Fundamentals of Inhibitors

For Training Purposes Only
FUNDAMENTALS
OF INHIBITORS
AV Santos & Associates : August 2010 :
Inhibitors
An Inhibitor is a substance which retards or

slows down a chemical reaction
reaction.
A Corrosion inhibitor is a substance which, when
added to an environment, decreases the rate of
attack by the environment on a metal.
Corrosion inhibitors are commonly added in
small amounts to acids,
acids cooling water,
water steam
and other environment, either continuously or
intermittently to prevent serious corrosion.
CORROSION INHIBITORS

Points of view of Corrosion

inhibitors
Their effects on the corrosion process.

Their interactions with various aggressive
environments.
Properties of the inhibitors themselves
Possible effects of inhibitors on unit
operations.
operations

INHIBITORS AND THE

ENVIRONMENT
Aqueous Systems
- It is the common corrosive environments to which
corrosion inhibitors are applied.
- Water is a powerful solvent capable of carrying many
different ions at the same time.
- The main factor which must be considered in the
application of corrosion inhibitors to aqueous systems
are salt concentration, pH, dissolved oxygen
concentration
t ti and
d the
th concentration
t ti off iinterfering
t f i
species.

AQUEOUS SYSTEM

Common Dissolved Substances and their

effects on corrosion inhibitors
Oxygen (O2) in neutral water, oxygen causes corrosion, if it is

reduced to less than 0.1 ppm by scavenging compounds or by
stripping sufficient corrosion control is thereby provide for some
stripping,
system. Oxygen can be utilized in passivating steel by adding a
passivating inhibitors. Organic inhibitors are seldom effective
against oxygenoxygen-caused attack unless they contain passivating
groups such as benzoate or nitrite.
Chloride (Cl) Steel is more difficult to passivate in the presence
of the chloride ion, therefore a higher concentration of passivating
inhibitors is required if Cl are present. Also chloride ions are
strongly
t
l absorbed
b b d by
b steel.
t l
Sulfate (SO) The effect of sulfate on passivity are similar to
those of chloride but to a lesser degree, sulfates or chlorides must
not be allowed to build up in a system by evaporating because
depassivation may occur.
Bicarbonate (HCO3) bicarbonate in hard waters can be utilized for natural

inhibition. If soft waters, corrosion inhibitors must be used if excess carbon
dioxide is present because of the acidic condition it produces.
Sulfides (S-) Sulfides precipitate many metal ions. For example, inhibitors
which contain zinc cannot be used. Oxidizing inhibitors are reduced by sulfide to
form free sulfur. They are effective only if an excess is used and the colloidal
precipitate of free sulfur can be tolerated.
Metal Cations Sodium (Na) and Potassium (K) ions have no particular effects
on inhibitors; Calcium (Ca) and Magnesium (Mg) may be used to form protective
precipitates but at high concentrations they interfere with inhibition by
precipitating non-protective deposits and also by precipitating inhibitors such as
phosphate (PO4) and Silicate (SiO3).
Acid (H+) hydrogen ion increase corrosion rates and increase the difficulty of
passivating steel. Passivation is used in sulfuric (H2SO4) and phosphoric acid
(H3PO4) but not in hydrochloric acid (HCI). Non-passivating organic or cathodic
inhibitors are preferred in pickling acids to avoid the disastrous consequences of
depassivation.
Alkali (OH-) In alkaline solutions, corrosion of steel is controlled by the rate of
oxygen diffusion through the precipitated corrosion products so corrosion rates
are low. Steel is easily passivated
in alkaline solutions.
8
WATER OF LOW
LOWTO
TO--MODERATE
SALT CONCENTRATION
Water of lowlow-to
to--moderate salt concentrations are
encountered in municipal
p water systems,
y
, cooling
g waters,,
marine and offshore activities and oilfield water injection
system.
In closed rere-circulating system, oxygen can be excluded
and corrosion often can be controlled by adjusting the
pH to an alkaline value.
In open systems corrosion is more severe and good
inhibition is imperative because metal absorb ions of
dissolved salts in water, an inhibitor has more difficulty
in reaching the metal surface and displacing absorbed
ion than it has in demineralized water, hence a higher
concentration of inhibitor is required.
Cooling water systems may be either recirculating or

once--through types.
once
Recirculating systems are more easily controlled by
inhibitors
hb
since higher
h h concentrations can be
b applied
l d
because the water is reused.
Sodium chromate or sodium nitrite are both effective
alloy steel closed recirculating system.
Sodium nitrite may form ammonia by reduction at
cathodic sites, therefore it should not be used in systems
which include brass or copper since these materials are
subject to stress corrosion cracking by ammonia.

10
HIGH SALT CONCENTRATIONS
Extremely high salt concentrations are used in aqueous

solutions for heat transfer in refrigeration systems. The
temperatures encountered are always low and since the
brines are recirculated, a high concentration of inhibitor
can be maintained economically.
Sodium Chromate is effective in refrigeration brines
provided there is no limitation due to its toxicity. If
physiological effects are a factor then disodium
phosphate can be used although it is not as effective as
sodium chromate in controlling corrosion.

11
Effects of pH
The pH of aqueous solutions is extremely important in

determining the type of corrosion inhibitor which is most
effective and most economical. Natural hard waters
retain compounds of calcium in solution because of the
equilibrium.
At high temperatures the reverse reaction occurs and
heated surfaces become coated with CaCO3. A
protective scale is produced also when Ca(HCO3)
becomes alkaline in the region of cathodic areas.

