SPE-169626-MS

Chemical Treatments Practices and Philosophies in Oilfields

M.A. Awan and S. M. Al-Khaledi, Kuwait Oil Company

Copyright 2014, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Oilfield Corrosion Conference and Exhibition held in Aberdeen, Scotland, UK, 12–13 May 2014.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Application of chemical treatments has become an essential part of everyday oilfield operations, to
achieve specific objectives, minimize production problems, reduce production costs and achieve product
specifications. Also, many process equipment performance and reliability problems can be solved
economically by proper selection and application of chemical treatment practices. For instance, the
corrosion problems that can be solved by changing metallurgy, reducing velocity, changing process
conditions, removing corrosives upstream, can credibly be prevented by using corrosion inhibitors.
With increasing oil production, rising water cuts, H2S related issues and increased effluent water
injection & disposal, the oilfield operating conditions are becoming more stringent, entailing the projects
to be engineered with higher projected life. Also, with growing HSE concerns and compliance with
environmental regulations, application of varied chemical treatments have become inevitable. Projects
have been undertaken for introducing new chemical treatments, bulk handling of production chemicals,
installation of chemical injections and monitoring systems. This necessitates periodic assessment of the
chemical treatment practices and philosophies, for selecting and effectively monitoring & controlling
performance of the chemical treatments by adopting a systematic approach.
To this effect our Company has deployed a huge network of chemical treatments and management
systems all over its fields, for protecting its facilities/equipment, improving their performance, achieving
quality, etc., taking into consideration; the process equipment problems, addressing HSE concerns and
effectiveness of chemicals, etc. By operating and adopting a systematic & structured approach the
chemical treatment practices have demonstrated proven performance. Those practices are not only cost
competitive, but often can be implemented on-stream without curtailing unit operations.

Introduction
The objective of this paper is to describe briefly the board range of production chemicals used in the oil
&gas production and effluent water handling facilities. What the chemicals are doing, how they act and
interact, and the practices and philosophies involved in chemical applications. Most of the information and
practices described are as applied in our Company.
There are specific objectives to be achieved by use of those chemicals. For instance chemical inhibitors
are used to prevent corrosion, scale formation or biological activity. Oxygen scavengers and polyelec-
trolytes flocculants are dosed into water injection systems. Antifoams are used in production separators,
2 SPE-169626-MS

gas dehydration units. Demulsifiers are used in oil water separation and crude desalting facilities.
Flocculants &Cougulants are required to clean up produced water for disposal. Biocides are used for
controlling microbiological activities in water systems. Many other chemicals are also used, i.e. drag
reducing agents for export pipelines, hydrate inhibitors for produced gas pipelines, wax and asphaltene
inhibitors in oil export lines. Wells stimulation, workover and sueeze treatments chemicals. In fact, a
highly diverse selection of chemicals is employed in oilfield operations.
The chemicals can be placed into three groups.
1. The production treating chemicals: The chemicals routinely injected to the produced fluids and
source water injected for waterflooding.
2. The gas processing chemicals: The chemicals used for freeze point depressions, sweetening &
dehydration of produced gas.
3. The stimulation and workover chemicals: These chemicals consist of acids and dense brines
alongwith their associated additives.
In addition to specific objective of using the chemicals, there are safety and integrity concerns as well.
The appropriate application of production chemicals helps ensure trouble free, and therefore safe
operations. Failure to predict and prevent a problem can lead to facilities failure. Also unnecessary
storage, transportation, handling and use of inflammable or toxic chemicals may be hazardous.
Why Production Chemicals are used?
Production chemicals are used almost in all activities of oil industry –from drilling to refining. Hereunder
is an arbitrary list of why production chemicals are used.
(i) Protect Facilities
– Prevent corrosion, blockages, bio-fouling in production, export pipelines, tankage, refining
facilities
(ii) Safer Operational Practice
– Facility failure
– Blockages
– Stuck valve (SSSV’s)
(iii) Improved Well Performance
– Improve drilling/workover performance and success rate
– Protect and improve infectivity index
– Polymers to shut-off water producing zones
(iv) Improved Reservoir Description
– Tracers for movement of injected water/gas
– Tracers for residual oil determination
– Origins of reservoir souring
(v) Improved Reservoir Performance
– Surfactant water flood activities
– Polymers for improved water flood conformance
(vi) Improved Separation of Produced Fluids
– Breaking oil/water emulsions
– Breaking foams
(vii) Clean up and disposal of Non-export Produced Fluids
SPE-169626-MS 3

Table 1—Process equipment problems and solutions

– Oil water clean up

– Filtration of suspended solids for water re-injection
– Gas re-injection
(viii)Improved Pipeline Operations
– Decrease pipeline pressure drop and reduce pumping costs
– Prevent jelling during shut down
(ix) Improved Export Quality
– Desalting/dewatering oil
– Dehydration and sweetening gas
– Decrease viscosity oh heavy oil
(x) Cut Production Costs
Many process equipment performance and reliability problems can be solved economically by the
proper selection & application of chemical treatments and monitoring system operation to ensure that
expected benefits are achieved and unexpected problems do not develop.
Process equipment problems often have possible mechanical, process conditions and chemical treat-
ment solutions as tabulated below (Table-1). Chemical treatment solutions may not only be cost
competitive with possible mechanical or process changes, but often can be implemented on-stream
without disrupting unit operations. Process changes also can be made on-stream within the existing
4 SPE-169626-MS

equipment limitations. Some process condition changes may require mechanical changes that involve
equipment shutdowns. All those factors must be considered while determining the most cost effective
solution.
Deployment of Production Treating Chemicals
The production treating chemicals include demulsifiers, scale and corrosion inhibitors, reverse emulsion
breakers, coagulants, flocculants, antifoams, surfactants and paraffin control chemicals. The types and
quantities are minimized for both technical and economic reasons. Overdosing can reduce performance
significantly or deployment of marginally effective chemicals can cause more operational problems than
they solve.
Appendix 1, illustrates where different chemicals may be injected in acrude oil production system. Not
shown, but of vital importance, are the sampling points and probes/test coupons needed to check
performance of the chemicals that they are working effectively.
Virtually all production treating chemicals are complex mixtures. The formulations sold by chemical
companies usually contain materials other than a single compound. Yet within this complexity, there is
a central functional group that defines the generic chemical type. As a minimum there will be a solvent.
Other components may be different compounds for the same specific purpose, amounts of different
compounds, other solvents or other chemicals are added for specific reasons, to allow better achievement
of the intended purpose of chemical deployment.
A list of the production chemicals used in the Company is given in Appendix 2.
Functional Purpose of Commonly used Production Chemicals
Functional purpose of the most commonly used production chemicals is briefly described hereunder;

Emulsion Breakers (Demulsifiers)

All crude oils contain impurities which can contribute to corrosion, heat exchangers fouling, catalyst
deactivation, etc. Water is present in wet crude oil either as free water or emulsified water (mixed water
droplets with crude oil and surrounded by thick film). Mineral salts are present in crude which are mainly
chlorides, carbonates, bicarbonates and sulphates of Na, with lesser amounts of Ca & Mg.The emulsions
need to be resolved and water removed to prevent process equipment problems (Corrosion, scaling,
fouling, etc.) and to meet specified export quality limits.
Emulsion breakers or demulsifiers are virtually used in all oil production operations to improve
separation of water droplets from oil. The most common compounds are oxyalkynated alkyl phenols,
formaldehyde resins, polyglycol esters, and alkylaryl suphonates. Almost all formulations contain one or
more of those compound as well as a surfactant dissolved in an organic solvent. All components of those
formulations are insoluble in water and dissolve in the oil phase. Typical dosing rates in the Company
operations are from 25 to 50 ppm based on oil properties.
Corrosion Inhibitors
Corrosion, destruction of a metal by chemical or electrochemical reaction with its environment, is a very
common phenomena in oilfield operations has been estimated that at least 80% of failures occurring in
production and pipelines operation are caused by corrosion of different types. Two principal corrodents
in oil and gas are H2S and CO2.Oxygen is also of major concern when present in the process water or
produced or injection waters.
Use of corrosion inhibitors is one method to control corrosion and minimize internal damage to
equipment. The most commonly used compound are the amide/imidazoline, amine or amine salts,
quaternary amine and heterocyclic amine types. Corrosion inhibitors are used in oil, gas, water streams.
Generally, oil soluble inhibitors, are preferred for oil production because of their greater effectiveness.
SPE-169626-MS 5

