude oil export pipeline.

Picture courtesy : https://www.materialsperformance.com/articles/chemical-treatment/2019/04/preventing-internal-corrosion-in-oil-and-gas-field-pipelines

IMPACT OF CORROSION IN OIL AND GAS FIELD

• Loss of production
• Economic : maintenance and replacement
• Environment
• Fatality
 TESORO FATALITY

• On April 2, 2010, Tesoro ,a petroleum refinery experienced a catastrophic

rupture of a heat exchanger
• Two women and five men lost their lives as a result of the accident
• Technically the accident caused by corrosion process called as High-
Temperature Hydrogen Attack (HTHA).
• HTHA occurs when atomic hydrogen diffuses into the steel walls of
process equipment. The hydrogen reacts with carbon in the steel,
producing methane gas. This reaction removes carbon from the steel, a
process commonly referred to as “decarburization. This corrosion type
typically occur at temperature above 400°C

Picture courtesy : http://www.csb.gov/assets/1/7/tesoro_anacortes_2014-may-01.pdf

 GENERAL MECHANISM

• In carbon steel, corrosion occur when the iron in the

steel pulled out from solid form as Fe(s) to be ionic iron,
Fe2+(aq)
• Chemically, corrosion is a reduction-oxidation reaction.
Iron oxidized because loss electrons
• Corrosion will start when there are 4 elements
• Anode
• Cathode
• Electrolyte
• Metallic path that allows electron flow

Picture courtesy : https://chem.libretexts.org/20%3A_Electrochemistry/20.8%3A_CorrosionBookshelves/General_Chemistry/Map%3A_Chemistry_-_The_Central_Science_(Brown_et_al.)/

 INTERNAL CORROSION

• In the oil and gas field, corrosion may be caused

by some ions and compounds such as CO2, H2S,
O2 and chloride.
• High pressure and temperature will accelerated
the corrosion rate
• CO2 exist in most field. H2S may exist as bacteria
activity. Oxygen not expect exist from downhole
but may ingress at topside facilities leaking.

Courtesy picture : https://www.researchgate.net/figure/Comparison-of-corrosion-rates-of-steel-in-the-presence-of-H-2-S-CO-2-and-O-2-adapted_fig4_328198474

OUTLINE

• OBJECTIVE
• INTRODUCTION
• INTERNAL CORROSION MITIGATION
• FILM FORMING CORROSION INHIBITOR
• SELECTION
• FIELD APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
 INTERNAL CORROSION
MITIGATION

Mechanical Chemical

Material Regular
Selection Cleaning
 CHEMICAL TREATMENT STRATEGY

• There are two effective strategy in chemical

treatment to inhibit corrosion rate : “Kill the
Enemy” and or “Build a Fortress”
• Kill the enemy means remove the corrosive
agents such us dissolved oxygen, CO2, H2S and
bacteria
• Build a shield means create a defense
environment such as form a film layer or
increase the pH

Courtesy Picture :https://www.economist.com/special-report/2018/01/25/the-future-of-war and https://greatb2bmarketing.com/competitor/competitive-fortress-for-your-b2b-company/

 CHEMICAL TREATMENT STRATEGY

KILL THE ENEMY BUILD A SHIELD

O2 H2S H2O CO2

Scavenger Scavenger Biocide Dehydration Absorber

Passivating pH Adjuster Filming

Cathodic (FFCI)
(anodic)
OUTLINE

• OBJECTIVE
• INTRODUCTION
• INTERNAL CORROSION MITIGATION
• FILM FORMING CORROSION INHIBITOR
• SELECTION
• FIELD APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
 FILM-FORMING CORROSION INHIBITORS (FFCI)

• FFCI is particularly useful for the

prevention of chloride, CO2, and H2S
corrosion
FFCI • They can be deployed in continuous
injection or batch treatment either
downhole or at the wellhead
• Typical dosages of active FFCI
components are often in the range 10–
100 ppm

and Courtesy Picture : https://www.oxiteno.us/how-inhibit-corrosion-in-oil-gas-industry-equipment/

MECHANISM OF FILMING CI*

Simple Mechanism of Filming CI :

1) CI adsorbs parallel or tilted onto the steel surface
2) The hydrophobic tail groups begin to protrude into the
aqueous phase
3) A film coverage is achieved and the tail groups are parallel
to each other and perpendicular to the metal surface
4) The film layer will reduce corrosion rate the inner steel
metal caused by corrosion agent (CO2, O2 and H2S)

* and Courtesy Picture : http://blog.daum.net/ourhistory2000/17358929

TYPES OF FFCIs

The most common categories of surfactant FFCIs are

• Phospate ester
• Sulphur compound
• Various nitrogenous compounds
• Amidoamines and imidazolines
• Amine salts of (poly)carboxylic acids
• Quaternary ammonium salts and betaines (zwitterionics)
• Polyhydroxy and ethoxylated amines/amidoamines
• Amides
• Other heterocyclics
 IMIDAZOLINE

• Imidazoline is the most popular FFCI

• Certain imidazoline-based FFCIs appear to
perform well even in high-pressure, high-
temperature (HPHT) conditions
• Traditional imidazoline-based CIs generally
show high acute toxicity.
• Imidazoline has specific strong smell, high pH,
and not has good solubility in water.

