INSTITUTO POLITCNICO

NACIONAL
ESCUELA SUPERIOR DE INGENIERA QUMICA E
INDUSTRIAS EXTRACTIVAS

ANLISIS DE LOS FENMENOS DE

CORROSIN ASISTIDA POR FLUJO (FAC)
PARA TUBERAS QUE TRANSPORTAN
RESIDUO DE VACO.

PRESENTA: M.C. JAIME BRAVO MNDEZ

DIRECTOR DE TESIS:
DRA. MANUELA DAZ CRUZ

INDICE

Introduccin al tema de Investigacin

Objetivo general
Objetivos especficos
Justificacin
Estado del Arte
Metodologa de trabajo
Cronograma de trabajo

INTRODUCCI
N

El petrleo:
Compuesto qumico que en trminos generales est
formado por una mezcla de hidrocarburos.
La palabra petrleo proviene del latn petra = piedra y
oleum = aceite, es decir aceite de piedra.
Se denomina hidrocarburos a aquellos compuestos
qumicos formados principalmente por tomos de
carbono e hidrgeno.
El petrleo contiene aproximadamente:
76 % Carbono
10 % Hidrgeno
14 % Trazas nitrgeno, azufre, oxgeno, algunos metales
como el sodio, nquel, vanadio, entre otros.

Clasificacin de acuerdo al grado API:

Sper ligero: Cuando su densidad se sita en valores por arriba de 39 API
Ligero: Entre 30 a 39.9 API
Mediano: Entre 22 a 29.9 API
Pesado: Entre 10 a 21.9 API
Extra pesado: Por debajo de 10 API

Internacionalmente el crudo son esta valuado conforme:

Parmetro

WTI

WTS

BRE
NT

DUB
AI

API

38-40

36

38.5

31.2

Azufre, %
en peso

0.3

1.6

0.4

2.01

En Mxico la disponibilidad relativa actual es de 17 tipos

de crudo pesado tipo Maya, comercializando tres de
ellos nicamente:
Parmetro

OLMECA

ISTMO

MAYA

API

38

33

22

Azufre, % en
peso

0.98

1.43

3.6

Destilacin primaria
Topping"

Gas de refinera

Proceso
de
refinacin

Gases licuados de
petrleo

Petrleo
Crudo
Desala

do

Destilaci
n
Atmosfri
ca

Destilaci
n a vaco

GLP

Gasolina
s
Queroseno
Gasleo /Gasleo
domstico
Residuo
Atmosfrico
Gasleo ligero
de vaco
Gasleo pesado
de vaco

Residuo de vaco
( RV)
Aceite
Desasfalt
desasfaltado
ado
Asfalto

RAT

GOV

Planta
de
Coquizaci
n
Retardad
a

DAO
6

Residuo de vaco (RV):

Son residuales pesados provenientes de la destilacin
Primaria o "Topping, que resulta de haber pasado previo
por una columna de destilacin que opera a presin
atmosfrica y una segunda columna de destilacin que
opera a condiciones de vaco, conociendo a este fluido como
residuo de vaco (RV).
En su composicin contiene:
Azufre (4 al 9%), Nitrgeno, Slurry, olefnicos, metales,
sales, sedimentos y asfltenos que provocan la corrosin
electroqumica en los materiales para tuberas que lo
transportan.
Las condiciones normales de operacin de estas tuberas
esta por encima de los 250C de temperatura y a una de
presin 20 kg/cm2

Residuo de vaco
(RV):
RAT

Destilaci
n a vaco

Hidrotratamie
nto

RV

Coquizaci
n

Hidrotratami
ento

Destilad
os
medios
y
pesados
Gas de
refinera
(fuel gas)
GL
P
Nafta hacia
pretratamient
o
isomerizacin
y/o reformado
Gasleo

Coque

ESQUEMA

T TRANSPORTE

DEL

RV

OBJETIVO
GENERAL
Estudiar y analizar el flujo de
los fluidos en una tubera que
transporta el residuo de vaco
mediante la construccin de
un modelo fsico y simulacin
matemtica.
Analizando el fenmeno de la
corrosin asistido por flujo
(FAC) y electro qumico para la
prediccin de la velocidad de
corrosin interna.