12
Gaseous Environment
Gaseous environments include the open
atmosphere,
t
h
th
the vapor phase
h
in
i tanks,
t k
natural gas in walls and the empty space
in packaging containers. Water and
oxygen are the principal corrosive agents
but the main problem in providing
inhibitors is to transport the inhibitors
from a source to the sites where corrosion
may occur.
13
The Open Atmosphere
It is applied directly to the metal surfaces to be

protected.
t t d
The most common method is the use of
chromates in paints. Zinc chromate and red lead
are used in primer coats.
Volatile inhibitors are never used in the open
atmosphere because they are impractical and
cannot saturate the vapor space.

14
Closed Vapor Spaces
The walls of tanks above a water line are subject to

extensive corrosion because the relative humidity is
always high and oxygen is plentiful if the tank is vented
to the atmosphere.
An oil layer containing about 15% lanolin is used in ship
ballast tanks to control corrosion.
A layer of oil on the surface helps to maintain a low
humidity and as the level is raised and lowered the walls
are coated with a layer of oil. The oil may contain an
organic inhibitor and an agent usually amine to cause
the oil to spread on the metal surface.
15
Effects of Elevated Temperature
Most effects of elevated temperature are adverse to

corrosion inhibition.
High temperatures increase corrosion rates (about
double for a 20F rise at a room temperature) and they
decrease the tendency of inhibitors to absorb on metal
surfaces.
Precipitate--forming inhibitors are less effective at
Precipitate
elevated temperatures because of the greater solubility
of the protective deposit.
Thermal stability of corrosion inhibitors is an important
consideration at high temperature.
16
Types of Inhibitors
Passivating Inhibitors
Passivating inhibitors are the most effective of
all inhibitors because they are stifle corrosion almost
completely. They also known as dangerous inhibitors
because under certain conditions they can accelerates
corrosion.
There are two types of passivating inhibitors: Oxidizing
anions such as chromate, nitrite which can passivate
steel in the absence of oxygen and the non
non--oxidizing
ions such as phosphate, tungsten, moluo
moluo--date which
require the presence of oxygen to passivate steel.
17
Cathodic Inhibitors
Inhibition by polarization of the cathodic reaction can be

achieved in several ways and several examples already
have been given. The three main categories of inhibitors
which affect the cathode reaction are cathode poisons,
cathode precipitates and scavengers.
Cathode Poison is the formation of hydrogen atoms or
recombination of hydrogen atoms to hydrogen gas on
the surface of the corroding metal. The rate of the
cathode reaction is showed and because anodic and
cathodic reactions must proceed as the same rate, then
the whole corrosion process is slowed.
18
Cathode Precipitates
The most widely used cathodic precipitation type

inhibitors are the carbonates of calcium and magnesium
because they occur in natural waters inhibition with
them usually requires only an adjustment of pH.
Many natural waters and municipal water supplies
contain calcium carbonate (limestone) in solution.
Limestone is dissolved in water by reaction to form
soluble calcium bicarbonate. Limestone can be caused to
precipitates again, forming a milky white suspension by
making the calcium bicarbonate solution more alkaline
by adding more calcium ions.
19
Organic Inhibitors
Organic compounds constitute a broad class of corrosion

inhibitors which cannot be designated specifically as
cathodic or anodic.
Cathodic or anodic effects alone are sometimes observed
in the presence of organic inhibitors. They affect the
entire surface of a corroding metal when present in
sufficient concentration.
Both anodic and cathodic are inhibited but to varying
degrees depending on potential of the metal, chemical
structure of the inhibitor and size of the molecule.

20
10
Oxygen Scavenger
Corrosion of steel in water above pH 6.0 is due to the

presence of dissolved oxygen which depolarizes the
cathodic reaction.
Oxygen scavengers are added to water either alone or
with a corrosion inhibitor to retard corrosion.
Organic corrosion inhibitors alone in the generated brine
water will slow general corrosion, but will not always
prevent pitting attack
attack.
The most common oxygen scavengers used in water at
ambient temperature are sodium sulfite and sulfur
dioxide.
21
Precipitation Inhibitor
These are filmfilm-forming compounds whose action is

general over the metal surface and interfere with both
g
anodes and cathodes in directly.
The most common inhibitors of this class are the silicates
and phosphates.
In nearnear-neutral waters containing a low concentration of
chlorides, silicates and phosphates cause passivation of
steel when oxygen are present but they behave as
anodic inhibitors
inhibitors.
Corrosion is localized in the form of pitting when
insufficient amounts of phosphate or silicate are added
to saline water.
22
11
Vapor Phase Inhibitors
Vapor Phase Inhibitors (VPI) are compounds which are transported

in a closed system to the site of corrosion by volatilization from a
source.
source
In boilers, volatile basic compounds such as morpholine or ethylene
ethylene-diamine are transported with steam to prevent corrosion in
condenser tubes by neutralizing acidic carbon dioxide.
Compounds of this type inhibit corrosion by making the environment
alkaline.
In closed vapor spaces, such as shipping containers, volatile solids
such as the nitrite, carbonate and benzoate salt of
dicyclohexylamine, cyclohexylamine and hexqmethylene are used.
The mechanism of inhibition by these compounds is not entirely
clear, but is appear certain that the organic portion of the molecules
merely provides volatility.
23
Application of Inhibitors
Concentration and Performance Terminology

