1

THE INFLUENCE OF NAPHTHENIC ACID AND

SULFUR COMPOUND STRUCTURE ON GLOBAL
CRUDE CORROSIVITY UNDER VACUUM
DISTILLATION CONDITIONS
Heather D. Dettman, N. Li and D. Wickramasinghe (NRCan)
J. Luo (U. of Alberta)

Presented to: COQA/CCQTA Joint Meeting

New Orleans, LA
February 10 11, 2010
 2
Mechanisms of Refinery Corrosion
Refinery corrosion occurs at temperatures
between 220C and 400C
Naphthenic (organic) acids (RCOOH) reach their
boiling points and condense on metal surfaces,
removing iron [Fe] and eventually causing pits
Sulfur-containing compounds decompose to form
hydrogen sulfide (H2S), where iron removal causes
general corrosion but can form protective films
Acids and hydrogen sulfide work together:
Fe + 2RCOOH Fe(RCOO)2 (oil soluble) + H2
Fe + H2S FeS (oil insoluble) + H2
Fe(RCOO)2 + H2S FeS + 2RCOOH
 3
Corrosivity, TAN, and Sulfur
Corrosivity does not always correlate with total
acid number (TAN) (Derungs, 1956; Messer
2004)
Are organic acid molecular species in some oils less
active that those in other oils?
Does high sulfide content result in iron sulfide film that
protects the plant metallurgy?
Another reason?
This project was conducted to improve the
understanding of the contributions of specific
structural features of organic acids and sulfur
compounds to corrosivity at refinery temperatures
 4
Corrosion Test Unit
Simulates corrosion in
vacuum distillation unit
Features:
1. Volume: 250 mL
2. Charge: Any crude or
Coupon locations refinery feed blend
in vapor phase
where vapor 3. No. of coupons: 4
condenses on
4. Operates under
metal surface
vacuum throughout the
temperature range
Coupon location
in liquid
 5
When Does TAN Correlate with Corrosivity?
10

Corrosion Rate (mm/y)

8

0
0 1 2 3 4 5 6

TAN (mg KOH/g)

Liquid - 300 C Vapor -300 C Liquid - 330 C Vapor -330 C

Liquid - 350 C Vapor -350 C

TAN correlates with corrosivity when different concentrations

of the same acids are tested. (Corrosion rates of carbon steel
coupons for commercial naphthenic acids [CMNA] in white oil.)
 6
When Does TAN NOT Correlate with Corrosivity?
TAN 3.00 3.39 0.60 3.22 1.36 1.31 2.33 4.15
S (wt%) 0.00 4.77 0.94 3.76 3.85 2.51 0.78 0.10

1.8
Corrosion Rate (mm/y)

1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
CMNA ATHB SA1 SA2 AB16 AB17 INT22 INT30
As Produced Oil Commercial Products

Liquid Phase Vapor Phase

When comparing corrosion rates for different crude oils.......?

 7
Corrosivity of Organic Acid Compounds

Liquid Phase Vapor Phase

Corrosion rates of carbon steel coupons for organic acid

compounds in white oil (TAN= 5.0mg KOH/g) at atmospheric
equivalent temperature (AET) of 300C (250C actual)
 8
What about Sulfur?

Sulfur compounds R-S-R H2S + by-products

Thermal Cracking
Sulfidic Corrosion

FeS

Model sulfur compounds were chosen to represent the different C-S

bonds found in petroleum. For example:
H H

R C S C R

H H S
Octyl sulfide Dibenzothiophene
Thermal decomposition studies of nine sulfur compounds dissolved in
white oil (1 wt% sulfur) were performed
 9
Thermolysis of Sulfur Compounds
70

60 S s
H2S Yield (wt% Feed Sulfur)

50
s
40

30
S
S
20

10 S

0 S S
200 220 240 260 280 300 320 340 360 380 400C

Temperature ( )
Dicyclohexyl disulfide Dibenzothiophene Sec-butyl disulfide
Benzyl sulfide 1,3-Dithiane Diphenyl sulfide
Benzyl phenyl sulfide Dodecyl sulfide Octyl sulfide

At temperatures as low as 200C (392F), within 2

hours -CH2-S- bonds (sulfides) crack and form H2S
 H2S Effects on Corrosivity of Organic 10

