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Chemicals for

Corrosion Prevention
INDEX

1 INTRODUCTION 3

2 CORROSION PROCESS 4
2.1 General 4
2.2 Chemistry of Corrosion 5
2.2.1 Corrosion Reactions 5
2.2.2 Potential Difference in the Corrosion Process 6
2.3 The Consequences of Corrosion 9
2.4 Overview of corrosion prevention methods 10
2.4.1 Selection of resistant materials 10
2.4.2 Passive Protection 11
2.4.3 Electrical Protection 12
2.4.4 Environmental Properties Modifications 13

3 CHEMICALS INJECTIONS 14
3.1 Chemicals for environmental modifications 14
3.1.1 pH Correction 14
3.1.2 Oxygen Removal 14
3.1.3 Use of aggressive solutions 16
3.2 General Considerations 16
3.3 Biocides 16
3.4 MEG Chemicals 19
3.5 Antiscaling 20
3.6 Corrosion Inhibitors 23
3.6.1 Corrosion Inhibitors Actions 23
3.6.2 Corrosion Inhibitors classifications 24
3.6.3 Inhibitor Composition 24
3.6.4 Inhibition Mechanisms 26
3.6.5 Cathodic and Anodic Inhibitors 28
3.6.6 Fields of Application 29

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1 INTRODUCTION

Corrosion is the deterioration of materials by chemical interaction with their


environment.

Corrosion is defined as the deterioration that a metal undergoes as a


consequence of a spontaneous chemical reaction between the environment
and the metal itself. The most widely used metal is iron (usually as steel).

Corrosion Definition by ISO:

Physical-chemical interaction between a metal and its environment which


results in changes in the properties of the metal.

It is important to realise that corrosive attack on a metal can only occur at the
surface of the metal, hence any modification of the surface or its environment
can change the rate of reactions. Thus we have a basis for designing methods
to protect metals from corrosion.

Figure INTRODUCTION .1 – Corrosion Process

The aim of this booklet is to describe the main chemicals used for corrosion
prevention in Oil & Gas plants. The Cathodic protection is only mentioned.

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2 CORROSION PROCESS

2.1 General

When iron or steel is exposed to atmospheric oxygen in the presence of water,


the well-known rusting process takes place.

Steel → Rust

The metal is degraded to form ferric rust, a red-brown compound, which is a


sure sign of electrochemical oxidation of the metal.

Figure CORROSION PROCESS.2 – Rust

We have all seen corrosion and know that the process produces a new and
less desirable material from the original metal; this can result in a loss of
function of the component or system.

We see most commonly the rust formed on the surface of steel. For this to
happen, the major component of steel, iron (Fe), at the surface of a
component undergoes a number of simple changes.

Corrosion:

 is a natural phenomena, it must be controlled at reasonable cost;

 is inherently probabilistic by nature, affected by a great variety of


parameters, then frequently difficult to be predicted in detail (unexpected)

 has consequences that can be catastrophic and tremendously expensive;

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2.2 Chemistry of Corrosion

2.2.1 Corrosion Reactions

The corrosion reactions are electrochemical reactions occurring at the metal


surface. These reactions can be anodic and cathodic.

The most common and important electrochemical reactions are in the


corrosion of iron.

As iron atoms undergo oxidation to ions, they release electrons whose


negative charge would quickly build up in the metal and prevent further anodic
reaction, or corrosion. Thus this dissolution will only continue if the electrons
released can pass to a site on the metal surface where a cathodic reaction is
possible.

At a cathodic site the electrons react with some reducible component of the
electrolyte and are themselves removed from the metal.

The rates of the anodic and cathodic reactions must be equivalent according
to Faraday’s Laws, being determined by the total flow of electrons from
anodes to cathodes which is called the “corrosion current”, Icor.

Since the corrosion current must also flow through the electrolyte by ionic
conduction the conductivity of the electrolyte will influence the way in which
corrosion cells operate.

The corroding piece of metal is described as a “mixed electrode” since


simultaneous anodic and cathodic reactions are proceeding on its surface.
The mixed electrode is a complete electrochemical cell on one metal surface.

The most common and important electrochemical reactions in the corrosion of


iron are thus:

Anodic reactions involve oxidation: electrons appear on the right hand side
of the equation. For example, metallic iron can produce ferrous ions by the
anodic reaction (corrosion):

-
Fe → Fe2+ + 2e

In a solution with higher pH, the anodic reaction produces a surface film of
ferric oxide according to reaction:

+ -
2Fe + 3H2O → Fe2O3 + 6H + 6e

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Cathodic reactions involve electrochemical reduction: electrons appear
on the left hand side of the equation. In corrosion processes the most common
cathodic reaction is the electrochemical reduction of dissolved oxygen
according to the equation:

- -
O2 + 2H2O + 4e → 4OH

The reduction of oxygen at an electrode will cause a rise in pH due to


hydroxide ion production.

