Best Practices in Refinery

Corrosion Control
PetroPeru
Talara, Peru
June 2003

William Fahey, Baker Petrolite

 Agenda
• Corrosion Theory
• Desalter Effects on Corrosion Control
• Crude Unit Corrosion
– Dew Point Corrosion
– Amine Salt Deposition
– Baker Petrolite Ionic Model
– Bisulfide/CO2 Corrosion
– Water Wash Programs
• Tower Top Corrosion
• Corrosion Inhibitors
• FCCU Corrosion
 What is the Cost of Corrosion?
• Equipment Repair and Replacement
• Plant Safety and Liability Issues
• Lost Throughput / Capacity Limitations
• Reduced Unit Reliability
• Reprocessing Costs
• Product Quality
• Downstream Unit Fouling
 Corrosion Theory
Why Does Corrosion Occur?

• Three Elements are Required for Corrosion to

Occur
– Something is Oxidized
• Anodic reaction
– Something is Reduced
• Cathodic Reaction
– Metallic Path
The Chemistry of Corrosion

Acid Corrosion Reaction

Fe + 2 HCl FeCL2 + H2

Oxidation
Fe Fe+2

Reduction
H+ H0
HS- H0 + HS=
Anodic, Cathodic Sites on a Metal

Fe+2 H+
Anodic
Fe+2
Cl-
Site

Fe+2 Cl-

e- e- e e e e
- - - - H+ H+
H2
H+

O
2
Cathodic
H+ +
H H2O
H+ Site
O
2 H+ H2O
H+ Cl-

Carbon Steel
 Environmental Factors on
Corrosion
• Concentration of corrodents
• Corrosion rates increase as the concentration of
corrodents increases
• Physical and chemical factors that affect the
concentration of corrodents have a direct effect on
corrosion rates
• Temperature
• Corrosion reaction rates increase with increasing
temperature
• The concentration of corrosive species present in a
given location is often a function of temperature
• Velocity
 Classifications of Crude Unit
Corrosion

• Aqueous Corrosion
• Acid Corrosion
• Bisulfide Corrosion
• CO2 Corrosion
• Above Dew Point Corrosion
• High Boiling Acid Azeotropes
• Organic Acids
• Neutralizer Salts
• High Temperature Corrosion
• High Temperature Sulfur Corrosion
• Naphthenic Acid Corrosion
 Common Corrosion Morphologies

General Corrosion Under-Deposit Corrosion

Pitting Environmental Cracking

 Crude Unit Corrosion Control
• Decrease Contaminates
– Desalter Operation
– Caustic Addition
• Decrease Concentration
– Water Wash
• React with the Corrosives
– Neutralizer Applications
• Protect the Metal Surface
– Film Forming Inhibitors
 Desalter Operation
Salt Hydrolysis
• Source of HCl in overhead systems: Salt hydrolysis

– MgCl2 + H2O + Heat ==> Mg(OH)2 + 2HCl

– CaCl2 + H2O + Heat ==> Ca(OH)2 + 2HCl
– NaCl + H2O + Heat ==> Na(OH) + HCl

• Salt hydrolysis a function of temperature

• High (>125 °C) desalter operating temperature can
lead to high water in crude solubility and increased
BS&W/Salt to the Atmospheric Tower.
 Magnesium and Calcium Chloride
Salt Hydrolysis vs. Temperature

90
Magnesium
80 Chloride
% Hydrolysis

70
60
50
40
Calcium
30
Chloride
20
10
Sodium Chloride
200 300 400 500 600 700

Temperature, °F
 Crude Unit Corrosion Control
Caustic

• Caustic Usage Guidelines

• Limit usage rates
– 2-5 ptb maximum
• Use overhead chlorides to control addition rates
– 20-30 ppm minimum
• Use dilute solutions
– 2-3 weight %
• Provide adequate mixing of solutions into crude oil
– Use injection quills
– Choose proper injection location
– Desalted crude booster pump suction
• Caustic Limitations
 Two Stage Desalters
Salts

