MERCURY…PETRONAS Research Sdn. Bhd.

What is Mercury

PRSB Hg Research Team

Managing Mercury in PETRONAS

Mercury In The Oil and Gas Industry

PRESENTATION OUTLINE

• Mercury occurs in hydrocarbons as a natural occurring geological contaminant

• Distribution of mercury species depends on the type of medium.

• A toxic contaminant, dangerous to personnel, can affect HSE and also the integrity of plant equipments

• Harmful to health, process equipment and environment

What is Mercury

HgCl2

CH3Hg CH3

Hgo

HgS

C2H5HgC2H5

CH3HgC2H5Hg2+HgI2

HgR2

- Vapor and Metallic Liquid- Natural Gas and Air

Hgo

HgR2

- Natural Gas, Air, Liquid Hydrocarbon- Water and Biomasses- Vapour and Organic Liquid

- Soil, Sludge and Water- Solid and Ionic Liquid

Elemental Mercury (Hg°)

Organic Mercury (R2Hg)

Inorganic Mercury (HgCl2, HgS)

Types of Mercury Species

Volcanoes.

Anthropogenic sourcesNatural sources

Weathering of rocks.

Combustion point sources.

Industrial and domestic discharge.

Sources of Mercury

Industrial Sources of Mercury

Electrical industries

Chlorine and caustic soda plants

Paints industries

Petroleum industries

Coal fired power plants

Broad Spectrum Impact of Mercury

Hg accumulation

Harmful Harmful to Healthto Health

Harmful to Harmful to Process EquipmentProcess Equipment

Harmful to Harmful to EnvironmentEnvironment

Bio Bio AccumulatesAccumulates

Al Heat Exchanger

Liq. Metal Embrittlement

(LME) Environ. Hg Cycle

Global Hg dispersion (weather)

Work - PPE

Minamata Incident

[Hg] increases higher the food chain

Health Effects Mercury

Excessive body tremors Brain neuron Degeneration (Study by Uni. Of Calgary)

Birth defects/retardation(Minamata Children)

Uncontrollable nervousness

Mood swingsMemory Loss

Source: USEPA Health Effects of Mercury

DISCLAIMER: Symptoms not solely caused by Hg poisoning. May also be caused by other toxic substances/diseases. Symptoms of Hg posoning may also display in other forms.

What is Mercury

PRSB Hg Research Team

Managing Mercury in PETRONAS

Mercury In The Oil and Gas Industry

PRESENTATION OUTLINE

Hg exist in trace levels in natural gas, condensate and crude oil as natural non hydrocarbon contaminant.

Oil and gas contributed about 16% of total Hg contamination (1986).

Harmful to hydrocarbon processing plants.

Can accumulate / deposit inside process units / metals.

Health hazards / exposure to workers.

Mercury In The Oil & Gas Industry

Explosion at Sonatrach’s-Skikda (Algeria) LNG Plant

Elemental Mercury Men at work

Mercury In The Oil & Gas Industry

Estimated world levels of Mercury in natural gas and condensate

Mercury ConcentrationLocation

Gas (µg m -3)

Liquids(µg kg-1)

Europe 100 - 150 -

South America 50 - 120 50 - 100

Gulf of Thailand 100 - 400 400 - 1200

Africa 80 - 100 500 - 1000

Gulf of Mexico USA) 0.02 - 0.4 -

Overthrust Belt (USA)

5 - 15 1 – 5

North Africa 50 - 80 20 – 50

Malaysia 1- 200 10- 100

Indonesia 200 - 300 10 - 500

• Bigham, M.D., " Field Detection and Implications of Mercury in Natural Gas", SPE Prod. Eng., May 1990, 120-124.

• Wilhelm, S.M., and McArthur, A., "Removal and Treatment of Mercury Contamination at Gas Processing Plant", Soc. of Pet. Eng., (SPE No. 29721).

Different concentration of Hg depending on the geographic locations.