- Corrosion inhibitors are sold in solid or liquid form. Most solids are
relatively
l
l pure but
b sometimes a solid
l d inhibitor
hb
is fused
f
d with
h another
h
ingredient or incapsulated where a controlled rate of solubility is
required.
- Liquids are usually preferred because of the ease with which they
can be transported , measured and dispersed.
- Organic inhibitors seldom have optimum characteristics of viscosity,
viscosity
freezing or boiling point, they are dissolved in an appropriate
solvent to achieve the properties desired. It is also often desirable
to blend the inhibitor with a demulsifier, dispersant, surfactant, antiantifoaming agent of synergetic agent.
24
12
Liquid inhibitors are solid by the gallon, part of which is solvent. The
amount of inhibitor present is expressed as percent active. A
gallon of inhibitor which is 20 percent by weight of inhibitor. In cold
climates where inhibitors are likely to be stored or used in sub
freezing temperatures.
freezing
- It may be impossible to use as concentrated a solution as in warmer

climates without resorting to more expensive solvents.
- Corrosion inhibitors are usually compared on the basis of their
inhibitor efficiencyy which is the p
percentage
g that corrosion is lowered
in their presence as compared to the corrosion rate which occurs in
their absence.

25
The inhibitor efficiency is calculated from the formula:
R0 R1
E=
x 100
R0
Where: E = inhibitor efficiencyy

R0 = corrosion rate in the absence of inhibitor
R1 = corrosion rate in the presence of inhibitor

26
13
Application Techniques
Continuous Injection
- This method is used for water supplies, oil field
injection water, onceonce-through cooling water, open
annulus oil or gas wells and gasgas-lift wells.
- Liquid inhibitors are injected with a chemical injection
pump,
p
p these pumps
p p are extremelyy reliable and require
q
little maintenance. Most chemical injection pumps can be
adjusted to deliver at the desired injection rate.

27
- Another form of continuous application is by the use of

slightly--soluble forms of solid inhibitors. The inhibitor
slightly
such as glassy phosphate or silicate in the form of a
cartridge
d is continuously
l reached
h d out by
b the
h passage off
fluid through the cartridge.
- Inhibitors in the form of sticks or pellets are used in oil
and gas wells to supply inhibitor continuously by their
natural slow dissolution.

28
14
Batch Treatment
- The most familiar example of batch treatment is the automobile
cooling system. A quantity of inhibitor is added at one time to
provide protection for an extended period. Additional inhibitor may
be added periodically or the fluid may be drained and replaced with
a new supply.
- Closed loop, cooling systems it is important that the inhibitor
concentration be measured occasionally to insure that a safe level is
maintained.
- It is also used in treating oil and gas wells. An inhibitor is deluted
with an appropriate solvent and injected into the annulus of openopenhole wells or into the tubing of gas wells that have a packer.
- In this application it is important that the inhibitor contact all
surfaces and that it has a good persistence. Most wells require
batch treatment about every two weeks.
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BATCH TREATMENT

30
15
Squeeze Treatment
- It is a method of continuously feeding inhibitor into an
oil well.
- A quantity of inhibitor is pumped into a well and is

followed by sufficient solvent to force the inhibitor to
absorbed by the formation from which it slowly escapes
to inhibit the produced liquid.
protection applied
pp
in this manner has been known
- The p
to last for a year.

31
Volatilization
- It is also connected to boilers and closed container. It is also the
inhibition of gas condensate corrosion.
- This treatment is also the same as used in batch and squeeze
treatment.
Coating
- Inhibitors are used in coatings exposed to the open atmosphere.
- When moisture contacts the paint, some inhibitor is leached out to
protect the metal. The inhibitor must be soluble enough to be
leached out in sufficient amounts to protect the metal but not to
soluble so that it will be lost rapidly.
- The most common coating inhibitors are zinc chromate and
plumbous orthophumbate (red lead) which passivate steel by
providing chromate and plumbate ions.
- These inhibitors are not effective against attack by sea water or
brines because the high chloride concentration prevents passivation
of steel.
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16
Problems in Application of
Inhibitors
A system must be carefully examined before a program of corrosion

inhibition can be p
planned effectively.
y
The examination must include a survey of any adverse effects an
inhibitor may have on the process in which it is to be used and an
analysis to detect the presence of interfering substance.
The most likely adverse effects which organic inhibitors may
produce are due to their polar nature.
The requirement that inhibitors must have functional groups that
are strongly absorbed also imparts to them some degree of surface
active properties.
They may behave as soaps, or detergents and cause foaming,
formation of emulsion or they may loosen scale formed before
inhibition was started.
33
Foaming
The most appropriate action to take in avoiding difficulty

g is to determine where foamfoam-forming
g
from foaming
conditions exist in the system.
This will consist of places where the inhibitor containing
fluid is agitated with a gas such as in a gas separator, a
counter current stripper or in a aerator.
There are three alternative remedies:
1. An antianti-foaming agent may be added.
2. tests can be made to select an inhibitor which does
not cause foaming.
3. the system can be shut down periodically and treated
with a slug of persistent inhibitor.
34
17
Emulsions
Emulsions consist of two immiscible liquid phases while

foams are composed of a gas and a liquid phase.
Conditions favorable for emulsion formation are the
presence of two liquid phases, agitation and an emulsion
stabilizer. In this case, the corrosion inhibitor may
behave as an emulsion stabilizer, so the procedure is to
shake the two liquid phases with inhibitor and measure
the time required for them to separate.
if the time required for separation is longer in the
presence of inhibitor than its absence, the inhibitor is
emulsion stabilizer.
35
Plugging
A system can be plugged as the result of an

inhibitors
inhibitor s loosening scale and suspending it in
the fluid.
The best preventive measure is to clean the
system thoroughly, if possible before inhibitor is
applied.
An alternate or supplementary method in
systems
t
which
hi h are very sensitive
iti to
t suspended
d d
solids to protect the sensitive parts with
temporary filters.
36
18
Creation of New Corrosion

Problems
Another possible adverse effect of inhibition is an
increased rate of corrosion of a metal in the system
other than the one for which the inhibitor was selected
to protect.
For Example:
Some amines protect steel admirably but will severely
attack copper and brass. Nitrites may attack lead and
lead alloys such as solder.
solder In some cases,
cases the inhibitors
may react in the system to produce a harmful product.
In order to avoid these problems you have to know the

metallic components of a system and be thoroughly
familiar with the properties
of the
For Training Purposes
Only inhibitor to be used.
37
Heat Transfer
Heat transfer is an important

consideration in applying corrosion
inhibitors.
Scaling of heat transfer should be avoided
or held to a minimum.
Excessive deposits of phosphates, silicates
or sulfates
lf t should
h ld be
b avoided
id d because
b
they are difficult to remove by chemical
means.
38
19
Economics of Inhibition
Prevention of corrosion by inhibition may be desirable for

several reasons:
1. To extend the life of equipment.
2. To prevent shut downs.
3. To prevent accidents resulting from brittle
(catastrophic) failures.
4. To avoid product contamination.
5. To prevent loss of heat transfer.
6. To preserve an attractive appearance.
39
The Concept and Development of Inspection

and Corrosion Monitoring
The concept of inspection and corrosion monitoring has developed

from two distinct areas, plant inspection techniques and laboratory
corrosion testing techniques
techniques, with the original aim of assessing or
predicting the corrosion behavior of plant and equipment between
shutdowns.
Objectives:
- is to obtain information on the state of operation equipment to
permit the better scheduling of maintenance work, to ease the
inspection load during shutdowns and to avoid unplanned shutdown
occurring because of unforseen deterioration of plant.
- is to obtain information on the interrelation between corrosion
processes and operating variables. To help diagnosis of the problem
and to allow improved control of corrosion and more efficient
operation of the plant.
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20
Development of Monitoring Method
As a Diagnostic Tool
- The most common use of onon-line monitoring is to
provide information for the solution of a corrosion
problem.
- Corrosion monitoring is one of the several tools
available to the investigator, but it is particularly valuable
in that it may provide information which is not easily
obtained in other ways, and thus lead to a better or
speedier solution.

41
To monitor the effectiveness of a Solution

- A logical extension of the diagnostic application is to
use corrosion monitoring techniques to establish whether
a solution has been effective.
- This can be done simply by continuing the original
investigation, but more permanent installations are being
used to an increasing oxtent to provide long term
assurance.
To provide Operational or Management

Information
- Corrosion can often be controlled by maintaining single
operational variable (e.g. temperature, pH, humidity)
within limits determined by prior monitoring or other
investigations. If the significant variable is measured for
other reasons, this measurement can be used directlyfor
corrosion control.
42
21
If the variable is not measured , or in more complex

cases where several variables interact, corrosion
monitoring information can be used by plant operators
to control plant operation so as to control corrosion.
A partt off a Control

As
C t l System
S t
An extension of the use of monitoring techniques to
provide operating information is to use the monitoring
information directly to control plant, or parts of plant.
The use of p
potential measurements to control anodic or
cathodic protection system is an example, as is the
more recent development of using monitoring signals to
control inhibitor or other additions to cooling water
systems.

43
Clearly, equipment used in this way required a high

standard of reliability, and some form of sell testing
feature, and a detailed understanding of the corrosion
behavior of the plant is essential to the successful design
of the control system.
As part of a Management System
The data from corrosion monitoring can be useful to
management in several ways. It can supplement other
inspection techniques, and improve the management of
maintenance and its coordination with production
p
schedules.
This approach is used to varying degrees of
sophistication in a number of industries. The same
information can also be used with benefits in
optimization and AVother
Santos & investigations.
Associates : August 2010 :
44
22
1.
2.
Developments in computers and data handling have

been an important stimulus in this areas, since a
substantial mass of the data has to be processed to a
manageable from.
Selecting Technique
Many techniques have been used for corrosion
monitoring. There are eight techniques in corrosion
monitoring.
Time for individual measurement some
techniques provide information that is effectively
instantaneous, while other are necessarily slower in this
respect.
Type of Information obtained some techniques
provide a measurement of corrosion rate, other
measure total corrosion, or the remaining thickness,
which is not exactly equivalent; yet others provide
AV Santos
& Associates : August
:
information on the
distribution
of 2010
corrosion
on the
45
corrosion regime.
3. Speed of response to change techniques which do not

provide an individual measurement quickly are obviously
unsuitable for situations where a fast response is required.
Not all techniques that provide effectively instantaneous
information are however capable of a fast response. Where
the measurement is of rate,
rate of corrosion regime
regime, a fast
response can be obtained, but if the measurement is of total
corrosion, remaining thickness or distribution of corrosion,
the speed of response is limited by the ability of the
technique to discriminate between successive readings.
4 Relation to Plant Behavior many of the more effective
4.
techniques provide information on the behavior of a probe
inserted into the plant, which does not necessarily reflect
the behavior of the plant itself. The information obtained is
in fact a measure of the corrosivity of the environment,
AV Santos & Associates
: August
2010 :
from which plant behavior
can be
inferred.
46
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5. Applicability to environment A fast response is most

readily obtained from electrochemical measurements which
require that the environment is an electrolyte; a high
electrolytic conductivity is not always necessary however.
Ninelectrochemical measurements can be used in gaseous
environments or non
environments,
non--conducting fluids,
fluids as well as in
electrolytes.
6. Type of corrosion Most corrosion monitoring techniques
are best suited to situations where corrosion is general, but
some provide at least some information on localized
corrosion.
corrosion
7. Difficult of interpretation Interpretation of the results
is often relatively straight forward if the technique is used
within its limitations. The interpretation of the results
obtained by some techniques
however,
but more difficult.47
For Training Purposes
Only
8. Technological Culture some techniques are inherently

technically sophisticated; this tends to limit their use to
organizations with a strong technological culture. Most
others are much less demanding in this respect.
In principle, the available techniques could be ranked in an

order or merit for each of these eight criteria. In practice,
the relative merits change with circumstances so that a
formal treatment of this type is potentially misleading. The
most useful general approach is therefore, to consider the
strengths
t
th and
d weaknesses
k
off th
the techniques
t h i
individually
i di id ll and
d
provides a reasonable starting point.