Acids under Refinery Conditions

Fe(RCOO)2 + H2S FeS + 2RCOOH
Low H2S generation
9 Enhanced corrosion in vapor phase
with little film formation
8
Corrosion Rate (mm/y)

7
(mm/y)

6 Fe + H2S FeS + H2 Fe + 2RCOOH Fe(RCOO)2 + H2

High H2S generation
5 No H2S present
Inhibited corrosion in liquid
4
Corrosion

phase due to significant

3 film formation
2
1
0
Octinywhite
CMNA l Suloilf +i de+CM NA CMNA
octyl sulfide Di phenyl
in whiteSul
oil +f phenyl
i de+CM NA
sulfide CM
CMNA inNA
white oil

i n Li q
Liquid i n Cond
Vapor Phase

Influence of presence (1wt% S) or absence of sulfur compounds on the

corrosion rates of commercial naphthenic acids (CMNA) in white oil (Total
acid number = 5.0mg KOH/g) for carbon steel coupons at atmospheric
equivalent temperature of 300C (250C actual)
 11

Why Does TAN Not Correlate with Corrosivity?

Model compound studies show that:
Small organic acid molecules (boiling point <
300C) are significantly more corrosive than larger
molecules (boiling point > 300C)
In liquid phase, chain and 1-ring acids are the most
corrosive; in vapor phase, chain and 1-ring cycloalkane
(naphthenic) acids are most corrosive
Vapor phase corrosion due to organic acids is
greatest at temperatures above the boiling point of
the acid
Sulfur compounds can decompose to form
hydrogen sulfide at temperatures as low as 200C;
acid corrosion can be inhibited or enhanced
depending on how much hydrogen sulfide is
present
 12
Crude Oil Analyses
Elemental (wt%) Density TAN
Crude Oil C H N S O (g/mL) (mg KOH/g)
ATHB 83.07 10.51 0.52 4.77 1.14 1.0100 3.39
SA1 86.77 10.64 0.60 0.94 1.05 0.9934 0.60
SA2 83.67 10.31 0.83 3.76 1.43 1.0090 3.22

AB16 81.89 12.66 0.44 3.85 1.16 0.9304 1.04 *

AB17 84.75 11.70 0.25 2.51 0.79 0.9319 1.27 *
INT22 86.34 11.77 0.34 0.78 0.76 0.9379 2.11 *
INT30 86.10 12.29 0.32 0.10 1.19 0.9282 4.15

As produced:
ATHB Athabasca bitumen
SA South America
Commercial products:
AB Alberta heavy oil or bitumen
INT Non-Canadian crude of non-disclosed
geographical location
* Crudes were topped at 204C for corrosion testing
 13
HTSD of Crudes
8 00 800

7 00

6 00
A 700

600
B

Temperature (C)
Temperature (C)

5 00 500

4 00 400

3 00 300

2 00 200

1 00 100

0 0
-1 00 0 20 40 60 80 10 0 -100 0 20 40 60 80 10 0

Weight % Off Weight % Off

A THB SA 1 S A2 AB 16 AB 17 INT22 INT30

High temperature simulated distillation (HTSD) of:

A Crudes, as produced
B Crudes, commercial products
 14
Analyses of Extracted Organic Acids
Organic Content in Elemental (wt%)
Acids Crude (wt%) C H N S O
CMNA - 74.35 11.97 0.00 0.00 13.68
ATHB-OA 2.68 78.06 10.29 0.37 3.75 7.54
SA1-OA 0.99 81.18 9.97 0.44 0.99 7.42
SA2-OA 2.22 78.14 10.48 0.82 3.54 7.02

AB16-OA 1.11 78.80 10.15 0.57 3.72 6.76

AB17-OA 1.43 77.96 10.06 0.58 4.75 6.64
INT22-OA 2.37 81.48 10.98 0.36 0.90 6.29
INT30-OA 4.83 81.09 11.66 0.34 0.27 6.64

CMNA Commercial naphthenic acids

Organic Acids Extracted from Crude Oils (Mediaas et.al., 2003)

As produced: Commercial products:
ATHB Athabasca bitumen AB Alberta heavy oil or bitumen
SA South America INT Non-Canadian crude of non-
disclosed geographical
location
 15
Crude Oil TAN versus Organic Acid Yield
6.00

5.00

TAN (mg KOH/g)

