technical response in the field of gas chromatography to changing market and technology demands...

Technical Response in the Technical Response in the Field of Gas Chromatography Field of Gas Chromatography

to Changing Market and to Changing Market and Technology DemandsTechnology Demands

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Introduction to Bahrain Petroleum Introduction to Bahrain Petroleum Company (Bapco)Company (Bapco)

Bapco was formed in 1929 and has been the Bapco was formed in 1929 and has been the cornerstone of the Kingdom of Bahrain’s economic cornerstone of the Kingdom of Bahrain’s economic development: development:

Bapco was established by Standard Oil Bapco was established by Standard Oil Company of California (SOCompany of California (SOCALCAL) and ) and

TEXTEXACO….. ACO….. CALTEX CALTEX

Bapco is now 100% owned by the Government of Bapco is now 100% owned by the Government of Bahrain, and is an integrated oil and gas companyBahrain, and is an integrated oil and gas company

Oil was first discovered in Bahrain in 1932Oil was first discovered in Bahrain in 1932

Striving for Excellence

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Bahrain RefineryBahrain Refinery Bapco operates the Bapco operates the Bahrain RefineryBahrain Refinery - a - a

world-class, world-scale refinery, exporting world-class, world-scale refinery, exporting products to the worldproducts to the world

First day of operation of the Refinery was First day of operation of the Refinery was 12 July 1936 - we are over 70 years old12 July 1936 - we are over 70 years old

CapacityCapacity 267,000bpd267,000bpd EmployeesEmployees 31203120

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Recent Bapco AchievementsRecent Bapco Achievements

Bapco has successfully managed to :Bapco has successfully managed to :

Commissioned the LSDP Project in 2007: able to Commissioned the LSDP Project in 2007: able to produce Euro V ultra low sulphur dieselproduce Euro V ultra low sulphur diesel

Commissioned Refinery Gas Desulphurisation Project in Commissioned Refinery Gas Desulphurisation Project in 2009: desulphurisation of all process gases2009: desulphurisation of all process gases

Received the Robert Campbell Award from the National Received the Robert Campbell Award from the National Safety Council of the US in October 2007 - first ever Safety Council of the US in October 2007 - first ever company outside of North America, and first refiner, to company outside of North America, and first refiner, to receive the awardreceive the award

Received the British 5-star award in 2008Received the British 5-star award in 2008

Spending $350 million on environmental projects: with Spending $350 million on environmental projects: with no return on investmentno return on investment


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OverviewOverview

Chronology of the rise and fall of oxygenated Chronology of the rise and fall of oxygenated gasolinegasoline

Effects of MTBE chemical and physical properties in Effects of MTBE chemical and physical properties in contamination of environment and refinery processescontamination of environment and refinery processes

Sources of MTBE contamination entering into refinery Sources of MTBE contamination entering into refinery processesprocesses

Role of analytical laboratories in prevention of MTBE Role of analytical laboratories in prevention of MTBE contaminationcontamination

Methods of analysis of MTBE/oxygenates as Methods of analysis of MTBE/oxygenates as constituent of gasolineconstituent of gasoline

Summary of the study carried out by Bahrain Summary of the study carried out by Bahrain Petroleum Refinery LaboratoryPetroleum Refinery Laboratory

ChallengesChallenges /Advantages /Gaps/Advantages /Gaps Concluding RemarksConcluding Remarks


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Methyl Tertiary-Butyl Ether Methyl Tertiary-Butyl Ether MTBE ProductionMTBE Production

First synthesized in the early 1960s and First synthesized in the early 1960s and commercial production began in 1979commercial production began in 1979

Classified as a volatile organic compound Classified as a volatile organic compound (VOC)(VOC)

Produced by a chemical reaction between Produced by a chemical reaction between methanol and isobutylenemethanol and isobutylene


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Gasoline

Changing Specs. of Auto FuelsChanging Specs. of Auto Fuels

MTBE used in gasoline since MTBE used in gasoline since late 1970slate 1970sStarted increasing during Started increasing during 1990s1990s

Lower BenzeneLower BenzeneRestrictions on Olefin & Restrictions on Olefin & AromaticsAromaticsDecrease emissions of Decrease emissions of COCOStriving for

Excellence

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Why is MTBE an Environmental Issue?Why is MTBE an Environmental Issue?

