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Alternative Fuels & Advance in IC Engines

IIT Kanpur Kanpur, India (208016)

Petroleum and its Refining

Course Instructor Dr. Avinash Kumar Agarwal Professor Department of Mechanical Engineering Indian Institute of Technology Kanpur, Kanpur

Introduction of Crude Oil

Our modern technological society relies very heavily on fossil fuels (crude oil) as an important source of energy. Crude oil (known as black gold) is a thick, dark brown or greenish flammable liquid, which is found in the upper strata of some regions of the Earth's crust. p y g with traces of other chemicals and compounds. p It is a complex mixture of various hydrocarbons along

Crude oil can be categorized as either "sweet crude" (where the sulphur content less than 0.5%) or crude " (where the sulphur content is at least 2.5%). 2 5%) "sour crude," Crude oil must undergo several separation processes so that its components can be obtained and used as fuels or converted to more valuable products such as petrol for cars, fuel oil for heating, diesel fuels for heavy transport, bitumen for roads. The process of transforming crude oil into finished petroleum products (that the market demands) is called crude oil refining.

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Introduction of Crude Oil Products

Petroleum products are produced from the processing of crude oil at petroleum refineries and the extraction of liquid hydrocarbons at natural gas processing plants. P t l i the th broad b d category t th t includes i l d Petroleum is that both crude oil and petroleum products. The main goal of petroleum refining is to take the undesirable components of the crude oil and upgrade them into more valuable products. Petroleum refining results in greater output than the input because of changes in the overall density of the refined products relative to that of the input oils. Gasoline, diesel, and jet fuel are among the most valuable products, whereas fuel oils and lubricants are sometimes sold at a loss.

Petroleum Products

Introduction of Oil Refinery

A refinery is a complex chemical plant that utilizes several different techniques to take a very rough feedstock, crude oil, and converts it into desirable products, such as gasoline, diesel etc. Oil companies invest large sums of capital into these refineries in hopes of making a large profit. Today, crude oil is refined all over the world. The largest oil refinery is the Paraguana Refining p , which can p , y Complex in Venezuela, process 94 940,000 barrels of oil each day. In fact, most of the oil industrys largest refineries are in Asia and South America. Nevertheless, the practice of refining oil was created in the United States, where it continues to be an important part of the nations economy.

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History of Crude Oil

3000 BC Sumerians use asphalt as an adhesive; Egyptians use pitch to grease chariot wheels; Mesopotamians use bitumen to seal boats. 600 BC Confucius writes about drilling a 100 feet gas well and using bamboo for pipes 1500 AD Chinese dig oil wells >2000 feet deep 1847 First rock oil refinery in England 1849 Canada distills kerosene from crude oil 1856 Worlds first refinery in Romania 1857 Flat-wick kerosene lamp invented 1859 Pennsylvania oil boom begins with 69 feet oil well producing 35 bpd 1860-61 Refineries built in Pennsylvania and Arkansas 1870 US Largest oil exporter; oil was US 2nd biggest export 1878 Thomas Edison invents light bulb 1901 Spindle 100,000 bpd era of dl top, Texas producing d b d kicks k k off ff modern d f oil l refining f 1908 Model Ts sell for $950/T 1913 Gulf Oil opens first drive-in filling station 1942 First Fluidized Catalytic Cracker (FCC) commercialized 1970 First Earth Day; EPA passes Clean Air Act 2005 US Refining capacity is 17,042,000 bpd, 23% of Worlds capacity

Scenario of Crude oil throughout the World

Economic activity and population drive increases the energy use. By 2040, Chinas energy use will be double the U.S. level however Indias a little more than half despite its faster GDP growth.

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Crude Oil: Formation and Exploration

Formation Dead marine animals and plant matter accumulated over millions of years, transformed into oil in sedimentary rocks due to heat and pressure. Deposits found beneath the crust, have a water body below and pressurized natural gas above.

Thick and dense rock layer seals of the deposit, ensuring no leakage.