4.00

3.00

2.00

1.00

0.00
0.00 1.00 2.00 3.00 4.00 5.00 6.00

Yield (wt% Crude)

 16
Distillation of Organic Acids from Crudes
800 800
700
A 700
B

Temperature (C)
600 600
Temperature (C)

500 500
400 400
300 300
200 bp<300C
200
100
most
100
corrosive
0
0
0 20 40 60 80 100
-100 0 20 40 60 80 100
Weight % Off Weight % Off

CMNA ATHB-OA SA1-OA SA2-OA AB16-OA AB17-OA INT22-OA INT30-OA

Organic acids from:

A CMNA and crudes, as produced
B Crudes, commercial products
 17
Corrosivity Results CMNA & Crude Oils
TAN 3.00 3.39 0.60 3.22 1.36 1.31 2.33 4.15
S (wt%) 0.00 4.77 0.94 3.76 3.85 2.51 0.78 0.10

1.8
Corrosion Rate (mm/y)

1.6 Corrosivity does not

1.4 correlate with TAN
1.2
1.0
0.8
0.6
0.4
0.2
0.0
CMNA ATHB SA1 SA2 AB16 AB17 INT22 INT30
As Produced Oil Commercial Products

Liquid Phase Vapor Phase

Corrosion rates of carbon steel coupons for CMNA in white oil

and crude oils at AET of 300C (250C actual)
 18
CorrosivityHigher
Results CMNA
corrosivity of CMNA is& Crude Oils
TAN 3.00 explained
3.39 0.60by its
3.22higher content
1.36 1.31of lower
2.33 4.15
S (wt%) 0.00 boiling
4.77 acid
0.94 components
3.76 3.85 2.51
(i.e. 50wt% 0.78 0.10
Corrosion Rate (mm/y) 1.8 have bp<300C)
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
CMNA ATHB SA1 SA2 AB16 AB17 INT22 INT30
As Produced Oil Commercial Products

Liquid Phase Vapor Phase

Corrosion rates of carbon steel coupons for CMNA in white oil

and crude oils at AET of 300C (250C actual)
 Boiling point distributions of organic acids in 19
Corrosivitythese Results
crudes donotCMNA & Crude
explain why SA2 and OilsINT30
TAN 3.00 have
3.39 higher
0.60 liquid
3.22 phase1.36corrosivity
1.31 than4.15
2.33 the
S (wt%) 0.00 other
4.77 crudes;
0.94 3.76 3.85 2.51
higher contents 0.78 &/or
of chain 0.101-ring

1.8 naphthenic acids in lowest boiling species are

Corrosion Rate (mm/y)

1.6 implicated
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
CMNA ATHB SA1 SA2 AB16 AB17 INT22 INT30
As Produced Oil Commercial Products

Liquid Phase Vapor Phase

Corrosion rates of carbon steel coupons for CMNA in white oil

and crude oils at AET of 300C (250C actual)
 20
Corrosivity Results CMNA & Crude Oils
Boiling point
distributions of
TAN 3.00 3.39 0.60 3.22 1.36 1.31 2.33 4.15
S (wt%) 0.00 4.77 0.94 3.76 3.85 2.51 organic acids in
0.78 0.10
these crudes do not
1.8
explain why AB16
Corrosion Rate (mm/y)

1.6
1.4
has high vapor
1.2
phase corrosivity
1.0
0.8
0.6
0.4
0.2
0.0
CMNA ATHB SA1 SA2 AB16 AB17 INT22 INT30
As Produced Oil Commercial Products

Liquid Phase Vapor Phase

Corrosion rates of carbon steel coupons for CMNA in white oil

and crude oils at AET of 300C (250C actual)
 Identification of Sulfidic Corrosion 21

Influences in Crude Oils

Replace the oil matrix with a sulfur-free
medium i.e. white oil
Organic acids isolated from each of the Global
crudes were dissolved in white oil at TAN values
similar or slightly lower than those of the original
crude oils tested
If the oil matrix has no influence on corrosion, the
corrosion rates of the white oil mixtures should be
the same as that of the original oil
If the oil matrix influences corrosion, the corrosion
rates of the white oil mixtures could be either
greater or lesser than those of the original oil
 22
Corrosivity Results Extracted Acids
Corrosion Rate (mm/y) 1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
CMNA ATHB- SA1- SA2- AB16- AB17- INT22- INT30-
OA OA OA OA OA OA OA
Extracted Organic Acids in White Oil
Liquid Phase Vapor Phase