Courtesy Picture : https://en.wikipedia.org/wiki/2-Imidazoline

 FFCIs FORMULATION

• Formulating an effective corrosion inhibitor is

a complex task. Laboratory and field testing
are often required for development of a
corrosion inhibitor.
• Some formula for some composition will be
share as generic guideline
• Gas with Water
• Gas, Oil and Water
• Oil with Water
• Water

Courtesy Picture : https://www.ohio.edu/engineering/corrosion/facilities-instruments/facilities/glass-cell

FFCIs FORMULATION

• Formula will depend on fluid composition that will be treated, field condition (temperature
and pressure), injection facilities and price as well
• Common composition :
• Active content such as imidazoline and or quaternary amine
• Surfactant to increase absorption performance
• pH adjuster such as glacial acetic acid (GAA) and dimer trimer acid (DTA) to increase its
effectiveness
• Mutual solvent to increase solubility in water such as isopropyl alcohol (IPA) and butyl cellosolve
(EGMBE)
• Solvent : commonly water as the cheapest solvent, to increase stability at high temperature
condition, formulator may add glycol.
FORMULA FOR GAS WITH WATER(2)

• For these pipelines with water, a volatile amine should be mixed with a water dispersible
film forming amine
• An example of formulation :
• Imidazoline : 15 – 25 %
• GAA : 7.5 – 12.5 %
• Methoxypropyl amine : 14 – 18 %
• Solvent (include mutual solvent) : Rest
FORMULA FOR GAS, OIL AND WATER(2)

• Inhibition of these 3 phase systems is perhaps most challenging.

• An example formulation would be as follows:
• Imidazoline :12 – 18 %
• DTA : 5 – 10 %
• GAA :4 – 8 %
• Methoxypropylamine : 12 - 18%
• Solvent : Rest
FORMULA FOR OIL AND WATER(2)

• For these systems the two phase inhibitor as shown below is the obvious choice.
• Formula may be as below :
• Imidazoline : 15%
• DTA : 7.5%
• GAA : 6.0%
• Solvent : 71.5%
FORMULA FOR WATER ONLY(2)

• It looks simple since just need to ensure the FFCI soluble in water but it may tricky in
the effectiveness since the presence of hydrocarbon will reduce the corrosion rate.
Hydrocarbon will thicken the film protection.
• The formulation may be as follow :
• Imidazoline : 15 – 25 %
• Surfactant NP-100 : 2 - 5%
• IPA or EGMBE : 15 – 25 %
• GAA : 12 - 14%
• Water : Rest
OUTLINE

• OBJECTIVE
• INTRODUCTION
• INTERNAL CORROSION MITIGATION
• FILM FORMING CORROSION INHIBITOR
• SELECTION
• FIELD APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
 QUALIFICATION
TEST

Compatibility Stability Performance Environment

Field
Storage Toxicity Biodegradability Bioaccumulation
Condition

Material Fluid Efficiency Properties

 COMPATIBILITY

• Material Compatibility
• Metal
• Non Metal
• Fluid Compatibility
• Production Fluid
• Chemical

Courtesy picture :https://www.element.com/materials-testing-services/polymer-testing-services/polymer-chemical-resistance-testing

 MATERIAL COMPATIBILITY - DEFINITION
Compatible means the CI will not react significantly or resulting negative effect with the
contacted material

• A series of tests should be carried out utilizing the CI and a variety of specimens that may contact
from the storage tank, daily tank, injection line, injection point and pipeline-flowline.
• Testing should focus first on the highest expected temperature to assess possibility of attack in the
most aggressive environment.
• The metal material could be as carbon steel, stainless steel, cooper, or alloys.
• The non metal material could be as plastic, rubber or composite.
MATERIAL COMPATIBILITY - PROCEDURE

• A specimen of material immersed in the Corrosion

Inhibitor (could be neat or as solution in liquid).
• Keep the test solution at the specified temperature.
Material Samples Exposure times of 1 to 3 weeks are recommended
• For metal, the test parameter is the corrosion rate
• For non metal, the test parameter are tensile strength,
dimension change and visual observation
• More detail for nonmetal compatibility test presented at
separate slides.
 FLUID COMPATIBILITY - DEFINITION
Compatible means the CI will not react significantly or resulting negative effect with the
other fluid.

• The compatibility of CI shall be check with any fluid that may contacted such as produced fluid or others
chemicals
• Produced fluid especially with produced water and liquid hydrocarbon
• Compatibility shall be observed between CI and any chemicals (such as Scale Inhibitor, Biocide, Oxygen
Scavenger, Reverse Demulsifier etc) that injected in the same stream/line and has possibility to contact
each other
• Observed parameter : change of color, precipitation, emulsion, heat increase, chemical change (by finger
print test)
 STABILITY - DEFINITION
Stability means that the properties of CI not significant changes under certain condition.
The properties could be phase separation, color, viscosity, pour point and effectiveness

The stability could be in two conditions :

• Storage : consider storage at warehouse or at field,
is the container exposed to direct sunlight ?
• Field Condition : consider the highest temperature
and pressure that exposed to the CI, where the CI
will be injected ? Is the viscosity will be critical
point (for example if the CI will injected through
umbilical to deep water).

