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Challenges in Opportunity
Crude Processing
16th April 2012

Thomas Lu
Industry Development Manager
Asia Pacific

Overview
Opportunity Crude Trends
(High TAN Crude) and its
challenges
Overview of Factors Affecting
Corrosion
Prevention Methods
High Temperature Corrosion
Control
Summary

Opportunity Crude Trends

Extra Heavy (< 22o API) as part of
crude slates (average globally)

Declining conventional
oil production
Opportunity crude oil
production forecast to
grow up to 20% by 2025

Fundamentals
Historic

Perspective

Problem since 1920s

Systematic study since 1950s
Chevron published correlation in 1980s
Nalco first Scorpion program in 1984
Nalco published Sulfidic corrosion phenomenon in
2005
Review of 25 years of Scorpion program published
in 2006

What are High Acid Crudes

Crudes

with a TAN of 1.0 or higher

O

CH

n
R = Alkyl Groups

C - OH

COOH = Carboxylic Acid

CH2 = Alkyl chain

Fundamentals
Measurement

TAN = Total Acid Number

Two common ASTM methods:
- D974 (colorimetric- older, used for distillates)
- D664 (potentiometric- more accurate but measures acid gases, in
addition to organic acids)
- Differences important on crudes, less significant on distillates)

UOP 565 / UOP 587 more applicable

Nalco NAT

Will it Cause Corrosion?

Majority of the challenge crudes on the market are high

acid crudes
Total acidity
Naphthenic acid content
Distribution of acids

Other species include organic acids, organic chlorides,

undesaltable chlorides, amines, etc.

High Temperature Naphthenic Acid Corrosion

Not all TAN is a problem

Measure of naphthenic acid content better gauge

of corrosivity

Distribution of Acid

Distribution can be used to determine likely areas

of concern
Some newer assays have this TAN data
Nalco has a library of high acid crude nap acid
distributions
- Relative comparison with respect to field experience

Corrosivity Testing
Laboratory

Test

unit

Test

metallurgy of the

inhibitor
effectiveness

Untreated

18
16

Treated

14
Corrosion Rate, MPY

apparatus
used to simulate
temperature and
shear stress

12
10
8
6
4
2
0
CS

5Cr

9Cr

410SS

Test Sample

Factors Affecting Corrosion

Vulnerable

HAC

Locations for

Preventative
Other

Methods

Impacts

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Examples: Vacuum Unit

Severe Corrosion on an Outer Bend of an Elbow Just
Upstream from the Collection Header

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Examples: Vacuum Bubble Cap Corrosion

Severe pitting Corrosion of Type 410

Stainless Bubble Cap from a Resid
Stripper Column

Another View of the Corroded Bubble

Cap

13

Examples: 5 Cr - 1/2 Mo Check Valve in

HVGO in Crude Unit

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Factors Effecting Corrosion

Temperature

Naphthenic acids concentrate above 450F (232C)

boiling range
Highest concentration in 600-800F (316-427C)
boiling range
Lowest temperature where attack occurs ~400F
(200C)
Lower molecular acids at water condensing locations:
HCOOH ; (CH3)n-COOH

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Factors Effecting Corrosion cont.

Velocity

At low velocity, turbulence caused by boiling and

condensing causes attack
At high velocity, rapid corrosion can occur
Limits well defined for conventional crudes

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Naphthenic Acid Corrosion of Carbon Steel

40

30

20

10

150
302

200
390

250
480

300
570

Temperature, oC (o F)

350
660

Corrosion Rate of Carbon Steel at 1.8 - 2.4 TAN

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Influence of Linear Velocity on

Corrosion Rates in Crude Oil
Material

TAN

Linear Velocity,
(ft/sec)

Corrosion Rates
at elbows (mm/yr)

C.S.

1.5

73

12

C.S.

1.5

26

5Cr-1/2Mo

1.5

73

5Cr-1/2Mo

1.5

26

0.6

9Cr-1Mo

1.5

73

0.7

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Corrosion Rates of Some Alloy Steels

During 7 Month Coupon Exposure in a Crude Unit

Temperature
oC (oF)
377 (710)

Acid No.

