Instituto Politécnico Nacional

Escuela Superior de Ingeniería Química e

Industrias Extractivas

“Corrosion in Refineries”
By:
Márquez Hernández Esperanza Alejandra
What is a Refinery?
 Refining: set of processes that are applied to crude oil in order to separate
its useful components and also adapt its characteristics to the needs of
society, in terms of finished products.
 A refinery is an industrial platform destined to the refining of petroleum, that
by means of a suitable process, diverse derivatives of the same one are
obtained.
Refinery

 The refineries are very different from each

other, according to the technologies and the
process schemes used, as well as their
capacity.

 There are to process heavy oils or mixtures of

both. Therefore, the products they obtain
vary from one to the other.

 Refining is accomplished in several stages.

This is why a refinery has numerous towers,
units, equipment and pipes.

“ Cadereyta Refinery”
 México
Refineries
 Cadereyta (Nuevo León)
 Cd. Madero (Tamaulipas)
 Minatitlán (Veracruz)
 Salina Cruz (Oaxaca)
 Tula (Hidalgo)
 Salamanca (Guanajuato)
 Equipments
 Process Furnaces.
 Steam boilers.
 Towers.
 Reactors.
 Heat exchangers.
 Storage tanks.
 Compressors
 Pumping Equipment.
 Burners Etc.
 Corrosion in “Primary Distillation
Plant”.
 The main evidence of this problem is manifested by a drastic reduction in the useful life
of the equipment and accessories of the refineries.
 One of the main areas where corrosion damage occurs, is located specifically in the
cold parts of the primary distillation towers, this is:

 Superior plates.
 Domes
 Heat exchangers
 Equipment for Condensation.
 Primary
Distillation
Plant.
Corrosive species
 One of the main corrosive species is
HCl, which is formed by the hydrolysis
of calcium and magnesium chlorides.
However, the oxidation of the metal is
not only due to the HCl formed, but to
the combined effect of other species
present in the feed, or generated in
the distillation operation, such as: H2S,
HS-, CO2, low-weight carboxylic acids
molecular, H2SO3 and H2SO4, among
others.
How are corrosive species produced?

 Crude oil entering the primary distillation tower as a feed load produces
vapors due to the boiling of oil and water. In addition, thermal hydrolysis of
the salts (xMyClz) is carried out, which also enter the charge, producing
HCl.
 The vapors of H2O y HCl ascend through the plates that make up the
tower, and they condense in the low temperature zones located in the
upper plates and in the dome of the tower, forming an aqueous solution of
HCl.
How is it controlled?
 The control of corrosion is carried out through the use of inhibitors and
neutralizers, whose performance depends on the type of feed load and the
concentration of salts and corrosive species present, such as H2S, CO2 and
organic acids.

 Neutralizers: different amines are used to control and maintain the pH of the
condensates in a range between 5.5 and 6.5, which is considered appropriate
to reduce corrosion damage.
 Inhibitors: they are used as substances that at low dosages, are capable of
significantly decreasing corrosion damage, differ in their mechanism of action.
Effect of HCl on primary distillation towers

 HCl is formed by the hydrolysis of sodium, calcium and magnesium chlorides,

according to the following reactions:
 Once the HCl is formed, the metal oxidation reaction and the hydrogen and
oxygen reduction reactions present according to the following reactions are
carried out:

 Which constitute the elementary reactions of the process of corrosion of steel in

acidic media, which in the case of primary distillation towers, is identified as the
main corrosive medium to metal.
Corrosion in the interior of a tower and in a
heat exchanger.

Corrosion in one of the upper plates of a Corrosion in one of the heat exchangers
primary distillation tower. coupled to a primary distillation tower.
Corrosion of steels in the presence of bitter acid
media
 Due to the presence of sulfur and H2S compounds in the feed stream or
generated in the primary distillation towers, the medium to which the metal is
generally exposed is actually composed of HCl and H2S, known as bitter acid
medium, because precisely in the presence of H2S.

 As the corrosion process of the steel progresses in media containing H2S, the
interface undergoes changes in the value of corrosion potential, and therefore
this phenomenon is modified.
Neutralizing amines
 They are used to adjust the pH value, as a control parameter against the corrosion
process of the primary distillation towers.
 Different types of neutralizing amines have been used in the distillation towers:

 Monoethanol Amina.
 Diethylene diamine
 Ethylenediamine.
 60% Ethylenediamine in water (E60).
 2-Etil-hexill-amina.
 amine peroxide.
Corrosion inhibitors
 substances capable of significantly reducing the corrosion phenomenon of a
material exposed to said environment, when added in small concentrations.
 Inhibitors can be classified as:
* Organic inhibitors.
* Film inhibitors.
* Descaling inhibitors.
* Interphase inhibitors.
Mixed
Anodic
Cathodics.
* Oxygen scavengers.
THANKS FOR YOUR ATTENTION