Naphthenic Acid

Corrosion Risk
Assessment and
Mitigation

RFM Tech Training – 2018

BORL Bina
19th Feb, 2019
Arindam Roy
Agenda

 Naphthenic Acid Corrosion background info

 Strategy to manage corrosion Risk
 Current Mitigation / Monitoring Strategy

2
What is a Naphthenic Acid ?
May have more
Naphthenic acids are a family of
than 1 acid group
hydrocarbons which have a fair degree of
variability.
O

R CH2 C - OH
n m

R = Alkyl Groups
Size of carrier molecule COOH = Carboxylic Acid
can vary CH2 = Alkyl chain

 The carboxylic acid group(s) are responsible for the reactive

behavior with metals, whilst the alkyl substituents –
especially the “R” group tails - are responsible for making the
metal salts oil-soluble.

3
Corrosion Types- Naphthenic Acid

Naphthenic Acid Structure

Very Soluble in hydrocarbon Carboxylic Acid Group

O O
R CH2 C C CH2 R
n m
m n
O O
Fe
Fe2+

4
Fundamentals

 High Temperature Corrosion that occurs in the absence of water

 Presence of Naphthenic acids in high temperature regions of the crude
unit
 Impacted by multiple variables
 Accelerated corrosion rates, somewhat unpredictable
 Measurement
 TAN = Total Acid Number (KOH titration) (Mg/gm KOH)
- Total acidic species measured, Other weak acids etc.

 Nalco NAT (measures just Naphthenic acids)

5
Factors Effecting Corrosion

 Temperature
 Naphthenic Acid Concentration
 Naphthenic Acid Type (Distribution)
 Sulphur Content in the feedstock (Sulphidation)
 Velocity
 Equipment Metallurgy

6
 Naphthenic Acid Distribution

0.8
PetroAndina 5.1
0.7 Cerro Negro 4.4
Naphthenic Acid Distillation Rate

DOBA 4.1
(% Naph Acid Distilled per oC)

0.6
Grane 2.24
0.5 Peregrino 0.8

0.4 Albacora 2.8

0.3

0.2

0.1
Diesel / Heavy
LGO Atmospheric
Vacuum Gas Oils & Residue
0.0 Gas Oil

200 300 400 500 600 700

Temp (deg C)

7
Influence of Linear Velocity on Corrosion Rates

Corrosion Rates at
Linear Velocity elbows
Material TAN
ft/sec (m/sec)
mm/yr (MPY)

C.S. 1.5 73 (22.5) 12 (472)

C.S. 1.5 26 (8) 6 (236)

5Cr-1/2Mo 1.5 73 (22.5) 2 (79)

5Cr-1/2Mo 1.5 26 (8) 0.6 (24)

9Cr-1Mo 1.5 73 (22.5) 0.7 (28)

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Vulnerable Locations for HAC Atmospheric Unit

Water
Key Wash Neutralizer* Inhibitor*
Typical Attack Location
Potential Attack Location
* * Exchanger
Wash
Water Caustic or Condenser
Desalter Other Top Gas

Reflux
Chemicals Pumparound
Drum
Crude
Oil Sour
Water
Desalter
(428°F) pH & Metal
(220°C) Analysis
Waste
Water AGO Naphtha
Preheat Liquid
Exchangers Atmospheric
Column

Preheat *Alternate Addition Locations

Furnace

9
Vulnerable Locations for HAC cont. Vacuum Unit

To
Vacuum Key
Vacuum
System Tower Typical Attack Location
Gas Oil
Potential Attack Location

Light VGO

Medium VGO

(428°F)
(220°C) Heavy VGO

Vacuum Tower Bottoms

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Overview of Nalco’s Risk Assessment Matrix
 TAN of the hydrocarbon
stream Risk Rating Action

 Sulphur level Low

Maintain existing monitoring schedule to confirm corrosion
rates are minimal

 Temperature Low-Moderate
Install some extra monitoring activity – Not necessarily
permanent monitoring.

