BIOGRAPHY - GEOSCANMetallurgy Effective Monitoring Corrosion Control Effective Monitoring High...

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.

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


• Process Management Tool

• Designed to Maximize Refiner:

–Operational Flexibility

–Safety

–EnvironmentalProtection

–Reliability

–Profitability


A Complex Process

• Temperature

Shee

rStr

ess

MPYMPY

Metallurgy

Sulfur

Acid Characterization &

Concentration

Ther

modyn

amic

s

Naphthenic Acid Corrosion


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


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


• 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

+


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


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


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


Crude

A

Crude

B

Crude

C

Crude Oil Assessment

Predict


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


• 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


Pumps

Control

Valves

Downstream of Welds and orifice plates

Couple

Pipe Bends

Especially with Thermocouple Points

ThermoCouple

Impingement Factor & Velocity


High Turbulence --- Column Internals

Tray

Bubbling

Areas

Undertray

Condensation

Total Trapout

Trays

Packed Sections

Support Beams

Internals

Bed

2 Phase Flow

Condensation

Vaporization

Thermodynamics


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


Predator AssessmentPredict


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

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

RCM Terms

RCM

Reference Plate

Pin Matrix

Rr

Channel Rc

Pin Array

RCM Response or output " Voltage measured

between adjacent pins

Pin

Monitor

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

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


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


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


Control

• Blending

• Phosphate Ester “Best in Class”

• Non Phosphorous - Phosphorous

efficacy without the fouling or catalyst

poisoning

• New patent pending molecules


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


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


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


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


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


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


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


• Safety

• EnvironmentalProtection

• Reliability

• OperationalFlexibility

• Profitability

Delivers

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