Shell Global Solutions

Crude Distillation Unit

Materials & Corrosion Issues

Corrosion Loops
Sergio Kapusta
Shell Global Solutions
 Typical Crude Distillation Unit NH3

CW
3-5% Caustic
Soda Solution Vortex Mixer

1% Crude Flash
Vessel SWS
pH
Cl
ions
Sour
&
Fresh Water
Gasoline
Desalter
LR
Effluent water pH
Acid Crude Oil
 CL 05 CRUDE
COLUMN

FLASH

CL 04A
VESSEL
CL 04B

CL 03

CL 06

Wash water Caustic

Desalter Injection
Injection

CL 02
Tank farm

CL 01
Demulsifier
To waste Injection
water treatment
unit
Typical CDU Equipment

¾ Storage tanks and charge lines

¾ Pre-heat train
¾ Desalter
¾ Furnace
¾ Column(s)
¾ Overhead system
¾ Ancillary equipment

Shell Global Solutions 4

Main Corrosion Mechanisms

¾ Wet-Oil in storage & preheat train

¾ Wet H2S Cracking, Hydrogen Induced Problems
¾ Caustic Cracking
¾ Naphthenic Acid & Sulphur Corrosion
¾ Acid Dew Point Corrosion
¾ Fouling and Under-deposit Corrosion

Shell Global Solutions 5

Non-Process Corrosion

¾ Chloride SCC

¾ Scaling & Flue-Gas Corrosion

¾ Furnace tube creep

¾ Corrosion under Insulation

Shell Global Solutions 6

 Causes of CDU overhead corrosion

very acidic corrosion &

salt
dew point fouling
deposition

injection of
unsuitable
neutraliser

poor
Salts in insufficient HCl
desalter +
crude neutralisation formation
performance

desalter
crude oil temperature dew point
too low corrosion &
caustic inj
wash water fouling
desalter effluent

NH3 content
of desalter NH3 enters
water CD column
Shell Global Solutions 7
CDU Corrosion Control

¾ Desalting
¾ Primary (caustic) Neutralisation
¾ Secondary (Ammonia/amine) Neutralisation
¾ Chemical inhibition
¾ Wash water
¾ Metallurgical upgrades

Shell Global Solutions 8

Desalting

Prime functions are:

¾ Remove salts (NaCl, MgCl2, CaCl2)
¾ Remove solids (FeS, clays)
¾ Reduce water (0.3 % w on crude)
Efficiency
Ö single stage 70 - 90 %
Ö double stage 90 - 98 %

Shell Global Solutions 9

Primary (Caustic) Neutralisation

Addition of 2 -5 % caustic soda to the crude

HCl + NaOH ------> H20 + NaCl
¾ NaCl is non-hydrostable and remains in residue
¾ About 95% of the potential HCl will be neutralised
¾ Target Cl < 10 - 20 ppm in overhead water
¾ NaOH may cause its own problems

Shell Global Solutions 10

Caustic cracking

Shell Global Solutions 11

Caustic Cracking Decision Tree

S ta rt

Y es
S tre s s
N o t S u s c e p tib le
R e lie v e d ?

N o

N A C E C a u s tic s o d a
N aO H S e rv ic e g ra p h T e m p e ra tu re
C o n c e n tra tio n F ig u re S 2 -2

Y es N o
P lo ts in A re a
“A ”?

Y es N o
N aO H conc <
5 % w t?

Y es N o
Y es N aO H conc <
H e a t tra c e d ? H e a t tra c e d ?
5 % w t?

M e d iu m S u s c e p tib ility N o H ig h S u s c e p tib ility Y es

N o Y es
S te a m e d o u t? M e d iu m S u s c e p tib ility

N o
N o
S te a m e d o u t?

Y es

L o w S u s c e p tib ility N o t S u s c e p tib le

1.

Shell Global Solutions 12

Secondary Neutralisation
¾ Ammonia or neutralising amines are added to neutralise HCl
in overhead

¾ Target pH 5.5 to 6.5

¾ Chloride salts (Ammonium or amine) may be deposited
¾ High pH can cause fouling by FeS

Shell Global Solutions 13

 Overhead pH Profile
Condensed water pH profile

pH
with neutraliser dosing (fixed dosing rate)
no neutraliser
6.5
target
control
range
5.5
This is what we measure
This is what we want to control

initial water Condenser temperature profile sour water in

dewpoint the accumulator
temperature
Shell Global Solutions 14
Overhead Corrosion Control

¾ Dry operation: top temperature > 10°C above dew point

¾ Cl in accumulator water < 10 ppmwt
¾ Water pH 5.5 to 6.5
¾ If unachievable, alternative methods should be used

Shell Global Solutions 15

Naphthenic Acid Corrosion
¾ Collective name for organic acids in crude
¾ TAN - Total Acid Number mg/KOH/g oil
¾ “Dry” high temeperature corrosion
R-COOH + Fe ----> R-COO Fe
¾ Temperature > 240 oC
¾ Occurs in: furnace tubes, transfer lines, side streams (HVU)

Shell Global Solutions 16

High Temperature Sulphur Corrosion

¾ Sulphur containing oils at temp > 230°C

¾ Corrosive compounds are Mercaptans, sulphides, H2S
¾ Carbon steel used up to about 320°C
¾ Chromium alloying increases resistance against sulphidation

Shell Global Solutions 17

Wet H2S Cracking
¾ Generic name for:
• Sulphide Stress Cracking (SSC)
• Hydrogen Blistering
• Hydrogen Induced Cracking (HIC)
• Stress-Oriented Hydrogen Induced Cracking (SOHIC)
¾ Susceptible steel exposed to an aqueous environment
containing H2S
¾ Occurs in overhead equipment

Shell Global Solutions 18

H2S Damage

H2S HS- + H+ H ads

H
H2 blistering
H
H

HIC SSC
(stepwise cracking)

Shell Global Solutions 19

High temperature creep
¾Stress below yield
¾High temperatures
¾Time dependent
¾Mechanism
1. voids at grain bounderies
2. multiple voids combining
3. microcracks
¾Detection by
– replicas
– U/T
Shell Global Solutions 20
CORROSION LOOPS
PRACTICAL WAY TO DESCRIBE, UNDERSTAND
AND CHECK DEGRADATION MECHANISMS IN A UNIT

¾PART OF THE UNIT SUBJECTED TO

ÏTHE SAME PROCESS CONDITIONS
(THE SAME PROCESS CONTROL)
ÏTHE SAME DAMAGE MECHANISMS
ÏTHE SAME MATERIALS SELECTION CRITERIA

Shell Global Solutions 21

CORROSION LOOPS
¾ Divides units into manageable groups of
similar characteristics

¾Useful for setting and agreeing operating

windows

¾Have been applied in Refineries, Chemical

Plants, Gas Plants

¾ Good experience as part of S-RBI approach

¾20 to 25 corrosion loops for a typical CDU
Shell Global Solutions 22
CDU Corrosion Loops NH3 and/or
T=???
Washwater

CW
3-5% Caustic
Soda Solution Vortex Mixer

1% Crude Flash
Vessel T=360 SWS
pH
Cl
ions
T=170 Sour
& T=340
Fresh Water
Gasoline
Desalter
Desalter
LR
pH
T=140 Acid Crude Oil
ShellT=20
Global Solutions 23
CDU Corrosion Loops
• Pre-heat train up to Desalter
• Desalter
• Downstream Desalter to Pre-Flash Vessel <200°C
• Caustic Injection Side Stream
• Furnace Inlet ----> Outlet ----> Tansferline
• Column T < 240°C
• Column T> 240°C
• Overhead line + HE + Accu + (top of column?)
• Column side streams

Shell Global Solutions 24

CDU Corrosion Loops

Storage tanks and charge line

¾ Corrosion due to water drop out
¾ Prevent by dewatering, flow velocity

Pre-heat train
¾ No major problems due to low temperature
¾ Fouling possible

Shell Global Solutions 25

CDU Corrosion Loops

Column
¾ Naphthenic acid, sulphur corrosion > 240 oC
¾ Acid corrosion in “wet” operation
Overhead system
¾ Acid dew point corrosion
¾ NH4Cl fouling, corrosion
¾ Wet H2S damage

Shell Global Solutions 26

DEGRADATION LIBRARY
Contents
¾Description of Damage
¾Additional Information / Comments
¾Basic Data (required for anaylsis)
¾General Materials Selection / Mitigation
¾Determination of Corrosion Rate / Cracking Susceptibility
¾Inspection techniques
¾References

Shell Global Solutions 27

Steps to determine corrosion rates

High Temperature H2S / H2 Corrosion

Start

Yes Is Material No
12% Cr Steel or
300 Series SS?

Material
Determine Estimated Determine Estimated
Corrosion Rate Corrosion Rate Type of
from Tables Temperature from Tables Hydrocarbon
T1-6 or T1-7 T1-2A thru T1-5B
H2S Concentration

Shell Global Solutions 28

CONTENTS

¾High Temperature H2S / H2 Corrosion

¾High Temperature Oxidation
¾Sulphidic and Naphthenic Acid Corrosion
¾Corrosion Under Insulation
¾High Temperature Hydrogen Attack
¾Sour Water Corrosion
¾Hydrochloric Acid Corrosion
Shell Global Solutions 29
CONTENTS

¾Sulphuric Acid Corrosion

¾Wet H2S Cracking
¾Caustic Cracking
¾Polythionic Acid Stress Corrosion Cracking
¾Chloride Stress Corrosion Cracking
¾Amine Corrosion
¾Corrosion in Hydrofluoric Acid (HF) Services
Shell Global Solutions 30
 Shell Global Solutions

Thank you for your attention!