Courtesy picture :https://www.atago.net/en/databook-viscosity_principle.php

 STABILITY - PROCEDURE

• Conduct the respective test for the CI before

No Parameter Initial After 2 weeks, Specification exposed at specified temperature and pressure
15oC, 25 bar
• Put sample at condition at storage or field
1 Color Yellow to Yellow to Yellow to dark brown condition
Brown brown
• Re-analysis the same parameter. Notify for any
2 Phase 1 phase 1 phase 1 phase changes.
3 Viscosity 15 45 Max 25 • Observed parameter : change of color, phase
(cps) separation, viscosity, chemical change (by finger
print test), etc
4 % Inhibition 92.1 % 91.8% Min 90
• Specification may be determine by considering
---- the field condition and equipment limitation
design.
• An example table shown in the left
 PERFORMANCE TEST
Performance conducted to evaluate the function of chemical to inhibit corrosion
(efficiency) and effect to the produced fluid due to its physical properties.
• Efficiency
• Weigh Loss Method • Properties
• Static Immersion Test
• Wheel Test • Oil-Water Partitioning
• Rotating Cage
• Electric Current Method
• Solubility
• Bubble Test • Emulsion
• Rotating Cylinder Electrode Test
• Flow Loop Test • Foaming
• Jet Impingement Test
• Specific Method • Film Persistency
• Weld Test
• Under Deposit Test
EFFICIENCY

• Efficiency means how effective the CI in the fluid could inhibit corrosion rate compare to non
treated fluid.
• The corrosion rates can be measured using mass loss or electrochemical methods.
• Using the methodologies, several variables, compositions of material, composition of
environment (gas and liquid), temperature, pressure, and flow, that influence the corrosion
rate in the field can be simulated in the laboratory.
• The performance of a corrosion inhibitor is influenced primarily by the nature of inhibitor,
operating conditions of a system, and the method by which it is added. The lab tests shall
consider this such as the temperature, pressure, shear stress, oil-water composition, corrosive
gas concentration (CO2 and H2S) and ions composition in the brine water.
STATIC IMMERSION TEST

• The working principle of this method is by calculate metal loss of

metal coupon before and after the test. More metal loss means
more corrosive.
• This is a basic test for other weigh loss test such as wheel test and
rotating cage.
• Coupons were weighed and fully immersed in triplicate in 200ml
of the various test solution for a period of 100 hrs. After the set
intervals of time, the metal coupons were wiped with cotton
damped with trichloroethylene for removal of the excess oil. Then
the specimens were cleaned with respective solutions as per
ASTM G1-90.
WHEEL TEST

• The procedure may refer to NACE Publication 1D182 Wheel

Test Method Used for Evaluation of Film-Persistent Corrosion
Inhibitors for Oilfield Applications
• The working principle of this method is by calculate metal loss of
metal coupon before and after the test.
• The method is an enhance of immersion static test by add
variable of dynamic flow.
• The pre-weight metal coupon immersed in the corrosive liquid,
in the tight capped glass bottle.
• The bottle is then rotated at a certain temperature and time.
• At the end, the coupon re-weight. Loss of weight then calculate
to % inhibition

Courtesy picture : https://www.techboxsystems.com/corrosion-wheel-test-2/

 ROTATING CAGE (RC)

• The working principle of this method is by calculate metal loss of

metal coupon before and after the test
• RC provides higher flow velocities than can usually be obtained
simply by stirring the solution.
• RC is a promising and reliable method to simulate pipeline flow
under laboratory conditions by rotating the specimens at speeds
upto 1500 rpm
• Advantage of RC inexpensive, compact, hydro dynamically
characterized and provides various flow conditions

Courtesy picture : https://shodhganga.inflibnet.ac.in/bitstream/10603/13315/7/07_chapter%203.pdf

 BUBBLE TEST

• The working principle of this method is by

measure the electric current density in solution.
The higher the current density that arises, the
more severe the corrosion will be and vice versa
• The bubble is the quickest test and the most
convenient as first screening test; it is conducted
with magnetic stirring of the test solution, without
control of the shear stress
• This is a basic method for others electric current
density method such as RCE and JIT

Courtesy picture : https://www.sciencedirect.com/science/article/abs/pii/S0920410514000965 and http://www.acminstruments.com/support/techniques/bubble-test and

 ROTATING CYLINDER ELECTRODE (RCE) TEST

• The working principle of this method is by measure the electric

current density in solution. The higher the current density that
arises, the more severe the corrosion will be and vice versa
• This method simulates the flowing fluid conditions
• Using a cylindrical electrode that continues to rotate
• The advantage of this method can also see the effect of fluid
velocity on the CI filming properties
• The RCE test system is compact, relatively inexpensive, and easily
controlled). It operates in the turbulent regime over a wide range
of Reynolds numbers.

Courtesy pictures
: https://www.researchgate.net/figure/The-setup-of-the-rotating-cylinder-electrode-
RCE_fig2_256913871 and https://pineresearch.com/blog/researchers-corrosion-electrochemistry/
FLOW LOOP TEST

• The most expensive, is the test better reproducing the

field conditions for corrosion inhibition.
• An experimental pipe that contains various corrosion
probes to monitor corrosion rates.
• Flow loops are used to evaluate corrosion inhibitors ither
in the laboratory or by attaching to a live pipe. The loop
simulates the flow regime, but the apparatus is relatively
sophisticated, and experiments are expensive and time
consuming.
• The loop is considered sophisticated to be an ideal
laboratory methodology under the scope of this guide.
 JET IMPINGEMENT TEST (JIT)

• JIT is a widely used technique to study

flow-induced corrosion.
• JIT is considered to simulate the
turbulence encountered at threaded
joints, bends, valves, welds, and so forth
in tubulars, flow lines, and pipelines