48
24
CORROSION IN CHEMICAL
CLEANING
Chemical Cleaning
It is a specialized
p
cleaning
g technique
q which is finding
g
extensive use today as a substitute or supplement for
conventional mechanical cleaning methods. A properly
implemented chemical cleaning program will provide
effective cleaning which is both rapid and economical.
The primary incentive for utilizing chemical cleaning is to
reduce unit downtime, and in most cases it is more
rapid, more efficient and less costly than mechanical
cleaning.
It can often be accomplished in place without having a
dismantle the equipment and the need for cranes,
hoists, and similarAVmechanical
equipment
can be
Santos & Associates : August
2010 :
49
reduced
CHEMICAL CLEANING

50
25
Proper application of chemical cleaning can also have

favorable effect on refinery fuel costs, manpower allocations
and preventive maintenance.
Chemical cleaning can be applied to almost any type of
process equipment. Exchangers, towers, drums, pipelines,
flare stacks
stacks, tanks
tanks, filters
filters, cooling jackets
jackets, boilers
boilers, and other
equipments have all been successfully cleaned by chemical
methods.
The most commonly used chemical cleaning method include

solvent cleaning, high pressure jet cleaning and pipeline pig
cleaning.
l
i
The
Th specific
ifi technique
t h i
to
t be
b used
d depends
d
d on the
th
equipment to be cleaned and the characteristics of the
deposit to be removed.

51
A STEP BY STEP PROCEDURE IN CHEMICAL CLEANING

1.
2.
3.
4.
5.
6.
Obtain and analyze a representative sample of the fouling

deposit.
Determine the solvent and/or other chemicals to be used
for cleaning. Perform a materials study to determine the
capability of the chemicals with the vessel material.
Determine the technique to be used on the specific piece of
equipment.
Plan cleaning operations and prepare tools and equipment.
Perform cleaning.
Follow--up, including final inspections, recording data and
Follow
review of equipment performance subsequent to return to
service.
52
26
1.
2.
3.
Chemical cleaning can be used safely and effectively

providing:
Materials of construction are reviewed prior to the treatment
to determine compatibility with the solvent.
A suitable inhibitor is used.
The treatment is intelligently controlled to avoid excessive
temperature and velocity as well as to check corrosive ions.
The possible hazards of cleaning equipment with chemicals

can be classified into two categories:
1. The hazards of handling the solvents and chemicals.
2. Hazards of toxic gases and vapors formed during the
chemical cleaning treatment.
However, if the proper precautions are taken in planning and
performing the chemical cleaning operation, these hazards
& Associates : August 2010 :
can be eliminated. AV Santos
53
-
CORROSION
-
Before a chemical cleaning job is performed, it is important

to know the materials of construction of the equipment to be
cleaned since the choice of solvents and inhibitors are
affected by metallurgical considerations.
Severe corrosion can occur when the incorrect solvent is
used. In some cases, acids, even when inhibited can cause
serious corrosion.
Refineries use many different types of alloys. Frequently a
single piece of equipment will be composed of several
different materials so that the solvent may provide an
electrolytic solution which establishes active corrosion cells.
Other considerations in preventing corrosion are proper
environmental control of solvent: temperature, velocity and
& Associates : August 2010 :
venting of gases. AV Santos
54
27
CORROSION

55
Excessive temperatures or velocities can cause corrosion

problems.
Corrosion of process equipment during a chemical cleaning
treatment will not occur to any appreciable extent providing
the job has been properly planned and the operation
properly controlled
controlled.
The most important factors that must be considered to

prevent corrosion are:
1.
2.
3.
The materials must be compatible

p
with solvents.
Suitable inhibitors must be used.
Treatment must be controlled properly.

56
28
A.
Materials
The materials of construction of the equipment to be cleaned
must be reviewed carefully to determine whether the materials
are compatible with the solvents to be used.
Carbon steels offers good resistance to inhibited hydrochloric
acid even at temperatures up to 200F however changes in
composition in carbon steel change the corrosion
characteristics.
Free machining, high sulfur steels are susceptible to acid
attack.
attack
Stainless Steel are more resistant to corrosion than carbon
steels.
Chromium-nickel alloys are especially resistant. Inhibited
hydrochloric acid should
not be used on high chromium steels
For
Training Purposes Only
57
containing little or no nickel.
CARBON STEEL

