Technical Response in the Field of Gas Chromatography to Changing Market and Technology Demands Technical Response in the Field of Gas Chromatography to Changing Market and Technology Demands 1

Introduction to Bahrain Petroleum Company (Bapco)  Bapco was formed in 1929 and has been the cornerstone of the Kingdom of Bahrain’s economic development: Bapco was established by Standard Oil Company of California (SOCAL) and TEXACO….. CALTEX  Bapco is now 100% owned by the Government of Bahrain, and is an integrated oil and gas company  Oil was first discovered in Bahrain in 1932 Striving for Excellence 2

Bahrain Refinery  Bapco operates the Bahrain Refinery - a world- class, world-scale refinery, exporting products to the world  First day of operation of the Refinery was 12 July we are over 70 years old  Capacity267,000bpd  Employees3120 3

Recent Bapco Achievements Bapco has successfully managed to : Commissioned the LSDP Project in 2007: able to produce Euro V ultra low sulphur diesel Commissioned the LSDP Project in 2007: able to produce Euro V ultra low sulphur diesel Commissioned Refinery Gas Desulphurisation Project in 2009: desulphurisation of all process gases Commissioned Refinery Gas Desulphurisation Project in 2009: desulphurisation of all process gases Received the Robert Campbell Award from the National Safety Council of the US in October first ever company outside of North America, and first refiner, to receive the award Received the Robert Campbell Award from the National Safety Council of the US in October first ever company outside of North America, and first refiner, to receive the award Received the British 5-star award in 2008 Received the British 5-star award in 2008 Spending $350 million on environmental projects: with no return on investment Spending $350 million on environmental projects: with no return on investment Striving for Excellence 4

Overview  Chronology of the rise and fall of oxygenated gasoline  Effects of MTBE chemical and physical properties in contamination of environment and refinery processes  Sources of MTBE contamination entering into refinery processes  Role of analytical laboratories in prevention of MTBE contamination  Methods of analysis of MTBE/oxygenates as constituent of gasoline  Summary of the study carried out by Bahrain Petroleum Refinery Laboratory  Challenges/Advantages /Gaps  Challenges /Advantages /Gaps Concluding Remarks  Concluding Remarks Striving for Excellence 5

Methyl Tertiary-Butyl Ether MTBE Production  First synthesized in the early 1960s and commercial production began in 1979  Classified as a volatile organic compound (VOC)  Produced by a chemical reaction between methanol and isobutylene Striving for Excellence 6

Gasoline Changing Specs. of Auto Fuels MTBE used in gasoline since late 1970s Started increasing during 1990s Lower Benzene Restrictions on Olefin & Aromatics Decrease emissions of CO Striving for Excellence 7

Why is MTBE an Environmental Issue? 8

Trace Oxygenates entering the Environment  Ethers in gasoline (MTBE, ETBE, TAME) in underground tanks  Problems with groundwater contamination  Greater toxicity than alcohol additives Striving for Excellence 9

Over ground Underground Petroleum Industry Discharge of MTBE Striving for Excellence 10

Chemical Structures Ethers Striving for Excellence 11

Physical Properties of Fuel Oxygenates CompoundMol.WtBP(ºc) Density g/mL Water Solubility MTBE g/100mL ETBE <0.1g/100mL (21ºc) TAME – DIPE g/100mL TAEE116.2––– TBA Miscible TAA – Methanol Miscible Ethanol Miscible Water181001NA Striving for Excellence 12

MTBE Phase out Striving for Excellence 13

REFINERY Refinery Waste Generation & Catalyst Poisoning Receiving feed stock Produced Waste water Product Export Tank Bottom Slop Oils CATALYST POISONING Striving for Excellence 14

Composition of Crude Oil Striving for Excellence Crude Oil does not naturally contain alkyl ethers 15

Effects of Trace Oxygenates in Refinery Traces of oxygenates poison catalyst resulting in:  Lower production yields  Lower product quality Striving for Excellence 16

Contamination Monitoring by Laboratory Testing Striving for Excellence Petroleum Laboratory 17