Equipment corrosion (aluminum and welded area)ƒ Stress crackingƒ Liquid metal enbrittlementƒ Aluminum oxidation

Catalyst Poisoningƒ Deactivation of active sitesƒ Hydrogenation catalystƒ Contaminated spent catalyst / adsorbent

Contaminated process units and productsƒ Decontamination processƒ Health and safety concernsƒ Lower product value / Off spect

Possible explosionƒ Formation of Hg-N and Hg-N-O in ammonia plant

Aluminum Heat Exchanger

Catalyst deactivation

Filter change out

Mercury In The Oil & Gas Industry

Mercury In Malaysia

Jerneh

Lawit

Resak

Duyong

Bekok C

Angsi

Guntong D

Sotong Collector

Beranang

Talisman

ANG

JE

LA

JDS

RDS

Trend on mercury concentration from offshore hydrocarbon is increasing.

Hg Concern

Mercury is being distributed along our pipelines, process units and final products

Gas ProcessingPlants

Liquefaction

Petrochemical Plants

LNG Export

End User

Upstream

Refineries & Export

Distribution of Mercury in PETRONAS facilities

What is Mercury

PRSB Hg Research Team

Managing Mercury in PETRONAS

Mercury In The Oil and Gas Industry

PRESENTATION OUTLINE

Mercury Management is the Niche Technology as in PETRONAS Technology Agenda approved by PETRONAS MC

FRONTIER TECHNOLOGY

NEW ENERGY RESOURCE

PETCHEMOILGASE&P

Leadership in selective technology; leveraging new technology for future positioning

A Leading Oil & GasMultinational of Choice

• Integrated Seismic Technology

• Integrated Basin Analysis

• Reservoir Characterisation & Modeling

• Enhanced Oil Recovery (Water Alternating Gas)

• CO2 Management

New Energy Resources

• Mercury Management

• Stranded Gas Monetisationwith Floating Facilities

• Nanotechnology• Hydrogen • Green

Technologies

Focus Areas for Future

Positioning

Aspiration/ Vision

Build strong capabilities in technology focus areas in E&P, Gas, Oil and Petchem in line with the Corporate Agenda as well as to position PETRONAS for future competitive advantage

Develop highly qualified technical leaders to spearhead development of key, pacing and emerging technologies by driving technology initiatives from concept until implementation

Build conviction that “Technology creates Value”

Technology Vision

Triple Plus

Targets

• Refining Catalysis Technology

• Development of Top Tier/ OEM Lubes

• Treatment of Low Quality Crudes

• Biofuels

• Biolubes

• Bio-Polymers

• Nano Polymer Compounds

• Alternative Feedstock Technology

• New Value Added Derivatives

• Unconventional Hydrocarbons

– Heavy Oil– Oil Shale– Methane

Hydrates– Oil Sands

• Solar

• Biomass

• Clean Coal Technology

by Businesses

Ver 3 - approved on 3 March 2008 Revised as key technology under the E & P

2005

2006

2007

2008

2009

• Setting up Hg Management Committee

• Preliminary Study• Baseline Study & Mercury Mapping• Control Diagnostic

• Setting up Hg Management Committee

• Preliminary Study• Baseline Study & Mercury Mapping• Control Diagnostic

• Enhance Hg Mitigation Program and Hg Risk Assessment

• Identify Future Requirements

• Enhance Hg Mitigation Program and Hg Risk Assessment

• Identify Future Requirements

• Hg Comprehensive Study• Develop Hg Database (Hg level for current, new

and future fields)• Assess Current Available Technologies• Formulate and set research priorities for

mercury mitigation program

• Hg Comprehensive Study• Develop Hg Database (Hg level for current, new

and future fields)• Assess Current Available Technologies• Formulate and set research priorities for