Courtesy picture : https://www.stress.com/flow-corrosion-effects-jet-impingement/ and https://www.corelab.com/sanchez/special-fluid-analysis/jet

 WELD TEST

• The aim of this research was to investigate the cause of

the severe localized corrosion that sometimes occurs at
welds in CS pipelines carrying hydrocarbons and
inhibited brines saturated with carbon dioxide.
• A rotating cylinder electrode (RCE) apparatus was
designed so that electrodes machined from the weld
metal, heat affected zone (HAZ) and parent material of
welded X65 pipeline steel could be galvanically coupled
and tested in high shear stress conditions.
Section of the weld in X65 pipeline steel showing the
parent material, weld metal and heat affected zone
WELD TEST RESULT

• Corrosion rate at welded

metal is higher compare to
parent metal or HAZ
• After 4 hours, 30 ppm
Corrosion Inhibitor injected to
the solution
• The corrosion rate for all
metal area decrease near to 0
mm/y after 8 hours (usually
corrosion rate specification is
0.1 mm/y)
UNDER DEPOSIT TEST

• The purpose of this test is to develop a representative laboratory test to

assess the performance of corrosion inhibitors under sand deposits
• Developed in IFE JIP
• Deposit specific i.e. sand, FeS, scale
• Ambient to 90 oC (194 oF)
• A multi-electrode array consisting of 24 carbon steel electrodes is used to
allow simultaneous testing of a range of surface conditions. The rods were
then mounted in a PEEK holder and the intervening space filled with epoxy
and then mounted in a PTFE cup. The lip of the PTFE cup was 1 cm above the
surface of the multi-electrode array to contain the sand during the test
RESULT OF UNDER DEPOSIT TEST

• .In this test, the inhibitor was only added after the corrosion rate had
stabilized (4 days), but in subsequent tests the inhibitor was added
immediately before coupling to save time.
• In all tests, within an hour of adding the inhibitor the polarity had reversed
so that the array electrodes were now anodic to the external electrode. In
Test 2, a peak average corrosion rate of around 4 mm/y was reached after
about 1 day.
• The severe anodic polarization of the array results from the more rapid
adsorption of the inhibitor on the external electrode, stabilizing the FeCO3
film, and the restricted access to the array because of the sand.
• It took about 12 days for the average corrosion rate of the array electrodes
to reach the acceptable value of 0.1 mm/y, which is related to the transport
properties of the inhibitor through the sand.
TEST MATRIX

JIT
 OIL-WATER PARTITIONING

• In order to prevent corrosion, the CI must be present in the

aqueous phase.
• This is achieved by partitioning or dispersion of the CI from the
hydrocarbon and is enabled by the CI being water dispersible or,
more commonly, water soluble.
• A determined concentration of CI mixed to the solution of water-
crude oil up to 24 hours. The water phase then separated, then
the efficiency test conducted and compared to condition without
mixing with crude oil.

Courtesy picture : https://purificationikwok.weebly.com/separating-funnel.html

SOLUBILITY

• To check the dispersal of the corrosion inhibitor in the carrier media

• The solubility of CI in carrier fluids (aqueous or liquid hydrocarbons) should be assessed at the prospective
storage temperature, often ambient temperature to -20°C. The main concerns are: loss of solubility of the
active ingredients, with the formation of solids or gunks, and phase separation due to changes in solubility.
• In a 100-mL graduated cylinder, make a solution of the appropriate concentration of the CI in the
recommended carrier (aqueous or hydrocarbon).
• Keep the solution at temperature for at least two weeks. Disqualify the product if a deposit or a separate liquid
phase forms within that period. Report any cloudiness or change in appearance of the liquid. Since the solubility
of inhibitors can vary quite drastically depending on the chemical composition of the water and hydrocarbon
phases, it is recommended that this test be repeated with actual field fluids if at all possible.
 EMULSION

• Most of CI contain surfactant to enhance its effectiveness. Surfactant may cause problem
such as create emulsion and foaming.
• The emulsions formed can be quite difficult to remove and can lead to separation
difficulties in the production facilities.
• Shake flask tests are used to evaluate whether the CI will cause the water/hydrocarbon
mixture to form an emulsion.
• Volumes of 100-mL (or other suitable volume) mixtures of oil phase and water phase
are tested. The ratios an be used depending on the system, for example.
• Inject CI at various dosage (from 0 ppm as blank until the 2 or 3 times of field dosage).
Hard shake minimum 100 times.
• Observe the separation, the emulsion layer and time required to separate.

Courtesy picture https://testoil.com/services/oil-analysis/demulsibility/

 FOAMING

• The purpose of this test is to evaluate whether CI cause

unacceptable foaming tendencies of field brine/condensate
mixtures in certain temperature and CI concentration.
• The method employs sparging gas through a glass frit into
a solution of chemical in either waters or hydrocarbons.
• The foam height and the stability of the foam are used to
assess the degree of foaming. The effect is compared to a
blank

Courtesy picture https://angusfire.co.uk/services/foam-testing-service/

FILM PERSISTENCY

• Is the capability of a corrosion inhibitor to form a stable and protective film able to
mitigate corrosion without being renewed. A high persistency is mandatory for corrosion
inhibitors to be used in the batch mode; however, persistency is a useful property also for
inhibitors for continuous treatments.2
• Persistency can be assessed in laboratory tests measuring the corrosion rate after
removal of the solution containing the inhibitor and replacing with the same solution free
of corrosion inhibitor; the time the system increases up to the baseline corrosion value is
a measure of the inhibitor persistency.
ENVIRONMENT EVALUATION

