Mercury Presentation

MERCURY… PETRONAS Research Sdn. Bhd.

PRESENTATION OUTLINE What is Mercury Mercury In The Oil and Gas Industry Managing Mercury in PETRONAS PRSB Hg Research Team

What is Mercury • 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

Types of Mercury Species HgCl2

HgR2

CH3Hg CH3

C2H5HgC2H5 HgR2 HgS

CH3HgC2H5

Hg2+

HgI2 Hgo

Hgo

Inorganic Mercury (HgCl2, HgS)

Elemental Mercury (Hg°) - Vapor and Metallic Liquid - Natural Gas and Air

- Soil, Sludge and Water - Solid and Ionic Liquid

Organic Mercury (R2Hg) - Natural Gas, Air, Liquid Hydrocarbon - Water and Biomasses - Vapour and Organic Liquid

Sources of Mercury Natural sources

Anthropogenic sources

Volcanoes.

Combustion point sources.

Weathering of rocks.

Industrial and domestic discharge.

Industrial Sources of Mercury

Paints industries

Coal fired power plants

Chlorine and caustic soda plants

Electrical industries

Petroleum industries

Broad Spectrum Impact of Mercury

Bio Accumulates

Hg accumulation

[Hg] increases higher the food chain

Harmful to Health

Minamata Incident

Harmful to Process Equipment

Harmful to Environment

Al Heat Exchanger

Global Hg dispersion (weather)

Liq. Metal Embrittlement (LME)

Environ. Hg Cycle

Work - PPE

Health Effects Mercury

Brain neuron Degeneration (Study by Uni. Of Calgary)

Memory Loss

Birth defects/retardation (Minamata Children)

Excessive body tremors

Mood swings Uncontrollable nervousness

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.

PRESENTATION OUTLINE What is Mercury Mercury In The Oil and Gas Industry Managing Mercury in PETRONAS PRSB Hg Research Team

Mercury In The Oil & Gas Industry ¾ Hg exist in trace levels in natural gas, condensate and crude oil as natural non hydrocarbon contaminant. ¾ Oil and gas contributed about 16% of total Hg contamination (1986). ¾

Harmful to hydrocarbon processing plants.

¾

Can accumulate / deposit inside process units / metals.

¾

Health hazards / exposure to workers.

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

Men at work

Elemental Mercury

Mercury In The Oil & Gas Industry ¾ Different concentration of Hg depending on the geographic locations. Location

Mercury Concentration Gas (µg m -3)

Liquids (µg kg-1)

100 - 150

-

50 - 120

50 - 100

100 - 400

400 - 1200

80 - 100

500 - 1000

0.02 - 0.4

-

5 - 15

1–5

North Africa

50 - 80

20 – 50

Malaysia

1- 200

10- 100

200 - 300

10 - 500

Europe South America Gulf of Thailand Africa Gulf of Mexico USA) Overthrust Belt (USA)

Indonesia

Estimated world levels of Mercury in natural gas and condensate • 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).

Mercury In The Oil & Gas Industry ƒ Equipment corrosion (aluminum and welded area) ƒ Stress cracking ƒ Liquid metal enbrittlement ƒ Aluminum oxidation ƒ Catalyst Poisoning ƒ Deactivation of active sites ƒ Hydrogenation catalyst ƒ Contaminated spent catalyst / adsorbent ƒ Contaminated process units and products ƒ Decontamination process ƒ Health and safety concerns ƒ Lower product value / Off spect ƒ Possible explosion ƒ Formation of Hg-N and Hg-N-O in ammonia plant

Aluminum Heat Exchanger

Catalyst deactivation

Filter change out

Mercury In Malaysia

Hg Concern

Lawit

LA JE

Jerneh Talisman

RDS ANG JDS

Resak

Beranang Guntong D

Angsi

Bekok C Sotong Collector

Duyong

¾ Trend on mercury concentration from offshore hydrocarbon is increasing.