 Velocity / turbulence Moderate

Install better monitoring equipment and attach access stubs for
injectors

 Piping
geometry (e.g. diameter Moderate- Install better monitoring equipment and chemical injectors.
High Have inhibitor ready
changes, bend radius)
Install full monitoring equipment and passivate with inhibitor
High
before running crude
 Piping metallurgy
 Remaining corrosion Very High
Install full monitoring equipment and passivate with inhibitor
before running crude.. The system is very critical.
allowance

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 Risk Assessment Matrix - Nalco Strategy
Risk Assessment OUTPUT SCREEN Ongoing program
Unit / Temp. Flow Tan Sulfur Metal Risk
o
System Description C M3/Hr % Used Assessment

CRUDE PREHEAT

CRUDE HEATER
Downstream 10-E-158
0 Inlet to E-159
SINGLE PASS U/S OF HEATER 151 A/B (2*8)
240
240
274
2529.90
1264.95
164.63
0.9
0.9
0.9
3.30
3.30
3.30
CS
CS
CS
Low-Moderate
Low-Moderate
Low-Moderate
Assesses the Risk associated
0 SINGLE PASS D/S OF HEATER 151 A/B (2*8) 365.6 2 phase 0.9 3.30 5Cr Moderate
0 TRANSFER LINE 365.6 2 phase 0.9 3.30 5Cr Moderate
HK SECTION HK (PA + PROD) DRAW OFF 254.8 1200.00 0.318 1.10 CS Low
0 HK PROD to Stripper 254.8 434.05 0.318 1.10 CS Low-Moderate

LGO SECTION
0 Stripper base pump 10-P-601 D/C
0 HK PA DRAW OFF PUMP 10P-202 D/C
LGO (PA + PROD) DRAW OFF
238.1
255.7
298.7
200.00
1200.00
1200.00
0.331
0.318
0.8
1.17
1.10
1.80
CS
CS
CS
Low-Moderate
Low-Moderate
Low-Moderate
Risk Zone
0 LGO PROD to Stripper 298.7 324.24 0.8 1.80 CS Low-Moderate
0 LGO stripper base pump 10-P-701 D/C 290 270.51 0.8 1.90 CS Low-Moderate
0 LGO stripper base pump 10-P-701 D/C 290 268.56 0.8 1.90 CS Low-Moderate
0 LGO Prod at outlet of 10E-902 255 257.50 0.8 1.90 CS Low-Moderate
0 LGO PA DRAW OFF LINE PUMP 10P-203 S/C 298.7 1200.00 0.8 1.80 CS Low-Moderate
0 LGO PA DRAW OFF LINE PUMP 10P-203 D/C 299.4 1200.00 0.8 1.80 CS Low-Moderate

Monitor the Risk of corrosion

0 LGO PA at the outlet of 10E-901 260 1200.00 0.8 1.80 CS Low-Moderate
HGO SECTION HGO (PA + PROD) DRAW OFF 341.8 1200.00 0.98 2.46 5Cr Low-Moderate
0 HGO PROD to Stripper 341.8 119.52 0.98 2.46 5Cr Low-Moderate
0 HGO stripper Overheads 336.2 2975.77 0.65 1.66 5Cr Low-Moderate
0 HGO stripper base pump 10-P-801 S/C 328.1 95.72 0.98 2.62 5Cr Low-Moderate
0 HGO stripper base pump 10-P-801 D/C 328.9 94.99 0.98 2.62 5Cr Low-Moderate
0 HGO Prod at outlet of 10E-905
0 HGO PA DRAW OFF LINE PUMP 10P-204 S/C
0 HGO PA DRAW OFF LINE PUMP 10P-204 D/C
200
341.8
342.4
85.38
1200.00
1200.00
0.98
0.98
0.98
2.62
2.46
2.46
CS
5Cr
5Cr
Low
Low-Moderate
Low-Moderate
Different
0 HGO PA at the outlet of 10E-153
0 HGO PA at the outlet of 10E-904
ATM RESIDUE SECTION Bottom line
290
279.1
358.3
1200.00
1200.00
1700.00
0.98
0.98
1.5
2.46
2.46
4.27
5Cr
CS
Low-Moderate
Low-Moderate
5Cr Moderate-High
monitoring tools
0 line from pumps 10-P-205 to VAC 359 1700.00 1.5 4.27 5Cr High
Vacuum Heater SINGLE PASS I/L TO VAC HEATER 101/A/B (2*8) 359 106.25 1.5 4.27 5Cr High
0 COMMON LINE TO EACH HEATER (2*1) 359 850.00 1.5 4.27 5Cr High
0 SINGLE PASS OUTLET ELBOW (2*8) 418.3 2 phase 1.5 4.27 5Cr High

