Mercury in the Oil & Gas Industry

– Understanding the Issues!

Presentation Overview

Introduction to Mercury

Mercury Related Incidents

Mercury & HSE

Understanding Gas Sampling & Analysis

Understanding Liquid Hydrocarbon Sampling & Analysis

Implications of Mercury Speciation

Various Case Study Examples

Summary

Questions and Answers

2
 What is Mercury?

A naturally occurring heavy metal

Highly toxic element which bio-accumulates in humans

Found in rocks, volcanoes, drilling mud, coal, crude oil and
natural gas

Released into the atmosphere through volcanic activity and
burning of fossil fuels

Present in several different forms which show different behaviour:
toxicity, bioavailability, solubility etc

Converted to methyl mercury by bacteria and algae

In the last century Hg levels have tripled
• but is also a result of global pollution

3
 Mercury Relationship/Trends in our
Industry

Mercury is not an issue in every oil and gas producing region

Certain geographical regions produce higher mercury level crude oil,

condensate and gas

High temperature reservoirs tend to produce elevated mercury levels

Light sweet crudes and condensates tend to have higher mercury

concentrations than heavy sour crudes

Hg globules
trapped in
shale

4
 IMPACT of Mercury!

Historical Failures:
• Skikda LNG plant, Algeria, 1973
• Anschutz Ranch, Wyoming, 1991
• Moomba, Australia, 2005

Unscheduled shutdowns of various offshore & onshore
facilities

Decontamination of FSOs, FPSOs and tankers

Disagreements between buyers & sellers

Generation of contaminated waste

Mercury poisoning of personnel

5
 Mercury: It Can Have Catastrophic
Consequences
Hg0

Cause

Courtesy of Popular Science

Effect

Skikda LNG Plant, courtesy of

PS Analytical Ltd

6
 Hg Induced Corrosion and
Background Information

Hg forms amalgams with most metals, melting point of Hg is
-39ºC so components operating at low temperatures will
condense liquid Hg

Many cases of Hg induced corrosion have occurred
worldwide. Corrosion of aluminium based heat exchangers,
rotors and condensers are common. Cost of replacement very
costly – plant shutdown!

Two types of mercury induced corrosion can occur:
1. Mercury Induced Stress Cracking (LME) – Water not required
4Hg + Al3Mg2 = 2MgHg2 + 3Al
2. Mercury Catalysed Oxidation by Water
2AlHg + 6H20 = 2Al(OH)3 + 3H2 + 2Hg

7
Effects of Mercury Released into
the Environment

Extreme toxic and bio-accumulates

Elemental mercury within water/soil may be
transformed by micro-organisms into methyl
mercury (high toxicity)

Methyl mercury binds strongly to proteins in the
bodies of fish and humans and is removed very
slowly

Methyl mercury can damage brains, kidneys, the
central nervous system and embryos

Minimata Incident

8
Exposure and Health Risks

Significant health risks

Mercury is absorbed into the body through three different routes;
inhalation, skin exposure and oral intake

Repetitive exposure to mercury vapour would lead to
accumulated levels of mercury in the body

Typical Exposure Situations
• Hydrocarbon liquid, produced water sampling
• Opening of drain valves
• Servicing of compressors & online instrumentation
• Changing of glycol & amine filters
• Launching and receiving of pigs
• Blow down of gas lines
• Draining of process lines
• Entering confined spaces
• Vessel or tank maintenance

9
 Mercury Exposure Limits
American Conference of
Governmental Industrial
Hygienists (ACGIH)
United Kingdom Health and
Safety Executive (HSE)
National Institute of Occupational
Safety and Health (NIOSH)
Occupational Safety and Health
Administration (OSHA)
National Institute of Occupational
Safety and Health (NIOSH)
Threshold Limit Value (TLV) – 0.025 mg/m3
(as Time Weighted Average)
Long-term Exposure Limit (LEL) - 0.025
mg/m3 (as 8 hour Time Weighted
Average)
Recommended Exposure Limit (REL) - 0.05
mg/m3
Permissible Exposure Limit (PEL) - 0.1
mg/m3
A limit which is considered to be Immediately
Dangerous to Life or Health (IDLH) of 10
mg/m3 (10000 µg/m3).
10
 Mercury and Human Lungs
Healthy human lung Effect of ingested mercury

11
Gas Sampling and Analysis

12
 General Sampling Procedures

Tedlar Bags (used at clients request)

Absorbing Solutions followed by cold vapour determination
(SGS can perform but highly advises against!)