Distribution of Mercury in PETRONAS facilities

Liquefaction

LNG

Export

Upstream

Gas Processing Plants Petrochemical Refineries Plants & Export

End User

¾ Mercury is being distributed along our pipelines, process units and final products

PRESENTATION OUTLINE What is Mercury Mercury In The Oil and Gas Industry

Managing Mercury in PETRONAS PRSB Hg Research Team

Mercury Management is the Niche Technology as in PETRONAS Technology Agenda approved by PETRONAS MC A Leading Oil & Gas Multinational of Choice

Aspiration/ Vision

by Businesses Leadership in selective technology; leveraging new technology for future positioning

Technology Vision E&P • Integrated Seismic Technology • Integrated Basin Analysis • Reservoir Characterisation Focus Areas & Modeling for Future Oil Positioning • Enhanced Recovery (Water Alternating Gas) • CO2 Management

GAS

• Mercury Management • Stranded Gas Monetisation with Floating Facilities

OIL

• Refining Catalysis Technology • Development of Top Tier/ OEM Lubes • Treatment of Low Quality Crudes

PETCHEM

• Bio-Polymers • Nano Polymer Compounds • Alternative Feedstock Technology • New Value Added Derivatives

NEW ENERGY RESOURCE

FRONTIER TECHNOLOGY

• Unconventional Hydrocarbons

• Nanotechnology

– Heavy Oil – Oil Shale – Methane Hydrates – Oil Sands

• Hydrogen • Green Technologies

• Solar

• Biofuels

• Biomass

• Biolubes

• Clean Coal Technology

New Energy Resources

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

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 Build conviction that “Technology creates Value”

Ver 3 - approved on 3 March 2008

Revised as key technology under the E & P

PETRONAS Mercury Management Roadmap ••Hg HgComprehensive ComprehensiveStudy Study ••Develop Hg Database Develop Hg Database(Hg (Hglevel levelfor forcurrent, current,new new and andfuture futurefields) fields) ••Assess AssessCurrent CurrentAvailable AvailableTechnologies Technologies ••Formulate and set research Formulate and set researchpriorities prioritiesfor for mercury mercurymitigation mitigationprogram program •• Enhance Enhance Hg Hg Mitigation Mitigation Program Program and and Hg Hg Risk Risk Assessment Assessment •• Identify Identify Future Future Requirements Requirements

M

RM E 2005 RT T O SH

Niche player in Hg Management

2009

2008 2007

2006

2010

M IU D E

RM E T

N LO

G

R TE

M

••Operate OperateHg Hgremoval removaltechnologies technologies ••Bench-scale Bench-scaleTask TaskSpecific SpecificIonic Ionic Liquids developed Liquids developed

••Short-listing Short-listingviable viabletechnologies technologiesand and development developmentofofnew newtechnologies technologies ••Piloting Pilotingofofnew newtechnologies technologies ••Embark Embarkon onresearch researchprojects: projects:Removal Removal– –Ionic Ionic Liquids, Measurement – OMMS Liquids, Measurement – OMMS •• Setting Settingup upHg HgManagement Management Committee Committee • Preliminary Study • Preliminary Study •• Baseline BaselineStudy Study&&Mercury MercuryMapping Mapping •• Control Diagnostic Control Diagnostic

PRSB Journey in Mercury Studies

Over 15 years experience

2003 1999 1997 1993

1989

y First research project on Hg for PGB y Develop anal. technique – Conventional & Unconventional

y Received first Hg Analyser (PSA) y Establish anal. method for gas and water sample y Initiate Hg Analytical & Monitoring Program y Hg removal pilot plant study at GPP1

y Hg Assessment for 8 OPUs y Performance Evaluation of MRU (PGB) y Establish sampling and AnalMethod for C3 & C4 y Study the effects of Hg on process units

y Most comprehensive Hg analytical facilities in Malaysia y Develop inhouse methods: - Total Hg y New Hg analyser Analyzer* & Hg y Provide support & Speciation (PhD) technical consultancy y Evaluation of MRU services for OPUs & Adsorbent third parties y Establish anal. & y Establish linkage with monitoring Prog for other lab & OPUs & third parties companies outside Malaysia y Provide technical support for OPUs