Corrosion rates of carbon steel coupons for CMNA and extracted

organic acids in white oil at AET of 300C (250C actual)
 23
Differences in Corrosivity Results
TAN 3.00 3.39 0.60 3.22 1.36 1.31 2.33 4.15
S (wt%) 0.00 4.77 0.94 3.76 3.85 2.51 0.78 0.10

0.6
0.4
Corrosion Rate (mm/y)

0.2
0.0
-0.2 CMNA ATHB SA1 SA2 AB16 AB17 INT22 INT30
-0.4
As Produced Commercial Products
-0.6
-0.8
-1.0
-1.2
-1.4
Difference (Organic Acids in White Oil - Oil)
Liquid Phase Vapor Phase
 24
Differences in Corrosivity Results
TAN 3.00 3.39 0.60 3.22 1.36 1.31 2.33 4.15
S (wt%) 0.00 4.77 0.94 3.76 3.85 2.51 0.78 0.10

0.6
0.4
Corrosion Rate (mm/y)

0.2
0.0
-0.2 CMNA ATHB SA1 SA2 AB16 AB17 INT22 INT30
-0.4
As Produced Commercial Products
-0.6
Negative-0.8
difference for AB16 vapor phase
corrosion-1.0
rate shows that sulfidic corrosion is
the predominant
-1.2 corrosion mechanism
-1.4
Difference (Organic Acids in White Oil - Oil)
Liquid Phase Vapor Phase
 25
Differences in Corrosivity Results
TAN 3.00 3.39 0.60 3.22 1.36 1.31 2.33 4.15
S (wt%) 0.00 4.77 0.94 3.76 3.85 2.51 0.78 0.10

0.6
0.4
Corrosion Rate (mm/y)

0.2
0.0
-0.2 CMNA ATHB SA1 SA2 AB16 AB17 INT22 INT30
-0.4
As Produced Commercial Products
-0.6
-0.8
Positive differences for corrosion rates
suggest sulfidic
-1.0 film formation provides
protection-1.2
for original crudes; protection does
not correlate
-1.4 with sulfur content.
Difference (Organic Acids in White Oil - Oil)
Liquid Phase Vapor Phase
 26
Differences in Corrosivity Results
TAN 3.00 3.39 0.60 3.22 1.36 1.31 2.33 4.15
S (wt%) 0.00 4.77 0.94 3.76 3.85 2.51 0.78 0.10

0.6
0.4
Corrosion Rate (mm/y)

0.2
0.0
-0.2 CMNA ATHB SA1 SA2 AB16 AB17 INT22 INT30
-0.4
As Produced Commercial Products
-0.6
-0.8
Positive differences for vapor phase
corrosion-1.0
rates for SA1, SA2 and INT30 also
indicate higher
-1.2 contents of chain &/or 1-ring
naphthenic
-1.4acids in lowest boiling species of
these crudes compared to those(Organic
Difference of Alberta
Acids in White Oil - Oil)
and INT22 crudes
Liquid Phase Vapor Phase
 27
CONCLUSIONS
TAN values of crude oils are not reliable
indicators of crude oil corrosivity
Crude corrosivity appears to be determined by:
Low boiling acids (i.e. bp<350C) where content of
chain and/or 1-ring naphthenic acids will be
important
Content of thermally-labile sulfur species
Hydrogen sulfide-generating ability of the crude
will be influenced by:
Content of CH2-S bonds in sulfur species
Thermal history of crude oil (field and plant)
 28
IMPLICATIONS OF RESULTS
If TAN does not correlate with crude
corrosivity, why is it used for setting crude
prices?
How does production method influence
corrosivity (i.e. SAGD versus mined?)
How does the content of low-boiling chain and 1-
ring naphthenic acids compared to the total organic
acid content, and the contents of thermally-labile
sulfur species work together to influence corrosivity
When can blending a high TAN crude with a
low sulfur, low TAN crude (or diluent?) result in
enhanced corrosion?
 29
Funding Acknowledgements

Alberta Science and Research Authority

(COURSE/Alberta Energy Research Institute
[AERI])
Canadian Association of Petroleum
Producers (CAPP)
Natural Resources Canada through partial
funding by the Canadian Program for Energy
Research and Development, and the
Technology and Innovation Program