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Trace Oxygenates entering the Trace Oxygenates entering the EnvironmentEnvironment

Ethers in gasoline (MTBE, ETBE, TAME) Ethers in gasoline (MTBE, ETBE, TAME) in underground tanks in underground tanks

Problems with groundwater Problems with groundwater contaminationcontamination

Greater toxicity than alcohol additivesGreater toxicity than alcohol additives


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Over ground

Underground

Petroleum Industry Discharge of MTBEPetroleum Industry Discharge of MTBE


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Chemical Structures Chemical Structures EthersEthers


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Physical Properties of Fuel Physical Properties of Fuel OxygenatesOxygenates

Compound

Mol.Wt BP(ºc)Density

g/mLWater Solubility

MTBE 88.15 55.2 0.741 5.1g/100mL

ETBE 102.18 71 0.7519 <0.1g/100mL (21ºc)

TAME 102.18 85-86 0.764 –

DIPE 102.18 68.5 0.724 0.20g/100mL

TAEE 116.2 – – –

TBA 74.12 82.2 0.786 Miscible

TAA 88.15 102 0.805 –

Methanol 32.04 64.6 0.791 Miscible

Ethanol 46.07 78.3 0.789 Miscible

Water 18 100 1 NA


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MTBE Phase outMTBE Phase out


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REFINERYREFINERY

Refinery Waste Generation & Refinery Waste Generation & Catalyst PoisoningCatalyst Poisoning

Receiving Receiving feed feed stockstock

Produced Produced Waste waterWaste water

Product ExportProduct Export

Tank Bottom Tank Bottom Slop OilsSlop Oils

CATALYST CATALYST POISONINPOISONIN

GGStriving for Excellence

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CRUDE OIL

HYDROCARBONS NON-HYDROCARBONS

ALIPHATICS AROMATICS NAPHTHENES SULFURS NITROGENS OXYGENS METALLICS

25% 17% 50% <8% <1% <3% <100PPM

C1 - C60 (C6H5)n CYCLOALKANESSH

S

NH

O

COOH

Composition of Crude OilComposition of Crude Oil


Crude Oil does not naturally contain alkyl Crude Oil does not naturally contain alkyl ethersethers

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Effects of Trace Effects of Trace

Oxygenates in RefineryOxygenates in Refinery

Traces of oxygenates poison catalyst resulting in:

Lower production yields Lower product quality


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Contamination Monitoring by Contamination Monitoring by Laboratory Testing Laboratory Testing


Petroleum LaboratoryPetroleum Laboratory

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Method Description MethodDetection

range

Determination of hydrocarbon types and oxygenates in automotive-motor gasoline — Multidimensional gas chromatography method

IP 566 0.8 -15 %

(V/V)

Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol and C1 to C4 Alcohols in gasoline by GC

ASTM D4815-04 0.1- 20%m/m

Oxygenates in gasoline by GC and oxygen Selective Flame Ionization Detector

ASTM D5599 0.1-20% m/m

Oxygenates, benzene, toluene C8-C12 aromatics and total aromatics in finished gasoline Gas Chromatography/ Fourier Transform Infrared Spectroscopy

ASTM D5986-96(2006)

0.1-20%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 D7059 - 04e1

15 to 900 ppm (m/m)

Some Established Analytical Methods for MTBE and Other Oxygenates in Petroleum Products


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NaphthaNaphtha Crude OilCrude Oil

Slop OilSlop Oil

Analysis of Oxygenates by Analysis of Oxygenates by Multidimensional Gas Multidimensional Gas

