SECTION 1

INTRODUCTION TO THE USE OF CHEMICALS

IN THE OIL INDUSTRY

INDEX
Page No.
1.

INTRODUCTION - WHY PRODUCTION CHEMICALS ARE NEEDED

2.

DEPLOYMENT

3.

HOW PRODUCTION CHEMICALS WORK - SOLVENTS AND

SURFACTANTS

3.1
3.2
4.

Solvent Effects
Surfactants

SELECTING PRODUCTION CHEMICALS

FIGURES 1-7
APPENDIX 1

1.

INTRODUCTION

The major aim of production engineers and chemists is to minimize production problems, reduce
production costs and to achieve export specifications. The Production Chemistry course is designed to
highlight the issues that lead to production problems and how these may be best solved. Solutions may
be through "engineering" means, such as ensuring that the correct designs are considered for wells,
facilities and pipelines in the first instance or during operations such as reducing the flowrates to
reduce the level of mixing between produced oil and water, making subsequent separation of these two
phases easier. Chemicals are also widely used, either as a suppliment to "engineering" solutions,
enabling greater flexibility to operate under more extreme conditions, or as a solution to production
problems in their own right. Throughout the manual both engineering and chemical solutions will be
discussed. In this section some of the commonly used chemicals are introduced and we discuss why
and where they are deployed and how they operate.
There are many specific objectives to be satisfied by use of Production Chemicals. Major areas are
deployment of chemical inhibitors to control corrosion, inorganic scale, hydrates, wax, asphaltenes or
biological activity. Demulsifiers and non-aqueous antifoams are frequently used in separation
facilities. Antifoams may also be needed for water injection deoxygenation towers. Oxygen scavengers
and polyelectrolyte flocculants may also be needed to prevent problems in water injection systems.
Flotation agents help clean up produced water for disposal. Drag reducing agents may be added to aid
flow in export lines or in water injectors.
There follows an arbitrary list of why production chemicals are used.
(i)

Safer Operational Practice

- preventing facility failure, blockages, stuck valves (SSSV's etc)

(ii)

Protect Facilities eg injection, production, export pipelines, tankage, refinery:

- preventing corrosion, blockages, biofouling

(iii) Improved Well Performance, including drilling/workover performance and success rate:
- protecting or improving Productivity and Injectivity Indices
(iv)

Improved Reservoir Description, eg using tracers

- for residual oil determination, origins of reservoir souringor movement of injected water/gas

(v)

Improved Reservoir Performance, eg:

- surfactant water flood activities
- polymers for mobility control or improved water flood conformance

(vi)

Improved Separation of Produced Fluids, eg

- breaking water/oil emulsions or gas/oil foams

(vii) Clean up and Disposal of Non-Export Produced Fluids, eg

- oily water clean-up or gas reinjection
(viii) Improved Pipeline Operations, eg
- reducing frictional pressure drop or preventing gelling during shut-down
(ix)

Improved Quality Export Hydrocarbons, eg

- desalting/dewatering oil, dehydrate/sweeten gas or reduce the viscosity of heavy oil

(x)

Cut Production Costs

As seen, production chemicals cut across all activities of the oil industry from drilling to refining.
It is vital that the correct chemicals are deployed and that their effects are fully understood.
Overdosing, or using only marginally effective chemicals can cause more operational problems than

they solve. For instance, oil/water separation problems can be made worse by blindly increasing the
emulsion breaker dosage. Sometimes chemicals can interfere with each other's function, for example
the corrosion inhibitor may fail in the presence of an incompatible scale inhibitor.
Appropriate deployment of production chemicals also help ensure safe operations, but this in turn
needs problems to be understood and predicted early enough. Sufficient time is required to identify
suitable chemicals and get them to the optimum location for deployment. However, unnecessary
storage, transport, handling and use of chemicals, some of which may be inflammable or toxic, may
increase safety risks.
The ambition of this opening session is to try to convey an understanding of what the chemicals are
doing, and how they act and interact. An overview is provided which helps to underline the principles
and philosophy involved in chemical deployment. Further details are given in the remaining sections.

2.

DEPLOYMENT

Figure1 shows typical chemicals which may be used in a crude oil production system, and where they
might be injected. Not shown, but of vital importance, are the sampling points and probes/test coupons
needed to check that the chemicals are working.
The notation used in Figure 1 for chemical types is as follows:
Corrosion Inhibitor
Scale Inhibitor
Biocide
Oxygen Scavenger
Antifoam
Demulsifer
Flocculant
Hydrate Inhibitor
Sulphide Scavenger
Wax Crystal Modifier
Polyelectrolyte Flocculant
Drag Reducing Agent

3.

CI
SI
B
OS
AF
D
FL
HI
SS
WM
PF
DRA

HOW PRODUCTION CHEMICALS WORK - SOLVENTS AND SURFACTANTS

With the variety of different chemicals it is impossible to detail the mechanisms by which each works.
However, there are a few general properties which are common to many production chemicals. In this
section we highlight two general ways in which they work and hence how they might be treated and
deployed, ie as either solvents or surfactants. This is by no means the only classification, but it is a
useful one.

3.1

Solvent Effects

Solvents are bulk phases able to 'carry' something else. The 'something else' is often a solid. It may be
a fully dissolved solid (called a solute - such as mineral salts), or a dispersed solid (finely divided,
possibly in permanent suspension - such as sand particles).
Typical examples of uses for solvent-like production chemicals are: hot toluene flushes to
wash/dissolve wax deposits in risers, methanol slugs to prevent hydrate formation during start -up of a
producer and circulating concentrated acids (HCl/HF) for well stimulations. Such solvents are
frequently toxic, volatile or inflammable, and are therefore to be treated with caution.
In addition to deploying solvent-like production chemicals, Production Chemists and Engineers are
concerned with four main solvent issues. Firstly there are the other 'bulk phase solvents'; liquid
hydrocarbons, water and gas, ie everything that we produce from a well. These are important to us
because they come loaded with 'carried' materials, and may be unstable with respect to releasing these
carried materials. For example, black oil contains dissolved waxes (high molecular weight paraffins)
and also asphaltenes (as dispersed solids). Water contains large amounts of salts which can exceed
their solubility limits as conditions change during production. Pressure or temperature regimes may
cause the precipitation of hydrates. Our concern is whether these phases will hold their load until they
are safely out of our risers/facilities/pipelines/tankage. If they won't, we may be able to prevent
separation or deposition (or reduce it to acceptable levels). This can be done through facilities design
or by changing operational practice (eg shorten residence time, keep flow turbulent, keep fluids hot or
at pressure, pig pipelines more often, extra workovers, use heated shovels etc). If that is impracticable,
unsafe, or too expensive we can resort to chemical additives to modify the solvent properties of the
produced bulk phases, thereby limiting the rate of solids deposition.
Our second concern is more straightforward - how will the 'solvent' interact with our hardware. An
obvious issue is corrosion. Although pure water itself is not very corrosive at all, hot water plus its
'carried' materials can be extremely corrosive. Dissolved oxygen can cause or catalyse corrosion.
Hydrogen ions (in acidic water containing sulphide or carbonate) make water a much better solvent for
metals than neutral (pH7) water. Dissolved salts also affect water properties, giving rise to localised
effects such as chloride induced stress corrosion cracking. Oil can also act as a solvent, eg dissolving
elastomer seals or plastic umbilicals, creating its own problems.
Our third concern is over some of the substances dissolved in the produced bulk phases. Hydrogen
sulphide and mercaptans in water, oil or gas may have to be removed chemically before our produced
fluids can be exported or disposed of. Dissolved oil in water is detected in some assays of the oil
loading in discharged water. Water (and perhaps added hydrate inhibitors) may also have to be
removed from gas prior to export.
Our final concern is with using oil/water/gas 'bulk phase solvents' as the delivery vehicle for other
production chemicals. Some chemicals have limited solubility and may precipitate out in unwanted
places if the solvency changes (e.g.the internal pipewall of a subsurface flowline may be much colder
than the temperature of the bulk fluids flowing through it). The chemical may have a choice of phases
to dissolve in, and must stay in the right phase for the chemical to go to the place where it is needed.
For example, a scale inhibitor must act in the water phase - it is not much use if it partitions strongly
into oil and never contacts the scaling salts in produced brine.
3.2

Surfactants

Surfactant stands for surface active agent.