This series of steps tells us a lot about the corrosion process:


1) Ions are involved and need a medium to move in (usually water);
2) Oxygen is involved and needs to be supplied;
3) The metal has to be willing to give up electrons to start the process;
4) A new material is formed and this may react again or could be protective
of the original metal;
5) A series of simple steps are involved and a driving force is needed to
achieve them.

2.2.2 Potential Difference in the Corrosion Process

The potential difference E across the interface between a metal and water
(electrolyte) is the key factor controlling both the products of corrosion
reactions and rate at which they are formed.

The potential difference itself is caused by layers of charges at the surface:

Electrons in the metal and excess anions or cations in the solution are showed
in the following figure:

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Figure CORROSION PROCESS.3 – Electric double layer at metal surface

This arrangement of charges is known as the double layer or Helmholtz layer

The state of charging of double layer and hence the magnitude of the potential
E can be changed as a result of using an external electrical current or by
electrode reactions such as the above anodic and cathodic reactions. For
example, in the presence of a high concentration of oxygen, the cathodic
reaction will remove electrons from the metal surface hence making the metal
more positively charged and increasing the potential E.

The role of the electrode potential E in defining the products of corrosion


reactions can be readily seen in the following figure:

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Figure CORROSION PROCESS.4 – Iron equilibrium diagram

The diagram is related to Iron at 25 oC in water. It shows the stable forms of


the element as a function of E and pH.

The figure above shows the corrosion products of iron as a function of


electrode potential and pH for iron at room temperature in the presence of
water. At negative potentials metallic iron itself is the stable form hence in this
region no corrosion is possible, and this is referred to as the immunity
condition. At higher potentials and acidic pH values ferrous ions will form
giving rise to active corrosion. Ferric ions are produce only at high potentials
above 0.7 V.

If the pH lies on the alkaline side of neutral then insoluble surface oxides will
form. The oxide Fe3O4 , known as magnetite or black iron oxide, is produced
at low electrode potentials.

At more positive potentials the oxide formed is Fe2O3 and this is usually
present as a thin adherent film. Since this oxide forms at the surface, its
presence acts to block the surface reactions and hence corrosion rates are
reduced. This is called passivation and the oxide film on the surface is known
as a passive layer. The corrosion rate is very low in the passivation
region of the diagram.

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The diagram above is widely used in corrosion technology to predict the
corrosion products which may be formed from a given metal under conditions
specified by the axes of the figure.

However the diagram does not tell the rate of corrosion which may be the
most important information required in a practical situation.

2.3 The Consequences of Corrosion

The consequences of corrosion are many and the effects on the safe, reliable
and efficient operation of equipment or structures are often more serious than
the simple loss of a mass of metal.

Failures of various kinds and the need for expensive replacements may occur
even though the amount of metal destroyed is quite small.

Some of the major harmful effects of corrosion can be summarised as follows:

 Reduction of metal thickness leading to loss of mechanical strength and


structural failure or breakdown. When the metal is lost in localised zones so
as to give a crack- like structure, very considerable weakening may result
from quite a small amount of metal loss;

 Loss of time in availability of profile-making industrial equipment;

 Reduced value of goods due to deterioration of appearance;

 Contamination of fluids in vessels and pipes (e.g. beer goes cloudy when
small quantities of heavy metals are released by corrosion);

 Perforation of vessels and pipes allowing escape of their contents and


possible harm to the surroundings;

 Loss of technically important surface properties of a metallic component;

 These could include frictional and bearing properties, ease of fluid flow over
a pipe surface, electrical conductivity of contacts, surface reflectivity or heat
transfer across a surface;

 Mechanical damage to valves, pumps, etc, or blockage of pipes by solid


corrosion products;

 Added complexity and expense of equipment which needs to be designed


to withstand a certain amount of corrosion, and to allow corroded
components to be conveniently replaced;

Corrosion can be avoided or delayed by:

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 detecting the corrosion danger at an early stage;

 choosing the proper material for a given environment;

 Applying / developing corrosion resistant coating and surface treatment


techniques;

 reducing the corrosivity of the environment by chemical treatment (inhibitors,


…)

Because the corrosion process takes place in the surface of metal, any
modification of the surface or its environment can change the rate of reaction.

