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INTRODUCTION TO PETROLEUM REFINING At the end of this chapter, you should be able: 1. To have the basic knowledge about petroleum and crude oil characteristics and processes 2. To acknowledge a bit about the history of petroleum 1.1 Introduction What is PETROLEUM?  Petro (rock) an...

INTRODUCTION TO PETROLEUM REFINING At the end of this chapter, you should be able: 1. To have the basic knowledge about petroleum and crude oil characteristics and processes 2. To acknowledge a bit about the history of petroleum 1.1 Introduction What is PETROLEUM?  Petro (rock) and oleum (oil)  Also known as crude oil Complex mixture of hydrocarbons and natural gas (NG) Hydrocarbons + NG = Petroleum PETROLEUM Hydrocarbons: contain hydrogen and carbon. NG: oxygen, nitrogen and sulfur  Petrochemicals  During refining of crude oil and the processing of natural gas, many by-products are produced  Also called as petroleum distillates  Chemical products derived from petroleum Aromatics (ex: benzene, Olefins; CnH2n toluene, xylene) (ex: ethylene, propylene, Synthesis gas (CO + H2) to butadiene) form ammonia and methanol HOW PETROLEUM & NG ARE FORMED?  HISTORY: North America -Distillation process starts to be used 1846: Canadian archeologist, widely. Abraham Gesner, developed a Petroleum distillation process -In 1850s, USA (kerosine was the main product) already produced kerosene at the rate of 8 million barrels per year 1859: Edwin Drake drilled the first oil for petroleum extraction (first mechanical drilling technique which is simple and effective) HISTORY: North America 1860s: Rapid growth of petroleum companies 1895: Standard Oil (biggest oil enterprise in US) tried to share the Petroleum market with Russia government but Russia rejected HISTORY: North America 1911: Standard Oil break-up to 34 companies HISTORY: North America 1928: Exxon, Mobil, Chevron, Texaco, Gulf, British Petroleum (BP) and Shell formed an international Organization called Seven Sisters plays important roles in petroleum extraction development and in transportation 1930s: Automobile industry was developed the level of petroleum production was sustained the prices of fuels and petroleum products were stabilized  ONSHORE DRILLING Drill Bits Lowering the Bit and Drill Collar into the Well Hole Positioning the Hoisting Equipment Working on an Onshore Drilling Rig OFFSHORE DRILLING PETROLEUM PRODUCT LIFE CYCLE In the oil industry, "Upstream" refers to petroleum exploration and production aspects (E&P). https://www.planete-energies.com/en/media/article/search-oil-or-gas-deposit “Midstream" business consists of transportation and processing. Pipelines and other transport systems can be used to move crude oil from production sites to refineries and deliver the various refined products to ‘downstream’ distributors. Horizon Singapore Terminals Pascagoula Refinery's (Subsidiary of Emirates National Oil Marine Terminal Company (ENOC)-owned Horizon Terminals Ltd) Ras Tanura Oil Terminal, Saudi Oil Terminal in Primorsk, Eastern Arabia Gulf of Finland Netherlands Antilles, Curacao, Shell oil refinery, one of world's largest refinery. An Oil Refinery  Transport Capacity Tanker truck 200 barrels Railroad tanker 1,500 barrels Barge 15,000 barrels Super tanker 1 millions barrels Large liquid 2 millions pipeline barrels/day Large gas pipeline 1 billion cubic feet/day Source: Petroleum Museum, Miri, Sarawak An oil feeder line in Kuwait Oil carriers in Prigorodnoye, Russia Railroad tanker Tanker truck "Downstream" business deals with marketing and sales which reaches consumers, represented by gasoline stations. Also involves processing and purifying of raw NG. Global oil production continued to grow in 2022 (4.2%), driven by the Gulf countries and the United States. The latter confirmed their leadership position, secured for several years by the exploitation of ”Shale Oil” Characteristics of Crude Oil Quality of crude oil is described based on 1. Density/ Specific gravity 2. Sulfur content, % Light vs Heavy Good Quality?  