C.S.

3+

48+

342 (648)

3.6

338 (640)
300 (570)

410SS

304SS

316SS

22

0.09

0.06

49+

0.5

33

0.08

3.6

48+

30

30

4.8

4.1

37

5.8

10

0.01

* Corrosion rates shown are MPY; data from literature

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Naphthenic Acids - Distillation profile

800
700

Temp (deg C)

600
500
400

C e r r o N e g r o ( V e n e z u e la )
DOBA
G ra n e
DAR
P e r e g r in o
P e t r o A n d in a
A lb a c o r a

300
200
100
0
0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

V o lu m e P e r c e n t

Profiles available for many crudes

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10

Prevention Methods

Blending
Typically , blend high TAN with low TAN crude
Blending primarily based on desired product mix
Metallurgy can become limiting
Crude compatibility needs evaluation
Sulfur in blend crude may be critical

Materials Upgrade
In mild service, 9 Cr - 1 Mo sometimes adequate
Usually 316L (2% Mo) minimum material
317L (3% Mo) often used
Structured packing requires 317L min.
When chloride stress corrosion cracking (CISCC) is a potential
problem, 2205 or 2507 have been used
When high corrosion and/or CISCC are a problem, I625 has
been used
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Prevention Methods cont

Use

of Inhibitors

Continuous use of high acid crudes (HAC)

- Successful applications exist for wide range of TAN and NAT
- Important to maintain monitoring in areas at risk
- Can be continuous or (depending upon strategy) until
metallurgy is upgraded.

Intermittent use of HAC

- Used when corrosion rates are excessive based on monitoring

Cost directly related to amount of equipment

protected

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High Temperature Corrosion Control

SCORPION High Temperature
Corrosion Control

25+ Years of Experience

>130 HAC Assessments Globally
Innovative Monitoring (FSM)
Most Comprehensive Chemistries

Best Practice in KM (KM, Downstream,

Our Brands, click on SCORPION logo)
Step 1. Assessment

Risk Assessment

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Risk Assessment
Unit /
System

Risk
Asse ssm ent
Modera te
Low
Low
Modera te
High
Low
Modera te
Modera te
Low
Modera te
Modera te
Low
Low
Modera te
Modera te
Modera te
Low
High
High

Description

Line from mix5 to split6

Line from split6 to furnace 302B control va lve manifold.
Crude to Furnace control valve
Furnace line s
Line from furnace colector to mix 6
Line from split6 to m ix6 (by-pass)
Furn.302B to Furn.151B &101B
Line from mix6 to split7
Line from split7 to furnace 101B m anifold valve
Manifold lines (inlets 101B)
101B Furnace lines convective area
101B Furnace lines radia tion area
Lines from furna ce 101B cole ctor to m ix7.1
Line from mix7.1 to mix7
Line from split7 to furnace 151B m anifold valve
Manifold lines (inlets 151B)
151B Furnace lines convective area
151B Furnace lines radia tion area
Lines from furna ce 151B cole ctor to m ix7.2
Line from mix7.2 to mix7

Example of Risk Assessment

High Acid Crude Assessment Output

Fuel Gas/Distillate
to Vacuum System

CP

CS

275oF

316SS

SCORPION Inhibitor
Injection Location

U26.1

LVGO

CP
CS

Corrosion Probe
Monitoring Location
385o F

F-1 Charge
Heater
316SS

5Cr
Atmos.
Resid

597oF
Vapor

CS

CP

CP

545-565F
HVGO

9Cr

750-760oF

316L
SS

5Cr

Feed
Surge
625-650oF Drum
(5Cr)

CS

U26.1

U25.1

CP
5Cr

CP
5Cr

316SS

5Cr

CP
CS

650-700oF
316L SS
5Cr

CP
9Cr

Flash Zone
750oF

OverFlash
9Cr

Quench

U25.1

600-650oF
5Cr

To DCU/Tk 434
P718

CP
5Cr

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Benchmarking Nalco Scorpion Applications

8
7
1% of Applications > 6

6
5
3% of Applications > 4

4
22% of Applications > 3

33% of Applications > 2

59% of Applications > 1

85% of Applications > 0.5

How Does SCORPION Work?