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

700

BEFORE coalescer AFTER coalescer 600

AFTER MRU

500

400

300

200

100

0

Ti me ( d a t e : hr s)

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

PRSB Journey in Mercury Studies Over 15 years experience

2007 - beyond 2006 2005

2004

y Hg bed performance and verification for PGB Miri y Development of Hg Mgmt precedure for Peninsular Malaysia Operation(PMO) begain y Develop Hg Hazmat handling for PMO y Hg awareness for PGB and PCSB y Develop Hg Hazmat procedure for Pigging and cleaning y Develop Hg Specific Health Risk assessment for PMO

y Hg bed performance and verification for PGB y Develop Hg Bed Profile study for MLNG y Develop and implement Hg Handling procedure for PMO y Complete Hg Baseline study for GPP A and B facilities y Evaluation of Hg removal technology for raw natural gas condensate

y Pilot study for removal for produced water y Hg Assessment for resak y Development of online production facilities mercury measurement y Hg Assessment for system for High Pressure Yetagun and Kambauk, liquid Hydrocarbon Myanmar. y Development of ionic liquid y First Hg Removal for for Hg removal in various Raw Condensate project hydrocarbon streams. executed y Development of PETRONAS y Hg Performance study (in-house ) Hg management for Raw Condensate procedure and guideline Removal Installation y Evaluation of potential technology for Hg removal for produced water y Pilot study for removal for produced water

Mercury Niche Technology in PETRONAS Hg Niche Technology

Removal & Disposal

Measurement

• Hg removal from raw condensate • Online Hg Measurement • Hg removal from produced water: System 9 SAAMS filters 9 Bentonite based adsorbent

Treatment

• Task Specific Ionic Liq’s

Mercury Niche Technology in PETRONAS Removal & Disposal 1. Hg Removal From Raw Condensate at OGT Kertih (MRU) ¾ World’s first mercury removal unit for liquid hydrocarbon application (NG condensate). ¾ Installed at RDS and JDS (OGT).

C A B Colour of condensate before and after MRU

JDS Mercury Removal System Onshore Gas Terminal, Kerteh

JDS Mercury Removal System Fully Installed and Completed

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

RDS Mercury Removal System Onshore Gas Terminal, Kerteh

RDS Mercury Removal System Fully Installed and Completed

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

Mercury Niche Technology in PETRONAS Removal & Disposal 2. Hg Removal in Produce Water (RESAK Platform) - SAAMS ¾ SAMMS ~ Self-Assembled Monolayers on Mesoporous Supports. ¾ Created by attaching a monolayer of molecules to mesoporous ceramic supports. ¾ A thiol-functional group attached at the each free end of the monolayer is designed to selectively bind mercury molecules.

Self-assembled monolayers on mesoporous supports (SAMMS)

Self-assembled monolayers PECO + DIALOG, INTERTEK, PRSB

Mercury Niche Technology in PETRONAS Test Results for SAAMS

• • •

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.

Mercury Removal from Produced Water – Resak Platform (SAAMS)

Test rig

Filter change out

SAMMS filters

Sampling

Troubleshooting

Analysis

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

Removal & Disposal

3. Hg Removal in Produce Water (RESAK Platform) – Bentonite (organoclay) 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.

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

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

Although operating at high flow rate, the adsorbent is still able to remove Hg effectively (< 2ppb).

Mercury Niche Technology in PETRONAS Measurement Development of Online Mercury Measurement System for High Pressure Liquid Hydrocarbon Hg monitoring of MRU is conducted manually (sampling and analysis).

Current practice

Laborious & may lead to personnel exposure as well as inaccurate results. Hg monitoring is expensive.