• Environment evaluation shall be conduct especially if the CI

will be discharged along with the treated fluid to the open
environment.
• Some of parameters in environment evaluation are :
• Toxicity
• Biodegradability
• Bioaccumulation

Courtesy picture https://en.wikipedia.org/wiki/Environmental_hazardl

TOXICITY

• Toxicity is the degree to which a

chemical substance or a particular
mixture of substances can damage an
organism.
• One method to classify toxicity is by
LC50 test
• LC50 is the concentration of the
chemical in the air or water that will
kill 50% of the test animals with a
single exposure
 BIODEGRADABILITY

• Biodegradability is the capacity for biological

degradation of organic materials by living
organisms down to the base substances such as
water, carbon dioxide, methane, basic elements
and biomass. Also known as biological oxygen
demand (BOD)
• Minimum BOD is 60%

Courtesy picture https://textilelearner.blogspot.com/2013/04/determination-of-biological-oxygen.html

 BIOACCUMULATION

• Bioaccumulation is the gradual accumulation of substances in an

organism. Bioaccumulation occurs when an organism absorbs a
substance at a rate faster than that at which the substance is lost or
eliminated by catabolism and excretion.
• Bioaccumulation could be calculated as KoW. Kow is defined as the
ratio of a chemical's concentration in the octanol phase to its
concentration in the aqueous phase of a two-phase octanol/water
system.
• Kow = Concentration in octanol phase / Concentration in aqueous
phase

Courtesy picture https://energyeducation.ca/encyclopedia/Biomagnification

OUTLINE

• OBJECTIVE
• INTRODUCTION
• INTERNAL CORROSION MITIGATION
• FILM FORMING CORROSION INHIBITOR
• SELECTION
• FIELD APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
APPLICATION

• Continuous
• Non continuous
• Batching
• Squeeze
• Stick
 CONTINUOUS INJECTION

• This is the most common application

• The injection could be at downhole, wellhead or topside, wherever the
corrosion predict to occur.
• CI injected continuously, 24 hours a day to provide continuous
protection
• CI in the daily tank pumped to the system using injection pump or gas
lift
• Dosage vary depends of type of active content, concentration,
corrosion severity and pump limitation
• Common dosage for oil field : 10 – 100 ppm based on produced water
• Common dosage for gas field : 0.5-2 pint/mmscf

Courtesy pictures Handout Oilfield Production Chemicals and Microbiology, HTS Consultants, 2007
CONTINUOUS INJECTION : DISPERSION

• One problem in CI injection is how to disperse

the molecules to the water phase
• Poor dispersion will lead to gunking, not fully
protection or even corrosion near the injection
point (some of Corrosion Inhibitor has low
pH).
• To increase dispersion, we may modify the
formulation or add additional equipment
named quill + (atomizer) nozzle
QUILL + NOZZLE

• The quill may be a simple open tubing or

notched tubing, parallel or perpendicular
spray nozzle.
• The nozzle will spray the CI into smaller
droplet so it will be easier to disperse.
• The nozzles may be adjusted in length
from top of the line, center or bottom
to deliver chemical into the desired
liquid flow.
EXAMPLE OF CONTINUOUS INJECTION RATE
CALCULATION
• In Oil Field
Produced Water Rate = 20,000 BWPD, dosage recommendation 20 ppm
Injection rate (liter/day) = (dosage x 106) / (produced water rate x 159)
= (20 x 106) / (20,000 x 159)
= 6.3 LPD
• In Gas Field
Gas Production Rate = 15 mmscfd, dosage recommendation = 2 pint/mmscfd
Injection rate (liter/day) = dosage x gas production rate x 0.473
= 15 x 2 x 0.473
= 14 LPD
BATCHING

• Batching is method to inject CI at high dose at specified interval period

• Batching injection considered for some reasons such as to provide thicker layer
protection film, for area that not covered by continuous injection or as additional
treatment
• Common dosage will be explain in the following slide depend on the batching mode.
 BATCHING – USING INJECTION PUMP

• This is common to applied in close system or semi close system when the water base liquid
mostly recirculated with minimum lose such as at Close Cooling Water System
• Also known as slug dose method.
• This method may also applied as additional treatment beside the continuous in order to provide
thicker protection layer.
• For Close Cooling Water with nitrite as active content, the injection rate is 1-5 liter CI per 2,500
liter water with interval batching every 1-4 week(s)
• For oil and gas field with amine as active content, the dosage is between 1000 – 5000 ppm for 3-6
hours injection
BATCHING : USING PIG

• The method could be conducted during pigging

job not as special corrosion inhibitor pigging
• The chemical put in between of lead pig and
Trailing pig tailing pig
• Batch-size volume is determined by:

Inhibitor + diluent • 3 mil film thickness on tubing interior

OR
Lead pig
• 5000 or 10000 ppm concentration in produced
fluid in annulus
OR
• 25-50 ppm based on well fluid production over
treatment interval between batches
 SQUEEZE

• A squeeze treatment is designed to place the

inhibitor back in the formation where it will adhere
to the reservoir rock. As the producing water
passes over the rock surface it will slowly dissolve
some of the inhibitor back into the water to
prevent scaling (in the formation and throughout
the processing system).
• Although the squeeze is considered a batch
treatment, the return of chemical is continuous

