BIOGRAPHY - GEOSCANMetallurgy Effective Monitoring Corrosion Control Effective Monitoring High...
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5th NCUT Upgrading and Refining Conference 2009 September 14-16, 2009
Edmonton, Alberta, Canada
BIOGRAPHY
Collin W. Cross
Betz GE Water and Process Technologies
Collin Cross received his Ph.D. in Physical Chemistry from the University of Oklahoma in 1994. During this time he pursued studies of the computational physics of Liquid Crystals. Following this he accepted a postdoctoral fellowship with the Keck Center for Computational Structural Biology in Houston. In 1996 Collin joined Betz/GE Water and Process Technologies as an Analytical Chemist. Since that time he has occupied various roles in R&D, and the Enabling Technologies groups. All of these roles have revolved around supporting process chemicals. Collin now occupies a position in the Technical Marketing organization. His areas of responsibility are for Corrosion Control, Antifouling and Fuel Additives.
Betz GE Water and Process Technologies 9669 Grogans Mill Road The Woodlands, Texas 77380 USA Phone: 1 281 681 5475 Fax: 1 281 363 7780 Email: [email protected]: www.gewater.com
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High Temperature Corrosion Control
and Monitoring for Processing Acidic
Crudes
Dr. Collin Cross
Presented at the 5th NCUT Upgrading and Refining Conference 2009, Edmonton, Alberta,
Canada. September 14-16, 2009.
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5th NCUT Upgrading and Refining Conference 2009
AvailabilityMeets Product
Requirements
Handling &
StorageProcessing HAC Energy Desalter
API
Flotation
TreatmentSlop
Waste
Treatment
Water
Discharge
Crude Unit
Corrosion
High
Temperature
Corrosion
Vacuum Unit
Corrosion
Define Product
Issue
Product Issues
Solvable
Overhead
Corrosion
Appropriate
Metallurgy
Effective
Monitoring
Corrosion Control
Effective
Monitoring
High
Temperature
Corrosion
Appropriate
Metallurgy
Corrosion Control
Condenser
Corrosion
Do Not Process
HAC
Process HAC
Process HAC
Define Issue
Issues
Solvable
Cost
Don’t Process
HAC
Naphthenic Acid Crude Impacts
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5th NCUT Upgrading and Refining Conference 2009
• Process Management Tool
• Designed to Maximize Refiner:
–Operational Flexibility
–Safety
–EnvironmentalProtection
–Reliability
–Profitability
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5th NCUT Upgrading and Refining Conference 2009
A Complex Process
• Temperature
Shee
rStr
ess
MPYMPY
Metallurgy
Sulfur
Acid Characterization &
Concentration
Ther
modyn
amic
s
Naphthenic Acid Corrosion
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5th NCUT Upgrading and Refining Conference 2009
Crude Tanks
Slop Tanks
START
To Sat.
Gas Plant
Hvy Gas Oil
Lt. Gas Oil
Lt. Nap.
Steam
Hvy. Nap.
Kerosene
Diesel
5
4
3
1
2
6
7
8
7
To Vacuum Unit
Atmospheric Column Nap Acid
Corrosion
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5th NCUT Upgrading and Refining Conference 2009
Crude Atm.
Frac. Bottoms
START
3
1
2
Lube Unit
FCC UnitHvy Gas Oil
Lt. Gas Oil
Oil/Water Sep.
Steam
Vacuum ResidCoker,
FCCU,
Asphalt
Blending
4
Vacuum Unit Nap Acid Corrosion
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5th NCUT Upgrading and Refining Conference 2009
• Crude Inputs
– NAN & TAN
– Fingerprint & Corrosion
– Characterization Sulfur etc.