OBJETIVOS
ESPECFICOS
Seleccin de un diseo de tuberas
existente que transporta RV en el sistema
de Refinacin de Petrleo en Mxico.

Construccin e implementacin de un
modelo fsico para estudiar el efecto del
flujo del RV.

Caracterizacin de los productos de

corrosin.

4
5
6

Obtencin de la velocidad mxima a la

corrosin para
dos cupones de aceros
comerciales.

Validacin de los resultados experimentales

mediante un programa de dinmica de
fluidos computacional (CFD) y apoyado en
la literatura correspondiente.

Obtencin de la ecuacin para la prediccin

de la velocidad de corrosin interna del RV.

JUSTIFICACIN
Se espera que durante los prximos 20 aos la disponibilidad del
petrleo crudo en Mxico sea del tipo Maya en sus diversas
concentraciones de azufre.
Debido a la escasez del petrleo Olmeca e Istmo se espera que
Pemex procese en los prximos 5 aos gasolinas a partir del residuo
de vaci lo que antes se destinaba a la generacin del combustleo y
asfaltos.
De acuerdo a la SENER, Pemex aumentar la produccin de destilados
a partir de los residuales pesados de la Refinera de Tula Hgo. para
producir combustibles con calidad ecolgica.
Procesando 76 MBD de residuo de vaco, hacia una planta de
coquizacin de alta conversin para aumentar la produccin de
gasolina, 48 MBD y 122 MBD Diesel.
Desde el punto de vista
cientfico y tecnolgico al estudiar la
prediccin de la velocidad la corrosin por FAC y electroqumica en el
transporte del RV se contribuye como herramienta de apoyo para la
seleccin de materiales de acuerdo a la caracterizacin del producto.
Con esto se aumenta la seguridad al personal operativo e
instalaciones as como la vida til de las tuberas y equipos para el
proceso de refinacin en Mxico.

ESTADO DEL ARTE

TITULO

AUTOR

CONTRIBUCIN

An Overview
Of
Naphthenic
Acid
Corrosion In
A Vaccum
Distillation
Plant

Paulo P.
Alvisi,
Vanessa
F.C.

Naphthenic acid corrosion where the flow regime affects the fluid
corrosivity occurred in a vacuum distillation plant after it had been
processed, The inspection after five years, reduced crude oil with a
total acid number of 1.2 mg KOH/g and a total sulfur of 0.8 wt%.
corrosion tested in 5 parts of the vacuum column.

Electrochemi
cal corrosion
behavior of
carbon steel
under
dynamic high
pressure
H2S/CO2
environment
Screening
method for
piping wall
loss by flow
accelerated
corrosion

2010

J.B.
Sardisco.,
W.B.
Wright and
E.C.

G.A. Zhang
2012

Region
Region
Region
Region

1
2
3
4

is
is
is
is

the
the
the
the

IMPT random packing.

tray and bubble caps.
column wall flash zone.
support grid, and region 5 is the transfer line.

The electrochemical corrosion behavior of carbon steel under dynamic

high pressure of H2S/CO2 environment was studied by in situ
electrochemical measurements and weight loss measurements.
Computational fluid dynamics (CFD) was also performed to simulate the
flow velocity and shear stress on specimen surface. The results show
that both the anodic and cathodic processes are activation controlled.
The impedance spectra are characterized by double capacitive
semicircles. The in situ electrochemical measurements are in
accordance with the CFD simulation of flow velocity and shear stress on
the specimen surface.
Flow accelerated corrosion (FAC) phenomenon has persisted its impact
on plant reliability and personnel safety.
In order to help expand piping inspection coverage,we have developed
a screening approach to monitor the wall thinning by direct current
potential drop (DCPD) technique.
Based on the WiRM results, susceptible locations can be identified for
further inspection by ultrasound technique (UT).
Finite element analysis results and a closed-form resistance model are
developed for the comparison with measured wall thinning by the
developed DCPD technique.
Verification experiments were conducted using UT as the reference. The
result shows that model predictions and the experimental results