ChromatographyChromatography


BAPCO Refinery Laboratory BAPCO Refinery Laboratory Trace MTBE Gas Trace MTBE Gas ChromatographChromatograph

Back Channel Front Channel

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ParametersParameters Front Channel Front Channel Back ChannelBack Channel

IntroductionIntroduction Automatic Liquid Samplers

Injection SystemInjection System Split/split less TPI

Sample TypeSample Type Crude Oil/Slop Oil Naphtha

Calibration Calibration TechniqueTechnique

Internal StandardExternal Standard

Valve Switch Valve Switch SystemSystem

Dean Switch

GC Configuration for Analysis GC Configuration for Analysis OxygenatesOxygenates


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GC Operating ConditionsGC Operating Conditions


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


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Oxygenates Original RT1st run 2nd run 3rd run 4th run 5th run 6th run 7th run

MTBE 12.33 11.938 11.917 11.84 11.772 11.811 11.761 11.777

Retention Time Comparisons of Retention Time Comparisons of MTBE, in the Front ChannelMTBE, in the Front Channel


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


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Oxygenates Original RT 1st run 2nd run 3rd run 4th run 5th run 6th run 7th run

ETBE 11.92 12.009 12.046 12.009 12.05 11.585 11.667 11.754

MTBE 12.33 12.33 12.368 12.332 12.375 12.025 11.909 11.989

DIPE 12.44 12.562 12.606 12.563 12.613 12.269 12.051 12.153

Retention Time Comparisons of Retention Time Comparisons of MTBE, ETBE, DIPE in the Back MTBE, ETBE, DIPE in the Back

ChannelChannel


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Challenges for Analysis of Challenges for Analysis of Oxygenates Oxygenates

Chromatographic ResolutionChromatographic Resolution Difficult resolution of DIPE, MTBE, ETBE and Difficult resolution of DIPE, MTBE, ETBE and

variance in the Elution timesvariance in the Elution times

SensitivitySensitivity To measure oxygenates down to low ppm To measure oxygenates down to low ppm Peak Tailing and shape, especially for MTBE Peak Tailing and shape, especially for MTBE

in Crude Oilin Crude Oil


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Overlaid Chromatograms with retention Overlaid Chromatograms with retention shiftshift

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Overlaid Chromatograms without Overlaid Chromatograms without retention shiftretention shift

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AdvantagesAdvantages

No Matrix effects of light hydrocarbons No Matrix effects of light hydrocarbons on oxygenates elution in naphtha on oxygenates elution in naphtha samplessamples

High temperature tolerance 350°C with High temperature tolerance 350°C with no column bleedno column bleed


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Methods under Development Methods under Development for Analysis of Oxygenates in Hydrocarbonfor Analysis of Oxygenates in Hydrocarbon

Two further ASTM standard methods Two further ASTM standard methods are proposed for approval using are proposed for approval using OxyPLOT OxyPLOT column column

Determination of C1 to C5 Oxygenates at Trace Determination of C1 to C5 Oxygenates at Trace Levels in High Ethanol Content Gasoline by Levels in High Ethanol Content Gasoline by Multidimensional Chromatography Multidimensional Chromatography

Determination of Oxygenates in Ethene, Propene, Determination of Oxygenates in Ethene, Propene, C4 and C5 Hydrocarbon by Gas ChromatographyC4 and C5 Hydrocarbon by Gas Chromatography


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Current Gaps in Analysis of Trace Current Gaps in Analysis of Trace Oxygenates in Petroleum SamplesOxygenates in Petroleum Samples

No standard Test Method for Trace Oxygenates in Crude oil/ Slop Oil

Requirement for further development of trace oxygenates in Naphtha


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Concluding RemarksConcluding Remarks


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

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Thank You Thank You MشــكرًاMشــكرًا


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Dean Switch Column FlowDean Switch Column Flow


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Capillary Flow Heart-Cutting 2-D GC Capillary Flow Heart-Cutting 2-D GC Deans SwitchDeans Switch


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technical response in the field of gas chromatography to changing market and technology demands...

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