Conventional Petroleum Drilling Drilling through the rock layer causes pressure release, pushing oil and gas to surface. When pressure is attenuated, oil can be pumped up. Advanced Petroleum Drilling

Various Sources of Petroleum and Drilling Arrangement

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Petroleum Refining Process

A petroleum refinery is a chemical plant that processes crude oil and produces several valuable products. A refinery contains different types of units that perform a variety of different operations. The main goal is to take the undesirable components of the crude oil and upgrade them into more valuable products.
At the top of the distillation column Short carbon chains Light molecules Low boiling points Gases & very runny liquids Very volatile Light colour Highly flammable At the bottom of the distillation column Long carbon chains Heavy molecules High boiling points Thick, viscous liquids

Low volatility Dark colour Not very flammable

Crude Oil Refining Stages

Detailed crude oil refining can be divided into following three categories: (i) Separation Units (ii) Finishing Units (iii) Conversion

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Crude Oil Refining: Separation Unit

These units take an incoming stream and separate it into different components. No chemical reactions occur in these units. Basic components of this unit can be given as: (i) Desalter Ions in the crude oil will corrode the pipes in the refinery and may deactivate the catalysts. It is important to remove these salts from the crude before any other processes are started. The process involves forcing water into the crude oil feed stream. This pulls out the salts and prevents corrosion. (ii) Atmospheric Distillation The distillation is performed at atmospheric pressures. The outputs of the distillation unit include light ends, kerosene, diesel, heavy gas oil, and atmospheric residue. id (iii) Vacuum Distillation This unit distills the atmospheric residue and produces light vacuum gas oil, heavy vacuum gas oil, and vacuum residue. The distillation occurs because the pressure inside of the unit is decreased to nearly zero, allowing the components of the atmospheric residue to boil at a lower temperature.

Crude Oil Refining: Separation Unit

(iv) Light Ends Unit The light ends unit consists of many different fractionators that separate the different components of the light ends fraction from atmospheric distillation. The separated components consist following components; , which are used for fuel to heat operations p throughout g the refinery; y; methane and ethane, propane and butane, which are mixed and compressed to be sold as Liquid Petroleum Gas (LPG); light straight run (LSR) naphtha (C5 and C6), which is used in gasoline pools; heavy straight run (HSR) naphtha, which is used as a feed stock for the catalytic reformer.

( ) Deasphalter D h lt (v) This unit takes the vacuum residue and pulls out all of the heavy particles leaving heavy gas oil that can be further refined or used as fuel oil, and asphalt, which is used in paving. (vi) Dewaxer This unit precipitates long n-paraffins out of heavy vacuum gas oil creating lubricating oils that will withstand low temperatures without solidifying.

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Crude Oil Refining: Finishing Unit

These units add the final touches before the product can be sold. Some chemical reactions may occur, but none that significantly alter the final product. (i) Blending These units take a variety of streams and mix them to meet certain criteria and compositions.

(ii) Hydrotreater Most crude oils today have a high sulfur content. Sulfur is a strong pollutant and must be removed to meet emission standards. Sulfur can deactivate catalysts in further refining units. Sulfur is removed by pumping hydrogen gas into any stream. The hydrogen reacts with a molecule and extracts the sulfur to produce hydrogen sulfide.

Crude Oil Refining: Conversion Unit

These units change the composition of input streams through chemical reactions. In the reactors, a low grade product is converted into a higher grade product. (i) Catalytic Reformer This unit takes HSR naphtha and unsaturates the hydrocarbons to produce aromatic rings and other various olefins. These aromatic rings and olefins are used in premium gasolines because of their high octane numbers.

(ii) Catalytic Cracker This unit transforms heavy gas oil into light distillates, such as gasoline and LPG and light cycle oil. The unit utilizes a catalyst to take long chain hydrocarbons and break (crack) them into shorter, more valuable hydrocarbons.

