On-site Quantification of Monoethanolamine in Crude Oils...– Reduces MEA to the overhead, thus...
Transcript of On-site Quantification of Monoethanolamine in Crude Oils...– Reduces MEA to the overhead, thus...
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© 2014 BAKER HUGHES INCORPORATED. ALL RIGHTS RESERVED. TERMS AND CONDITIONS OF USE: BY ACCEPTING THIS DOCUMENT, THE RECIPIENT AGREES THAT THE DOCUMENT TOGETHER WITH ALL INFORMATION INCLUDED THEREIN IS THE
CONFIDENTIAL AND PROPRIETARY PROPERTY OF BAKER HUGHES INCORPORATED AND INCLUDES VALUABLE TRADE SECRETS AND/OR PROPRIETARY INF ORMATION OF BAKER HUGHES (COLLECTIVELY " INFORMATION"). BAKER HUGHES RETAINS ALL RIGHTS
UNDER COPYRIGHT LAWS AND TRADE SECRET LAWS OF THE UNITED STATES OF AMERICA AND OTHER COUNTRIES. THE RECIPIENT FURTHER AGREES TH AT THE DOCUMENT MAY NOT BE DISTRIBUTED, TRANSMITTED, COPIED OR REPRODUCED IN WHOLE OR
IN PART BY ANY MEANS, ELECTRONIC, MECHANICAL, OR OTHERWISE, WITHOUT THE EXPRESS PRIOR WRITTEN CONSENT OF BAKER HUGHES, AND MA Y NOT BE USED DIRECTLY OR INDIRECTLY IN ANY WAY DETRIMENTAL TO BAKER HUGHES’ INTEREST.
© 2014 BAKER HUGHES INCORPORATED. ALL RIGHTS RESERVED. TERMS AND CONDITIONS OF USE: BY ACCEPTING THIS DOCUMENT, THE RECIPIENT AGREES THAT THE DOCUMENT TOGETHER WITH ALL INFORMATION INCLUDED THEREIN IS THE
CONFIDENTIAL AND PROPRIETARY PROPERTY OF BAKER HUGHES INCORPORATED AND INCLUDES VALUABLE TRADE SECRETS AND/OR PROPRIETARY INF ORMATION OF BAKER HUGHES (COLLECTIVELY " INFORMATION"). BAKER HUGHES RETAINS ALL RIGHTS
UNDER COPYRIGHT LAWS AND TRADE SECRET LAWS OF THE UNITED STATES OF AMERICA AND OTHER COUNTRIES. THE RECIPIENT FURTHER AGREES TH AT THE DOCUMENT MAY NOT BE DISTRIBUTED, TRANSMITTED, COPIED OR REPRODUCED IN WHOLE OR
IN PART BY ANY MEANS, ELECTRONIC, MECHANICAL, OR OTHERWISE, WITHOUT THE EXPRESS PRIOR WRITTEN CONSENT OF BAKER HUGHES, AND MA Y NOT BE USED DIRECTLY OR INDIRECTLY IN ANY WAY DETRIMENTAL TO BAKER HUGHES’ INTEREST.
On-site Quantification of
Monoethanolamine in Crude Oils
Sai R Pinappu
COQA 2014 Fall Meeting
San Francisco, CA
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Outline
• Tramp amine sources
• Challenges processing tramp amine contaminated crudes
• Tramp monitoring technologies
• Today’s tramp amine monitoring requirements
• Improved solution: TOPGUARD™ field amine measurement
services (FAMS)
• Field application
TOPGUARD is a trademark of Baker Hughes Incorporated.
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Tramp Amine Sources
Tramp amines in slops (Example: Amine unit)
Tramp amines in desalter wash water
Quality of incoming crude oils – Tramp amines from H2S
scavengers is the major source
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Tramp Amines Increase Desalter pH
• Increased partitioning of amines to crude oil
• Stabilized emulsion layer
– Increased BS&W in the desalted crude
– Higher chloride concentration in the overhead water
– RNH2 + HCl RNH3Cl
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Current Industry Standard Tramp Amine Monitoring Methods
Analytical
Technique Detection Limit Lab/Field
Interferences/
Limitations
Typical
Analysis Time
Specialist
Requirement
IC ASTM D6919-09,
E1151
0.1 ppm Lab
Other aliphatic
amines, high
conductivity ,not
specific
1-2 days Yes
GC/GC-MS1,2 0.4 ppm Lab
Nitriles, aromatic
amines, derivatization
required
1-2 days Yes
LC3 0.2 ppm Lab Derivatization required 1-2 days Yes
1. S.Meseguer Llouret., C.Molins Legua., P. Campins Falco., Journal of Chromatography A 978 (2002) 59-69
2. F. Sacher., S. Leng., H,J, Brauch., Journal of Chromatography A 764 (1997) 85-93
3. Y. Moliner Martinez., R. Herraez Hernandez., P. Campins Falco., Journal of Chromatography A 1164 (2007) 329-333
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Current Baker Hughes Monitoring and Modelling Capabilities
• Ion Chromatography
– Modified ASTM method
– Often takes several days to receive results
• Total Nitrogen method
– Relies on subtraction of N from neutralizer and NH3 from the total N
– If excess N remains, it is labeled “tramp”
– Does not specify whether tramp N is from MEA • Cases where MA is the
primary source
Baker Hughes recognized the need for a new, fast, on-site method to quantify MEA
to support enhanced corrosion risk prediction and mitigation.