Water soluble inhibitors are used in water treatment operations and waterfloods. Continuous treatment
from 20-30 ppm is required for oil and water treatments, whereas gas may require up to 100 ppm, on the
basis of its liquid contents.

Scale Inhibitors
Formation of scales is a common phenomenon in oilfield operations. Common scales found in oilfield
waters are carbonates & bicarbonates, sulphates of Ca, Ba &Sr, and oxides &sulphides of Fe. Extent of
scales formation depends on variables, such as; total dissolved solids (TDS), operating temperature &
pressure, pH of water, partial pressure of dissolved gases, suspended solids, corrosion products, etc.
Although scales formation can be prevented by; avoiding mixing of incompatible waters, pH control,
removal of scale forming constituents & dissolved gases, softening of water, etc., but scale control
chemicals (scale inhibitors) are widely deployed in oilfield operations. Scale inhibitors when injected into
water streams in small amounts normally from 20 –30 ppm, delay, reduce or prevent scale formation.
Scale inhibiting chemical must be present at all times to prevent scale deposition. Scale inhibitors function
by inhibiting the growth of the scale crystals, provided effective chemical has been chosen. Organic scale
inhibitors are the most widely used scales control chemicals. Most common types are; organic phosphate
esters, phosphonates, acrylic-type polymers, etc. All formulations are highly water soluble. For squeeze
treatments in wells high concentrations of 5000 ppm or more may be used.
Scale inhibitors and corrosion inhibitors are being injected at numerous locations where corrosion and
scales formation phenomena are likely, within production facility (called gathering center). A typical list
of injection point’s location is given in Table 2. The chemical injection, sampling and corrosion
monitoring point locations are shown in Appendix – 3.

Biocides
Oilfield water may contain several types of microorganisms i.e. algae, fungi, bacteria. Bacteria are present
in different shapes and extremely small sizes, and multiply with incredible speed, implying that a single
bacterium can be a thriving colony of millions of bacteria in a very few hours which can flourish under
extremely broad range of conditions. Various bacteria especially sulfate reducing bacteria (SRB) must be
controlled to prevent corrosion or fouling of equipment or wells. SRBs cause more serious problems in
oilfield waters than any other type of bacteria. They reduce sulfate ions in water to sulfide ions, resulting
in H2S as a by-product.
SRB’s activities can result; in pitting corrosion beneath a growing bacterial colony, some scale or
sludge, generation of H2S that can increase the corrosivity of the water, increase in the possibility of
sulfide cracking and blistering, formation of insoluble sulfide – an excellent plugging material. Aldehydes,
quaternary ammonium salts, and amine acetate salts are the most commonly used. All biocides are highly
water soluble. Intermittent slug treatments at 200 ppm of biocide are used to achieve good bacterial
control. Biocides are used alternatively (Biocides A&B) to cope with the immunity gained by bacteria. In
view of the toxicity of the biocides and growing restrictions by the Environmental Protection Agencies,
considerable efforts continues to be focused on the selection and application of environmentally friendly
biocides in the Company operations.