Classification of Oil  Quality of crude oil based on MATURATION  HIGHER QUALITYLIGHTER COLOUR (golden or amber)  Colors of Crude Oil NORTHEASTERN UTAH NORTHWESTERN ILLINOIS PANHANDLE REGION TEXAS  Good Quality? PANHANDLE REGION TEXAS UPPER NILE, SUDAN A B  FROM A BARREL OF OIL Distillation FROM A BARREL OF OIL THE TRANSFORMATION Refining Process Platform Platform ~ July 1882 , recorded by British Resident of the Baram district in Sarawak. ~ Oil was used by the local residents for medicinal purposes and later for lighting lamps and waterproofing boats. ~ The first oil well (the Grand Old Lady) was drilled by Shell (previously known as Anglo- Saxon Petroleum Company) in The Grand Old Lady, Miri, 1910 Sarawak ~ 1910, Sarawak Shell was granted the sole right to explore for petroleum in Sarawak struck oil in the town of Miri Lutong Oil Refinery, Miri ~ 1914, Shell also built Malaysia's first oil refinery in Lutong, Miri Brighton Beach Oil Refinery, Miri ~ 1950s, sea exploration ~ 1962, two areas offshore in Sarawak ~ 1968, exploration in peninsular Malaysia ~ 1971, first oil field discovered.  “Orient Explorer” - a jack-up rig, was the first offshore rig used in Malaysia Source: Petroleum Museum, Miri, Sarawak Present Malaysia’s oil and gas fields can be found mainly offshore of Peninsula Malaysia and east coast. Most of the country's oil fields contain low-sulfur, high- quality crude. 37 oil fields and 11 gas fields and others are under development.  Oil fields that produces high quality blends of crude can be found in the east of Peninsula Malaysia mainly, Tapis, Labuan, Miri, Bintulu and Dulang.  More than half of the country's oil production comes from the Tapis field - very light and sweet with API gravity of 44° and sulfur content of 0.08% by weight  January 2010 - producing 693,000 barrels of oils and 192 million cubic metres of gas per day  Esso Production Malaysia Inc. (EPMI), an affiliate of ExxonMobil Corporation, is the largest crude oil producer in Peninsular Malaysia, accounting for nearly half of Malaysia's crude oil production.  EPMI operates 7 fields near the peninsula, and one-third of its production comes from the Seligi field.  The Seligi-F platform, with its 28 wells, is the newest satellite in the Seligi field, located 165 miles off the coast of Terengganu , Peninsular Malaysia. Source: Petroleum Museum, Miri, Sarawak ~ Malaysia has 6 refineries, with a total processing capacity of 544 832 bbl/d. Petronas -Kerteh (Terengganu) -Sungai Udang (Melaka) Shell -Port Dickson (Negeri Sembilan) -Lutong (Sarawak) ExxonMobil -Port Dickson (Negeri Sembilan)  The 3 largest refineries are: 1. Shell Port Dickson refinery (155,000 bbl/d) 2. Petronas Melaka-I (92, 832 bbl/d) 3. Melaka-II refineries (126, 000 bbl/d) Thank you  A BARREL OF OIL 1 bbl = 42 US gallons = 35 Imperial gallons = 5.61 ft3 = 158.8 l Oil prices (above $100/barrel), Venezuela has larger reserves than Saudi Arabia due to its crude reserves derived from bitumen 1.2 EXPLORATION & PRODUCTION OF PETROLEUM At the end of this chapter, you should be able to: 1. Describe the formation of oil and gas trap. 2. Identify the important factors and types of rocks in oil and gas trap. 3. Explain the methods to locate oil. 4. Identify the functions of the drilling tools. 5. Explain the techniques to enhance the oil recovery. EXTRACTION OF PETROLEUM Locate the Extract/ Drilling oil field Recover the oil  Extraction of Petroleum Risky and costly to Risk large investors and amount of governments due money up to to commercial hundreds of failures Exploration of millions Petroleum Could harm the environment Property leasing  This business is money driven hence business aspect of making money drive the technical work, not the other way around HOW OIL & GAS TRAP? 1 Source Rock Heat from within earth Decomposition of organisms with mud and ‘cooked’ the mud’s silt, along with sand, clay and minerals, and organic remains into a solidified into rocks soup of HC (petroleum + NG). 