Level Level
A B

Demulsifier Rate

Salts
BS&W
Polymer Rate
Effluent Water
pH
 Desalter Optmization

• Mix Valve Delta P

• Wash Water Rate
• Demulsifier
• Interface Level
• Mud Wash
• Slop Oil
• Temperature
 Crude Unit Corrosion Control
Neutralizer

• Purpose of Neutralizers

RNH2 + HCl ==> RNH3+ Cl-

• Use the most effective neutralizer to meet the system

conditions.
– Water Wash System
– Salt Formation Potential
– Tramp Ammonia
– Cost
 Crude Unit Corrosion Control
Neutralizer

• Important Neutralizer Characteristics

• Amine phase solubility
• Amine base strength
• Neutralizer hydrochloride salt properties
 pH
0.
0

0
1
2
3
4
5
6
7
8
9
10
11
12

0.
7
1.
4
2.
1
2.
8
3.
5
4.
2
4.
9
5.
6
6.
3

7
7.
7
8.
4
9.
1
9.
8
10
.5
11
.2

P ro d u c t(m l)
11
.9
12
.6
Neutralizer

13
.3

14
14
.7
15
.4
16
.1
16
.8
17
.5
18
.2
Crude Unit Corrosion Control

18
.9
 Crude Unit Corrosion Control
Neutralizer
9

6
pH of C on de nsa te

1
220 210 200 190 180 170 160 150 140 130 120 110 100
Te m pe ra tu re (°F)
Crude Unit Corrosion Control
Amine Hydrochloride Salt Corrosion

• Moist Deposit
– All Salts are Hygroscopic
– Insufficient Water to Dissolve
– Salt Itself is a Weak Acid
• Corrosion Attack
– Accelerated
– Localized, Pitting
• Both Solids and Melts are Possible
 Crude Unit Corrosion Control
Amine Hydrochloride Salt Corrosion

• Effects of Ammonia
– Ammonia contamination can cause problems
• Leads to poor dew point pH control
• Increases rates of bisulfide corrosion
• Causes ammonium chloride salt deposition
– Sources of Ammonia:
• Intentional use as neutralizing agent
• Present in desalter wash water (Stripped sour
water)
• Present in plant slop
 Conflict in Corrosion Control
• Strong Acid Corrosion
– Increase pH to Decrease Corrosion
– Result of Neutralizer Under-Use
– Need pH Data to Control

• Amine Salt Corrosion

– Salt Under Deposit Corrosion
– Result of Neutralizer Over-Use
– Need Thermo Data to Avoid
 Conflict in Corrosion Control
Salt Formation
• Neutralizer Salt Formation
– RNH2(g) + HCl(g) RNH3Cl(solid/melt)
– Amine Hydrochloride Salts are Weak Acids
• Occurs Before Aqueous Dewpoint
– Formation Depends on
– Partial Pressure - Pi = (yi)(Ptotal)
– Temperature
• Formation Occurs When:
– (PHCl)(PAm) Exceeds Limit
– Temperature Drops Below Limit
 Conflict in Corrosion Control
Ionic Model

• Calculates the aqueous dew point temperature

– Possibility of acid corrosion after dew point
– Possibility of salt formation before dew point
• Calculates pH for all locations with condensed water
– Optimizes neutralizer rate
• Predicts the formation of corrosive salts
– Calculates the salt formation temperature at any
location in the system
– Identifies proper neutralizer
 General Acid Corrosion
Sample pH Profile
6.5
6
5.5
5
pH

4.5
4
3.5
Aqueous
220 180 140 100
Dewpoint T em p eratu re Accumulator
 Overhead System
Phase Relationships
VAPOR PHASE
SALT DEPOSITION
RNH2(g) + HCl(g) RNH3Cl(s)
SUBLIMATION

Vapour SOLID or LIQUID SALT

SOLUBILITY
Liquid HYDROCARBON PHASE
Liquid
Equilibrium
DISSOCIATION
RNH2(aq) + HCl(aq) RNH +(aq) + Cl -(aq)
PROTONATION

AQUEOUS PHASE
 Conflict in Corrosion Control
Ionic Model Key Outputs

• Determines if a Amine Neutralizer Salt could form.

• Provides pH as a Function of Temperature

– pH is Quantified
– Improved Understanding in the Dewpoint Region
– Not Available with Non-Ionic Models
 Corrosion Control
pH Control Range
mpy
600
500
400
300
200
100
0
0 2 4 6 8 10 12
pH
 Ionic Model

• Ionic Model predicts salt deposition under

equilibrium conditions
• Predicts dew point pH
• Useful as guide for TPA conditions
• Analysis identifies amines
• May be able to design for non-equilibrium
conditions
 Aqueous Corrosion
Bisulfide Corrosion

• Aqueous Bisulfide Corrosion

– H2S Is Liberated From Crude Oil Upon Heating and
Distills Overhead
– H2S Becomes More Soluble in Aqueous Condensate
As Overhead System Temperatures Decrease
– Once Dissolved, H2S Can Dissociate to Form Bisulfide
Ion (HS-)
– Degree of Dissociation Is pH Dependent
 Aqueous Corrosion
Bisulfide Corrosion
• Aqueous Bisulfide Corrosion
– Bisulfide ion is corrosive to carbon steel:
2Fe + 2HS- ==> FeS + H2
– Corrosion Rate is pH dependent
• Below pH of 5 Little Corrosion. H2S Only
• Increases at pH of 5.0-7.5 because of the increasing
concentration of bisulfide ion in this range
• Above pH 8.0 corrosion rates decrease because of
the formation of a dense and adherent iron sulfide
scale
• Above pH 9 Most is S=
 Hydrogen Sulfide Dissociation
vs. pH
100
90
80 HS- + S-2
% Dissociation

70
60
50 H2S + HS-
40
30
20
10
H2S
0
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0

Condensate pH
 Aqueous Corrosion
Bisulfide Corrosion

• Interaction of HCl, Bisulfide Corrosion Mechanisms

– FeS forms a Protective Layer on Metal Surface
– However, at Low pHs the Protective Iron Sulfide
Scale Can Be Removed:

FeS + 2HCl ==> FeCl2 + H2S

– Low pHs Prevent Further Protective Sulfide Film

Formation
 Crude Unit Corrosion Control
Water Wash

• Purpose of Water Wash

• Control of water dew point location
– Put dew point location where you can
treat it
– Put dew point location where you can
monitor corrosion rates
• Dilution of corrosive acids and salts
• Control of salt and corrosion product
deposition
 Crude Unit Corrosion Control
Water Wash
• When to use water wash
• Where corrosion rates are high and can’t be
controlled by other means
• Where overhead system salt deposition is a
problem
– “Dry” systems (<2-3% overhead water)
– Low overhead velocities
• When chloride loadings are high (> 75 ppm
Cl)
 Crude Unit Corrosion Control
Water Wash

• Wash water sources

– Free of scale-forming dissolved solids
– Low in oxygen (<20 ppb)
– Low particulate iron content
– Good pH control
• Boiler feed water
• Steam condensate
• Recycled accumulator water
 Crude Unit Corrosion Control
Water Wash
• Where to add water wash
• Overhead vapor line
– Provides long contact time
– Turbulent flow in line aids mixing
– Upstream of water dew point location
• Inlet to each fin-fan nozzle
– Assures water distribution to each
exchanger
– Hardware intensive
• Downstream of filming inhibitor injection
location
 Crude Unit Corrosion Control
Water Wash

• How Much Water Wash?

• Use ProAct to calculate minimum
requirement
• Add 25-50% excess to provide adequate
amount for deposit control
• Provide means to measure rates reliably
and accurately
 Crude Unit Corrosion Control
Water Wash

• Use Proper Spray Nozzles

• Full cone spray nozzles to maximize

surface to volume ratio
• Use alloy nozzle to prevent cold nozzle
corrosion
• Orient nozzle in direction of process flow
 Tower Top Corrosion
• Acid Corrosion
– Water Condensation in Cool Areas
– Non-Equilibrium Water
• Shock Condensation
• Underdeposit Salt Corrosion
– Amine Salt Deposits
– Salt Carry Over from TPA
• Underdeposit Fouling Corrosion
 Pumparound Systems