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Crude Oil Refining: Conversion Unit

(iii) Hydrocracker This unit performs the same operation as the catalytic cracker, but uses hydrogen gas instead of a catalyst to break long hydrocarbon chains into shorter ones. In this process, feedstock is light vacuum gas oil and the products are light and middle distillates. (iv) Thermal Cracker This unit uses heat to break larger molecules into smaller ones, but is rarely used today. (v) Visbreaker This unit employs a mild version of thermal cracking to convert vacuum residue into light and middle distillates, fuel oil, and coke or heavy gas oil into slightly lighter fuel oil. (vi) Alkylater This unit converts short olefins (ethylene, propylene, and butenes) and isobutane chains into branched C7 and C8 chains via strong acids and heat. (vii) Delayed Coker This unit uses a very severe version of thermal cracking to convert vacuum residue into light and middle distillates, as well as coke.

Other Refining Technique: Solvent-Refining Process

This process uses chemicals (fairly safe recyclable solvent) to dissolve one part of the oil from another. It removes heavy materials and wax (undesirable component by extraction).

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Refined Petroleum Products

Products refined from the liquid fractions of crude oil can be placed into ten main categories. These main products are further refined to create materials more common to everyday life. The ten main products of petroleum are: (i) (ii) ( ) (iii) (iv) (v) (vi) Asphalt Diesel Fuel Oil Gasoline Kerosene Liquefied Petroleum Gas (LPG)

(vii) Lubricating Oil (viii) Paraffin Wax (ix) (x) Bitumen Petrochemicals In all above mentioned products, gasoline and diesel are the major constituent. Both of them are mainly used for automotive applications. Jet fuel is the other major faction used for used for aviation application.

Refined Petroleum Products

Asphalt Asphalt is commonly used to make roads. It is a colloid of asphaltenes and maltenes that is separated from the other components of crude oil by fractional distillation. p is usually y stored and transported p at around 3 300F. Asphalt Diesel Diesel is any fuel that can be used in a diesel engine. Diesel is produced by fractional distillation between 392F and 662F. Diesel has a higher density than gasoline and is simpler to refine from crude oil. It is most commonly used in transportation. Fuel Oil heat Fuel oil is any liquid petroleum product that is burned in a furnace to generate heat. Fuel oil is also the heaviest commercial fuel that is produced from crude oil. The six classes of fuel oil are: distillate fuel oil, diesel fuel oil, light fuel oil, gasoil, residual fuel oil, and heavy fuel oil. Residual fuel oil and heavy fuel oil are known commonly as navy special fuel oil and bunker fuel; both of these are often called furnace fuel oil.

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Refined Petroleum Products

Gasoline Almost half of all crude oil refined, is made into gasoline. It is used as fuel in IC engines. Gasoline is a mixture of paraffins, naphthenes, and olefins, although the specific ratios of these parts depend on the refinery where the crude oil is processed. Gasoline is called different things in different parts of the world. Some of these names are: petrol, petroleum spirit, gas, petro-gasoline, and mo-gas. Kerosene Kerosene is collected through fractional distillation at temperatures between 302 F and 527F. It is a combustible liquid that is thin and clear. Kerosene is most commonly used as jet fuel and as heating fuel. In the early days of oil, kerosene replaced whale oil in lanterns. Now, kerosene is used as fuel in portable stoves, kerosene space heaters, and in liquid pesticides. Liquefied Petroleum Gas (LPG) Liquefied petroleum gas is a mixture of gases that are most often used in heating appliances, aerosol propellants, and refrigerants. Different kinds of liquefied petroleum gas, or LPG, are propane and butane. At normal atmospheric pressure, liquefied petroleum gas will evaporate, so it needs to be contained in pressurized steel bottles.