2.4 Overview of corrosion prevention methods

Corrosion prevention techniques can be generally based on:

 Selection of resistant Metals (Metal Selection and Surface Conditions);

 Passive protection (protective paints and coatings) ;

 Change of Electrical Status (Cathodic or Anodic Protection) ;

 Environmental Properties Modifications (adding the inhibitors, Ph


modification, removal of oxygen, etc) ;

2.4.1 Selection of resistant materials

No metal is immune to corrosion in all environments, but through monitoring


and understanding the environmental conditions that are the cause of
corrosion, changes to the type of metal being used can also lead to significant
reductions in corrosion. Metal corrosion resistance data can be used in
combination with information on the environmental conditions to make
decisions regarding the suitability of each metal.

The practical list of noble materials which can be used, conveniently, in


industrial applications is indeed very short: excluding precious metals, such as
gold and platinum, it restricts to copper alloys that can be used in acid media
(typically Monel, i.e., a 60% Ni – 40%Cu alloy).

A much longer list of passive materials with practical ennoblement behaviour,


is available, such as stainless steels and nickel base alloys.

The development of new alloys, designed to protect against corrosion in


specific environments are constantly under production. Hastelloy® nickel

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alloys, Nirosta® steels and Timetal® titanium alloys are all examples of alloys
designed for corrosion prevention.

Proper monitoring and the elimination of unnecessarily vulnerable surface


conditions, along with taking steps to ensure that systems are designed to
avoid reactive metal combinations and that corrosive agents are not used in
the cleaning or maintenance of metal parts are all also part of effective
corrosion reduction program.

2.4.2 Passive Protection

Corrosion prevention is also obtained by a physical separation of the exposed


metal surface from the environment by a barrier made of a coating or
painting.

Coating the metal is carried out in order to interpose a corrosion resistant


coating between metal and environment.

Coatings consist of resins, pigments, solvents, and additives. Resins or


binders hold all paint constituents together and enable them to cure into a thin
plastic film. Resins are made up of polymers, which are chosen based on
physical and chemical properties desired in the finished product.

The coating may consist of:

 another metal, e.g. zinc or tin coatings on steel ;

 a protective coating derived from the metal itself, e.g. aluminium oxide on
“anodised” aluminium:

 organic coatings, such as resins, plastics, paints, oils and greases

The action of protective coatings is often more complex than simply providing
a barrier between metal and environment.

Paints may contain a corrosion inhibitor (See following chapter)

Zinc coating in iron or steel confers cathodic protection.

2.4.3 Electrical Protection

Since corrosion is an electrochemical process its progress may be studied by


measuring the changes which occur in metal potential with time or with applied
electrical currents.

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Conversely, the rate of corrosion reactions may be controlled by passing
anodic or cathodic currents into the metal.

If, for example, electrons are passed into the metal and reach the
metal/electrolyte interface (a cathodic current) the anodic reaction will be
stifled while the cathodic reaction rate increases. This process is called
cathodic protection and can only be applied if there is a suitable conducting
medium such as earth or water through which a current can flow to the metal
to be protected. Cathodic protection may be achieved by using a DC power
supply (impressed current) or by obtaining electrons from the anodic
dissolution of a metal low in the galvanic series such as aluminium, zinc or
magnesium (sacrificial anodes). Similar protection is obtained when steel is
coated with a layer of zinc. Even at scratches or cut edges where some bare
metal is exposed the zinc is able to pass protective current through the thin
layer of surface moisture.

In certain chemical environments it is sometimes possible to achieve anodic


protection, passing a current which takes electrons out of the metal and
raises its potential. Initially this stimulates anodic corrosion, but in favourable
circumstances this will be followed by the formation of a protective oxidised
passive surface film.

Figure CORROSION PROCESS.5 – Cathodic Protection

2.4.4 Environmental Properties Modifications

Corrosion is caused through chemical interactions between metal and


surrounding environment. By removing the metal, or changing, the type of
environment, metal deterioration can be immediately reduced.

Methods to reduce the sulphur, chloride or oxygen content in the surrounding


environment can limit the speed of metal corrosion

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Chemical treatments of the environment can have different aims:

 pH control;

 Oxygen removal;

 use of aggressive solutions, such as strong acids, to remove scale or


oxides on metal surface

 Injection of chemicals for three main purposes:

 to reduce bacterial activities (by the injection of so-called biocides);

 to prevent scaling (antiscaling chemicals) ;

 to reduce hydrates (glycol) ;

 to reduce corrosion rate, by means of so-called corrosion inhibitors.