Stainless Steel Bombs (SGS will not endorse & advises
strongly against such use!)

Stainless Steel PTFE or Sulfinert-coated Bombs (endorsed
by SGS)

Continuous/direct sampling at source on gold adsorbents
(endorsed by SGS and highly advised)

13
Tedlar Bags – AAS/AFS (JLPGA
pt.2 + UOP 938)

Advantages
Relatively low cost
Disposable thereby eliminates cross-contamination

Disadvantages
Small sample volumes and thereby low sensitivity
Some adsorption of mercury on walls
Only suitable for C1 – C3
14
 Trapping in Absorption Solutions &
Analysis by AAS (JLPGA pt.2)

HIGH PRESSURE LOW PRESSURE

Waste

Flow
Meter
Heated Valve Assembly
Advantages
Trapping Solution
Low cost
Large sample volumes
Mercury is preserved in solution
Disadvantages
High blanks in trapping solutions & high human error
Long sample collection times
Solutions are then analysed by AAS or AFS
Not suitable for heavier fractions,C5
15
 Stainless Steel Sulfinert Coated
Cylinders
Gold tubes in
Series Flow Meter

Heater Valve
Assembly

Advantages
 Easy to collect sample
 High sample volume with ability to re-analyse
 Excellent for C1 – C4
 No need for cleaning, just inert gas flushing

Disadvantages
 Difficult to transport
 Pressure drop, causing cooling and condensation of C5+,
overcome by heated valve assembly (high pressure gas sampling
system)
16
 Sampling Using the High Pressure
Sampling System: ISO 6978

Primary 15 psig
Bypass Relief Secondary
Valve Bypass

P1 P2 Flowmeter
PVR1
PIPELINE

Sample IN
V1
1/4 inch teflon
braided hose spiking
6ft port

Tube 1

Flowmeter heated
block
Tube 2
Key
P1 - Pressure Gauge
V1 - Isolation Valve
PVR1 - Heated SS Regulator
P2 - Pressure Gauge

17
 Examples of Hg levels in SEAP
Hydrocarbon Gases
Country Hg conc. (µg/Nm3)
A 0.2-300
B 1000-1300
C 450-1000
D 2-500
E 0.1-1
F 1-300
G 250-1400

NB: Well-head samples can contain significantly

higher mercury levels!

18
 Liquid Hydrocarbon
Sampling and Analysis

19
 Measurement of Total Mercury in
Crude Oils & Condensates

UOP 938: Total Mercury & Mercury Species in Liquid HCs –

pyrolysis technique with AAS detector

Volatilisation & amalgamation at elevated temperature with AFS
detector (light condensates/naphtha – ASTM method in draft)

Total Mercury in Liquid HCs – pyrolysis technique with
Zeeman-corrected AAS detector (Lumex 915+, ASTM method
in draft)

Aqua Regia Extraction at elevated temperature with CV-
AFS/AAS or ICP-OES detection

20
 Sampling & Sample Representation
Critical Factors!

Over 90% errors are made when dealing with mercury

• During sampling period
• Static/dead sample
• Storage containers
• Shipment
• Non-homogeneous sample
• External contamination
• Lack of mercury science education
• Cross contamination from a previously used containers/ships
• Conditioning time for mercury levels to stabilise in sample
matrices
• Type of treatment required for sample matrices is dependent
on mercury species present
21
 Mercury Chemistry…Simple!?

Total Mercury

Particulate Dissolved
Mercury Mercury

Amalgamated Organic Ionic Elemental

mercury Mercury Mercury Mercury
Mercury Absorbed to
particulates (Wax/Si)

Divalent
Mercury Unknown Species
Insoluble
Mercury in /and Complex
Mercury compounds
Organic Phase

22
 Mercury Speciation Challenges

Difficult to detect accurately the complete Hg species using

current testing methods therefore obtaining Hg mass balance is
problematic

Hg species in crude oil is not fully understood and more
research is required

Volatile nature of Hg, results in changes during treatment,
storage and shipment

Logistics of representative sampling, transportation and sample
restoration presents some unique challenges – not a simple
case of just ‘analysis’