2 Reservoir Rock Liquids and vapors emitted from the source HC expelled from rocks moved upward through sediment pores source rockmove and accumulated between the grains of (migrates) through sediment reservoir rock Seal Rock/ 3 Impermeable Rock Contained water which pushed the lighter oil and gas upward until they hit the impermeable rock How Oil & Gas Trap?  3 important elements for oil & gas trap: 1. A source for the oil & gas (black waxy shales) 2. A porous reservoir/ sedimentary rock to accumulate the oil & gas (storing hence porous) (IMPORTANT FACTOR : Porosity & Permeability) 3. An overlying seal rock/impermeable rock to prevent the oil & gas from escaping POROSITY VALUES FOR AN OIL RESERVOIR Percentage Description 0-5% Insignificant 5-10% Poor 10-15% Fair 15-20% Good 20-25% Excellent Ref: Levorsen, 1967 POROSIMETER  measure porosity NG compresses and needs less porosity than an oil reservoir. As the gas reservoirs located deeper, it will need very little porosity because of the very high pressure. PERMEABILITY VALUES FOR AN OIL RESERVOIR Percentage Description (millidarcy) 1-10 md Poor 10-100 md Good 100-1000 md Excellent Ref: Levorsen, 1967 PERMEAMETER  measure permeability The greater permeability of a rock, easier it is for the fluids to flow thru rock. HIGHER POROSITY, GREATER PERMEABILITY OIL & GAS TRAP Sand grains Pore spaces (Contained Oil) Conventional sedimentary rock: 1. Sandstones (intergranular porosity) 2. Limestones (moldic porosity) 3. Dolostones (intercrystalline porosity) Source: Petroleum Museum, Miri, Sarawak How Oil & Gas Trap? Structural Trap: Understand the subsurface deformation processes - Anticline traps: Formed by a folding of rock - Fault traps: Formed when reservoir rock is split along a fault line - Salt domes: Formed because the below ground salt which is less dense than the above rock, is moving upwards slowly hence deform and break up rock along the way Stratigraphic Trap: Study of the origin, composition and distribution of the rock layers. Hydrocarbon traps result from changes in rock type or pinch-outs, unconformities or other sedimentary features How Oil & Gas Trap? WHO FINDS OIL? Interpreting subsurface Geoscientists structure or configuration through gravity, seismic, etc. -Geophysicists -Geologists Understanding the rocks -Geochemists Understanding the subsurface fluids (petroleum) How to Locate Oil? Sensitive gravity meters - measure tiny changes in the Earth's gravitational field that could indicate flowing oil Sensitive magnetometers - measure tiny changes in the Earth's magnetic field caused by flowing oil How to Locate Oil? Satellite images - record infrared and ultraviolet light Seismology - Creating shock waves that pass through hidden rock layers and interpreting the waves that are reflected back to the surface - Computer processes the geophones data then convert to Seismic lines/ Seismograph - Structure, Density, Shapes of rocks HOW TO LOCATE OIL? Placing Geophones Seismograph  Seismology (Onshore) Thumper/Vibrator - On land we used to use dynamite to create shock waves. - ‘Thumper' truck drives to the site, raises itself up on hydraulic lifts, and then begins vibrating. - The sound waves travel downward, hit something solid, reflected back to the surface where sensors (used to be called stingers) are placed along the ground. - Sensors are connected back to a recording device.  SEISMOLOGY (OFFSHORE) - Send down sound waves, let them reflect, and pick up the reflection with sensors (hydrophones or, on land, seismographs). - The speed will change depending on the make up of the rock type. - The reflected wave returns at a speed characteristic of the material it has been travelling through. - The result is a set of seismic lines that the geologists and hydrogeologists interpret. Different types of oil rigs used for various depths. DRILLING FOR OIL & GAS DRILLING FOR OIL & GAS Wells were drilled with cable tools in which a heavy drill bit on a cable was repeatedly dropped up and down on the ground to literally "chop" a hole down to the trap. Rotary drilling: a bit on the end of a of drill pipe is rotated.  