When possible, the environmental composition is changed in order to reduce


aggressiveness or to promote self-protection condition of the metal by the
formation of a passive film (passivation) or protective scales.

The aim of this booklet is to describe the main methods of corrosion


prevention by modification of environmental properties.

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3 CHEMICALS INJECTIONS

3.1 Chemicals for environmental modifications

3.1.1 pH Correction

Raising the pH of environmental can reduce its corrosiveness.

For instance, an increase in pH helps form a passive oxide film on carbon


steel, stainless steels and nickel-based alloys. Attention should be paid for
metals such as aluminium, zinc or lead. As far as carbon and low alloy steels
are concerned, a pH above 10 up to 12 strongly promote passivity on steel
and so protection even in the presence of oxygen.

Methods for pH correction can include:

 varying the pH to modify the ability of water to form encrustations;

 the addition of alkaline substances to avoid acid condensates;

With reference to the latter treatment, it should be remembered that the


presence of acid substances such as CO2 and HCl, which in the dry vapour
state do not cause corrosion problems, does render condensates highly
aggressive. In these cases, the control of acidity involves the use of
neutralizers such as ammonia or various amines injected into the vapour
stream, for example before they enter the condensers at the head of crude
distillation columns, or added to the feed water of steam generators.

A pH control treatment is often performed on gas pipeline where in case of


water condensation corrosion rate can be reduced by increasing pH. This
treatment is convenient because of low amount of electrolyte, i.e., condensed
water. In case formation water is entrained, the treatment may result less
convenient than the use of a corrosion inhibitor, due to the high dosage
required. Typical chemicals used are sodium bicarbonate or hydroxide or
even amines, these latter exhibiting also an inhibition effect.

3.1.2 Oxygen Removal

Oxygen removal in association with an alkaline pH, for instance about 10,
represents an effective chemical treatment to reduce corrosion rate of carbon
and low alloy steels.

In neutral or near-neutral solutions, where oxygen reduction is the cathodic


reaction, the removal of oxygen produces a reduction up to a halt of the
corrosion rate, provided the pH exceeding neutrality.

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Removing oxygen from neutral or alkaline waters reduces and in practice
stops the corrosion of carbon steel. This is done with physical methods by gas
stripping or a vacuum treatment to reach residual oxygen contents of 0.015
ppm (sufficient for boiler feed waters at low or medium pressure) or with
chemical methods (injection of an oxygen scavengers) often coupled with
physical methods to bring the oxygen content to a few ppb.

Typical Oxygen scavengers are:

 Hydrazine N2H4

 Sodium bisulphite NaHSO3

These substances act by the following reactions respectively. Hydrazine


(reaction occurring at T > 140 °C, hot environment)

N2H4 + O2 2H2O + N2

 Bisulphite (reaction at low temperature could environment)

At low temperature, sulphites are used through the following chemical


reaction:

2 Na HSO3 + O2 2 NaHSO4

1 ppm of O2 requires about 8 ppm of NaHSO3

Hydrazine may partially decompose to form ammonia according to the


reaction N2H4 4NH3 + N2; this produces a beneficial alkalinity which
encourages the separation of protective films of magnetite on steel.

Another advantage of hydrazine compared to sulphite is that the latter does


not cause an increase in the salinity of the water. However, hydrazine reacts
with oxygen at an appreciable velocity only at temperatures above 140 °C.
Moreover, problems of toxicity make using this substance inadvisable.

Typical oxygen removal treatment comprises: a first stage of physical oxygen


removal in a deoxygenating column, by vacuum or gas stripping, and a
second stage consisting on the injection of an oxygen scavenger at column
bottom.

Oxygen Scavengers are used in water injection systems.

3.1.3 Use of aggressive solutions

When chemical treatment are performed to clean metal surface or to remove


scale, acid solutions are used.

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Strong acid, while inhibited to minimize corrosion rate during treatment
(although of short duration, for instance a few hours up to a couple of days, as
a maximum) are generally used, especially for cleaning purposes. For scale
removal, organic acid are also used, as edta, oxalic, phosphoric acids. These
acids are reactive against scale while much less aggressive against carbon
steel.