Refined Petroleum Products

Lubricating Oil Lubricating oils consist of base oils and additives. Different lubricating oils are classified as paraffinic, naphthenic, or aromatic. The most commonlyknown lubricating oil is motor oil, which protects moving parts inside an internal combustion engine. Paraffin Wax Paraffin P ffi wax is i a white, hit odorless, d l t t l tasteless, waxy solid lid at t room temperature. t t Th melting The lti point i t of f paraffin wax is between 117F and 147F, depending on other factors. It is an excellent electrical insulator, second only to Teflon, a specialized product of petroleum. Paraffin wax is used in drywall to insulate buildings. Bitumen Bitumen, commonly known as tar, is a thick, black, sticky material. Refined bitumen is the bottom fraction obtained by the fractional distillation of crude oil. paving Bitumen is used in p g roads and waterproofing p g roofs and boats. Bitumen is also made into thin plates and used to soundproof dishwashers and hard drives in computers. Petrochemicals Petrochemicals are the chemical products made from the raw materials of petroleum. These chemicals include: ethylene, used to make anesthetics, antifreeze, and detergents; propylene, used to produce acetone and phenol; benzene, used to make other chemicals and explosives; toluene, used as a solvent and in refined gasoline; and xylene is used as a solvent and cleaning agent.

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Refined Petroleum Products

Name Refinery Gas Gasoline Naphtha Kerosene (paraffin) Diesel Oil Lubricating Oil Fuel Oil Greases and Wax Bitumen Number of Carbon Atoms 3 or 4 7 to 9 6 to 11 11 to 18 11 to 18 18 to 25 20 to 27 25 to 30 above 35 Boiling Point (C) below 30 100 to 150 70 to 200 200 to 300 200 to 300 300 to 400 350 to 450 400 to 500 above 500 Uses Bottled gas (propane or butane). Fuel for car engines. Solvents and used in gasoline. Fuel for aircraft and stoves. Fuel for road vehicles and trains. Lubricant for engines and machines. Fuel for ships and heating. Lubricants and candles. Road surface and roofing.

Fuels: Properties for Automotive Application

(1) Calorific Value Solids and Liquids -Defined as the heat liberated in kJ by complete combustion of 1 kg of fuel. For Gases Expressed in kJ/m3 of gas at S.T.P. Further classified as higher calorific value (HCV) and lower calorific value (LCV): (a) Higher Calorific Value (HCV) All fuels containing hydrogen in the available form will react with oxygen during combustion to generate steam. The steam may condense when the products of combustion are cooled to initial temperature. This results is maximum heat being extracted. This heat value is called Higher or Gross Calorific Value (HCV) (b) Lower Calorific Value (LCV) It is the difference in the HCV and the heat absorbed by water during its conversion to vapor, constituents supplied at air temperature. t of f latent l t t heat h t depends d d on the th pressure at t which hi h the th phase h h h occurred, d which hi h is i Th The amount change has difficult to estimate. It may be assumed for the evaporation to take place at saturation pressure corresponding to Std. temperature of 15 C. The latent heat corresponding to this saturation temperature is 2466 kJ/kg. Hence, L.C.V. = (H.C.V. x . 2466) kJ/kg Here , x fraction of water vapor present in the products of combustion for 1 kg of fuel.

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Fossil Fuels: Composition and Properties

Fuel Petrol Paraffin Diesel Oil Heavy fuel oil Specific Gravity 0.74 6.79 0.87 0.95 % composition by weight C 85.4 86.3 86.3 86.1 H2 14.6 13.6 12.8 11.8 S 0.1 0.9 2.1 HCV kJ/kg 46900 46500 46000 44000

Liquid Fuels

Fuel H2 C lG Coal Gas Town Gas Coke Oven gas Producer Gas 27 55 50 6

Percentage Volumetric composition CO 7 14 8 23 CH 48 8 23 29 3 C2H4 13 2.5 4 0.2 CO2 3 2 2 5.8 N2 2 3.5 7 62

Calorific Value kJ/m3 HCV 31900 19500 21300 5000 LCV 29000 17500 19300 4800

Gaseous Fuels

Fuels: Properties for Automotive Application

(2) Flash point Lowest temperature at which a volatile substance can vaporize to for a ignitable mixture with air. Different from Auto-ignition temperature which does not require an ignition source or Fire point viz. temperature above which the fuel continues to burn after being ignited. (3) Pour point Lowest temperature at which the liquid becomes semisolid and loses its flow characteristics.