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

OMMS

Mercury Niche Technology in PETRONAS

Process Streams (e.g. MRU)

Manual Sampling

Manual Analysis

Manual approach

Sample Introduction System

Sample Treatment

Detection System

A fully Automated System

Data Logging System

Mercury Niche Technology in PETRONAS

Treatment

Development of Task Specific Ionic Liquids for Mercury Removal for applications in the Petroleum Industry ¾ Allows for custom designed IL that exhibit the necessary chemical, physical and toxicological attributes needed to remove mercury. Task Specific ILs

¾ Removal of various species of mercury from various hydrocarbon streams. ¾ Portrays PETRONAS as being distinctive in the area of mercury management.

Onshore

Offshore

Heavy Metals Removal Studies (Bioremediation) Heavy Metals

Phytoremediation*

Hg Removal (PPMSB)

Biological/Chemical

Screen various plants

Land farm Mercury Arsenic

Sludge farm

Lead Sampling

*Treatment or removal of heavy metals utilizing plants.

Lab analysis

PETRONAS Mercury Management Guideline (PHgMG)

8 Chapter collection

The Mercury Management Committee (away-day)

• • • •

Worlds first Mercury Management Guideline. Championed by GBU. Contains 8 Chapters. Covers everything from sampling, analysis, engineering, HSE, waste handling, and more.

Handover ceremony to GTS completed

PETRONAS Mercury Management Guideline (PHgMG) Area Coverage in PHgMG CHAPTER 0

AREA COVERAGE Preface

CHAPTER 1

Background

CHAPTER 2

Hg Sampling in Various Mediums

CHAPTER 3

Hg Measurement

CHAPTER 4

Hg Risk Management

CHAPTER 5

Hg Removal System

CHAPTER 6

Hg Decontamination Guidelines

CHAPTER 7

Hg Waste Management

CHAPTER 8

Hg Emergency Response Plan (ERP)

PETRONAS Mercury Management CoP on AXIS

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

PETRONAS Mercury Management Yesterday, Today and Tomorrow

Development of task specific ionic liquid mercury removal for various streams 2007-2010 On-line mercury measurement system for high pressure condensate 2007-2010 Jointly developed PETRONAS first guideline Hg on management 2007-2008 Mercury removal for produced water 2006-2007 Mercury speciation study for GPP including flaring system 2006 Mercury speciation study for Resak 2006 Mercury removal project for high pressure raw NG condensate 2005-2006 Mercury removal for naphtha stream (PPMSB) 2002 Development of mercury management procedure 2004 Mercury removal Bed Profiling 2003-2005 Development of Mercury Speciation for light liquid hydrocarbon 1998-1999 Development of Rapid method for total mercury for NG condensate 1996-1999 Mercury base line study for various PETRONAS OPUs 1997, 2002, 2004, 2005, 2006 Mercury Removal in Malaysian Natural Gas pilot plant study 1989

Achievements Ongoing project/s

PRESENTATION OUTLINE What is Mercury Mercury In The Oil and Gas Industry Managing Mercury in PETRONAS

PRSB Hg Research Team

PETRONAS Research SDN. BHD.

PETRONAS Research SDN. BHD. 2006 Petroleum Research & Scientific Services 1992 Petroleum Research Institute 1988 Laboratory Service Dept. 1978

Hg Research Team Members

Dr. Azman Bin Shafawi

Tg M Uzaini Bin Tg Mat

Sharizal Bin M Azam Shah Wong

M Hanif Bin M Halim

Mahpuzah Bt Abai

M Faizal Bin Taha

Mercury Testing Facilities at PRSB Portable Hg Analyser

Merlin - Cold Vapour Atomic Flouresence Spectrometry

Total Mercury Analyser - Vaporiser-AFS

PSA Sir Galahad - Mercury vapour analyser

Adsorption Rig for Hg Adsorbent Test

FIMS - Cold Vapour Atomic Adsorption Spectrometry Mercury Speciation -GC-AFS

PRSB Hg Research Team Community Linkages PETRONAS OPUs

Service Entities

Technology Entities

Universities

Working together directly and/or indirectly with selected entities.

Thank You