Generally, a surfactant can be envisaged as having a 'hydrocarbon tail', which likes to be immersed in
hydrocarbons and hates being in water and an 'electrically charged head', which likes to be surrounded

by water. A surfactant molecule, (Figure2) will be moved around by various forces until it reaches a
position of lowest free energy. It may not be fixed there, but it will stay a relatively long time, and
more surfactant will be found there at any given time than in higher energy environments. In bulk
water, the hydrocarbon tails tend to clump together so they are out of contact with the water
(Figure3). In bulk oil, the charged heads tend to aggravate so they are out of contact with the oil
(Figure4). At an oil/water interface, both ends can stay in their respective compatible phases
(Figure5). A typical scene for a 'water soluble' surfactant in a production environment might be as
shown in Figure6. In each of these cases, surfactant molecules are always found at interfaces, and it
is this property that makes them important to Production Chemists. For instance, corrosion inhibitors
and scale inhibitors have to operate at a solid/water interface, demulsifiers at a water/oil interface or
antifoam agents at a liquid/gas interface.
To be fully effective, the surfactant must be attracted to the right interface. For instance, to make a
surfactant less water soluble (more oil soluble) it must be attracted more towards the oil. This may be
achieved by increasing the tail size, decreasing the head size, adding salt to the water, having a lighter
oil (or adding light ends) or by adding another oil soluble surfactant. However, any of these changes
may reduce the performance of the chemical for the task required.
A few points not always appreciated are:
(i)

The solvency of each bulk phase (for the head and tail parts separately) helps determine where
the surfactant will be attracted to and how it will pack at any interface. Therefore the type of oil
'solvent' makes a difference. It is therefore not surprising that there are no "universal" inhibitors
that work effectively in all environments.

(ii)

If a surfactant needs to be finely balanced between oil and water and won't work unless that
precise balance is maintained, then almost any change to operational parameters may reduce its
effectiveness. As an example, the salinity of produced water may change when injection water
breaks through at producing wells. This may affect the performance of a demulsifier and
necessitate a change in chemical to maintain optimum efficiency.

(iii) Production Chemical surfactants are mixtures comprising by-products and unreacted precursors
in addition to the active component. An inactive species in the mixture may be more strongly
adsorbed at the target interface than the active. Thus, If the dose level is increased, the 'effective'
surfactant can end up swamped by the less effective part. It is possible to overdose as well as
underdose.
(iv)

Natural surfactants in the crude oil can have an enormous effect. Also, they are often first to the
interface, and may be difficult to displace. This is particularly the case with water in oil
emulsions, which become more stable and harder to treat when aged because natural surfactants
in the crude have time to migrate to the interface and pack more effectively.

In summary, a surfactant is attracted to an interface. Figure 7 shows the interfaces at which several
classes of Production Chemicals operate. Further details of surfactants and interfaces are given in
other sections, and more specifically in the Appendices at the end of this section.

4.

PRIORITIES IN SELECTING PRODUCTION CHEMICALS

The best form of defence is always to understand the likely problems in advance. Regular monitoring,
good sampling procedures, forward prediction and preparation well in advance are recommended,
rather than waiting until a problem has halted production before tackling it. Nonetheless, there is no

point in seeking a cure for a problem which isn't there. Clearly a good predictive capability is
important.
Ideally, part of any chemical selection process should be to examine how 'robust' the chemical is, both
in terms of its activity and ease of physical deployment. For instance, is it effective over a range of
operation conditions? Will it be quickly dispersed into the correct phase on deployment? Is it supplied
in the right solvent and in the desired physical form? How sensitive to dosage levels is it, since pumps
are not always accurate? Is it compatible with other chemicals and fluids present?
Another important criterion is whether it is possible to conduct simple quality assurance checks on the
chemical in a field situation. New batches should ideally be examined for active concentration, and for
their efficacy in some performance related test.
Finally, it is not always sound economics to change to a cheaper chemical. There is a premium on
'trouble-free' operations, and the penalty for failure if deploying a new but cheaper chemical could be
high, particularly for long trials.
Most developments rely upon the use of chemicals for effective and safe operations. However, as
discussed above the number and action of the variety of chemicals can be very wide. Careful
management is necessary to ensure that the chemicals do their job and do not upset other operations.
In Section 15 we discuss chemical management in some detail.