Reverse Breakers (Reverse Demulsifiers)

The reverse breakers are used to help remove droplets of oil from the effluent water before disposal into
the evaporation pit or disposal/injection into wells. The most common are low molecular weight
polyamines and polyamines quaternary ammonium compounds. Some formulations include chlorides of
Zn, Al and Fe. Reverse breakers are highly water soluble, and usually injected from 10 – 25 ppm.
6 SPE-169626-MS

Table 2—Scale & Corrosion Inhibitors Injection Points in a Gathering Centre (Typical)

Coagulants and Flocculants

Efficiency of solid/liquid separation can be greatly improved by the application of synthetic polymer
flocculants, particularly where sedimentation, filtration and centrifugation processes are extensively used.
Natural water soluble flocculants include guar & other gums and starches, whereas synthetic polymers are
anionic, cationic and available in wide range of molecular weights and ionic charges. The organic types
SPE-169626-MS 7

of these chemicals are nearly of similar formulations to the reverse breakers, but not modified to achieve
lower surface tension.
Coagulants, inorganic hydrolysable salts of aluminium (Alum), are used in water treating. Synthetic
coagulants are cationic and low molecular weight chemicals.
Both coagulants and flocculants are highly water soluble. Coagulation is basically hydrostatic and
brought about by reduction of the repulsive potential of the electrical layer, whereas flocculation is
brought about by the action of high molecular weight materials where the chemical forms a bridge
between two or more particles.
Antifoams
Dissolved gases in crude oil under high reservoir pressure are liberated in the low pressure environment
of oil-gas separators. But often disengagement of gas from crude oil results in foaming. Also some crude
oils have foaming tendencies. Foaming may result in crude oil loss in the form of droplets carry over in
the gas stream. Silicones and polyglycol esters can be used for reducing foams. Both types will distribute
in oil but solubility is usually low. The antifoams are usually diluted with solvents and injected from
10 –20 ppm.
Hydrate Inhibitors
Hydrates (ice like)solids can be formed in gas systems in the presence of water. Solid hydrates can form
across pressure control valves, where sudden pressure drop takes place due to expansion of gas followed
by cooling. Hydrate inhibitors are used to depress the hydrate formation temperature. Methanol is often
injected into a gas stream to prevent hydrate formation. Formation of hydrates during cooling may be
inhibited by injecting glycol. Most commonly used is triethylene glycol because of its lower cost and
superior operating characteristics. Hydrate inhibitor must be present at the point, where gas is cooled to
its hydrate formation temperature. The required concentration of the inhibitor in water can range from low
range of 1-2 % to as high as 40-50 %, depending on quantity of liquid water in gas. Although much of
the inhibitor shall dissolve in water, but some fraction will go to oil and gas phases as well.
Gas Dehydration
Triethylene glycol (TEG) is used for dehydrating gas which provides adequate corrosion protection for
gas transportation pipelines. In the gas dehydration system, TEG comes in contact with wet high pressure
gas in a multistage counter flow contactor. Dry gas is exported, whereas wet glycol is regenerated for
re-using. Resulting TEG losses are made-up with freshly added TEG. Water based silicone antifoam
emulsion is used for controlling foaming in the wet TEG regeneration system.
Paraffin Treating Chemicals
Vinyl polymers, sulphonates salt and mixtures of alkyl polyethers& aryl polyethers are commonly used
chemicals, for preventing solids formation or sticking of solids to the walls of the system. Paraffin
solvents, usually refinery cuts are used to remove accumulation of solids. Inhibitors are used in 50-300
ppm range, whereas the solvents (aliphatic or aromatic) may range from a few to nearing 100 percent for
cleaning out a vessel.
Selecting Chemicals and Chemical Treatments Programs
For selecting chemical treatment solutions of process equipment problems, the first step is to investigate
the available chemical technology and estimated costs. References should be solicited from other
companies that have experienced similar problems and renowned chemical companies with proven
experience should be contacted. Some preliminary risk analysis work should be done for determining the
feasibility of chemical treatments, considering the possibilities of downstream fouling or plugging,
8 SPE-169626-MS

Figure 1—Schematic of Primary Storage Facility

Figure 2—Schematic of Secondary Storage Facility

impacts on downstream equipment/processes, corrosive &environmental effects, associated hazards, etc.

