On-site Quantification of Monoethanolamine in Crude Oils...– Reduces MEA to the overhead, thus reducing MEA – HCl salt formation temperature •Make operational changes (e.g. increase

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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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-50

-25

+0

+25

+50

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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-25

+0

+25

+50

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

+

+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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-5

+

+5

+10

+15

+20

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+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

)




~5 260

MEA

15

Brine pH

Mitigation: Apply Caustic

Default


Increasing

Corrosion Risk

LOW RISK

HIGH RISK

17

Control

Corrosion Risk = Medium

8.5

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-5

+

+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

)




~5 260

MEA

4

Brine pH (controlled)

Mitigation: Apply Caustic + EXCALIBUR program

Default


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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On-site Quantification of

Monoethanolamine in Crude Oils

Sai R Pinappu

COQA 2014 Fall Meeting

San Francisco, CA

Documents

On-site Quantification of Monoethanolamine in Crude Oils...– Reduces MEA to the overhead, thus reducing MEA – HCl salt formation temperature •Make operational changes (e.g. increase