FIC

Crude

TI
Overflow TI
Weir

To
Product Stripper

TIC FIC

Total LIC
Drawoff

FIC

To
Product Stripper
 Acid Dew Point Corrosion

• HCl is soluble in hydrocarbons

• Water condenses on piping and
exchanger tubes
• Low pH acid corrosion
• FeS corrosion products may
accelerate underdeposit
corrosion
 Shock Condensation Acid
Corrosion

• Cold TPA return causes shock

dew point condensation
• Low pH Corrosion
• Underdeposit Corrosion
• Often flow patterns found
 Non-Equilibrium Water

• Water from shock condensation

is carried down tower into TPA
• Low dew point corrosion
• Low point transfer line failures
 Amine Salt Corrosion

• Amine Salts form in cool areas

• Amines are hygroscopic
• Amine salt corrosion
 Amine Salt Non-Equilibrium

• Amine salts formed in TPA are

carried down tower and into the TPA
• Wet amine salt corrosion
• Underdeposit corrosion
• Salts may be formed by shock
condensation
 TPA Corrosion Control Measures

• Acid Dew Point

– Corrosion Control Program
– Metallurgy
– Temperature
– Optimize Desalter
• Non-Equilibrium Shock Condensation
– Metallurgy
– Corrosion Control Program
– Temperature
 Crude Unit Corrosion Control
Filming Inhibitor

• How Inhibitors Work

• Adsorb into corrosion deposit film

• Make these films less permeable to ion

transport

• Slow the rate of diffusion of ions to and

from the metal surface
 Crude Unit Corrosion Control
Filming Inhibitor

• Chemical Description
• High molecular weight
• Non-volatile
• Typically amine compounds
• Hydrophobic, hydrophilic functional
groups
Filming Inhibitor Adsorption onto
a Metal Surface

Corrosion Inhibitor Filming Mechanism

Condensed water droplet Inhibitor molecules

Fe ++ 22
H++ Cl

Corrosion deposit film

Pipe wall
Common Inhibitor Structures

Diamides O
O
R1-C-NH-CH2-CH2-NH-CH2-CH2-NH-C-R

Imidazolines
H2
C O
N CH2
R1-C NH-CH2-CH2-NH-CH2-CH2-NH-C-R

Phosphate Esters O
O
R-O-P-OH R1-O-P-O-R2
and
OH OH
Water Soluble Amines

RCHN+X-
 Corrosion Inhibitor Injection

• Continuous Injection
• Dosage Dependent on the Situation
– Normally 3-12 ppm
– Water Soluble 200 ppm
• Injection Quill
• Slip Stream
CORROSION MONITORING

• In Situ Monitoring
• Stream Analysis
– Water Analysis
– Hydrocarbon Analysis
• Non-destructive
• Representative Monitoring
• Theoretical Analysis
• Historical Analysis
CORROSION MONITORING
In Situ Monitoring

– Coupons
– E/R Probes
– Hydrogen Probes
• Do Not Measure Corrosion
• Location is Critical
• Subject to Leakage
 CORROSION MONITORING
COUPONS

• Average Corrosion Rate

• Location is Critical
• Requires Longer Exposure
• Can Run Surface Analysis
 CORROSION MONITORING
CONSIDERATIONS

• Location
• Metallurgy
• Surface Preparation
• Stress
 CORROSION MONITORING
Electrical Resistance Probes
• Short Term Data
• Location is Critical
• Frequent Readings
• Data Logging
• Choice of Metallurgy
• Suppliers
– Corrpro
– Metal Samples
CORROSION MONITORING
STREAM ANALYSIS

• Condensed Water Analysis

• Hydrocarbon Stream
• Deposit Analysis
• Failure Analysis
 CORROSION MONITORING
WATER ANALYSIS

• Environment
– pH
– Acids
• Corrosion Products (Fe, Cu)
• Inhibitor Distribution
• Desalter Performance
 CORROSION MONITORING
Non-destructive

• UT
• X Ray
• Hydraflux Hydrogen Monitoring
 CORROSION MONITORING
Historical Analysis
• Shut Down Reports
• Unit Audits
– System Review
– Failure Analysis
– Inspection Records
• Process Changes
• Operational Parameters
• SPC Analysis
 FCCU Corrosion Control