Drilling for Oil & Gas Drilling fluid (water & mud) is Drilling fluids pumped down the pipe to flow through the bit & lubricates the bit, washes away the cuttings, and maintains pressure in the hole to prevent the well from becoming a blowout. The mud flows back to the surface through the gap between the drill pipe and the hole. This gap is called the Annulus. Annulus Mud circulation in the hole DRILLING FLUIDS Also called ‘MUD’ Functions : 1.Lubricates the drilling tools 2.Washes up rock cuttings 3.Balances pressure of fluids in the rock formations below WHY? To prevent BLOWOUT Drilling Process turntable  Place the bit, drill collar and drill pipe in the hole.  Attach the kelly and turntable and begin drilling.  As drilling progresses, circulate mud through the pipe and out of the bit to float the rock cuttings out of the hole.  Add new sections (joints) of drill pipes as the hole gets deeper.  Remove (trip out) the drill pipe, collar and bit when the pre-set depth (from a few hundred to a couple-thousand feet) is reached. Drill pipes Christmas tree @ Well head -blowout preventer (BOP) Nodding Donkey/Pump Jack (Onshore) Drilling Wells ENHANCED OIL RECOVERY (EOR) Primary Recovery - Makes use of the natural conditions in the reservoir to drive out the oil after a well is drilled - Pressure from the underground will help to bring the fluids to the top - After that, technology such as pumps will be used to help continue to bring fluids to the top - Oil recovered : 15 - 20% of the original oil in place 1. Solution Gas Drive 2. Gas Cap Drive 3. Water Drive Solution gas Solution Gas Drive Gas Cap Drive Well head Water underpressure Water Drive OIL RECOVERY Secondary Recovery Enhance or replace the primary recovery techniques Recovery factor after primary and secondary: 35-45% Rely on the supply of external energy into the reservoir 1. Water flooding Involve injecting water into the underground reservoir to displace the oil where it can be lifted to the surface by pumps. 2. Immiscible gas injection (CO2, nitrogen) Injection of low pressure gas to maintain reservoir pressure OIL RECOVERY Tertiary Recovery - Generic term : Enhanced Oil Recovery (EOR) - Take over when secondary recovery no longer effective - Increase the mobility of oil by heating the oil, reducing its viscosity hence easier to be extracted - Cogeneration plant: Uses gas turbine to generate electricity and the waste heat to produce steam, then injected into the reservoir - Oil Recovery : 30 – 60% of the original oil in place. 1. Steam injection /Thermal processes - Raise the temperature of the oil - Reduces the oil's viscosity - Improves its ability to flow through the reservoir 2. Miscible techniques - Injection of a gas such as NG, N2, LPG or CO2 - Raising the pressure within the reservoir - Expand in the reservoir - Push the additional oil to the wellbore 3. Chemical injection - Involves "polymers" to increase the effectiveness of water injection DRILLING FOR OIL & GAS DEEP WATER PLATFORMS(OFFSHORE)  JACK UP RIG PLATFORM Can be jacked up above the sea using legs that can be lowered, much like jacks. Water depths : 400-550 feet (120-170 m) They are designed to move from place to place, and then anchor themselves by deploying the legs to the ocean bottom using a rack and pinion gear system on each leg FIXED PLATFORM Built on concrete or steel legs, or both, anchored directly onto the seabed, A deck for drilling rigs, production facilities and crew quarters. Water depths :1,700 ft (520 m). The Grane Platform, Norway SEMI-SUBMERSIBLE PLATFORM Hulls (columns and pontoons) for the structure to float and sufficient weight to keep the structure upright. It can be moved from place to place Can be ballasted up or down by altering the amount of flooding in buoyancy tanks Anchored by chain, wire rope Water depths : 200 to 10,000 Oil Platform P-51 off the Brazilian coast feet (60 to 3,000 m). TENSION LEG PLATFORM (TLP) Floating platforms tethered to the seabed in a manner that eliminates most vertical movement of the structure. Water depths : 6,000 feet Conventional TLP (2,000 m). The "conventional" TLP is a 4-column design which looks similar to a semisubmersible. SPAR PLATFORM Spars are similar with the seabed like TLPs Spars designed in three