Inhibitors

work by forming an extremely tenacious

and persistent passive surface

Currently

there are three types of SCORPION

inhibitors supplied by Nalco
Phosphorous-based
Sulphur-based
Phosphorous and Sulphur based

Nalco

possessed patents on Phosphate ester

chemistry, and possesses patents on Sulphur and
combination chemistries.

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How Long Does the Film Persist?

C o r r o s io n

R a te

a n d

H A C

C ru d e

1 0

6 0
In h ib it o r (E C 1 2 4 5 A )

5 0

Corrosion Rate (mpy)

8
7

4 0

6
5

3 0

4
2 0

3
2

1 0

% HAC Crude / Inhibitor (ppm)

C o r r o s io n R a te
% H A C C ru d e

1
ul

ul

Ju
l

-J

-J
16

6-

11

un

Ju
l
1-

un
-J

-J
26

21

un

16
-J
un

Ju
n

-J
11

Ju
n

6-

1-

ay
-M

ay

27
-M
ay

22

17
-M
ay

ay
M

-M

7-

12

2M
ay

27
-A
pr

22
-A
pr

17
-A
pr

Ap
7-

12
-A
pr

ar
-M

2Ap
r

28

ar
-M
18

23
-M
ar

0
8M
ar
13
-M
ar

3M
ar

0
Date

Example shown: >14 days

A lot less for a transfer line

Depends on velocity and turbulence

Impact of Inhibitor
D O B A C o rro s i v i t y T e s t i n g

1.0

Corrosivity (mm/yr)

0.9
0.8

410SS

0.7

9 C h ro m e

0.6

5 C h ro m e

0.5

C a rb o n S te e l

0.4
0.3
0.2
0.1

C a r b o n S te e l
5 Chrom e

0.0

9 Chrom e
U n tr e a te d

LVG O C U T
370-425 C

T r e a te d

410SS
U n tr e a te d

H VG O C U T
510-555 C

T r e a te d

Inhibitor Comparative Performance w/Various Crudes

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Naphthenic Acids other impacts

Impact

on Tank Farm

Poor water removal

Emulsion formation in
tankage

Impact

on Desalter

Emulsion in desalter
Oil undercarry
Water carryover

Tank

Farm Solutions

Tank mixers
Crude blending
Tankage dehydration
additives
Desalter

Solutions

Increase wash water

Increase temperature
Increase mixing
Demulsifier selection
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Summary

Processing opportunity crudes (e.g. High TAN) can

significantly improve refinery profitability, often offer
>US$10/bbl discounts

Testing can be done before the crude arrives to identify

potential risks in desalting, fouling, corrosion, and waste
plant

Communication between buyers, refiners and crude

process aid suppliers is key to successful introduction

Planning ahead can allow the refiner to reduce unknown

risks associated with running Challenge/Opportunity
Crudes

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SCORPION High Temperature Corrosion Control

Crude Challenge Low TAN, High Sulfur
SCORPION High Temperature Corrosion Control

Proven effective against Sulfidic attack in the lab

Proven effective against Sulfidic attack in the field 2008 - present

EuroCorr 2007 paper, Hydrocarbon Engineering article, September 2008;

Chemical Inhibition of High Temperature Sulphidic Corrosion in Lab Evaluations

and Petroleum Refinery Applications, C. Claesen, S. A. Lordo, G. Scattergood

2008 paper, March 2009 article in Hydrocarbon Engineering

Chemical Inhibition of Sulfidic Corrosion at Chinese Refinery, V. Chua, G.

Scattergood

Protecting Your Plant and Profits

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Thank you

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