Solution For Processing Naphthenic Acid Crude
• Asset Inputs
• Flow, Pipe Size, Velocity, Temperature,
Pipe Configuration and Spatial
Relationship, Pipe Geometry,
Impingement Factor, Metallurgy,
Predator Assessment Output
•Highlight critical impact areas
•Identification of specific priority points within critical impact area
•Monitoring requirements/schedule, location & sensor type
•Analysis requirements/schedule & location
•Chemical injection requirements /chemistry & application
•Baseline conditions & entitlement (expected gain)
•Develop program controls /Data Interpretation / training / documentation & improvements
Predator Assessment
+
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5th NCUT Upgrading and Refining Conference 2009
Technologies
Predict - Determine the impact before it
occurs
Monitor - Measure the asset condition and
the rate of change
Control - Implement corrective actions to
maintain the asset integrity and optimize
process efficiencies
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5th NCUT Upgrading and Refining Conference 2009
TAN / NAN Distribution
0
0.5
1
1.5
2
2.5
Crude 350/500 600/650 750/900
TAN
NAN
Total Acid Number vs. Nap. Acid Number
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5th NCUT Upgrading and Refining Conference 2009
Vacuum Resid
0.89 mg/g Vs 0.12 mg/g
Crude
Charge
• 1.34 mg/g Vs.
0.93 mg/g
Diesel
1.74 mg/g Vs 0.96mg/g
Kerosene
0.75 mg/g Vs. 0.35 mg/g
To Vacuum Unit
Hvy Gas Oil
1.74 mg/g Vs
1.54 mg/g
Lt. Gas Oil
TAN VS NAN
AGO
1.95 mg/g Vs 1.09 mg/g
•Organic & inorganic acids
•Esters
•Phenolic compounds
•Lactones
•Resins
•Salts of weak acids (soaps)
•Basic salts of polyacidic
bases
•Salts of heavy metals
•Additives--i.e.. inhibitors &
detergents
TAN Vs. NAN TANPredict
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5th NCUT Upgrading and Refining Conference 2009
Crude
A
Crude
B
Crude
C
Crude Oil Assessment
Predict
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5th NCUT Upgrading and Refining Conference 2009
Corrosion of CS and SS at TAN = 5.0
Sulfide Inhibiting Effect
0
40
80
120
160
mp
y
CS CS + H2S SS SS + H2S
500 °F
600 °F
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5th NCUT Upgrading and Refining Conference 2009
• Tools to develop strategies for processing
opportunity crude
– Opportunity Crude Oils
– Monitoring Program
– Chemical injection Points
– Operating parameters
• Establishes
– Base line conditions
– Opportunity Improvement
– KPI
– Criteria for success
– Plans for continuous improvement
Predator AssessmentPredict
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5th NCUT Upgrading and Refining Conference 2009
Pumps
Control
Valves
Downstream of Welds and orifice plates
Couple
Pipe Bends
Especially with Thermocouple Points
ThermoCouple
Impingement Factor & Velocity
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5th NCUT Upgrading and Refining Conference 2009
High Turbulence --- Column Internals
Tray
Bubbling
Areas
Undertray
Condensation
Total Trapout
Trays
Packed Sections
Support Beams
Internals
Bed
2 Phase Flow
Condensation
Vaporization
Thermodynamics
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5th NCUT Upgrading and Refining Conference 2009
Refinery piping
configuration
obtained during
Predator
Assessment
Pipeline configuration
simplified in terms of
components and
geometry
Corrosion models developed
for individual components
