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Searching for Mercury
COQG Meeting
New Orleans, LA
March 6, 2008
Tony Nguyen Laboratory DevelopmentAmericas
Crude Oil Quality Group
COQG
www.intertek-cb.com
Presentation Overview
Introduction to Intertek
Mercury Measurement Techniques
Recent Studies of Sticky Mercury in Hydrocarbon Production and Processing
Impact of Extraction of Mercury from Sampling Containers
Functional and Molecular Speciation
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Worldwide Network
We provide testing, inspection and certification services the world over
www.intertek-cb.com
Global Network
Laboratories 355
Offices 578
People 20,000
Countries 110
Floated May 2002
Market capitalization at 31st Dec 2006 £1.3bn
Corporate website www.intertek.com
www.intertek-cb.com
ISO 6978 Part II
ScopeNatural Gas
EquipmentGold AmalgamationAtomic Fluorescence (AFS) or Atomic Absorption (AAS)Heated Manifold Sampling
Detection0.001 ug/M3 – 1 ug/M3
PrecisionNot Given in Method
PIPE
LIN
E
P1
Primary Bypass
V1
P2
15 psigRelief Valve
Secondary Bypass
FlowmeterPVR1
Sample IN
Tube 1
Tube 2
heatedblock
spikingport
Flowmeter
1/4 inch teflonbraided hose6ft
KeyP1 - Pressure GaugeV1 - Isolation ValvePVR1 - Heated SS RegulatorP2 - Pressure Gauge
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JLPGA-S-07
ScopeLPG
EquipmentGold Amalgamation
CVAAS
Heated Vaporization
Detection0.01-1000 ng Hg mass
PrecisionNot Determined
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UOP 938
ScopeLiquid Hydrocarbons
EquipmentNippon Instruments SP3D
Detection0.1-10000 ng/ml
PrecisionNot estimated in the methodCalibrated by Serial dilution of traceable standards
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LUMEX
High Throughput
Above 30ppb data equivalent to UOP 938
Oil, Gas, and Water
Zeeman Corrected CVAA
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Speciation - Functional and Molecular
Functional Speciation
Volatile
Particulates
Water soluble
Others
Molecular Speciation
GC-ICP-MS
Elemental Mercury
Methyl Mercury
Ionic Mercury
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Hg Speciation by GC-ICP-MS
1.0Time-->
Abundance
0
50
95
2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0
Elemental Mercury
300 ng/g
Methyl Mercury
50 ng/g
Ionic Mercury
150 ng/g
Calibration Standard
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Abundance
0
100
200
300
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0Time-->
Sample 1Total Hg conc. of 714 ng/g
Elemental Mercury
290 ng/g
Ionic Mercury
430 ng/g
Hg Speciation by GC-ICP-MS
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Time-->
Abundance
0
100
200
300
400
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0
Sample 2Total Hg conc. of 530 ng/g
Elemental Mercury
210 ng/g
Ionic Mercury
320 ng/g
Hg Speciation by GC-ICP-MS
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Mercury Studies
Mercury in Feedstocks, LPG, Naphtha, Condensate,and Effluent WaterTransformation of Mercury TypesFunctional SpeciationRefinery And Plant Mass BalancesMercury Removal Process Planning/TroubleshootingLiquid Asset Mercury Distribution StudiesMercury Adsorption Studies
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Mercury Mass BalanceRefinery Study
Issue: Refining: On Site Mercury Study
Poor Mass Balance
Investigation: Sampling Containers -Potential adsorption of Hg onto glass surfaces.