Courtesy pictures Handout Oilfield Production Chemicals and Microbiology, HTS Consultants, 2007
 VOLUME OF SQUEEZE TREATMENT
D =A x B x C
1000
D= Volume of CI (liter)
A= Recommended dosage in ppm
B= Produce Water in BWPD
C= days of protection
• Each production chemical company has own formula
depend on the chemical type and concentration.
Picture beside is only an example.
• Example : how many corrosion inhibitor shall be
prepared for squeeze job if the recommended
dosage is 20 ppm, average produce water = 2,000
BWPD. The protection days is 3 months (90 days)
• D = (20 x 2,000 x 90) / 1000
= 3.600 liter
STICK

• Stick CI is CI in solid form

• Used when liquid CI is not applicable such as no chemical injection line
• Mechanism : the solid CI dropped to the annulus or the production tubing then it will be
slowly dissolved in liquid phase due to its solubility (usually in water).
• The dosage not easy to control since the solubility in the liquid phase will depend on
time and temperature.
• Ammount of sticks per treatment : 3 – 5 stick for duration 1 – 4 weeks.
 Normal operation

V1 Valve 1 (V!) close

Valve 2 (V2) open

Valve 3 (V3) open

V2 Step of Stick Application

V2 1. Close V3
2. Close V2
3. Open V1
V3 4. Insert sticks through V1
5. Close V1
6. Open V3 for 15-30 minutes, Open Valve V2
GAS CORROSION INHIBITOR DOSAGE
Field Condition Characteristic Kind of CI Treatment Method

> 1 bbls water / MMSCF Water soluble- oil dispersible

A. Wet Gas
Dosage 5 - 20 ppm based on
High tendency of corrosion
fluid
Pigging should be done
- Low Velovity < 50 ft/sec regularly following with
continuous injection
> 50 ft/sec
- High Velocity Have high film persistency Continuous injection
Possible of erosion

< 1 bbls water / MMSCF Continuous injection

B. Dry Gas Oil soluble - water dispersible
Low corrosion rate Dosage 0.5 – 1.0 pint /MMSCF

- Low Velocity < 50 ft/sec Volatile corrosion inhibitor

> 50 ft/sec Have high film persistency

- High Velocity
Possible of erosion
WET AND DRY GAS DEFINITION

1. Refer to Engineering Data Book, IATMI, 1994 : Dry Gas if water

content max 7 (in US) or 10 (in Indonesia) lbs/mmscfpd
2. Champion Technologies Technical Brief of Cortron® R-2378: A
‘dry’ gas corrosion inhibitor : Dry Gas Champion’s definition of dry
gas pipelines in this document are separated pipelines that carry
less than 3 bbls liquid/mmscf of water and condensate.
3. According to the NACE Internal Corrosion Course : maximum
water at Dry gas was 7 lbs per MMSCF
4. NACE Standard Practice SP0206-2006 "Internal Corrosion Direct
Assessment Methodology for Pipelines Carrying Normally Dry
Natural GAS (DG-ICDA" defines dry gas as A gas above its dew
point and without condensed liquids
OUTLINE

• OBJECTIVE
• INTRODUCTION
• INTERNAL CORROSION MITIGATION
• FILM FORMING CORROSION INHIBITOR
• SELECTION
• FIELD APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
MONITORING

• Monitoring of CI performance means activities to review

the effectiveness to inhibit corrosion rate
• The ideal monitoring program shall be as combination of
some methods not as one or only two methods
• The monitoring result could be used as
recommendation for dosage optimization, change type
of CI, add or reroute injection point and others follow
up that could maximize the corrosion protection using
Corrosion Inhibitor Chemicals (Process Improvement)
 CORROSION RATE SPECIFICATION

• Allowable maximum corrosion

rate may be calculated from
the design life, corrosion
allowance or based on
references.
• Each company may determine
their own specification
• Table beside is an example of
corrosion rate rating.

Reference : NACE STD SP0775-2018 : Preparation, installation, analysis and interpretation of corrosion coupons in oilfield operations.
UNIT CONVERSION OF CORROSION RATE

• Two common unit rate of

corrosion is mill per year (mpy)
and millimeter per year (mmy)
• For example 1 mmy = 39.4
mpy
• Table beside provide
conversion of some corrosion
rate unit
AN EXAMPLE OF INTERNAL CORROSION RATE
DETERMINATION
• A pipeline has corrosion allowance 3 mm, designed for 20 years life
services.
• The pipeline fluid is crude oil with produced water. Contain CO2 with
minimum level of H2S. Only uniform corrosion that expected.
• Theoretical corrosion rate specification = 3 mm/20 years = 0.15
mm/y.
• For further safety factor, we may put 50% of theoretical corrosion
rate = 0.075 mm/y = 3.0 mpy.
TYPE OF MONITORING

• Corrosion Rate Monitoring

• Corrosion Coupon
• Probe Coupon

• Wall Thickness inspection

• Ultrasonic Thickness (UT) Inspection
• Intelligent Pigging.

• Water Analysis
• Residual CI
• Total iron
 CORROSION COUPON (1)

• The common method in the oil and gas field

• Work philosophy : calculate metal loss of coupon during specified
exposure days.
• Metal loss converted to corrosion rate
• Coupon : metal strip or disc that immersed in the fluid
• Could show local and general corrosion
• Cannot differentiate erosion and corrosion
• Need minimum 15 days to monitor the result. Lower corrosion rate
need longer exposure days.
• 3 types of coupon : flat, rod, disc and spool.