mercury mitigation program

SHORT TERM

MEDIUM TERM

LONG TERM

• Operate Hg removal technologies• Bench-scale Task Specific Ionic

Liquids developed

• Operate Hg removal technologies• Bench-scale Task Specific Ionic

Liquids developed

• Short-listing viable technologies and development of new technologies

• Piloting of new technologies• Embark on research projects: Removal – Ionic

Liquids, Measurement – OMMS

• Short-listing viable technologies and development of new technologies

• Piloting of new technologies• Embark on research projects: Removal – Ionic

Liquids, Measurement – OMMS

2010Niche player in Hg Management

PETRONAS Mercury Management Roadmap

20031999

1997

1993

1989

First research project on Hg for PGBDevelop anal.

technique –Conventional & Unconventional

Received first Hg Analyser (PSA)Establish anal.

method for gas and water sampleInitiate Hg

Analytical & Monitoring ProgramHg removal pilot

plant study at GPP1

Hg Assessment for 8 OPUs Performance

Evaluation of MRU (PGB)Establish sampling

and AnalMethod for C3 & C4Study the effects

of Hg on process units

Develop inhouse methods: - Total Hg Analyzer* & Hg Speciation (PhD)Evaluation of MRU

AdsorbentEstablish anal. &

monitoring Prog for OPUs & third partiesProvide technical

support for OPUs

*Technique has won the first prize: Innovative Category by Royal Society of Chemistry (RIC), UK (March 2000) & technique is adopted by PSA latest analyser.

Most comprehensive Hg analytical facilities in MalaysiaNew Hg analyserProvide support &

technical consultancy services for OPUs & third partiesEstablish linkage with

other lab & companies outside Malaysia

Over 15 years experience

PRSB Journey in Mercury Studies

COALESCER PERFORMANCE-JDS (30/04/06 - 18/10/06)

0

100

200

300

400

500

600

700

Ti me ( d a t e :hr s)

BEFORE coalescer

AFTER coalescer

AFTER MRU

2007 - beyond2006

20052004

Hg bed performance and verification for PGB MiriDevelopment of Hg

Mgmt precedure for Peninsular Malaysia Operation(PMO) begainDevelop Hg Hazmat

handling for PMO Hg awareness for PGB

and PCSBDevelop Hg Hazmat

procedure for Pigging and cleaningDevelop Hg Specific

Health Risk assessment for PMO

Hg bed performance and verification for PGBDevelop Hg Bed

Profile study for MLNGDevelop and

implement Hg Handling procedure for PMOComplete Hg Baseline

study for GPP A and B facilitiesEvaluation of Hg

removal technology for raw natural gas condensate

Hg Assessment for resakproduction facilitiesHg Assessment for

Yetagun and Kambauk, Myanmar. First Hg Removal for

Raw Condensate project executedHg Performance study

for Raw Condensate Removal InstallationEvaluation of potential

technology for Hg removal for produced waterPilot study for removal

for produced water

Pilot study for removal for produced waterDevelopment of online

mercury measurement system for High Pressure liquid HydrocarbonDevelopment of ionic liquid

for Hg removal in various hydrocarbon streams.Development of PETRONAS

(in-house ) Hg management procedure and guideline

Over 15 years experience

PRSB Journey in Mercury Studies

Mercury Niche Technology in PETRONAS

Hg Niche TechnologyHg Niche Technology

Removal & DisposalRemoval & Disposal MeasurementMeasurement TreatmentTreatment

• Hg removal from raw condensate• Hg removal from produced water:

SAAMS filtersBentonite based adsorbent

• Online Hg Measurement System

• Task SpecificIonic Liq’s

Mercury Niche Technology in PETRONAS

Removal & DisposalRemoval & Disposal

1. Hg Removal From Raw Condensate at OGT Kertih (MRU)

World’s first mercury removal unit for liquid hydrocarbon application (NG condensate).

Installed at RDS and JDS (OGT).