The costs of chemical treatments and the required support services, and the benefits compared with the
possible process and mechanical solutions should be evaluated.
Methods and procedures for on-stream monitoring of the chemical treatments and system performance
must be developed for evaluating effectiveness of the chemical treatment programs. Chemicals testing
should be planned and scheduled involving well versed chemical vendors, and the process plant
supervisors/operators so that their concerns are addressed as well. The chemical injection system to be
used must be well designed and installed conforming to the company safety standards. Well planned and
executed chemical treatment tests should yield sufficient data to evaluate and justify a permanent
treatment program and select an effective and reliable chemical.
SPE-169626-MS 9

It’s important to review performance of the chemical treatments on at least quarterly to yearly basis,
to ensure expected benefits are achieved and the unforeseen problems are no encountered. The perfor-
mance factors, possible changes or improvements and possibilities of optimizing the chemical treatment
programs and chemical costs should be discussed and reviewed regularly with the chemical vendors.
Handling of chemicals
The Company has deployed a large number of chemicals supplied in standard 55 USG standard drums.
Handling of thousands of drums has been quite cumbersome encountering numerous problems, i.e. storage
of the drums, transporting to several distant field locations, piling &disposing-off empty drums, storage
conditions, maintaining inventories, bulging/rupturing/leaking of drums, health & environmental con-
cerns, etc. Therefore, it was decided to eliminate manual handling of drums by a more safe, economical
and practical way of bulk handling of chemicals (initially for abundantly used chemicals).The bulk
handling facilities comprise of a central storage facility (Primary Storage Facility) for receiving the
chemicals from the suppliers in road tankers, and subsequently distributing those by specifically designed
road tankers to the storage locations in the fields (Secondary Storage Facilities). The Primary Storage
Facility is provided with loading & unloading pumps, ethernet based Terminal Automation System (TAS),
utilities, control room & offices, fire-fighting, safety & public address systems, etc. The Secondary
Storage Facilities have been provided at the Gathering Centers, with filling connections, instrumentation/
controls, pumping facilities, etc. to the Day Tanks.
A schematic of primary and secondary storage facilities for bulk handling of chemicals is shown in
Figures 1 & 2 respectively.

Acknowledgments
The authors’ thank Kuwait Oil Company for providing an opportunity to submit this paper for the SPE
International Oilfield Corrosion Conference and Exhibition (May 12–13, 2014 – Aberdeen, UK).

Biography
Sadoun Al-Khaledi is a Team Leader with Operations Technical Services Team at Kuwait Oil Company
– Kuwait, and has more than 20 years experience. Al-Khaledi leads a team of multi-disciplinary seniors
(specialists & engineers). Al-Khaledi directs and advises on; conceptualizing of multi-disciplinary
projects, new projects development, technical studies, facilities performance enhancement & de-
bottlenecking, Geographical Information Systems & Master Reservation Records and career develop-
ments. Al-Khaledi holds a BS degree in mechanical engineering from the Wentworth College – Massa-
chusetts, USA. Al-Khaledi has presented a number of papers at the SPE Conferences earlier.
Mukhtar A. Awan is a specialist (process engineering) with Operations Technical Services Team at
Kuwait Oil Company – Kuwait. Awan has been providing process engineering support for a number of
oil & gas, chemical treatments and water handling projects. Awan has conducted many “in-company”
training courses for professional development of the junior engineers. Awan holds a BS degree in
chemical engineering from the University of Engineering and Technology Lahore.

References
1 Kuwait Oil Company, Contract No. 42955, “Bulk Handling Facilities for Production Chemicals”,
Feb. 2010 – Nov. 2012.
2 Facility Internal Corrosion Status Report, issued by Inspection & Corrosion Team, Kuwait Oil
Company, October, 2013.
10 SPE-169626-MS

Appendix-1
SPE-169626-MS 11

Appendix-2
12 SPE-169626-MS

Appendix-3 Chemical Injection, Sampling & Corrosion Monitoring Point Locations

SPE-169626-MS 13
14 SPE-169626-MS