Paulo P. Alvisi
The most vulnerable
unit of (NAC) in a
crude oil refinery is
the
vacuum
distillation plant.
Although naphthenic
acids with several
molar masses may be
present in crude oil.
This fact occurs in
heavy vacuum gas
oil (HVGO), which is
the fraction that
normally acquires
the highest total
acid number (TAN).
In a refinery, a given
hydrocarbon fraction
always contains in
some level sulfur
compounds
with
different
chemical
affinities to Fe.
For
example,
the
sulfur sulfide (H2S)
can
produce
superficial films (FeS):

However, the film will not be formed

by the interaction with compounds
like thiophene (C4H4S).
A dangerous situation may occur if
the sulfur compound were able to
produce water as it occurs in: R2S =
O + H2 -----R2S + H2O The hydrogen is
produced by the corrosion reaction
and the sulfur compounds produced
are sulfoxides (R2S = O).

Theory: mechanism and

interfering variables Fe
+2R[CH2]n COOH = Fe(R[CH2]n
COO)2 +H2
where R denotes the naphthenic linked
to carboxyl, and the corrosion
products, the complex
Fe(R[CH2]nCOO)2, is soluble in oil.
It must be observed that the acid
tends to dissociate as R[CH2]nCOO
and
H+ evenkinds
in an organic
liquid
Different
of corrosion
environment
morphologies connected to

NAC
Region 1 random packing. (specified
with higher Mobearing SS 316 with
>2 wt% Mo).
Region 2 is the tray and bubble
caps. (AISI 316 SS with >2 wt% Mo.)
Region 3 is the column wall flash
zone. The material of the column
wall is the AISI 410 SS (3 mm in
thickness).
Region 4 is the support grid, NAC
occurred at 355 C. The material is
the AISI 304 SS
Region 5 the transfer line. This is a
damage produced by NAC (at 380 C)
where the flow regime strongly
fluid corrosivity.
is 5Cr
Their affects
criticalthe
points
as furnace
tubes
0.5Mo (wt%)
alloy steel.
and elbows,
transfer
line, The
walls, and
thickness
of pipes
is 12
mm.be built
trays of
vacuum
column
must
with Mo-bearing stainless steel such

Kyung Ha Ryua
CFD simulation
The CFD simulation was performed using a
commercial software package of Solidworks
2009. Firstly, model was constructed according to
the experimental setup, the dimensions of the
outer and inner cylinders. The fluid was assumed
to be incompressible and a je turbulence model
was used to numerically solve all simulation:

The corrosion rate of carbon steel under dynamic high

pressure of H2S/CO2 environment increases obviously
with the increase of partial pressure of H2S/CO2 and
fluid flow velocity. At high partial pressure ratio of
CO2/H2S, the corrosion process is dominated by CO2
corrosion. With the increase of partial pressure ratio of
H2S/ CO2, the corrosion process switches to H2S
corrosion control.
CFD simulation shows that the flow velocity on
specimen surface is 3.4 m/s and the shear stress is 48
Pa when the gap is 2 mm and the rotating rate of rotator
is 1500 rpm.
The designed experimental setup facilitates the
realization of in situ electrochemical measurement
under dynamic high pressure of H2S/CO2 environment.

