Professional Documents
Culture Documents
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
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.
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
Steel → 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:
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2.2 Chemistry of Corrosion
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.
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 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.
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
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.
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Figure CORROSION PROCESS.4 – Iron equilibrium diagram
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.
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.
Contamination of fluids in vessels and pipes (e.g. beer goes cloudy when
small quantities of heavy metals are released by corrosion);
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;
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detecting the corrosion danger at an early stage;
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.
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alloys, Nirosta® steels and Timetal® titanium alloys are all examples of alloys
designed for corrosion prevention.
a protective coating derived from the metal itself, e.g. aluminium oxide on
“anodised” aluminium:
The action of protective coatings is often more complex than simply providing
a barrier between metal and environment.
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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.
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Chemical treatments of the environment can have different aims:
pH control;
Oxygen removal;
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3 CHEMICALS INJECTIONS
3.1.1 pH Correction
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.
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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.
Hydrazine N2H4
N2H4 + O2 2H2O + N2
2 Na HSO3 + O2 2 NaHSO4
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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.
3.3 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.
Organic
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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
Chlorine Disadvantages
Aldehydes ;
Sulphur compounds
Amines;
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.
Sulphur compounds:
Amines
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3.4 MEG Chemicals
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:
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.
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3.5 Antiscaling
Scaling
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.
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.
Chemical removal
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the acid soluble scales consisting mainly of carbonates (MxCO 3) and
sulphides (MxSy) and
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
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,
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.
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3.6 Corrosion Inhibitors
1. It may restrict the rate of the anodic process or the cathodic process by
simply blocking active sites on the metal surface;
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.
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.
Safe or dangerous ;
Solvents are added prevent separation and make inhibitors less viscous so
they are easier to apply.
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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;
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.
Imidazolines
Fatty acids
To assure high effectiveness, turbulent flow conditions are required to help oil
wetting.
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Typical water soluble inhibitors are:
quaternary amines
amine salts
imidazoline salts
Insoluble or less soluble salts can form (an excess of active principle in the
formulation is necessary).
Adsorption Inhibitors
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.
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
Magnesium salts;
Polyphosphates
Anodic inhibitors reduce the corrosion rate due to retarding anodic reactions.
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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.
Chromate (CrO42-)
Nitrite (NO22-);
Molybdate (MoO42-);
Orthophosphate (PO43-).
Cooling systems
Drilling mud
Oil well
Protection of pipelines
Refinery units
Steam generators
Technologic vessel
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