Corrosion potential
RCM placement
Chemical injection
locations
Priority AssessmentPredict
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5th NCUT Upgrading and Refining Conference 2009
Predator AssessmentPredict
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5th NCUT Upgrading and Refining Conference 2009
Local (more sensitivity)
Rate
Measurement
Integrated
Measurement
Global (less sensitivity)
Hydrogen Diffusion
Fully Integrated Suite Covers Sensor Gaps
Hi Temp UT
RCM
Probes / CouponsFe / Ni Ratios
PCOM
Monitor
Guided Acoustics
PCOM
Plus+
Odometer
Speedometer
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PredatorTM
Resistance
Corrosion Monitor! High temperature
capability > 950 F
! Able to install without shutdown
! Calculates wall thickness by measuring the electrical resistance and comparing to the initial baseline
! Fully automated operation
Measures 2% change in wall thickness with 6-Sigma accuracy
Patented technology designed to eliminate electronic noise
Optimum Coverage 1 Square Meter
Monitor
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RCM Terms
RCM
Reference Plate
Pin Matrix
Rr
Channel Rc
Pin Array
RCM Response or output " Voltage measured
between adjacent pins
Pin
Monitor
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20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2
6
5
4
3
2
1
000
0 0 0 0 0 0 0 0 -1 0 0 -1 0
320
0 0319320
0
0 0 0 0 0 0
320
0
319
0 0 0 0
319 320
0 319320
0
0 0 0 0 0 0 0 0
319
0 0 0 0 0
319
0 319319
0
0 0 0 0 0 0 0 0
319320
0 0 0 -1 0 0 319319
0
0 0 00 0 0 0
320
0 0 0 0 0 0 0
320
319
0
319
00 0 0 0 0 0
319
0 0 0 0 0 -1 -1 0
0
1
ROW
COL
Sample RCM ReportWall < 320 mils
Start Date: 2/3/2005
Stop Date: 6/14/2005
Sample Thickness Report
Remaining Wall
Plotting Threshold
Time
Interval
Monitor
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20 19 18 17 16 15 14 1312 11 10
9 87
65
43
2
6
5
4
3
2
1
000
0 0 0 0 0 0 0 0 -1 0 0 -1 0 0 0 06
00
0 0 0 0 0 0 0 0
7
0 0 0 0
5
0 0 7
00
0 0 0 0 0 0 0 0
5
0 0 0 0 0 0 0 5
00
0 0 0 0 0 0 0 0 0 0 0 0 0 -1 0 0 7
00
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 6
00
0 0 0 0 0 0 0
5
0 0 0 0 0 -1 -1 0
0
1
Column
RowSample RCM Report
Corrosion Rate > 5 MPY
Start Date: 2/3/2005
Stop Date: 6/14/2005
RCM Corrosion Rate
Report
Pipe
Bottom
Top of
Pipe
MPY
• Each channel corresponds to unique real estate on pipe surface.
• Exception Reporting " Only channels above a threshold are plotted.
Monitor
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5th NCUT Upgrading and Refining Conference 2009
Baseline Performance
~ One year data from the RCM indicates a maximum wall loss of 11
mil, a maximum corrosion rate of 11 mpy and 29+ years remaining
service life.
AGO Corrosion-RCM & CFD
19 2.3 1.9 4.5 5.2
18 2.3 1.8
17
16 1.6 1.9 3.2
15 2.2 1.6
14 2.9 2.0
13 1.7
12
11 3.9 3.4
10 2.0 7.5 2.4
9
8 5.9 3.0 4.6 2.4 4.7
7 2.2
6 1.8
5 4.1
4 11.0
3
2 1.6 3.8
1 2.6 2.0 2.4
1 2 3 4 5 6 7
Monitor
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5th NCUT Upgrading and Refining Conference 2009
0 14.4 17.6
1 8.3 13.3 21.4 15.5 7.5
2 5.4 3.5 7.2
3 8.1 14.8 9.2
4 7.6 10.7 4.9
5 7 11.5 14 5.1 8.1
6 10.9 5.1
7 5 12.5 13.1 2.3 4.6 3.8
8 6.2 15.4 16.1 5.4
9 8.6
10 8 1.9 4.6
11 7.1 3 9.3 5
12 6.5 9.2 4.3
13 3 3 6.4
14
0 1 2 3 4 5 6 7 8 9
Corrosion Tower Shell
21.4 mpy represents nominal 2.4% wall loss and indicates 17+ years
remaining.