3.2 General Considerations

When a chemical injection is performed, especially in upstream facilities, as


wells, wellheads, flow-lines, manifold and separators, the specific purpose of
the treatment can be various, as

 Control bacterial activity by means of biocides

 Avoid scaling such as calcareous deposits (use of antiscaling)

 Avoid hydrate formation in gas lines by MEG chemicals;

 Most important chemical injection treatment is the reduction of corrosion rate


through corrosion inhibitors injection;

3.3 Biocides

Biocides are chemicals used to sterilize solution and limit growth of bacteria
and microorganisms. Biocides are used often in association with oxygen
scavenger injection because by the oxygen anaerobic conditions settle up.

The main Biocides characteristics are:

 Organic

 Demonstrated effectiveness versus SRB (sulphate reducing bacteria) /


aerobes

 Able to penetrate deposits to access sessile bacteria

 Compatible with system / other chemicals / downstream refinery processes

 Low environmental impact

 Customer awareness of toxicity hazards + handling requirements

Biocides are used often in association with oxygen scavenger injection


because by the oxygen anaerobic conditions settle up.

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Biocides can be classified as:

 Oxidizing

 Non-oxidizing.

Among oxidizing types, chlorine is the most used because economical, broad
spectrum activity, simple monitoring dosage. Chlorine is used to sterilize
solution. It is effective against algae, microorganisms and aerobic bacteria. It
is ineffective against Sulphate Reducing Bacteria and bio-film. To control
growth of anaerobic bacteria, whose main strain in Sulphate Reducing
Bacteria type, synthesis chemical must be used. Attention should be paid
when used because they are strong poisons and dangerous pollutants.

Chlorine Advantages

 it is economical

 it has broad spectrum activity

 monitoring dosages and residual is simple

Chlorine Disadvantages

 operator hazard concerns

 ineffectiveness against biofilm bacteria

Non-oxidizing type biocides are:

 Aldehydes ;

 Sulphur compounds

 Quaternary phosphonium salts ;

 Amines;

 Quaternary amine compounds;

Aldehydes:

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Formaldehyde is used because economical. Its disadvantages are high
dosages requirement and reactivity with ammonia, hydrogen sulphide and
oxygen scavengers.

Glutaraldehyde has some more advantages, as broad-spectrum activity,


relatively insensitive to sulphide, compatible with many other chemicals,
tolerance to salts and hardness. For this, it is widely used in the petroleum
industry, in a blend with other biocides and surfactants to increase its
effectiveness.

Sulphur compounds:

 Isothiazolone is compatible with brines, good anti-sessile bacteria activity,


degradable. Its drawbacks are incompatibility with sour system and
expensiveness.

 Carbamates are effective against SRB and spore formers, effective in


alkaline pH. As drawbacks they require high concentration and react with
metal ions.

 Metronidazole is effective only against anaerobic organisms. Most used in


squeeze applications.

Quarternary phosphonium salts

Quaternary Phosphonium Salts are relatively new. Used in water injection


systems because stable in formation. In general they have good stability, low
toxicity and are unaffected by sulphides.

Amines

Amines and Diamines have the advantages of a broad-spectrum activity,


effective in sulphide bearing waters and a good surface activity through a good
filming effect. As main disadvantages, they react with other chemicals and are
less effective in waters with high levels of suspended solids, because filming
effect weakens.

Quaternary amine compounds

Quaternary Amine Compounds show many advantages, as broad-spectrum


activity, good surfactancy, good persistency and low reactivity with other
chemicals. As main disadvantages, they are inactivated in brines, can produce
foams and are slow acting.

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3.4 MEG Chemicals

A hydrate is a solid structure where a gas molecule is surrounded by a cage of


water molecules. It is formed at high pressures and low temperatures.
Hydrates are very similar to snow and ice and can form plugs in pipelines
leading to blockage.

The formation of hydrates can plug pipelines or increases friction loss.

To prevent such hydrates, injecting a substance like mono ethylene glycol


(MEG) will lower the freezing point of water by diluting the system, just like an
anti freeze agent. A lower freezing point ensures that solid structures of water
cannot form and hence there will be no formation of hydrates.

To reduce the formation of hydrates, high concentrations of glycol are injected


in wet gas pipeline.

MEG is transported in a so-called MEG loop. Here, MEG is injected into the
natural gas pipeline at the wellhead and flows with the natural gas to
processing site onshore. The MEG transported from the reservoir is called rich
MEG and lean MEG respectively.

Using MEG, water in the pipeline will at some point condensate due to
temperature drop.

Since MEG has lowered the freezing point, this water will be in liquid form.
Liquid water leads to a problem with corrosion.