Method DescriptionMethod Detection range Determination of hydrocarbon types and oxygenates in automotive-motor gasoline — Multidimensional gas chromatography method IP % (V/V) Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol and C1 to C4 Alcohols in gasoline by GC ASTM D %m/m Oxygenates in gasoline by GC and oxygen Selective Flame Ionization Detector ASTM D % m/m Oxygenates, benzene, toluene C8-C12 aromatics and total aromatics in finished gasoline Gas Chromatography/ Fourier Transform Infrared Spectroscopy ASTM D (2006) %V/V Hydrocarbon Types, Oxygenated Compounds and Benzene in Spark Ignition Engine Fuels by Gas Chromatography ASTM D6839(2007) >15%V/V Determination of individual Components in Spark Ignition Engine Fuels by 100Metre Capillary High Resolution GC ASTM D 6729(2004) 1-30 %m/m Standard Test Method for Determination of Methanol in Crude Oils by Multidimensional Gas Chromatography ASTM D e1 15 to 900 ppm (m/m) Some Established Analytical Methods for MTBE and Other Oxygenates in Petroleum Products Striving for Excellence 18

Naphtha Crude Oil Slop Oil Analysis of Oxygenates by Multidimensional Gas Chromatography Striving for Excellence BAPCO Refinery Laboratory Trace MTBE Gas Chromatograph Back Channel Front Channel 19

Parameters Front Channel Back Channel IntroductionAutomatic Liquid Samplers Injection System Split/split lessTPI Sample Type Crude Oil/Slop OilNaphtha Calibration Technique Internal StandardExternal Standard Valve Switch System Dean Switch GC Configuration for Analysis Oxygenates Striving for Excellence 20

GC Operating Conditions Striving for Excellence 21

Front Channel: Chromatogram of the Internal Calibration Standard for Crude Oil/ Slop Oil Striving for Excellence 22

OxygenatesOriginal RT1st run2nd run3rd run4th run5th run6th run7th run MTBE Retention Time Comparisons of MTBE, in the Front Channel Striving for Excellence 23

Back Channel: Chromatogram of the External Calibration Standard for naphtha analysis Striving for Excellence 24

OxygenatesOriginal RT1st run2nd run3rd run4th run5th run6th run7th run ETBE MTBE DIPE Retention Time Comparisons of MTBE, ETBE, DIPE in the Back Channel Striving for Excellence 25

Challenges for Analysis of Oxygenates Chromatographic Resolution  Difficult resolution of DIPE, MTBE, ETBE and variance in the Elution times Sensitivity  To measure oxygenates down to low ppm  Peak Tailing and shape, especially for MTBE in Crude Oil Striving for Excellence 26

Striving for Excellence Overlaid Chromatograms with retention shift 27

Striving for Excellence Overlaid Chromatograms without retention shift 28

Advantages  No Matrix effects of light hydrocarbons on oxygenates elution in naphtha samples  High temperature tolerance 350°C with no column bleed Striving for Excellence 29

Methods under Development for Analysis of Oxygenates in Hydrocarbon Two further ASTM standard methods are proposed for approval using OxyPLOT column  Determination of C1 to C5 Oxygenates at Trace Levels in High Ethanol Content Gasoline by Multidimensional Chromatography  Determination of Oxygenates in Ethene, Propene, C4 and C5 Hydrocarbon by Gas Chromatography Striving for Excellence 30

Current Gaps in Analysis of Trace Oxygenates in Petroleum Samples  No standard Test Method for Trace Oxygenates in Crude oil/ Slop Oil  Requirement for further development of trace oxygenates in Naphtha Striving for Excellence 31

Concluding Remarks Striving for Excellence The two-dimensional GC technique, despite the challenges, has shown itself to be not only cost effective but also one of the most practical analytical tools for this type of trace analysis. This is due to the Deans switch system using heart cut to resolve analytes from one column to another, which yields a faster analysis time. This work requires further development to enable improved optimisation of operating conditions. 32

Thank You شــكراً Striving for Excellence 33

Dean Switch Column Flow Striving for Excellence 34

Capillary Flow Heart-Cutting 2-D GC Deans Switch Striving for Excellence 35