Courtesy pictures https://www.cosasco.com/disc-coupon-holder-6202.html and :http://www.maksur.com/corrosion-monitoring-systems.html

 CORROSION COUPON (2)

• Basic calculation of corrosion rate by coupon is

metal loss
• Based on beside formulation, corrosion rate
calculation depends on metal weight loss, exposed
days and density of metal. For iron as common
corroded metal in oil and gas, the density is 7.88
CR = Corrosion Rate in mpy
W = Weight loss (mg) g/cm3 so the calculation will be as below “
A = area of coupon (inch2)
d = density of metal (g/cm2)
t = time exposure (days)
 ELCTRICAL RESISTANCE (ER) PROBE

• Resistance probe : calculate corrosion rate based

on electrical resistance / current
• ER measurement are based on fact that as
corrosion progresses the metal become thinner,
then the ER will increase proportionally(3)
• Quick result (could be set in every minutes)
• Cannot detect pitting corrosion
• Not working properly for dirty liquid since the
contaminant could cover the probe.
• The result may not accurate but good to show
trending.

Courtesy pictures : https://www.alspi.com/erintro.htm and http://en.zkwell.com.cn/product.php?cid=40

ULTRASONIC TESTING (UT) INSPECTION

• Usually used at surface facilities

• UT is a family of non-destructive testing techniques based
on the propagation of ultrasonic waves in the object or
material tested
• UT will measure the thickness of material and compare to
the previous and initial thickness
• Could be use at most of static equipment, at any size and
any place as long as it could be accessed.
• UT are low cost, could detect corrosion location but need
experienced operator and tested surface shall be cleaned
from paint and scale.
 INTELLIGENT PIGGING

• Intelligent Pigging is an inspection technique whereby an

inspection probe, often referred to as a "smart" pig, is
propelled through a pipeline while gathering important
data, such as the presence and location of corrosion or
other irregularities on the inner walls of the pipe *
• Advantages : . It allows pipelines to be cleaned and
inspected without having to stop the flow of product. It
also allows the a pipeline to be completely inspected
without having to send inspectors down its entire length.
Finally, it provides cleaning and inspection services at the
same time, saving companies both time and money. *

* https://inspectioneering.com/tag/pigging#:~:text=Intelligent%20Pigging%20is%20an%20inspection,inner%20walls%20of%20the%20pipe.
Courtesy pictures : https://www.openpr.com/news/2095424/intelligent-pigging-market-is-expected-to-see-growth-rate
RESIDUAL CORROSION INHIBITOR

• Most of the CI’s molecules will form layer with the inner side of
metal, some molecules will be degraded due to reaction with
others chemicals or by relative high temperature and the others
will be as free molecule in water known as residual CI (the rest of
CI’s molecules).
• High residual means the amount of CI is enough or even
excessive. Low residual means the amount of CI is not sufficient
or CI may not compatible with other chemicals or not stable with
the field condition
• Residual CI at field may different depend on type of active content
and treated system. For example residual amine at pipeline may
vary from 5 to 20 ppm while residual nitrite at close cooling water
system shall be keep between 400 – 1000 ppm
• Residual CI could be measured by spectrophotometric method.
TOTAL IRON

• Iron count : corrosion rate calculated based on

dissolved iron in water
• Easy Calculation
• Useful to monitor trending
• Shall consider iron content from produced water
• Show total corrosion + erosion
• Cannot use to locate the corrosion point
• Cannot differentiate general and local corrosion
• Not accurate for corrosion caused by H2S
• Not accurate for new installation pipe
 IRON - MANGANESE (Mn) COUNT*

• The concentration of Mn in iron alloys used in oilfield

downhole equipment is typically 0.5 to 1.5%. Therefore, the
supposition is that the ratio of Mn to Fe in produced water
should be about 1:100
• If the Fe:Mn ratio > 100, extraneous or non corrosion-
related iron may be present in the formation water
• If Mn content >1% of the Fe content, Fe may deposited as
scale, or is present in the hydrocarbon phase, or that Mn is
produced from the formation

*NACE Standard RP0192-98 Item No. 21053 Monitoring Corrosion in Oil and Gas Production with Iron Counts
OUTLINE

• OBJECTIVE
• INTRODUCTION
• INTERNAL CORROSION MITIGATION
• FILM FORMING CORROSION INHIBITOR
• SELECTION
• FIELD APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
1. COMPARISON OF TWO TYPE OF CI(10)

• To give a better understanding of the methodology of corrosion

inhibitor performance evaluation in real condition of gas
production, two type of Corrosion Inhibitor tested in two
production wells
• The first chemical is FF-NCI, a film-forming /neutralizing
inhibitor, which provides a neutralizing function of carbonic acid
by the raising of the pH of the environment, and the covering
function to isolate the aggressive water from the metal surface.
• The second chemical is FFCI, a film-forming inhibitor, which
offers only a covering function of the carbon steel structure
• As shown at picture beside, both chemicals show similar
presence of peaks.
1. COMPARISON OF TWO TYPE OF CI(10)

• The FF-NCI was injected in well A, meanwhile, the FFCI was used in
the well B.
• Each inhibitor was injected in the first pipe (testing pipe)
downstream of the choke using a dosing pump as shown in picture
beside
• The continuous treatment is carried out in two stages:
• The 1st is to make a shock treatment required for forming a layer of
the inhibitor on the testing pipe surface (the period of this step
reached 24 h with an injection rate of 20 g/m2/d),
• The 2nd step is to maintain the inhibitor film; the concentration of
the inhibitor is reduced to a low dose in this mode of treatment in
order to optimize its injection rate
 1. COMPARISON OF TWO TYPE OF CI(10)

