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

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

2. 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

3. 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 1936 - we are over 70 years old • Capacity 267,000bpd • Employees 3120

4. Recent Bapco Achievements Bapco has successfully managed to : • 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 • Received the Robert Campbell Award from the National Safety Council of the US in October 2007 - first ever company outside of North America, and first refiner, to receive the award • Received the British 5-star award in 2008 • Spending $350 million on environmental projects: with no return on investment Striving for Excellence

5. 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 • Concluding Remarks Striving for Excellence

6. 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

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

8. Why is MTBE an Environmental Issue? Striving for Excellence

9. 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

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

11. Chemical Structures Ethers Striving for Excellence

12. Physical Properties of Fuel Oxygenates Striving for Excellence

13. MTBE Phase out Striving for Excellence

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

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

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

17. Contamination Monitoring by Laboratory Testing Petroleum Laboratory Striving for Excellence

18. Some Established Analytical Methods for MTBE and Other Oxygenates in Petroleum Products Striving for Excellence

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

20. GC Configuration for Analysis Oxygenates Striving for Excellence

21. GC Operating Conditions Striving for Excellence

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

23. Retention Time Comparisons of MTBE, in the Front Channel Striving for Excellence

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

25. Retention Time Comparisons of MTBE, ETBE, DIPE in the Back Channel Striving for Excellence

26. 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

27. Overlaid Chromatograms with retention shift Striving for Excellence

28. Overlaid Chromatograms without retention shift Striving for Excellence

29. 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

30. Methods under Development for Analysis of Oxygenates in Hydrocarbon Two further ASTM standard methods are proposed for approval using OxyPLOTcolumn • 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

31. 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

32. Concluding Remarks 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. Striving for Excellence

33. Thank You شــكراً Striving for Excellence

34. Dean Switch Column Flow Striving for Excellence

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