Naphthenic Acid

Corrosion Control Strategies

Randy Rechtien
Baker Petrolite Corporation

© 2006 Baker Hughes Incorporated

 Discussion Topics
• Challenges of processing high nap acid crudes

• Overview of nap acid corrosion

– Mechanisms
– Effects on unit operation

• Corrosion control strategies

– System assessment
– Mitigation options
– Monitoring protocol

© 2006 Baker Hughes Incorporated

 TANK FARM CONSTRAINTS
1. Increased sludge (asphaltene instability, solids)
2. Difficult dewatering (high viscosity oils)
PREHEAT AND DESALTER CONSTRAINTS
WASTE
1. DropWATER TREATMENT
in desalting efficiencyPLANT
(low gravity crudes)
1.
2. Increased
Increased toxicity of water to WWTP (alkali metal naphthenates)
T-4 desalter upsets (water and solids carryover)

2.
3. More oily undercarry
Increased (stable emulsions)
fouling (asphaltene destabilization)
T-3
CORROSION EFFECTS
~
~

1. Increased
T-2
corrosion in tower and OH system (increased contaminants)
Wash Water
2. Corrosion in high temperature circuits (naphthenic acids)
T-1
API Separator
ST-
ST-1

Amine Unit Skims

ST-
ST-2 Wastewater
Solids Treatment Plant

SWS Tank Skims

Coker
Flare K.O. Drum
© 2006 Baker Hughes Incorporated
 Examples of Naphthenic Acid Structures

O COOH
COOH CH2CH2CH2 C
COOH

OH R
R R

COOH
COOH

COOH

R R
R

COOH

COOH
© 2006 Baker Hughes Incorporated
 Naphthenic Acid Corrosion Mechanism
• Occurs in the range of 400oF (200oC) to 750oF (400oC)
• Non-aqueous mechanism
• Nap acids typically concentrate in the gas oil boiling range
• Attack is accelerated in high velocity / high shear areas
• Iron attacked by naphthenic acid forms iron naphthenate
and atomic hydrogen:

Fe + 2 RCOOH Î Fe(RCOO)2 + 2 H°

• Atomic hydrogen diffuses through the metal and then

recombines on the external surface to form molecular
hydrogen:
2 H° Î H2

© 2006 Baker Hughes Incorporated

 Typical Areas of Crude Unit
Susceptible to Nap Acid Corrosion

Atmospheric Vacuum
Column Column
Desalter
LVGO
Crude 450°F
Charge (230°C)

Diesel

AGO
HVGO
550°F
(285°C)

600°F
(315°C)
275°F 500°F 650°F
(135°C) (260°C) (345°C)

Hot Crude Atmospheric

Preheat Heater 620°F
650°F
Exchangers (325°C)
(345°C)
680°F
(360°C) VTB
© 2006 Baker Hughes Incorporated
 SMARTGUARD Naphthenic Acid
Corrosion Control Strategies
• Assessment
– Feedstock / process stream characterization
– System evaluation / high risk circuits

• Mitigation
– Crude blending
– Metallurgy upgrade
– Chemical inhibition

• Monitoring
– Establish monitoring protocol
– Optimize corrosion management program

© 2006 Baker Hughes Incorporated SMARTGUARD is a trademark of Baker Hughes Incorporated

 Stream Characterization
Acidity Measurements
• TAN (Total Acid Number)

• SCAN (Specific Carboxylic Acid Number)

– Analytical tool developed by Baker Petrolite
– Measures acidity only from carboxylic acids
– Same reported units as TAN (mg KOH/gm oil)
– Better predictor of high temperature corrosivity
than TAN

© 2006 Baker Hughes Incorporated

 Comparison of TAN and SCAN
Crude and Gas Oil Streams
1
TAN SCAN
0.9
0.8
Acid Number (mg KOH/g oil)