23
Example of Typical Mercury
Species Witnessed in a Crude Oil

Mercury Species % of Total Hg

Particulate mercury 65
Amalgamated 45
Weakly bound 20
Dissolved mercury 35
Ionic mercury 15
Elemental mercury 14
Unknown species 5
Organo mercury <1

24
 Examples of Hg levels in SEAP
Hydrocarbon Liquids
Country Matrix Hg conc. (ppb/wt)
A Crude oil 20-200
B Crude oil 250-1000
C Condensate 20-40
D Condensate 150-300
E Crude oil 2-400
E Condensate 150-1000
F Crude oil 500-2000
G Crude Oil 100-150
E Prod. water <1-50
C Prod. water 20-100+
NB: Well-head samples can contain significantly
higher mercury levels!
25
Mercury Assets

26
Case Study Examples

Liquid Hg!
27
 Field Example
Export Gas
MEG
Produced Gas
Cooler Cooler LTS

Inlet Gas Discharge

Sepa Scrubber

Conden Heater

Conden
Separator
MEG/H2O

Produced Export
Fluid Oil
Prod
Sepa

Produced Liquid Hg Present

Water Mercury Detected

28
 LPG Example

Liquid mercury found trapped in low points of the chillers during

shutdown

Both propane and butane chillers had trapped liquid mercury

Mercury content measured at >1000 µg/m3 in both propane and
butane tanks.

Solution: mercury removal bed (MRU) commissioned

Mercury content of propane and butane reduced to the agreed
specification using the beds.

Prior to MRU, majority of the mercury was being offloaded with
the cargoes.

29
 Particulate and Pipeline Related Issues
Examples Mercury (mg/kg)
Oil Pipeline Wax 0.2 - 2

Oil Particulates 2 - 20
Oil Tank Sludge 18 - 4000
Gas Pipeline Sludge 1000 – 13000
(0.1 – 1.3%)
Pipeline Corrosion Residues/Dip tubes 1000 – 20000
(0.1 – 2%)
LP Flare Strainer/DPP Turbo Expander 4000 – 100000
solids (0.4 – 10%)

N.B: 1%/wt is equivalent to 10,000mg/kg of total mercury!

30
 Liquid Metal Embrittlement (LME)

 Crack initiated near the

flange weld on the outlet
nozzle of a Propane Cold
Box
 Elemental mercury was
found emerging from the
crack
 LME was identified as the
cause of failure

31
 Mercury Corrosion in SS Tubing
SEM image

Arrow shows the area where the

leakage was observed

32
 EDX Spectrum
EDX spectrum identifies the presence of a high level of mercury in the
base metal (316 stainless steel)

2,000
Hg Hg

1,500
Counts

1,000 Hg

500
O Si Ca Cr Fe

0
2 4 6 8 10 12 14
keV
33
 DST - Mercury Contamination!?

Background:
• Customer requested SGS to determine potential mercury
presence/contamination of their 3rd party 3-phase test separator prior to use
on their upcoming Drill Stem Test
• They wanted to ensure that the reservoir fluid samples were not
contaminated by mercury from the test separator

Our Role:
• Design a method that would enable the test separator to be tested as
accurately as possible
• Determine the total mercury levels in the outlet gas. Establish the test
separator background mercury concentration

Project results:
• Customer was able to conduct DST project knowing that should they
encounter mercury levels in the resulting reservoir fluids then they would
have a basis for determining if the mercury was due to the properties of the
reservoir fluids (inherent mercury) or because of test separator
contamination (external mercury)
34
 Summary

Mercury contamination of produced gas, condensate, and oil has
commercial, HSE, asset integrity, and legal impact for all
producers

Mercury is soluble in oil, water, and gas and can therefore
distribute itself throughout the entire operation

Produced solids, scales, and corrosion products can also
become significantly contaminated with mercury

Certain regions of the world are known to produce hydrocarbons
with elevated mercury concentrations – SEAP is one!

High temperature reservoirs produce more mercury than low
temperature reservoirs

Because the occurrence of mercury is difficult to predict, all
welltests should include mercury determination
35
 Thank you for your attention
Questions and Answers
Environment
Hide
Consumer Products Source Rock
Waste Streams

Refineries Reservoir
Chemical Plants
Hg
Pipelines Cycle!
Tankers

Gas, NGL's Pipelines

Sales Crude Gas & Liquids