58
29
STAINLESS STEEL

59
Chromium-nickel alloys

60
30
The Type 300 series stainless steels behave on one of

three different manners when in contact with
solutions:
1. Passive stainless steels in the passive condition require a
continuous
ti
supply
l off air
i or oxygen to
t maintain
i t i the
th passive
i
film on the metal surface.
2. Active if the passive film is removed, the surface is in an
active state and the stainless steel is no more corrosion
resistant than carbon steel.
3. BorderlineBorderline- this condition exists when some areas are passive
and others active. Pitting occurs at the activated areas. The
pits result in stressed areas and cracks develop causing the
metal to fail.
61
Pro-Copper and its alloys may be cleaned with non-oxidizing

acids.
Copper, phosphor-bronze, admiralty metal, yellow brass, and
cupro-nickel can be cleaned with inhibited hydrochloric acid.
Aluminum and its alloys may be cleaned with mild alkalis and
oxidizing acids.
Inhibited hydrochloric acid or strong alkali such as caustic
cannot be used. Chromic acid as well as mixtures of sodaash, trisodium phosphate, and sodium metasilicate can be
used in many cases without danger of corrosion.
Lead is satisfactory with weak sulfuric acid, however,
hydrocholic acid as well as caustic are corrosive to lead.
62
31
B. Inhibitors
-
Inhibitors are added to acid solvents to retard corrosion of

equipment during chemical cleaning.
There are many types of inhibitors available for different
uses. Certain inhibitors are best suited for particular metals.
Presence of brass, bronze cast iron, carbon steel and
stainless steel as well as the scale characteristics in many
cases influence choice of inhibitors.
The most important and effective inhibitors available are

classified into four different types:
(1). Inorganic (2). Organic metal (3). OrganicOrganic-aliphatic (4).
Organic--aromatic.
Organic
63
The effectiveness of an inhibitor depends on the film formed

between the acid and the steel surfaces. This film is formed
during the acid attack on the steel or other metallic surface.
When acid attacks steel, iron is dissolved at the anodic areas
as ferrous ions and hydrogen is formed at the cathodes.
C. Treatment Control
-
1.
2.
All inhibitors have certain temperature limitations. These

limitations are usually defined as to separate critical
temperature points:
The temperature at which the inhibitor becomes ineffective.
The temperature at which the complete decomposition of
the inhibitor occurs.
64
32
TREATMENT CONTROL

65
maximum safe treating temperature for most inhibitors is in

the range of 180F to 200F. The temperature at which the
inhibitor decomposes is somewhat higher.
If the effective inhibition temperature is exceeded, the effect
off th
the iinhibitor
hibit can be
b restored
t d by
b lowering
l
i the
th temperature.
t
t
Prolonged periods at temperatures exceeding the effective
limit can result in corrosion even though the inhibitor is not
permanently destroyed.
Excessive solvent velocities while circulating inhibited acid
can also cause equipment damage. Inhibitors are not
effective on surfaces when flow velocities are high or when
the flow is very turbulent. However, limited circulation is
frequently necessaryAV after
the equipment
is filled with solvent
Santos & Associates
: August 2010 :
66
33
Safety
Personnel must exercise all precautions in chemical
cleaning operations in order to eliminate the
dangers associated with handling the various
solvents and chemicals and from toxic gases formed
during actual cleaning activities.
Some of the materials used in chemical cleaning can
cause severe burns or skin irritations.
The most dangerous are sulfuric acid, chromic acid,
caustic and phenolic compound.
67
d Sulfuric acid and caustic soda can cause severe burns of

the eyes and skin.
Chromic acid can causes severe skin irritation and phenol
can cause severe burns or death through skin absorption.
Other materials may also cause mild burns or skin
irritations and must be handled carefully. And some
chlorinated solvents are toxic.
Personnel handling solvents and chemicals should be
provided with safety clothing. Protective rubber gloves and
goggles are mandatory; rubber suits and hat may also be
necessary.
68
34
The most serious hazards in chemical cleaning are created by

toxic gases and vapors which are generated during the
cleaning process.
Particularly hazardous are the volatile hydrides of sulfur,

arsenic
i and
d phosphorous.
h
h
Any
A off these,
th
when
h contacted
t t d by
b
solvents, can generate toxic gases. These gases are formed
by two methods:
1. By the action of dilute acid on sulfides, phosphides and

arsenides..
arsenides
2. By the solution of nascent hydrogen on compounds of these
metals. Nascent hydrogen may be formed by attack of acid
on steel and copper.
69
- Hydrogen sulfide can be vented to the atmosphere

providing a convenient high point is available and only small
quantities are generated.
-
Sulfide deposits,
deposits, which from hydrogen sulfide when
t t d with
treated
ith h
hydrochloric
d hl i acid
id are common in
i a refinery.
fi
Cyanides are formed in fluid catalytic cracking and these
deposits can be found in the vapor recovery units. These
are primarily ferro
ferro--ferri cyanides characterized by bluish
deposits.
Arsenic may come from admiralty brass, crude or from
cooling or process water. Some inhibitors contain arsenic.
These inhibitors should not be used to inhibit acid for
chemical cleaning.
70
35
Phosphorus is found in steel and could produce phosphine in

the presence of nascent hydrogen.
These gases may be detected by specially designed detectors

or by laboratory methods. The presence of hydrogen sulfide
can be determined qualitatively with a MSA ( Mine Safety
Appliance) Hydrogen Sulfide detector or qualitatively with a
strip of filter paper moistened with lead acetate.
MSA Hydrogen Cyanide Detector is satisfactory to detect this

gas. However,, anyy hydrogen
g
y g sulfide and mercaptans
p
present
p
must be scrubbed out with lead acetate and acetic acid.
Hydrogen released during acid cleaning operations can

cause a serious explosion when mixed with air and ignited.