The cause of this is the presence of CO2, which in contact with water forms a
weak carbonic acid (H2CO3), as shown in the following reaction:

CO2 (g) + H2O (l) H2CO3

Long pipelines are constructed of carbon steel.

Carbonic acid will corrode the iron in the pipeline wall, producing iron
carbonate. This iron carbonate can precipitate in the production fluid and
follow the gas and liquid flow, causing problems downstream.

Fe + H2CO3 FeCO3 +H2

To combat this problem, pH-stabilizing is implemented. Here, pH is increased


from the sour condition of the reservoir into more neutral conditions. This is
done by injecting an alkaline chemical, sodium hydroxide (NaOH), together
with the MEG.

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3.5 Antiscaling

Scaling

Scaling is the deposition of a mineral salt on processing equipment. Scaling


occurs when water has high levels of minerals like calcium carbonate, which
can build-up on surfaces.

Slight scaling can be considered beneficial in that the inside surfaces of metal
pipes become coated with harmless minerals that act as a barrier to corrosion.
Increased levels of scaling, however, can be harmful.

Figure Chemicals Injections .6 – Corrosion and Scaling

Scaling can be a serious problem for the oil and gas industry.

Scale can occur in all parts of a gas production system and due to several
different mechanisms. Common for them are that the system is within, or
brought into, a supersaturated regime. Scaling is a result of supersaturation of
mineral ions in the process fluid.

This supersaturation of ions is caused by several factors. An important


contributor is the production of high salt content water like formation water
from the well. This increases the ionic concentrations, possibly leading to
deposition of scales.

Scale can be removed chemically or mechanically after deposition. Also, scale


formation can be prevented before deposition occurs

Chemical removal

Scales can be divided into two major categories:

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 the acid soluble scales consisting mainly of carbonates (MxCO 3) and
sulphides (MxSy) and

 the acid insoluble scales consisting mainly of sulphates (MxSO4)

The M refers to a metal ion, for example calcium, and x/y refers to
stoichiometric ratios. Acid soluble scales, the use of a strong acid can
dissolve the precipitated scales. For calcium carbonate, hydrochloric acid
may be used. Scales that cannot be solved by acids require other treatments.
These scales can be removed by using a strong chelating agent. A chelating
agent is a complex molecule which breaks up the scale by isolating and tying
up the metallic ions in the scale.

Chemical scale removal is usually a cheap and easy way to remove scales,
but the effectiveness of the removal depends on surface to volume ratio of the
scale. If the scale has a large surface area compared to the volume, like
porous materials, the scale will be broken down quickly. This is due to the
large contact area between the chemical agent and the scale. If a scale has a
low surface to volume ratio, like a non-porous material, only the exterior
surface will be in contact with the chemical agent. Because a non-porous
scale will be broken down only from the exterior surface, while a porous
material will be broken down from the exterior and interior surface, the
removal of a non-porous scale will be much slower.

Mechanical removal

There are many different ways of removing scales mechanically. One can use
simple milling or impact techniques.

Scales rarely forms evenly along tubules, and therefore the energy required to
remove the scales vary greatly. If the speed of the milling device is not set at a
sufficiently high speed, there is a risk of stalling. Impact techniques works
much like a jack hammer, hammering the scales until they break. These
impact techniques work best for brittle scales. Another technique is to use
explosives induce shock vibrations to the pipe, causing brittle scales to break
off. This method is effective against thin layers.

Prevention of scale

The cost of scales removal can be quite costly. Therefore it is sensible to


prevent the formation of scales.

 One of the easiest ways is to dilute ion rich waters with fresh water, reducing
the concentration of ions and thus the saturation of the system.

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 Another way is to use a scale inhibitor.

Scale inhibitors can hinder scale growth in several ways, where some of
them are:

 Absorption onto the surface of the scale nuclei to make combination with
other crystals difficult,

 absorption on a surface defect of a crystal preventing further growth

 use a chelating agent

One problem with chelating inhibitors is that a stoichiometric ratio often is


required.

This creates large amounts of waste. These kinds of inhibitors are also
sensitive to equilibrium changes. Absorption inhibitors attack the crystalline
structures and not ions themselves. Therefore, an amount 1000 times lower
than the stoichiometric ratio is needed, resulting in reduced treatment cost.

Another problem with chemical inhibitors is the calcium carbonate itself.


Calcium carbonate has three different crystal structures. The variation is
crystal structures demands different inhibition mechanisms for different crystal
structures. This can explain why certain inhibitors after some time apparently
stop working. Than, scale formation occur and some times even more
aggressive than before inhibition.