0.7
0.6

0.5
0.4

0.3
0.2
0.1
0
Raw Crude AGO LVGO HVGO

© 2006 Baker Hughes Incorporated

 Other Stream Characterization Data
• Compositional analysis
– Sulfur content
– Metals content
• Iron, nickel, chromium, vanadium
• Ratio of metal levels typically more meaningful

• Laboratory testing
– Simulated process conditions
– Comparative corrosivity
• Metallurgy type
• Inhibitor type and dosage

• Crude oil assay information

© 2006 Baker Hughes Incorporated

 System Assessment - Overview
• Purpose: Identify areas of the
system that are at risk

• Focus on key factors that affect

nap acid corrosion
– Acid concentration
– Sulfur levels
– Operating temperature
– Equipment metallurgy
– Velocity

© 2006 Baker Hughes Incorporated

 System Assessment - Methodology
• Analysis conducted on circuit-by-circuit basis
– Discrete “break points” identified
• Temperature
• Metallurgy
• Pipe size
• Circuit details captured in assessment spreadsheet
• Calculations performed to determine severity of risk
• Each circuit assigned a risk potential
– Low (Green)
– Medium (Yellow)
– High (Red)
• Concern levels are inter-dependent
– For example:
• High sulfur offsets high TAN
• High velocity can offset moderate TAN

© 2006 Baker Hughes Incorporated

 System Assessment – Sample Output
Diameter Temperature
Equipment Stream Name Metallurgy Flow (bpd) (in) (°F) TAN
Vacuum Surge Drum Reduced Crude CS 49817 12 446 0.8 HIGH
Line Reduced Crude CS 49817 12 446 0.8 HIGH
Exchanger Reduced Crude 12Cr 49817 8 554 0.8 HIGH
Line Reduced Crude CS 49817 8 554 0.8 HIGH
Exchanger Reduced Crude SS 49817 8 608 0.8 LOW
Line Reduced Crude 5Cr 49817 8 608 0.8 HIGH
Exchanger Reduced Crude SS 49817 8 608 0.8 LOW
Line Reduced Crude 5Cr 49817 8 608 0.8 HIGH
Exchanger Reduced Crude SS 49817 8 644 0.8 LOW
Line Reduced Crude 5Cr 49817 8 644 0.8 HIGH
Line LVGO CS 16153 12 374 0.5 LOW
Line LVGO CS 16153 8 374 0.5 LOW
Exchanger LVGO CS 10114 6 293 0.5 LOW
Line HVGO SS 49666 14 662 1 LOW
Line HVGO SS 49666 12 662 1 LOW
Line HVGO CS 7246 6 464 1 HIGH
Flow control valve HVGO CS 7246 4 464 1 HIGH
Line HVGO CS 25814 8 464 1 HIGH
Flow control valve HVGO CS 25814 6 428 1 HIGH
Line HVGO 5Cr 25814 8 428 1 HIGH
Line Overflash SS 1962 8 752 0.5 LOW
Line Overflash SS 1962 6 752 0.5 LOW
Pump Overflash 5Cr 1962 2 752 0.5 MEDIUM
Line Overflash SS 1962 3 752 0.5 LOW
Flow control valve Overflash SS 1962 2 752 0.5 LOW
Line Vac Resid 5Cr 17964 12 752 0.5 MEDIUM
Line Vac Resid 5Cr 17964 12 752 0.5 MEDIUM
Pump Vac Resid 5Cr 17964 4 752 0.5 MEDIUM
Line Vac Resid 5Cr 17964 8 752 0.5 MEDIUM
Exchanger Vac Resid CS 17964 8 446 0.5 MEDIUM
Line Vac Resid CS 17964 8 446 0.5 MEDIUM
© 2006 Baker Hughes Incorporated
 Mitigation Options

• Blend to TAN/SCAN limits

– Continue to realize profit while minimizing
corrosion effects

• Metallurgy upgrade
– 317 SS (or 316 SS with minimum 2.5% Moly)

• Corrosion inhibitors

© 2006 Baker Hughes Incorporated

 SMARTGUARD Corrosion Inhibitors TM

• Composition
– Thio-phosphate esters (sulfur and phosphorus-based)
– Sulfur group is key feature
• Sulfur has well-known affinity for metals
– e.g.,pre-sulfiding of catalysts
• Brings phosphorus to metal surface more efficiently

• Functionality
– Produces a stable iron-phosphorus complex
– Provides protective barrier at metal surface

• Performance
– Proven effective over a wide range of process conditions
and crude types
– Downstream effects are minimized
• More thermally stable than traditional phosphate esters
• Lower phosphorus content than traditional inhibitors

© 2006 Baker Hughes Incorporated

 Inhibitor Application Guidelines

• Passivation Treatment
– Establish passive surface at start-up
– High inhibitor dosages for short time

• Maintenance Treatment
– Maintain passive surface
– Lower dosage continuously
– Recommendations based on assessment results
– Dosage optimized with monitoring

© 2006 Baker Hughes Incorporated

 Nap Acid Corrosion Control Program
Inhibitor Application – HVGO Circuit
100 25
Inhibitor Dose
Corrosion Rate

80 20

Corrosion Rate (mpy)

Inhibitor Dose (ppm)

60 15

40 10

20 5

0 0

© 2006 Baker Hughes Incorporated

 Monitoring Objectives

• Evaluate the effectiveness of corrosion

control program

• Establish operational constraints/limits

• Serve as an early warning of changes in

system corrosion

© 2006 Baker Hughes Incorporated

 Monitoring Nap Acid Corrosion
• Compositional measurements
– TAN, SCAN, sulfur
– Phosphorus residuals
– Metal levels/ratios

• Metal loss/Corrosion activity

– ER probes and weight loss coupons
– Ultrasonic thickness measurements
– Digital radiography
– Field Signature Method (FSM)
– Hydrogen permeation measurements

© 2006 Baker Hughes Incorporated

 Hydrogen Permeation Measurements
• Measures rate of hydrogen release at
external wall of pipe or vessel

• Rate of external hydrogen release is

related to the corrosion activity
occurring on the internal surface

• Hydrogen permeation is a function of:

– Temperature
– Metal thickness
– Metallurgy
– Corrosion mechanism

• Baker Petrolite has developed a

“corrosion index” which allows for
comparison across entire unit
© 2006 Baker Hughes Incorporated
 Hydrogen Permeation Measurements
• Advantages
– Mobile and portable instrument
– Temperatures up to 1100°F (600°C)
– Non-intrusive measurement in minutes
– Measurement reflects real-time corrosion activity

• Other features
– Data-logging capability
– Fixed collectors available for use under insulation
– Intrinsically safe for refinery application

© 2006 Baker Hughes Incorporated

 Hydrogen Permeation Measurements
Monitoring Survey Results

SMARTGUARD Corrosion Index

2

200
9

65

Raw Hydrogen Flux Data

© 2006 Baker Hughes Incorporated

 Corrosion Monitoring Using Hydrogen Permeation
Field Case Study – Vacuum Tower
22
Overflash HVGO
20

HVGO Inhibitor
18
Overflash Inhibitor Pump On
Injection Started
16
HVGO Inhibitor
Pump Off
14
Corrosion Index

12

Target
10

0
24-Jun 1-Jul 8-Jul 15-Jul 22-Jul 29-Jul 5-Aug 12-Aug 19-Aug

© 2006 Baker Hughes Incorporated

 Summary
• “Opportunity” crudes present a challenge to refiners
because of higher nap acid levels

• Nap acid corrosion can diminish unit safety and

equipment reliability

• Techniques are available to address nap acid corrosion

– Risk assessment
– Crude blending
– Metallurgical upgrades
– Corrosion inhibitors

• Comprehensive monitoring program is necessary to

ensure corrosion control strategies are effective

© 2006 Baker Hughes Incorporated