A B CColour of condensate before and after MRU

JDS Mercury Removal System Fully Installed and Completed

JDS Mercury Removal System Onshore Gas Terminal, Kerteh

The JDS MRU successfully removed Mercury with a removal efficiency of > 96%

RDS Mercury Removal System Fully Installed and Completed

RDS Mercury Removal System Onshore Gas Terminal, Kerteh

The RDS MRU successfully removed Mercury with a removal efficiency of > 99%

Removal & DisposalRemoval & Disposal

2. Hg Removal in Produce Water (RESAK Platform) - SAAMSSAAMS

Mercury Niche Technology in PETRONAS

SAMMS ~ Self-Assembled Monolayers on Mesoporous Supports.

Created by attaching a monolayer of molecules to mesoporousceramic supports.

A thiol-functional group attached at the each free end of the monolayer is designed to selectively bind mercury molecules.

Self-assembled monolayers onmesoporous supports (SAMMS)

Self-assembled monolayers

PECO + DIALOG, INTERTEK, PRSB

Mercury Niche Technology in PETRONAS

• Above chart indicate the performance of the adsorbent. Testing lasted > 25 days.• As the throughput (flowrate) into the test skid increased, the mercury concentration at

the outlet test skid will increased. • The lowest concentration (0-2 ppb) was achieved at 4.8 GPM (series), while the

highest concentration (18-25 ppb) was achieved at 9.7 GPM.

Test Results for SAAMS

SAMMS filtersTest rig Troubleshooting

Sampling AnalysisFilter change out

Mercury Removal from Produced Water – Resak Platform (SAAMS)

Removal & DisposalRemoval & Disposal

3. Hg Removal in Produce Water (RESAK Platform) – BentoniteBentonite ((organoclayorganoclay))

Mercury Removal from Produced Water – Resak Platform (Bentonite based adsorbent)

MR Media

• Ability to remove organic and elemental mercury.• Carrier: Sodium Bentonite coated with Quaternary Amine (avoid swelling due to H2O).

• Impregnated with sulfur.

MR (+) Media

• Ability to remove all types of mercury compounds.• Carrier: Sodium Bentonite coated with Quaternary Amine• Made utilizing silane (silicone + alkane) chemistry.• Impregnated with sulfur.

Tie in location of MercSorb adsorbent rig on Mercury Removal Test Skid.

Mercury Removal from Produced Water – Resak Platform (Bentonite based adsorbent)

Although operating at high flow rate, the adsorbent is

still able to remove Hg effectively (< 2ppb).

Mercury Niche Technology in PETRONAS MeasurementMeasurement

Development of Online Mercury Measurement System for High Pressure Liquid Hydrocarbon

OMMS

Automates entire monitoring process

Acquisition of ‘real-time’ mercury levels

Minimizes, if not eliminates personnel exposure during monitoring

Will be the first online Hg measurement system for high pressure liq. hydrocarbons

Hg monitoring of MRU is conducted manually(sampling and analysis).

Laborious & may lead to personnel exposureas well as inaccurate results.

Current practice

Hg monitoring is expensive.

Mercury Niche Technology in PETRONAS

Sample Introduction System

Manual Sampling Manual AnalysisProcess Streams (e.g. MRU)

Sample Treatment Detection System Data Logging System

A fully Automated System

Manual approach

Mercury Niche Technology in PETRONAS TreatmentTreatment

Development of Task Specific Ionic Liquids for Mercury Removal for applications in the Petroleum Industry

OffshoreOnshore

Task Specific ILs

Allows for custom designed IL that exhibit the necessary chemical, physicaland toxicological attributes needed to remove mercury.

Removal of various species of mercuryfrom various hydrocarbon streams.

Portrays PETRONAS as being distinctive in the area of mercury management.

Heavy Metals Removal Studies (Bioremediation)

Phytoremediation*

Heavy Metals

*Treatment or removal of heavy metals utilizing plants.