(4) Heat of formation The free energy of chemical elements at 1 atm. 25 C arbitrarily assumed to be zero. Standard free energy of formation (Enthalpy of formation) of a compound,

gf0 , is the free energy

change is formed directly g when one mole of the compound p y from its constituent elements. The constituents are at 298 K & 1 atm. The value will be different at different conditions.
Compound CO CO2 Water H (J/ kg. mole) -110 x 106 -394 x -286 x 106 106 G (J/ kg. mole) -137 x 106 -395 x 106 -237 x 106

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Fuels: Properties for Automotive Application

(5) Octane Number Rating of SI engine fuels is based on its antiknock property. The property is compared with that of a mixture of iso-octane (C8H18) nad normal heptane (C7H16). Iso-octane rating 100, heptane- rating 0). Octane number is the percentage by volume of, iso-octane in a mixture of iso-octane and normal heptane, which exactly matched the knocking intensity in a standard engine under standard conditions. (6) Cetane Number Cetane number is the percentage by volume of normal cetane in mixture of reference fuels that gives same knocking intensity as of the fuel under standard conditions. Reference fuels are normal cetane (rating 100) and alpha methyl naphthalene (rating 0). ( ) Knocking (7) ki Characteristics h i i Difference between time of injection and actual combustion termed as ignition lag. Increase in ignition lag increase in amount of fuel being accumulated in the cylinder. Hence, combustion afterwards, leads to abnormal release of energy causing knocking. Lag leads to problems in starting, warm up and exhaust smoke. Hence, high Cetane rating fuel preferred.

Fuels: Properties for Automotive Application

(8) Antiknock Quality Abnormal burning causes unwanted temperature and pressure surges in the cylinders, affects the efficiency. Antiknock quality resists the tendency for detonation during combustion. It t depe depends ds o on se self ignition g to c characteristics a acte st cs a and d co composition pos t o o of t the e fuel. ue . Better SI engine less knocking higher compression ratios better efficiency -more power output.

(9) Volatility Depends on fractional composition of the fuel in terms of hydrocarbon components. Standard process of measuring the volatility of the fuel is by distillation at atmospheric pressure, in presence of its vapor. The fraction that boils off at a particular temperature is measured. Characteristic points 10, 40, 50 & 90 % of fuel evaporation and the temperature at which boiling ceases. Distillation curves for Petrol

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Fuels: Properties for Automotive Application

(10) Starting and Warming up Certain part of the fuel should vaporize at room temperature for easy starting. Hence, the distillation curve temperature values for 0 -10 % boil off should be relatively low. As the engine warms up, the temperature will gradually reach operating value. (11) Crankcase Dilution Liquid fuel in cylinders deteriorates oil quality or dilutes the oil causing weak oil films between rubbing surfaces. So, the upper portion of distillation curve should have low boil off temperatures so that all the fuel is vaporized before combustion. (12) Vapor Lock Characteristics Faster vaporization of fuel can affect the carburetor metering or stop fuel flow due to vapor lock in passages. This requires the presence of high boiling point components throughout the distillation curve, which contradicts the previous requirements. Hence, the about requirements must be optimized for desired temperature.

Fuels: Properties for Automotive Application

(13) Sulphur Content Free sulphur, H2S and other such compounds may corrode the fuel lines and fuel control devices. Sulphur may also combine with oxygen and later with water to form sulphurous acid. Low ignition temperature of Sulphur can promote knocking. (14) Gum Deposits Storage of the fuel causes hydrocarbons or impurities to oxidize and form gum like substances. These can hinder the normal operation of valves and piston rings. (15) Corrosion and Wear Should not damage the system in operation. Associated with presence of sulphur and impurities. (16) Handling Easily flow under wide range of conditions Low Pour point. High Flash and Fire point.

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