configurations: 1."conventional" one-piece cylindrical hull 2."truss spar" - midsection is composed of truss elements connecting the upper buoyant hull with the bottom soft tank (permanent ballast) 3."cell spar" - multiple vertical cylinders. The spar has more inherent stability than Devil's Tower Spar Platform a TLP since it has a large counterweight at the bottom Ability to move horizontally and to position itself over wells at some distance from the main platform location. Water depth : 2000-10000 ft DRILLING BARGE Used mostly for inland, shallow water drilling (ex: lakes, swamps, rivers, and canals) Drilling barges are large, floating platforms Towed by tugboat from location to location. DRILLING SHIP A drillship is a maritime vessel that has been fitted with drilling apparatus. It is most often used for exploratory drilling of new oil or gas wells in deep water but can also be used for scientific drilling. Most drillships are outfitted with a dynamic positioning system to maintain position over the well Water depths :12,000 ft (3,700 m). Moveable Rigs (for exploratory wells) Drilling Barge Drillingship Jack Up Rig Semi-submersible rig FIELD PROCESSING Objectives: - purify the oil and gas - dispose any harmful contaminants  Desalting/Dehydration - removal of water bound in an oil-water emulsion and is carried out through a combination of chemicals, application of heat and electricity and the proper retention time in the demulsifier. Sweetening - refers to the removal of H2S, typically by means of stripping with natural gas available from the reservoir. Stabilization - refers to the removal of light gas components dissolved in the oil in order to increase its vapor pressure. There are various techniques for accomplishing this. Note that removal of light gases occurs at conditions where H2S can also vaporize, so some sweetening occurs simultaneously. NEW OIL & GAS FIELD DISCOVERY IN MIRI JANUARY 2013 VIDEO 1.3 COMPOSITION AND CLASSIFICATION OF CRUDE OIL AND PETROLEUM PRODUCTS At the end of this chapter, students should be able: 1. To differentiate the types of hydrocarbons and non-hydrocarbons 2. Identify the basic properties of crude oil  COMPOSITION OF PETROLEUM Petroleum: - Complex mixture of hydrocarbon molecules. Hydrocarbon: - Organic compounds of Carbon & Hydrogen atoms (1-60 carbon atoms) Crude Oil - Unrefined petroleum product - Vary in appearance and composition - consistency : water to tar like solids - color : clear to black COMPOSITION OF PETROLEUM C1 - C4 : gases C5 – C19 : liquids C20 - > : solids COMPOSITION OF CRUDE OIL & NG Element Crude oil Natural gas Carbon 84-87% 65-80% Hydrogen 11-14% 1-25% Sulfur 0.06-2% 0-0.2% Nitrogen 0.1-2% 1-15% Oxygen 0.1-2% 0%  COMPOSITION OF PETROLEUM Hydrocarbon Average Range Four different Paraffins 30% 15 to 60% types of Naphthenes 49% 30 to 60% hydrocarbon Aromatics 15% 3 to 30% molecules appear in crude oil. PARAFFINS - known as Alkanes - CnH2n+2 - saturated HCs - straight or branched (isomers) 1. Straight : lighter, gases & paraffin waxes General formula : CnH2n + 2 2. Branched : heavier, higher octane number General formula CnH2n + 2, n > 3 AROMATICS - known as Arenes/Aryl HCs - unsaturated but very stable - C6H2n-6 - rings contain six carbon atoms, with alternating double and single bond between the carbons - can add paraffin side chains to replace the hydrogen attached to the ring carbons NAPHTENES - known as Cycloalkanes/ cycloparaffins - CnH2n - ringed structures with one or more rings - rings contain only single bonds between the carbon atoms  NAPHTENES - Typically liquids at room temperature - Monocycloparaffins predominate - Dicycloparaffins – heavier ends of naphtha  OLEFINS - Known as alkenes (CnH2n) - Usually formed during processing (seldom naturally) - Undesirable in finished products because the double bonds are reactive hence the compounds are easily oxidized and polymerized - Does not exist in crude oil Other Hydrocarbons Alkynes: triple bond (alkynes), CnH2n-2 Non-Hydrocarbons Sulfur compounds - H2S, mercaptans, sulfides, thiophenes, etc - elemental sulfur - causes