Hg Removal (PPMSB)

Screen various plants

ArsenicMercury

Lead

Land farm Sludge farm

Biological/Chemical

Lab analysisSampling

PETRONAS Mercury Management Guideline (PHgMG)

• Worlds first Mercury Management Guideline.• Championed by GBU.• Contains 8 Chapters.• Covers everything from sampling, analysis, engineering,

HSE, waste handling, and more.

The Mercury Management Committee (away-day)

Handover ceremony to GTS completed

8 Chapter collection

PETRONAS Mercury Management Guideline (PHgMG)

CHAPTER AREA COVERAGE

00

CHAPTERCHAPTER 11

CHAPTERCHAPTER 22

CHAPTERCHAPTER 33

CHAPTERCHAPTER 44

CHAPTERCHAPTER 55

CHAPTERCHAPTER 66

CHAPTERCHAPTER 77

PrefacePreface

BackgroundBackground

Hg Sampling in Various MediumsHg Sampling in Various Mediums

Hg MeasurementHg Measurement

Hg Risk ManagementHg Risk Management

Hg Removal SystemHg Removal System

Hg Decontamination GuidelinesHg Decontamination Guidelines

Hg Waste ManagementHg Waste Management

CHAPTERCHAPTER 88 Hg Emergency Response Plan (ERP)Hg Emergency Response Plan (ERP)

Area Coverage in Area Coverage in PHgMGPHgMG

PETRONAS Mercury Management CoP on AXIS

http://pww.axis.petronas.com.my/cop/cop_PETRONAS%20Mercury%20Management/default.aspx

Mercury Management Community of Practice

Achievements

Ongoing project/s

Mercury Removal in Malaysian Natural Gas pilot plant study 1989

Mercury base line study for various PETRONAS OPUs 1997, 2002, 2004, 2005, 2006

Development of Rapid method for total mercury for NG condensate 1996-1999

Development of Mercury Speciation for light liquid hydrocarbon 1998-1999

Mercury removal Bed Profiling 2003-2005

Development of mercury management procedure 2004

Mercury removal for naphtha stream (PPMSB) 2002

Mercury speciation study for Resak 2006

Mercury speciation study for GPP including flaring system 2006

Mercury removal project for high pressure raw NG condensate 2005-2006

Mercury removal for produced water 2006-2007

On-line mercury measurement system for high pressure condensate 2007-2010

Development of task specific ionic liquid mercury removal for various streams 2007-2010

Jointly developed PETRONAS first guideline Hg on management 2007-2008

PETRONAS Mercury Management Yesterday, Today and Tomorrow

What is Mercury

PRSB Hg Research Team

Managing Mercury in PETRONAS

Mercury In The Oil and Gas Industry

PRESENTATION OUTLINE

PETRONAS Research SDN. BHD.

Laboratory Service Dept. 1978

Petroleum Research Institute 1988

Petroleum Research & Scientific Services 1992

PETRONAS Research SDN. BHD. 2006

M Hanif BinM Halim

Sharizal Bin M Azam

Shah Wong

Dr. Azman Bin Shafawi Tg M Uzaini Bin Tg Mat Mahpuzah Bt Abai

Hg Research Team Members

M Faizal Bin Taha

Mercury Testing Facilities at PRSB

Portable Hg Analyser

Merlin - Cold Vapour Atomic

Flouresence Spectrometry

PSA Sir Galahad - Mercury vapour

analyser

Total Mercury Analyser - Vaporiser-AFS

Mercury Speciation -GC-AFS

Adsorption Rig for Hg Adsorbent

Test

FIMS - Cold Vapour Atomic

Adsorption Spectrometry

PRSB Hg Research Team Community Linkages

Technology EntitiesTechnology EntitiesService EntitiesService Entities

UniversitiesUniversities

PETRONAS PETRONAS OPUsOPUs

Working together directly and/or indirectly with Working together directly and/or indirectly with selected entities.selected entities.

Thank You