Corrosion Risk Monitor
? ?
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Today’s Tramp Amine Monitoring Requirements
• Fast onsite quantification
• Lower detection limits
• Onsite prediction of corrosion risk potential
• Timely mitigation strategies
• Flexibility to use for multiple analytes
• Portable
• Ease of use
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TOPGUARD Field Amine Measurement Services
• Field asymmetric ion mobility
spectrometry was identified as
potential technology platform
• Developed customized methodology
to determine MEA in crude oils
– Proprietary sample preparation
protocols were developed
– Minimized interferences and
increased sensitivity
– Instrument operating parameters
were optimized
– Proprietary data processing and
modeling capabilities are applied
MEA replicates at
different
concentrations
MEA
TOPGUARD FAMS SCAN
MEA Detection & Reproducibility at Various
Concentrations
MEA peak location identified and quantified down to 1 ppm
with excellent reproducibility (RSD ≤ 10%)
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TOPGUARD FAMS Correlates with IC
• Good agreement with IC
data on crude samples,
± 20% of the IC result
• Calculated overhead MEA
using TOPGUARD FAMS
in agreement with IC
• Detection of MEA down to
1 ppm in crude oils
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TOPGUARD FAMS Features & Benefits
Features
• On-site measurement
• Portable
• Fast: 1 hour per sample
• MEA sensitivity down to 1 ppm in
crude oil
• Ease of use
Benefits
• Real-time screening of feedstock for
amine content
• Improved prediction of corrosion risk
potential
• Flexibility to use for multitude analytes
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TOPGUARD FAMS – Analysis Process
Step 1 - Sample Collection &
Preparation Step 2 - TOPGUARD FAMS Analysis
Step 3 - TOPGUARD CRM Calculations
Adjust desalter
pH to remove
MEA, avoid salt
Mitigation
Strategies
Adjust caustic to
control chlorides
Modify tower,
OH operations
to avoid salt
Adjust
neutralizer rate
to control pH
Step 4 – Determine Appropriate
Mitigation Strategy
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Mitigation Options
• Apply caustic
– Reduces overhead chlorides, thus reducing MEA –HCl salt formation temperature
• Use EXCALIBURTM contaminant removal program
– Reduces MEA to the overhead, thus reducing MEA – HCl salt formation temperature
• Make operational changes (e.g. increase tower operating temperature)
– Increases “Salt ∆T,” thus reducing the risk of salt deposition
– Often a costly and undesirable option
• Adjust crude blend ratio
– Reduces contaminants to the overhead, thus reducing the risk for salt deposition
– Often a costly and undesirable option
EXCALIBUR is a trademark of Baker Hughes Incorporated.