Result: Better Mass Balance
Most samples must be measured both in liquid and on container surface
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Extraction of Adsorbed HgPetroleum Distillate in Glass VOA Vials
Total Hg ppb wt
Extracted Hg ppb wt
Hg in Liquid ppb wt
81681154
87987183
918894242
917895221
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Mercury Mass BalanceLaboratory Distillation
Issue: Hg Distribution StudyPoor Mass Balance on Distillate Cuts From ASTM D2892
Investigation: Mercury Adsorption on GlassDistillation Column
Result: Significant Hg recovered from distillation column. Improved mass balance
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Distribution Study Closure Investigation
61.6728,000Strong Oxidizer
4,500Amino Acid 3
6,500Amino Acid 2
524,500Amino Acid 1
38.5075,000Acid Wash 3
125,000Acid Wash 2
250,000Acid Wash 1
22.94484,842Distillate Cuts
2,429,700Whole Crude
% Hg RecoveredTotal Hg (ng)Sample
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Crude Oil – Hg recovered fromglass Sample Containers
Issue: Total Hg measurements in known high mercury crude oil
Investigation: Mercury Adsorption on glass containers.
Result: Extraction of glass recovered additional 300 ng/g (30%) Hg
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Total Hg in Crude Oil Sample after Extraction
1349 ppb wt.Total Hg in Crude
30.1% increase312 ppb wt.Extracted Hg using strong oxidizer
1037 ppb wt.Hg in liquid hydrocarbon
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Hg Measurements and ExtractionsGlass and Teflon Sampling Containers
Issue: How much Hg adsorbs to Teflon v. Glass
Investigation: Investigate analytical techniques to measure extracted and total Hg on representative refinery distillate.
Result: Consistent Total Hg results obtained with either extraction from Teflon or Glass. More repeatable extraction obtained from Teflon.
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Total and Extracted HgVOA & Teflon Containers
Petroleum Distillate
19.9919.4519.3020.6719.4120.17Total Hg(ppb wt)
3.863.763.264.742.796.07Extraction
16.1215.6816.0415.9216.6214.10Liquid Phase
Teflon BottlesVOA Bottles
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Hg Measurements on Hydrocarbon AssetsAs Received at the Refinery
Issue: Inconsistent Hg results from samples as received
Investigation: Investigate sampling techniques to ensure representative sampling event at the refinery
Result: Consistent results obtained with improved attention to sampling and extraction of Hg in the sample containers
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Effects of Extraction on Hg Measurementsin Liquid Condensate
67
95
129
135
Hg Result
ppb wt
-
-
166
163
Total Hg
ppb wt
1 L Glass
Schott Duran
2
1 L Glass
Schott Duran
1
1 L Unlined
Metal Can
4
1 L Unlined
Metal Can
3
Sample ContainerSample
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Corroborative Analyses Confirm “Sticky” Mercury Adsorbed to Sample Receivers
0
200
400
600
800
1000
1200
1400
1600
Distillate 1 Distillate 2 Distillate 3 Distillate 4 Distillate 5 Distillate 6 DewarFlask
Distillate Cut
Extr
acte
d H
g C
onte
nt (p
pb)
LumexICP-MS
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Corroborative Analyses Confirm “Sticky” Mercury Adsorbed to Sample Receivers
0
50
100
150
200
250
300
350
Cut 1Cut 2Cut 3Cut 4Cut 5Cut 6Cut 7Cut 8Cut 9Cut 10Cut 11Cut 12Cut 13Cut 14Cut 15
Distillate Fraction
Extr
acte
d H
g C
onte
nt (p
pb)
LUMEXICP-MS
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SummaryThe existing databases for liquid assets in our industry do not include “sticky” mercury and should be updated.
Intertek has developed techniques to allow accurate measurementsof total mercury in hydrocarbon liquids including the mercury sticking to the sample container.
Corroborative analytical techniques provide insight into analytical uncertainty.
Re-evaluate all mercury data if it does not include this newly confirmed phenomenon of “sticky” mercury.
Intertek is the leading provider of vital analytical technology and experience globally.
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Contact Us
Mr. Tony NguyenLaboratory Development - Americas
Office: +1.713.456.1181Cell: +1.832.606.0201
Email: [email protected]
Mr. Peter A. SpitzRegional Technical Development Manager
Office: +65.6265.5385Cell: +65.9678.3198
Email: [email protected]