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3.6 Corrosion Inhibitors

3.6.1 Corrosion Inhibitors Actions

An inhibitor of a chemical reaction is a substance that decreases the rate of a


chemical reaction.

A corrosion inhibitor is a chemical additive, which, when added to a corrosive


aqueous environment, reduces the rate of corrosion. Corrosion inhibitors are
substances which, when added in small quantities to aggressive
environments, can slow down or stop corrosion processes.

The substances are extremely numerous and of very different natures

The technique of adding inhibitors to the environment of a metal is a well


known method of controlling corrosion in many branches of technology.

A corrosion inhibitor may act in a number of ways:

1. It may restrict the rate of the anodic process or the cathodic process by
simply blocking active sites on the metal surface;

2. Alternatively it may act by increasing the potential of the metal surface so


that the metal enters the passivation region where a natural oxide film
forms.

3. A further mode of action of some inhibitors is that the inhibiting compound


contributes to the formation of a thin layer on the surface which stifles the
corrosion process.

Generally speaking, they work by modifying the surface layer of the metallic
material to be protected so that the reaction rate is reduced. The consequent
increase in reaction resistance sometimes results from the inhibition of the
cathodic process and/or the anodic process; in other cases it results from the
establishment of passive conditions.

Therefore, corrosion inhibitors react with the metal's surface causing


corrosion, thereby, interrupting the chemical reaction that causes corrosion.
Inhibitors can work by adsorbing themselves on the metal's surface and
forming a protective film. These chemicals can be applied as a solution or as a
protective coating via dispersion techniques.

3.6.2 Corrosion Inhibitors classifications

Major end-use industries for corrosion inhibitors are petroleum refining, oil and
gas exploration, chemical production and water treatment facilities.

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The benefit of corrosion inhibitors is that they can be applied in-situ to metals
as a corrective action to counter unexpected corrosion.

Inhibitors can be:

 Safe or dangerous ;

 Organic or inorganic inhibitors;

 barrier layer formers;

 Adsorption or barrier layer former

 anodic, cathodic or mixed

3.6.3 Inhibitor Composition

A corrosion inhibitor is a chemical additive. Corrosion inhibitors are often


emulsions that are able to form an organic film on the parts to be protected.

A typical commercial C.I. is formulated as follows

 active principle (the “true” inhibitor);

 solvent (for pumpability & partitioning requirements);

 surface active components (demulsifiers, dispersants);

Figure Chemicals Injections .7 – Corrosion Inhibitor Composition

Solvents are added prevent separation and make inhibitors less viscous so
they are easier to apply.

A treating chemical contains an active compound and one or more additives.


Additives help the treating chemical achieve its purpose. A typical treating

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chemical often contains only about one-third active ingredients. The other
two-thirds of the treating chemical are solvents or additives such as
surfactants, demulsifiers, etc

Treating chemicals must remain in liquid form while they are stored in tanks or
drums. For example, water is added to water-soluble corrosion inhibitors to
improve their application. Solvents also lower the pour point, the minimum
temperature at which the chemical remains a liquid.

A corrosion inhibitor can take action if it reaches the metal surface. Therefore,
two conditions have to be met:

 clean surface from dirt, deposit and any substances may act as a barrier;

 physical contact of the inhibitor (its active principle) with metal surface;

In multiphase hydrocarbon streams, there is a prevailing phase which wets the


surface of the container (typically a pipeline) for most of the time. According to
this condition, to assure that the inhibitor comes in contact with metal
surface, it has to be present in the prevailing phase.

Therefore, inhibitors used in oil & gas can be classified on the basis of their
solubility as well as their selection: for instance, if in a multiphase stream,
water is the prevailing phase, so that with the highest probability will wet the
container surface, the inhibitor must be of a water soluble type, and similarly
oil soluble when oil phase is the prevailing one. In some conditions, the use of
dispersible inhibitor in a phase can help increase inhibitor efficiency.

Oil soluble inhibitors

Typical oil soluble inhibitors are:

 long chain primary amines

 Imidazolines

 Fatty acids

 Phosphate esters (generally more effective at high temperatures and high


velocities)

To assure high effectiveness, turbulent flow conditions are required to help oil
wetting.

Water soluble inhibitors

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Typical water soluble inhibitors are:

 quaternary amines

 amine salts

 imidazoline salts

Main characteristics are:

 more effectiveness in stratified flow conditions;

 solubility decreases in very concentrated brines (high total dissolved solids);

 Insoluble or less soluble salts can form (an excess of active principle in the
formulation is necessary).