VAC. DIST. CIRCUIT

0 TRANSFER LINE
VAC. DIST. Pump 11P-401 s/c
418.3
140.3
2 phase
829.79
1.5
0.705
4.27
2.03
5Cr
CS
High
Low
Mitigate the corrosion issue
LVGO CIRCUIT LVGO Pump P-501 S/c 231.3 136.69 1.32 2.71 CS Low-Moderate
0 LVGO Pump P-501 D/c 232.4 136.07 1.32 2.71 CS Low-Moderate
HVGO CIRCUIT HVGO DRAW LINE & Pump S/c 293.7 2217.90 1.6 2.65 CS Moderate
0 HVGO PUMP 11P-601 d/c 295 2202.08 1.6 2.65 CS Moderate-High
0 HVGO TO FT-204 I/L
0 HVGO TO FT-203 I/L
0 HVGO TO FT-203 O/L
295
209.5
209.5
330.00
1402.81
1402.81
1.6
1.6
1.6
2.65
2.65
CS
CS
2.65 SS321
Moderate-High
Low-Moderate
Low
Chemical inhibition/
0 HVGO TO E-158 (Common header)
0 HVGO TO E-158
0 HVGO TO E-157
295
295
209.5
1914.79
957.40
1810.15
1.6
1.6
1.6
2.65
2.65
2.65
CS
CS
CS
Moderate-High
Moderate-High
Moderate-High
Metallurgical up
HHVGO CIRCUIT HHVGO DRAW LINE
0 HHVGO Pump 11P-701 S/c
0 HHVGO Pump 11P-701 d/c to 10E-907
394
298.9
300.9
99.59
204.96
203.68
1
1
1
4.70
4.70
4.70
5Cr Moderate-High
CS
CS
High
High
gradation
0 10E-907 outlet 234 196.42 1 4.70 CS Moderate-High
VAC.RESIDUE PUMP 11P-801 S/c 360 1003.92 0.6 5.37 5Cr High
0 VAC.RES. QUENCH to 10E-908 (Common header) 280 301.70 0.6 5.37 5Cr High
0 VAC.RES. QUENCH to 10E-908 280 100.57 0.6 5.37 5Cr Moderate-High
0 VAC.RES. QUENCH at 10E-908 outlet 275 294.23 0.6 5.37 5Cr Low
. VAC. RES. To exchanger 10E-159 364.7 681.43 0.6 5.37 5Cr High
13
0 VAC. RES. at exchanger 10E-159 outlet 301.2 660.80 0.6 5.37 5Cr Low
Risk Assessment Output

14
How can a refiner prevent Naphthenic acid
corrosion?

Crude Choice Blending Metallurgy Chemical

TAN Number Crude Mixing Molybdenum SCORPION

NAT Number Adjust TAN / S 317 L

Sulfur Content

Combination of all
4 is most effective!
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Prevention Methods cont.
 Materials Upgrade
In mild service, 9 Cr - 1 Mo sometimes adequate

Usually 316L (2% Mo) minimum material

317L (3% Mo) ideally preferred

Structured packing requires 317L min.

Recent work on modified 316nb (2.5% min. Mo) appears promising

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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How Does Corrosion Inhibitor Work?
 Inhibitors
work by forming an extremely tenacious and
persistent passive surface
 Synergistic effect with sulphur
 Currentlythere are three types of Corrosion inhibitors
supplied by Nalco
Phosphorous + Sulphur based
Phosphorous-based
Sulphur-based

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Best Practice- Typical Injection Facilities

Metering Pumps

Bulk Tank or Portafeed

Diluent

Alloy Injection Quill

BPG031 Corrosion - SCORPION® Injection Equipment Requirements.pdf

18
High Temperature Quill Design
Full circumference weld here

Aluminum Cooling Fins

Weld here

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Inspection & Monitoring
Inspection & Monitoring

 Monitoring Techniques
 On stream high temperature UT/RT
 Retractable coupons
 Electric resistance probes
 Corrosion monitoring loop
 Field signature method (FSM) technology
 Hydrogen flux probes
 New methods
 Sensor UT Gauge

 Recommend using more than one method due to corrosion

attack pattern

21
Monitoring Methods

22
Potential Associated Concerns
Operability Limits

 Naphthenic
acid concentration is not usually the limitation
when processing HAC – Corrosion can be effectively
mitigated
 Other factors have to be taken into account such as;
Desalter limitations
Overhead corrosion control issues
Product quality effects
Balanced Crude Slate

 Thesefactors have to be both predicted and managed to

minimize risk

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Summary

 Naphthenic acid crudes can be processed safely and

profitably
 Keysuccess factor is to act proactively as much as possible
– MANAGE THE RISK
 Fully survey the system
 Implement full monitoring program
 Have correct injection facilities available in case required
 Continually review results and implement changes as
necessary

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