Baseline PerformanceMonitor
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5th NCUT Upgrading and Refining Conference 2009
Control
• Blending
• Phosphate Ester “Best in Class”
• Non Phosphorous - Phosphorous
efficacy without the fouling or catalyst
poisoning
• New patent pending molecules
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5th NCUT Upgrading and Refining Conference 2009
Effect of Inhibitor Type on Corrosion Rate
0
2
4
6
8
10
12
14
16
Class
1
Class
1
Class
1
Class
1
Class
2
Class
2
Class
2
Class
2
Class
2
Class
3
Class
3
Class
3
Class
4
Class
4
Class
5
Class
5
Class
5
Class
5
Class
6
Class
6
Class
7
Class
7
Class
7
Class
8
Class
8
Inhibitor Type
mp
y
Conditions:
VEN LVGO, 600 F, 1018CS
100 ppm active
Untreated Corrosion Rate
Control Phosphate Ester Comparisons
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5th NCUT Upgrading and Refining Conference 2009
HVGO Corrosion
0
5
10
15
20
25
3-Ja
n
17-J
an
3-Feb
17-F
eb
2-M
ar
11-M
ar
25-M
ar
30-A
pr
20-M
ay
12-J
un
6-Ju
l
Date
HVGO
PatentedPredator
61N
Started
Case HistoryER Probe
Data Predator
61N
Control
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5th NCUT Upgrading and Refining Conference 2009
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
1/3 1/10 1/17 1/24 2/3 2/10 2/17 2/24 3/2 3/3 3/11 3/13 3/25 4/22 4/30 5/10 5/20 5/27 6/12 6/23 7/6 7/21
Date
Fe/N
i R
ati
o
Desalted Crude
Vacuum Resid
Patented
Predator 61
N Started
Case HistoryFe / Ni Data
Predator 61N
Control
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5th NCUT Upgrading and Refining Conference 2009
Case History Case History
Predator 6tN1401Predator 6tN1401
1.501.53
2.232.40
Diesel
2.102.44
1.962.47 HVGO
VTB
Atmos
Bottoms
NAN
TAN
0.241.00
Atmos
Tower
Vacuum
Tower
LVGO PA2.20
2.65AGO
Control
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5th NCUT Upgrading and Refining Conference 2009
AGO Stream Corrosion - Previous Competitive
Phosphorous Program
0
5
10
15
20
25
mpy
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35
Corrosion
3 Week Rolling Average
Case History 6N1401Case History 6N1401Control
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5th NCUT Upgrading and Refining Conference 2009
AGO Stream Corrosion- Current DM20074
0
2
4
6
8
10
12
mpy
1 2 3 4 5 6 7 8 9 10 11 12 13
Corrosion
3 Week Rolling
Average
Case History DM20074Case History DM20074Control
![Page 34: BIOGRAPHY - GEOSCANMetallurgy Effective Monitoring Corrosion Control Effective Monitoring High Temperature Corrosion Appropriate ... lf u r cd haractera ton & Concentration h e r m](https://reader033.fdocuments.us/reader033/viewer/2022053004/5f084afa7e708231d4214a97/html5/thumbnails/34.jpg)
5th NCUT Upgrading and Refining Conference 2009
Predator Program Recommendations
P H
A
A
PA
UT
PA
H
P
A
PHPRCMUT
UT
A
H
P
RCM
UT
P
H
RCM
A
UT
Chemical Injection
Metals Analysis
UT Readings
RCM
Hydrosteele
Corrosion Probes
RCM
61N
61N
61N
61N
![Page 35: BIOGRAPHY - GEOSCANMetallurgy Effective Monitoring Corrosion Control Effective Monitoring High Temperature Corrosion Appropriate ... lf u r cd haractera ton & Concentration h e r m](https://reader033.fdocuments.us/reader033/viewer/2022053004/5f084afa7e708231d4214a97/html5/thumbnails/35.jpg)
5th NCUT Upgrading and Refining Conference 2009
• Safety
• EnvironmentalProtection
• Reliability
• OperationalFlexibility
• Profitability
Delivers