Volatile (used in gas phase)

3.6.4 Inhibition Mechanisms

The following table shows examples of common inhibitor systems classified by


their modes of action.

Adsorption Inhibitors

Adsorption inhibitors reduce the corrosion rate due to polarization of the


metal by extremely thin layer of their molecules adsorbed on the surface.
Decrease of the effective surface area results in reduction of the corrosion
rate. Adsorption inhibitors are substances (mainly organic) capable to form
chemisorbed bonds with surface metal atoms.

Adsorption inhibitors are used quite widely in many proprietary mixtures which
are marketed to control corrosion.

For example, radiator fluids in the cooling circuits of engines frequently contain
amines such as hexylamine C6H3NH2, or sodium benzoate. These act as
inhibitors of the anodic reaction.

Corrosion inhibitors are also used in the metal cleaning field. For example, it is
possible to clean steel articles by immersion in sulphuric acid; H2SO4.The acid
would normally attack the metal, causing corrosive loss. This can be
minimised by adding antimony trichloride, SbCI 3, a specific inhibitor for
preventing the corrosion of steel in acidic media. Oxides and foreign metals
such as zinc will readily dissolve in the presence of SbCl 3 , which acts only on

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the steel itself. Amine inhibitors are sometimes present in volatile corrosion
inhibitors.

Passivating inhibitor

The second class of inhibitors are those which cause the potential of the
metals to rise into the passivation region. They are all oxidising agents,
containing elements in their higher oxidation states. For example nitrite, which
is used as an additive in cooling fluid circuits for the control of corrosion of
steel, is a mild oxidising agent which can raise the potential of steel into the
passivation region. A traditional pigment used in paints is red lead, Pb3O4.

Likewise zinc chromate ZnCrO4 is also widely used in corrosion control as a


passivating inhibitor. The passivating inhibitors all share the common property
of conferring protection on a metal by using its own natural oxide film.

Surface Layer Inhibitor

The last category of corrosion inhibitors are those which form a surface layer
of a foreign chemical compound provided by the inhibitor itself. For example
phosphate is widely used as an additive in boiler water or cooling circuits and
in pickling baths for metals. Phosphate produces a surface layer of ferric
phosphate FePO4 on steel which provides a measure of corrosion protection
and is an excellent base for paints. Chromate is an extremely important
industrial inhibitor in spite of its toxicity and unfavourable environmental
problems.

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Table Chemicals Injections .1 – Corrosion Inhibitors

Mode of Action Example


Amines, antimony trichloride
Adsorption
RNH2, SbCl3
Nitrite, chromate, red lead
-
NO2
Passivating
CrO42-
Pb3O4
phosphate
silicate
hydroxide
Surface layer
H2PO4-
-
H2SiO42
OHHCO3-

3.6.5 Cathodic and Anodic Inhibitors

Cathodic inhibitors reduce the corrosion rate due to retarding cathodic


reactions. A cathodic inhibitor causes formation of insoluble compounds
precipitating on the cathodic sites in form of a barrier film.

The following compounds are used as cathodic inhibitors:

 Zinc salts (zinc hydroxide, zinc phosphate);

 Calcium salts (calcium carbonate, calcium phosphate);

 Magnesium salts;

 Polyphosphates

Anodic inhibitors reduce the corrosion rate due to retarding anodic reactions.

An anodic inhibitor shifts the equilibrium of the corrosion process to the


passivation zone causing formation of a thin invisible passivation oxide
film on the anodic sites, which increases the anode potential and depresses
the oxidation process. Reduction of the effective anode area results in
decrease of corrosion rate.

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Anodic inhibitors have a serious disadvantage: at low concentrations they
cause increase of corrosion rate therefore it is important to avoid decrease of
the inhibitor content below the optimum level.

The following compounds are used as anodic inhibitors:

 Chromate (CrO42-)

 Nitrite (NO22-);

 Molybdate (MoO42-);

 Orthophosphate (PO43-).

3.6.6 Fields of Application

Corrosion problems may occur in numerous systems within the petroleum


industry. These include:

 Cooling systems

 Drilling mud

 Oil production units

 Oil storage tanks

 Oil well

 Protection of pipelines

 Refinery units

 Steam generators

 Technologic vessel

Many compositions involve environmentally dangerous products, such as


chromates, fatty amines of high molecular weights, imidazolines, etc.

The use of some of the alternatives, for instance, polyphosphate or


polyphosphonate is limited because they precipitate in the presence of the
salts of alkaline earth metals or because of their high costs.

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