Parameter FF-NCI FFCI • The FFCI outperforms the FF-NCI with an

Corr Rate (µm/y) efficiency that exceeds 99% at low injection rate.
- Before Injection 400 1200
• It provides good compatibility and stability all
- After Injection 60 10
through its injection path.
Inhibitor Efficiency (%) 85 99
pH • Meanwhile, the application of FF-NCI significantly
- Before Injection 5.42 4.8 reduced the corrosion rate of carbon steel
- After Injection 6.43 4.8 structures, but it involved the formation of
Inhbitor Rate (liter/mm )
3
1.02 0.5 deposits in the gas processing plant
Deposit Yes No • From table beside, the increase of pH not affect
Foaming No No the effectiveness of corrosion inhibition
2. CORROSION INHIBITOR FOR SOUR SYSTEM(11)

• A French refinery faced tremendous corrosion and safety issues in the overhead system at their sour
water stripper.
• Severe corrosion was found in the overhead, but was also seen in the overhead lines, water drum, and
reflux line.
• Corrosion in the reflux line, especially downstream of the reflux pump, measured, on average, 40 mils per
year.
• 10-15% concentration of NH4HS found in the reflux line sample. Typically, any concentration greater
than 4% indicates the potential for corrosion.
• Deposit analysis confirmed that the problem in this case was primarily due to NH4HS salts and the
associated under deposit corrosion.
2. CORROSION INHIBITOR FOR SOUR SYSTEM(11)

• A FFCI was selected, as it is specifically designed for sour,

high pH environments, and is also a very effective salt
dispersant
• Initially, it was injected at 75 ppm, directly into the overhead
line to immediately protect the entire overhead system,
including condensation drum and reflux line.
• Once a strong enough protective film was established, the
chemical dosage was optimized to approximately 30 ppm
• As shown at picture beside, the corrosion rate decrease
from 35-42 mpy to max 5 mpy after stable treatment
operation
3. DEPOSIT EFFECT

• Corrosion rate at some spots of Tier Gas

Line not meet requirement (max 2 mpy)
• Some study and trial :
• Chemicals : change the type of chemicals
 no effect
• Erosion effect : monitor by SS coupon 
low weight loss

MAY • Chemical injection mode : use nozzle

sprayer / atomizer  no significant effect
3. DEPOSIT EFFECT

• During pigging job, it was found a lot of deposit

(most likely sand and silt).
• To study the deposit effect, a laboratory test
conducted by mix CI with sand at various
weight
• Refer to graph beside, it was found that sand
may adsorb the CI or it may a competition
between iron and silica (in sand) to attract the
CI molecule
• Recommendation are : conduct regular pigging
then following by batching Corrosion Inhibitor.
OUTLINE

• OBJECTIVE
• INTRODUCTION
• INTERNAL CORROSION MITIGATION
• FILM FORMING CORROSION INHIBITOR
• SELECTION
• FIELD APPLICATION
• MONITORING
• FIELD CASES
• SUMMARY
SUMMARY

• Internal corrosion at oil and gas field usually caused by dissolved gas such as O2, CO2 and H2S
• Film Forming Corrosion Inhibitor used to reduce corrosion rate by produce dynamic film protection
against corrosion dissolved gas.
• FFCI is a specialty chemicals. Composition may different for each field depends on corrosion gas
concentration, fluid composition, temperature, pressure and materials used.
• Selection of Corrosion Inhibitor usually include the performance, stability and compatibility
• Application of Corrosion Inhibitor depends on corrosion location, type of corrosion, previous field
experiences and the injection facilities
• Monitoring corrosion will provide data for continues improvement in term of quality and cost.
• No single monitoring method could be used to explain the corrosion phenomenon at each field.
Combination of some method will provide better understanding
REFERENCES

1. Production Chemicals for the Oil and Gas Industry, Malcolm A.Kelland, CRC Press, page 195-217
2. Product Bulletin of Akzo Nobel Surfactants, Corrosion Inhibitors for Oilfield Production
3. Investigation Report Catastrophic Rupture Of Heat Exchanger (Seven Fatalities), U.S. Chemical Safety And Hazard
Investigation Board, 2014
4. ASTM G170 Standard Guide for Evaluating and Qualifying Oilfield and Refinery Corrosion Inhibitors in the Laboratory
5. NACE Item No 24259 Laboratory Evaluation of Corrosion Inhibitors Used in Oil and Gas Industry
6. https://shodhganga.inflibnet.ac.in/bitstream/10603/13315/7/07_chapter%203.pdf
7. https://www.icorr.org/wp-content/uploads/2020/06/2011-03-15-Clariant_Corrosion-Inhibitors-and-Corrosion-Inhibitor-
Selection.pdf
8. https://core.ac.uk/download/pdf/140429.pdf
9. https://www.researchgate.net/publication/273755924_Testing_of_inhibitors_for_underdeposit_corrosion_in_sour_conditions
10. https://doi.org/10.1007/s13202-021-01287-y
11. Case Study from SUEZ : pHilmPLUS* 5K15 Filming Inhibitor Resolves Corrosion and Safety Concerns in Sour Environment