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Process Refining Application
Gulf Coast Refinery
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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28
MEA
-H
Cl T
ower
Top
Sal
t ∆
T (°
F)
MEA - HCl Tower Top Salt ∆T (°F)
TOPGUARD FAMS IC
Corrosion Risk Free - No Mitigation Required
64% of data required NO MITIGATION
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1 2 3 4 5 6 7 8 9 10
MEA
-H
Cl T
ower
Top
Sal
t ∆T
(°F)
MEA - HCl Tower Top Salt ∆T (°F)
TOPGUARD FAMS IC
What to Do when Mitigation is Needed
Mitigation Required
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+
+5
+10
+15
+20
+25
+30
0:00:00 0:00:00 0:00:00 0:00:00 0:00:00 0:00:00
ME
A D
elt
a T
(T
ovd -
TM
EA
,salt)
(°F
)
VLO St. Charles MEA Salt Delta T (°F)
ΔT = +25°F ΔT = +15°F High Risk
Tower T (°F) OVHD Cl- (ppm)
14 260
MEA
15
Brine pH
8.5
Mitigation: MEA ~15ppm, ∆T ~ (0 – 5)°F
Default
Corrosion Risk = High
Increasing
Corrosion Risk
LOW RISK
HIGH RISK
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0:00:00 0:00:00 0:00:00 0:00:00 0:00:00 0:00:00
ME
A D
elt
a T
(T
ovd -
TM
EA
,salt)
(°F
)
VLO St. Charles MEA Salt Delta T (°F)
ΔT = +25°F ΔT = +15°F High Risk
Tower T (°F) OVHD Cl- (ppm)
~5 260
MEA
15
Brine pH
Mitigation: Apply Caustic
Default
Corrosion Risk = High
Increasing
Corrosion Risk
LOW RISK
HIGH RISK
17
Control
Corrosion Risk = Medium
8.5
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-5
+
+5
+10
+15
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0:00:00 0:00:00 0:00:00 0:00:00 0:00:00 0:00:00
ME
A D
elt
a T
(T
ovd -
TM
EA
,salt)
(°F
)
VLO St. Charles MEA Salt Delta T (°F)
ΔT = +25°F ΔT = +15°F High Risk
Tower T (°F) OVHD Cl- (ppm)
~5 260
MEA
4
Brine pH (controlled)
Mitigation: Apply Caustic + EXCALIBUR program
Default
Corrosion Risk = High
Increasing
Corrosion Risk
LOW RISK
HIGH RISK
5.5 – 6.0
Control
Corrosion Risk = Low
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Tramp MEA, MEA-HCl Risk Management
TOPGUARD field amine measurement services provides refiners:
• Quick identification of amine-contaminated crude oils
• Quantification of tramp amines and translation to corrosion risk potential
• Timely implementation of mitigation programs to minimize corrosion
– Adjustments to crude tower operations
– Optimization of EXCALIBUR contaminant removal program
– Proactive planning and blending optimization
• Achievement of targeted operating efficiency and profitability goals
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© 2014 BAKER HUGHES INCORPORATED. ALL RIGHTS RESERVED. TERMS AND CONDITIONS OF USE: BY ACCEPTING THIS DOCUMENT, THE RECIPIENT AGREES THAT THE DOCUMENT TOGETHER WITH ALL INFORMATION INCLUDED THEREIN IS THE
CONFIDENTIAL AND PROPRIETARY PROPERTY OF BAKER HUGHES INCORPORATED AND INCLUDES VALUABLE TRADE SECRETS AND/OR PROPRIETARY INF ORMATION OF BAKER HUGHES (COLLECTIVELY " INFORMATION"). BAKER HUGHES RETAINS ALL RIGHTS
UNDER COPYRIGHT LAWS AND TRADE SECRET LAWS OF THE UNITED STATES OF AMERICA AND OTHER COUNTRIES. THE RECIPIENT FURTHER AGREES TH AT THE DOCUMENT MAY NOT BE DISTRIBUTED, TRANSMITTED, COPIED OR REPRODUCED IN WHOLE OR
IN PART BY ANY MEANS, ELECTRONIC, MECHANICAL, OR OTHERWISE, WITHOUT THE EXPRESS PRIOR WRITTEN CONSENT OF BAKER HUGHES, AND MA Y NOT BE USED DIRECTLY OR INDIRECTLY IN ANY WAY DETRIMENTAL TO BAKER HUGHES’ INTEREST.
© 2014 BAKER HUGHES INCORPORATED. ALL RIGHTS RESERVED. TERMS AND CONDITIONS OF USE: BY ACCEPTING THIS DOCUMENT, THE RECIPIENT AGREES THAT THE DOCUMENT TOGETHER WITH ALL INFORMATION INCLUDED THEREIN IS THE
CONFIDENTIAL AND PROPRIETARY PROPERTY OF BAKER HUGHES INCORPORATED AND INCLUDES VALUABLE TRADE SECRETS AND/OR PROPRIETARY INF ORMATION OF BAKER HUGHES (COLLECTIVELY " INFORMATION"). BAKER HUGHES RETAINS ALL RIGHTS
UNDER COPYRIGHT LAWS AND TRADE SECRET LAWS OF THE UNITED STATES OF AMERICA AND OTHER COUNTRIES. THE RECIPIENT FURTHER AGREES TH AT THE DOCUMENT MAY NOT BE DISTRIBUTED, TRANSMITTED, COPIED OR REPRODUCED IN WHOLE OR
IN PART BY ANY MEANS, ELECTRONIC, MECHANICAL, OR OTHERWISE, WITHOUT THE EXPRESS PRIOR WRITTEN CONSENT OF BAKER HUGHES, AND MA Y NOT BE USED DIRECTLY OR INDIRECTLY IN ANY WAY DETRIMENTAL TO BAKER HUGHES’ INTEREST.
On-site Quantification of
Monoethanolamine in Crude Oils
Sai R Pinappu
COQA 2014 Fall Meeting
San Francisco, CA