Where j is the turbulent kinetic energy, E is its rate of

dissipation, p is the density of fluid, u is the velocity of
fluid, Mt is the turbulent or eddy viscosity, Gk is the
Both the anodic and cathodic processes of carbon steel
turbulent Prandtl number for the turbulent kinetic
under high pressure of H2S/CO2 environment are
energy, Ge is the turbulent Prandtl number for the
controlled by charge transfer reaction step.
dissipation rate, Gk is the turbulent kinetic energy
The increase of rotating rate of rotator increases the
generated due to the mean velocity gradients, C1e is flow velocity and shear stress on the specimen surface,
the first experimental model constant for the dissipationwhich enhances the
rate, C2e is the second experimental model constant
mass transfer process and hinders the formation of
for the dissipation rate. During the simulation process,

Kyung Ha Ryua

Experimental verification of
NaRM
To identify the feasibility of the
NaRM method, we performed
the preliminary testing for a
carbon steel elbow specimen
with a 2.5-in. diameter.
First we prepared grid lines and
measured local thickness by UT
and estimated wall loss by
NaRM with a probe spacing of
20cm (2 + 0.75D).
Then the outer wall of extrados
was
gradually
thinned
We
suggested
Equipotential Switched-DCPD to support existing FAC management effort based on UT by
bymechanical
grinding.
rapidly screening
FAC-active area.
If the DCPD change shows sign of degradation, we can apply successive reduction of probe spacing to
specify defect locations for
UT inspection. For on-line monitoring of specific areas, we have developed a Narrow Range Monitoring
method. Both analytical and experimental demonstrations have been presented to show excellent
agreement and signal quality.

METODOLOGA
DE TRABAJO

Sistema de (RV)

Simulacin matemtica

Diseo

Modelacin fsica

Recopilacin
informacin y
caracterizacin (RV)

Solid Works (Diseo Tub,

anlisis de flujo, anlisis de
Esfuerzos Tub.)

Experiment
acin

Ansys - Fluent (Simulacin de

flujo).
Preparacin
de probetas
para tres
aceros
comerciales

Validacin del
modelo con
datos
experimentale
s

Obtencin de
la ec. De
velocidad de
corrosin

Anlisis
de
resultad
os

Tcnicas de caracterizacin:
+ MEB (scanning electron
microscopy)
+ Energy dispersive
spectrometer
+ (UT) Ultrasound technique
+ DRX

Redaccin
de Artculo y
Tesis.

19

Cronograma de Trabajo

Investigaci
n

Resultados
Resultados
Simulacin
Simulacin
matemtica
matemtica
Modelacin
Modelacin
fsica
fsica

Tiempo (6 semestres)

AVANCE EXPERIMENTAL

PROPIEDADES FISICO
QUMICAS (RV)

Las propiedades de RV enunciados

varan de acuerdo a cada refinera en
Mxico, dichos datos fueron estimados
en el ao 2012 por PEMEX REFINACIN
en las instalaciones de Refinera
Miguel Hidalgo, y fueron proporcinados
para fines de investigacin para el
presente trabajo.

AVANCE EXPERIMENTAL

BANCO DE PRUEBA

Consiste en dos depsitos, el primero inyecta el qumico a utilizar a

un segundo depsito o directamente al circuito de tubera, el fluido
una vez mezclado con los dems componentes es enviado a travs
de una bomba centrfuga. El el fluido se encuentra en circuito cerrado
provocando erosin - corrosin en la pieza de trabajo.

AVANCE EXPERIMENTAL

BANCO DE PRUEBA FSICO:

AVANCE EXPERIMENTAL

BANCO DE PRUEBA:

PROPUESTA DE PIEZA DE TRABAJO

Pieza de prueba:
Se pretende realizar
pruebas de laboratorio en
dos tipos de materiales
para determinar su
comportamiento en
simulacin fsica y
matemtica analizando la
corrosin por FAC y en su
caso electroqumica.

AVANCE EXPERIMENTAL

CARACTERSTICAS METALOGRFICAS
DE LOS MATERIALES PROPUESTOS

CRONOGRAMA DE TRABAJO
Actividad \Semestre
Revisin bibliogrfica
Diseo e instalacin del
equipo experimental
Caracterizacin de
productos de corrosin
del RV.
Validacin del modelo con
datos experimentales
Uso de tcnicas
experimentales, MEB,
DRX
Obtencin de la ec. para
la vel. de corrosin RV
Anlisis de resultados
Redaccin de tesis

1 2 3

GRACI
AS

Pregunta
s