• Corrosion Mechanism
– Bisulfide Corrosion
– Salt Deposition
– Cyanides
– Hydrogen Blistering
• Corrosion Control Programs
– Water Wash Options
– Water Soluble Inhibitor
– Oil Soluble Inhibitor
– Light Ends Units
 FCCU Corrosion Control
• High pH Bisulfide Corrosion
– H2S, NH3, and HCN are produced by thermal
or catalytic cracking of Sulfur and Nitrogen
compounds in conversion unit feedstocks
– The pH level of aqueous condensates is
increased in the presence of ammonia:
NH3 + H2O ==> NH4+ + OH-
 FCCU Corrosion Control
• High pH Bisulfide Corrosion
– The solubility of H2S in aqueous condensate,
and the % ionization of H2S to bisulfide ion
(HS- ) increase with increasing pH:
H2S + NH4+OH- ==> NH4+HS- + H2O
– Bisulfide ion attacks carbon steel, producing
iron sulfide and hydrogen:
2 HS- + Fe ==> FeS + S-2 + H2
Conversion Unit Corrosion Mechanisms
• Bisulfide Corrosion is Accelerated by Cyanides
– Bisulfide corrosion is normally not aggressive due
to the formation of a protective iron sulfide
corrosion product film
– However, HCN gas is soluble in high pH aqueous
condensate, forming cyanide ion:
HCN + NH4+OH- ==> NH4+CN- + H2O
– Cyanide ion removes the protective iron sulfide film,
forming ferrocyanide ion:
FeS + 6 CN- ==> Fe(CN)6-4
 FCCU Corrosion Control
• Corrosion Is Typically Controlled by a Combination
of Techniques
– Water wash
• Dilutes and removes corrosive materials
• Controls solids deposition
– Corrosion inhibitors
• Minimize bisulfide attack of steel surfaces,
reducing hydrogen production
• Permeation inhibitors also slow hydrogen
penetration into steel surfaces
• Help control solids deposition
– Ammonium Polysulfide
• Reduces concentration of free cyanides
 Intercooler After Cooler

Naphtha
Compressor Compressor

FRACTIONATOR
Reflux

MAIN
Water Water
Light Cycle Oil
Heavy Cycle Oil

Steam

Steam
Generators Gas Gas
Fuel
BFW
Gas

DEETHANIZER/ABSORBER
Gas
Oil

DEPROPANIZER

DEBUTANIZER
Feed Feed
Exchangers

LEAN OIL
Slurry Clarified C3s C4s
Recycle Slurry Oil
to Storage
Slurry
Settler

Slurry to FCC
GASOLINE
Blending
 FCCU Corrosion

H IG H
O V ER H EA D 1S T S T A G E IN T E R S T A G E 2N D S T A G E PR ESSU R E
C O O LER C O M PR ESSO R C O O LER C O M PR ESSO R C O O LER TO
V A PO R D E -E T H A N IZ E R
F R O M M A IN /A B S O R B E R
F R A C T IO N A T O R

W A SH W A SH
W A TER W A TER

SO U R W A TER
W A SH W A TER
TO
D E -E T H A N IZ E R
R EFLU X L E A N O IL N A PH TH A /A B S O R B E R

W A TER SO L U B L E
C O R R O S IO N IN H IB IT O R

M A IN F R A C T IO N A T O R IN T E R S T A G E H IG H P R E S S U R E
O V ERH EA D A CC U M U LA TO R SE PA R A T O R SE PA R A T O R
Oil Soluble Inhibitor Injection Locations
NAPHTHA SLIPSTREAM

OIL SOLUBLE
CORROSION
INHIBITOR
NAPHTHA
OIL SOLUBLE SLIPSTREAM
CORROSION FUEL GAS
INHIBITOR

LEAN OIL

COMPRESSED GASES

MAIN FRACTIONATOR MIXED C 3

OVERHEAD GASOLINE
AND SEPARATOR
LIQUIDS

FCC
GASOLINE MIXED C
4

DEBUTANIZER DEPROPANIZER

DE-ETHANIZER/ABSORBER