71
Inhibitors retard this reaction, however, hydrogen evolution

cannot be stopped completely and must be vented properly.
Carbon Dioxide is evolved from deposits containing
carbonates when reacted with hydrochloric acid. It is not
poisonous and is not normally considered dangerous, but it
can cause suffocation. The gas is heavier than air and tends
to settle in low places.
Sulfur dioxide is formed from deposits containing sulfates. It
has an extremely disagreeable odor and is severely irritating
to respiratory organs.
organs
The hazards created by gases evolved during the cleaning
process can be eliminated if proper precautions are used.
Non--toxic gases can usually be safely vented to the
Non
atmosphere.
72
36
If chemical cleaning is being done in a confined place or

enclosed building vent hoses should be extended out of
doors.
Occasionally, solvent return hoses can be used as vents,
t i gases may be
toxic
b vented
t d to
t a fl
flare where
h
they
th can be
b
burned safely.
Disposal of such gases by venting up a chimney is not always
effective, however, with un favorable atmospheric conditions,
the gas could settle back to the ground and create a serious
hazard.
No smoking or welding should be permitted during any stage
of the cleaning operation.
73
The following table lists various gases occasionally encountered,

their source and reasons why they are dangerous.
Gas
Hydrogen
y g
Sulfide
Source
Sulfide deposits
p
mainly iron sulfide
Effect
Poisonous
Arsine
Arsenic compounds
also from metals & oils
Poisonous
Phosphine
Phosphorous compounds
& Phosphorous in steel
Poisonous
Hydrogen
Cyanide
Cyanide compounds found

in cat.Forcracking
Training Purposes Only
Poisonous
74
37
Gas
Sulfur Dioxide
Source
Sulfite compounds
Effect
dangerous to eyes
suffocating odor
irritating
g to respi
respipratory organs.
Carbon Dioxide
Carbonate deposits
non
non--toxic.
causes suffocation
Hydrogen
Acid attack on steel
Explosive
Nitrous oxide
HCL reaction with

nitrate compounds
used
For for
Trainingpassivating
Purposes Only
Asphyxiating
75
HAZARDOUS SYMBOLS

76
38
OTHER CHEMICAL CLEANING METHODS

-
a.
b.
c.
d.
e.
Several other specialized chemical cleaning techniques have

been successfully applied to a limited extent to clean various
equipment. These may entail greater expense and have less
versatility
tilit so th
thatt th
the occasion
i tto use iis rare. Th
These methods
th d
include the following:
Ultrasonic vibration
Pressure fracturing of tube deposits
Explosive methods
Chlorinated solvent vapor phase method
High circulation rate
77
ULTRASONIC VIBRATION

78
39
EXPLOSIVE METHOD

79
HIGH CIRCULATION RATE

80
40
Controlled oxidation is a technique being developed to

remove carbonacious deposits from towers. The principle
involves the controlled flameless combustion of the cokecoke-like
deposits. Temperatures are controlled at approximately 900F
with inert gas.
The vapor phase cleaning method is for tank cleaning
application and utilizes an airair-steam mixture to atomize
solvents selected to remove heavy layers of oil impregnated
rust deposits from the tank shells.
COORDINATION AND CONTROL OF CHEMICAL

CLEANING
- Considerable technical control and coordination are required
in order to make a chemical
cleaning
program
most effective.
AV Santos & Associates
: August 2010
:
81
A prime objective is to minimize equipment turnaround times

and thorough preplanning and scheduling are extremely
important if this is to be achieved. Capable and adequate
supervision must be provided.
D i major
During
j turnarounds,
t
d improper
i
scheduling
h d li and
d control
t l
can result in having in having large groups of men waiting for
equipment or materials or for other units to be completed
before they can proceed with their particular jobs.
The interdependence of various operating units makes it
essential that schedules be adhered to as closely as possible.

82
41
GOOD DESIGN APPROACH CAN PREVENT CORROSION

PROBLEMS
1. Structural Steel Shape - always present a problem. However,
because they are a basic building materials, they must be
lived with. The outside of an angle is difficult to coat
because coatings tend to pull away from a point or shape
edge.
2. Sharp edge or squaresquare-cut steel should be eliminated
wherever p
possible. Coating
g materials tend to run awayy from
an edge. If the coating is applied by brush and the painter
brushes away from the edge, the coating is invariably
brushed off.
83
STRUCTURAL STEEL SHAPE

84
42
SHARP EDGE 0R SQUARE

CUT STEEL

85
3. Riveted structure or tank can cause difficulty; the coating

discontinuities are formed around rivets. There are 3
ordinary rivet shapes round, pointed and countersunk.
4. Welded Joints in process equipment, steel tanks, and
structures are preferable to bolted or riveted joints, from a
corrosion design standpoint.
5. Rough Welding is another difficulty: rough welds should be
ground smooth. All welds should be double coated for sure
protection. Weld flux is a strongly
p
g y alkaline hydroscopic
y
p
material.
6. Skip
Skip--Welding
Welding-- is widely used in the construction of
equipment. This is the technique of welding a 2 in. bead,
Santos10
& Associates
: August 2010
:
then skipping 2,4,8 AV
and
in. before
laying
another 2 in.
bead.
86
43
RIVETED STRUCTURE

87
WELDED JOINT

88
44
ROUGH WELDING

89
SKIP WELDING

90
45
7. Lap
Lap--welding
welding-- is yet another method of tank construction.
Here welding is continuous on the outside only, leaving the
plates lapped on the inside. As can readily be seen, this
provides a crevice extremely difficult to coat properly, into
which moisture, corrosive gases and corrosive liquids can
easily penetrate.
penetrate
8. Steel angles placed back to back, are often used to form
trusses for a building structure, these angles are ordinarily
separated approximately in. gap is difficult to protect
properly wherever corrosive conditions exist. Corrosive
f
fumes
penetrate
t t it readily.
dil
9. Cone roofs or unbrellaunbrella-type roofsroofs- on storage tanks usually
consists of a center pole with II--beam rafters extending out to
the edge of the tankAV and
the steel plate roof laid directly on
Santos & Associates : August 2010 :
For
Training
Purposes Only
91
top of these II--beams.
LAP WELDING

92
46
STEEL ANGLES

93
CONE ROOF

94
47
Pipe should be an ideal type of surface to protect against

corrosion. It is cylindrical and, in general, does not have any
sharp or supports for any structure exposed to severe
corrosion.
C ti insulation
Coating
i
l ti is
i another
th practice
ti which
hi h requires
i
attention
tt ti
and which often causes considerable difficulty. In areas of
severe corrosion in a plant, the insulation itself may
deteriorate if there is any way for fumes to reach it.

95
NON--DESTRUCTIVE TESTING/INSPECTION
NON
INTRODUCTION
Non--destructive testing may be defined as the science of
Non
examination of materials or manufactured articles, in order
to determine their fitness for certain purposes, without
impairment of their desirable properties.
LIQUID PENETRANT INSPECTION
- Liquid
Li id penetrant
t t processes are non
non--destructive
d t ti ttesting
ti
methods for detecting discontinuities that are open to the
surface. They can be effectively used in the inspection of
nonporous, metallic materials, both ferrous and ferrous.
Penetrant inspection is basically a simple process.
96
48
LIQUID PENETRANT
INSPECTION

97
MAGNETIC PARTICLE INSPECTION

- Magnetic particle inspection is a nonnon-destructive method of
detecting the presence of cracks, laps, burst, tears, splits,
seams inclusions, segregations, laminations, shrinks, cold
shuts, porosity, lack of fusion and similar discontinuities in
ferro--magnetic materials
ferro
materials, such as iron and steel.
steel This method
will detect discontinuities that are open to the surface, but
too fine to be seen with the naked eye.
EDDY-CURRENT INSPECTION
EDDY- It is consists of observing the interaction between
electromagnetic fields and metals. EddyEddy-current methods of
inspection are effective with both ferro
ferro--magnetic and
nonferro--magnetic metals.
nonferro
98
49
MAGNETIC PARTICLE
INSPECTION

99
EDDY--CURRENT INSPECTION
EDDY

100
50
Application of EddyEddy-current and Electromagnetic methods of

inspection to castings can be divided into the categories:
1.
2.
Detecting near surface flaws such as cracks, voids,

inclusions, blowholes and pinholes (eddy current
i
inspections)
ti
)
Sorting according to alloy, temper, electrical conductivity,
hardness and other metallurgical factors (primarily
electromagnetic inspection)

101
THE END
102
51
REMINDER
Always refer to the appropriate codes and standards
for your technical requirements

103
If you need further assistance, you may contact

Victor Lachica and Tony Santos
Mobile: +63+63-917
917--867
867--5878
Mobile: +63
+63--917
917--819
819--5664
Email: victorlachica@gmail.com
cxc.services@gmail.com
104
52
Thank you very much!!!

105
We would like to acknowledge

all persons, and/or organizations
for the information used in this training material

106
53

Fundamentals of Inhibitors

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Fundamentals of Inhibitors

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For Training Purposes Only

An Inhibitor is a substance which retards or

For Training Purposes Only

AV Santos & Associates : August 2010 :

Points of view of Corrosion

Their effects on the corrosion process.

AV Santos & Associates : August 2010 :

For Training Purposes Only

INHIBITORS AND THE

AV Santos & Associates : August 2010 :

AV Santos & Associates : August 2010 :

For Training Purposes Only

Common Dissolved Substances and their

Oxygen (O2) in neutral water, oxygen causes corrosion, if it is

Bicarbonate (HCO3) bicarbonate in hard waters can be utilized for natural

For Training Purposes Only

Cooling water systems may be either recirculating or

AV Santos & Associates : August 2010 :

For Training Purposes Only

HIGH SALT CONCENTRATIONS

Extremely high salt concentrations are used in aqueous

AV Santos & Associates : August 2010 :

The pH of aqueous solutions is extremely important in

AV Santos & Associates : August 2010 :

For Training Purposes Only

The Open Atmosphere

It is applied directly to the metal surfaces to be

AV Santos & Associates : August 2010 :

For Training Purposes Only

Closed Vapor Spaces

The walls of tanks above a water line are subject to

Effects of Elevated Temperature

Most effects of elevated temperature are adverse to

For Training Purposes Only

Inhibition by polarization of the cathodic reaction can be

For Training Purposes Only

The most widely used cathodic precipitation type

Organic compounds constitute a broad class of corrosion

AV Santos & Associates : August 2010 :

For Training Purposes Only

Corrosion of steel in water above pH 6.0 is due to the

These are filmfilm-forming compounds whose action is

For Training Purposes Only

Vapor Phase Inhibitors

Vapor Phase Inhibitors (VPI) are compounds which are transported

Concentration and Performance Terminology

For Training Purposes Only

- It may be impossible to use as concentrated a solution as in warmer

AV Santos & Associates : August 2010 :

The inhibitor efficiency is calculated from the formula:

Where: E = inhibitor efficiencyy

AV Santos & Associates : August 2010 :

For Training Purposes Only

AV Santos & Associates : August 2010 :

- Another form of continuous application is by the use of

AV Santos & Associates : August 2010 :

For Training Purposes Only

AV Santos & Associates : August 2010 :

For Training Purposes Only

- A quantity of inhibitor is pumped into a well and is

AV Santos & Associates : August 2010 :

For Training Purposes Only

A system must be carefully examined before a program of corrosion

The most appropriate action to take in avoiding difficulty