corrosion - hydro-desulfurization: remove sulfur compounds - sweetening: remove obnoxious sulfur compounds, convert to odorless sulfides NON-HYDROCARBONS Nitrogen Compounds - include trace metals - form nitrogen oxides in furnaces - Decomposition : ammonia & cyanide corrosion Oxygen Compounds - phenols, ketones, carboxylic acids NON-HYDROCARBONS Trace metals - Ni, Fe,V - Small quantities, removed in refining process - Remove arsenic, vanadium, nickel-poison catalysts Naphtenic acid - organic acids - corrosive at T > 450°F NON-HYDROCARBONS Salts - Inorganic salts : sodium chloride, calcium chloride in suspension or dissolved in entrained water (brine) - Removed or neutralized – poison catalyst, corrode equipment, fouling Carbon dioxide Results from decomposition of bicarbonates  CRUDE OIL PROPERTIES 1. Pour Rough indicator of the relative paraffinity point & aromaticity of the crude The temperature where the liquid (oil) becomes semi-solid and loses its flow characteristics Lower pour pt: -Lower paraffin content -Higher aromatic content (heavier oil) CRUDE OIL PROPERTIES  CRUDE OIL PROPERTIES 2. Carbon Residue (wt%) Roughly related to the asphalt content of the crude & to the quantity of the lubricating oil fraction that can be recovered Determine the amount of carbon which remains after combustion with a limited amount of O2 The lower of carbon residue means more valuable of the crude Method to calculate Carbon residue in weight %: 1. Ramsbottom Carbon (ASTM D-524) 2. Conradson Carbon (ASTM D-189)  CRUDE OIL PROPERTIES 3. Salt Content (NaCl) - NaCl>10lb/1000bbl – Desalting process - Can cause corrosion problem if not removed 4. Nitrogen Content wt% - N2>0.25wt% (Undesirable) - Can cause poisoning to catalyst used corrosion like H2 blistering 5. Metals Content, ppm - Affect the activities of catalyst hence lowering product distribution - Vanadium above 2 ppm can cause severe corrosion to turbine blades  CRUDE OIL PROPERTIES 6. API An arbitrary scale expressing the gravity or density of liquid petroleum products Gravity (range 10-50) Defined as American Petroleum Institute (API) gravity Higher API gravity : more paraffinic crude, higher yields of gasoline, the lighter the compound Lower API gravity : more aromatic crude, lower yields of gasoline, the heavier the compound modulus 141.5 API = − 131.5 SG 141.5 SG = API + 131.5 A measure of how heavy or light a petroleum liquid is compared to water Higher API gravity than water – floats when mix with water CRUDE OIL PROPERTIES  CRUDE OIL PROPERTIES 7. Sulfur content % - Measured by ASTM - The relative content of sulfur in natural oil: -“SWEET” which means it contains little sulfur (< 0.5 wt%) -“SOUR” which means it contains large amount of sulfur (> 0.5 wt%) CRUDE OIL PROPERTIES 8. Total Acid Number (TAN) To monitor the oxidation of lubricating oils during use and acidic crude oils Cause rapid corrosion of the fractioning columns; higher acidic require expensive alloy steel equipment TAN is the no of mg of KOH required to neutralize acids in1 g of oil  Composition of Petroleum Refining process Crude Oil Products Chemicals, catalysts, heat, pressure  PETROLEUM PRODUCTS Petroleum products are usually grouped into three categories: 1. Light distillates (LPG, gasoline, naphtha), 2. Middle distillates (kerosene, diesel), 3. Heavy distillates (heavy fuel oil, lubricating oils, wax, asphalt). This classification is based on the way crude oil is distilled and separated into fractions (called distillates and residuum)  PETROLEUM Crude oil is separated into PRODUCTS Distillate fractions by fractional distillation. The fractions at the top of the fractionating column have lower boiling points than the fractions at the bottom. The heavy bottom fractions are often cracked into lighter, more useful products. All of the fractions are processed further in other refining units. C1-C4 gases 20oC C5-C9 naphtha 70oC C5-C10 gasoline 120oC C10-C14 kerosene, paraffin oil 170oC C14-C20 diesel oil 270oC C20-C50 lubricating oil C20-C70 fuel oil 600oC >C70 residue THE PITCH DROP EXPERIMENT AT THE UNIVERSITY OF QUEENSLAND Thank You