Occupational Hygiene in the Oil & Gas Industry Day 1 – Section 3 Basic Petroleum Chemistry 1. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Introduction Composition Of Crude And Petroleum Products 1. Names of hydrocarbons and their groupings into hydrocarbon types. 2. Most important physical and chemical properties of specific hydrocarbons. 3. General chemical nature of crude petroleum and the refining operations which produce the petroleum products. 2. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry PARAFFINS • Formula = Cn.H(2n+2) where n = the number of Carbon atoms • Crude petroleum and its products contain compounds of carbon and hydrogen. • Carbon has a combining power (bonds) of 4 and hydrogen has a combining power (bond) of 1. • Simplest hydrocarbon molecule contains one Carbon atom and 4 hydrogen atoms and is C1H4 known as METHANE. Natural Gas 3. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Ethane C2H6 Methane CH4 Propane C3H8 iso-Butane C4H10 n-Butane C4H10 4. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry OLEFINS • Formula = C(n).H(2n) where n = the number of Carbon atoms • BUTENE C4H8 known as Butene-1 one double linkage (bond) on • Double, or even a triple linkage between carbon atoms. This type of linkage increases chemical activity. 5. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry 6. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry NAPHTHENES • Naphthene or cyclic structure - carbon atoms form a ring with only two linkages available for hydrogen or substation (described later). • The simplest form is 3 carbons CYCLOPROPANE C3H6 7. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Cyclohexane C6H12 8. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry AROMATICS • Combination of hydrogen and carbon based on a six carbon atoms ring with an unsaturated type linkage. BENZENE C6H6 • Benzene is a known carcinogen and requires special health considerations. • Benzene in gasolines is generally limited to 1% or less • Series of compounds known as AROMATICS 9. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Benzene C6H6 10. © 2013 Petroch Services Pty Ltd Toluene C7H8 BP Version J11002– Occupational Hygiene in the Oil & Gas Industry ortho Xylene C8H10 meta Xylene C8H10 para Xylene C8H10 Xylene isomers 11. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Two aromatic rings can join to form Naphthalene Three aromatic rings can join to form Anthracene 12. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Four or more aromatic rings can join to form ‘Polynuclear Aromatics’ C20H12 Benzo(a)pyrene which is a potential carcinogen. 13. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry PONA • Paraffins, Olefins, Naphthenes and Aromatics. (PONA) • Petroleum chemists and engineers use PONA to describe the broad composition various refinery hydrocarbon streams (or distillation cuts or boiling ranges) and their approximate “PONA” composition. 14. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Summary of Product Types from Petroleum Carbon Number C1-C4 Boiling Range Deg. C Deg. F <0 <30 Name Natural gas (LNG), Liquified Petroleum Gas (LPG) C4-C12 0-200 30-392 Gasoline, Naphtha C12-C15 200-300 392-572 Kerosene, Jet Fuel C15-C25 300-400 572-750 Gas Oil, Heating Oil, Diesel, Lube Oil >400 >750 >C25 Residuum, Asphalt (Bitumen), Paraffin Wax 15. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Other hydrocarbon derivatives • Oxygen – specifically hydroxyl group – OH produce ALCOHOLS • Methane becomes Methanol • Ethane becomes Ethanol (found in wines, spirits and beer) • Propane becomes Propanol (or Isopropanol used in hand cleaners). 16. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry 17. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Sulphur Compounds • Hydrogen Sulphide H2S – a special case- Toxic Gas • Aliphatic Sulphides – Mercaptans R-SH 18. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Aliphatic Sulphides 19. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry CHEMICAL REACTIONS IN A REFINERY Gasoline Treating • Mercaptans are mixed with Caustic solution (Sodium Hydroxide NaOH) to react and produce an organic sodium sulphide which is soluble in water and removed. 20. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Cracking Reaction • Fluidized Catalytic Cracker (FCC) or Thermofor Catalytic Cracker (TCC). T • Catalyst ‘cracks’ or breaks longer hydrocarbon molecules into smaller fractions • Produces wide range of hydrocarbons from gases through to heavy residuum 21. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Alkylation Reaction • Reaction of two gases Isobutane with Butene/Propylene to produce Alkylate • Alkylate- gasoline blend stock high octane (RON 100) used in motor gasolines & aviation gasolines. • Catalyst - Sulphuric acid or Hydrofluoric acid 22. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Isomerization Reaction • Changes straight chain paraffins into isomers which have higher octane rating • normal Pentane (octane 68) into Isopentane (octane 92) • Gasoline blend stock 23. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Dehydrocyclization Reaction • Changes straight chain paraffin into a ring or cyclic formation (aromatic) with increase in octane rating • Normal Heptane C7H16 (octane zero) transformed into Toluene (octane 120) • Valuable gasoline blend stock. • Hydrogen gas produced - used in other processes. 24. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Hydrogenation – Sulphur removal • Breaking the molecule and converting the sulphur radical into hydrogen sulphide and joining the hydrogen atoms to the free linkages (bonds) 25. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Sulphur Recovery • Hydrogen sulphide gas is converted into elemental yellow sulphur by burning in air to convert to Sulphur Dioxide SO2 • SO2 then reacted with Alumina catalyst to produce elemental sulphur. 26. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Naphthene Dehydrogenation • Catalyst & temperature break hydrogen from cyclic structure Cyclohexane to form Benzene and 6 Hydrogen atoms • Octane increase 83 to 100+. 27. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Oxidiser Reaction - Bitumens • Reacts heavy vacuum treated residuum with air to polymerise heavy hydrocarbons (heavier molecules) • Produces bitumen for road making. • Two hydrogen atoms stripped off and reacted with air (oxygen) to produce water (steam) 28. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry End of Section 3 Basic Petroleum Chemistry 29. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry