FUEL USED IN IC ENGINES AND REFINERY PROCCESSES; EME-505

FUEL USED IN IC ENGINES

An article on fossil fuels

Internal Combustion Engines are the generators of the energy mainly used for transportation. Almost more than 90% of the total IC Engines run on fossil fuels or different derivatives of petroleum.

IC Engines are a kind of open cycle heat engine where heat is supplied to the engine by the combustion of working fluids thus releasing huge amount of energy due to the combustion processes of the working fluids. Combustible working fluids are called fuels.

The natural petroleum oil is the largest single source of internal combustion engine fuels. Petrol and Diesel are the most used among them. The boiling point of petrol is 30°C to 200°C and that of diesel oil is from 200°C to 375°C.

Fuels of most of the IC Engines are the derivatives of Petroleum like gasoline, diesel oil, kerosene, jet fuel etc. All of these fuels are produced during the fractional distillation of Petroleum Oil obtained from crude from oil wells.

The fuels used in the IC Engines are designed to satisfy the performance requirements of the engine system in which they are used. As a result the fuels must have certain

• (i) physical,
• (ii) chemical and
• (iii) combustion properties.

Following are the some characteristics a fuel must have in order to produce the desirable output to the engine performance.

1. A fuel must have a large energy density to be capable to release huge amount of energy during its combustion in side the combustion chamber.
2. A fuel must posses a good combustion quality to produce large amount of energy in smooth way.
3. A fuel must have high thermal stability or pre-ignition may occur.
4. A fuel must show a low deposit forming tendency else gum formation and other deposit forming processes will hamper the combustion process.
5. A fuel must be non-toxic, easy to handle and storage.

CRUDE PETROLEUM OIL:

Petroleum or often referred as "Crude Oil" is a naturally occurring inflammable mixtures of liquid and mud and it contains a complex mixture of different hydrocarbons of various molecular weights. It is mainly recovered through a process called "Oil Drilling".

Oil Wells and Gas Wells:

An oil well produces mainly crude oil with some natural gas dissolved in it. In contrast a gas well produces natural gases although it may contain heavier hydrocarbons like pentane, hexane or hepthane in gaseous state due to the extreme pressure and temperature inside the well, but at surface conditions condensation starts and forms "Natural Gas Condensate" or simply known as Condensate.



COMPOSITIONS OF CRUDE WELL:

Basically, crude well is the muddy mixtures of different hydrocarbons of different molecular weights. Alkanes, Cyclo-alkanes or napthenes, aromatics. It contains nitrogen, oxygen, sulfur and phosphorous. It may also contains metallic compounds too.

Four different types of hydrocarbon molecules appear in crude oil. The relative percentages are widely varied from oil to oil. They are:

• i) Paraffins (alkanes,  C_nH_{2n + 2} )
• ii) Olefins (alkenes, C_nH_2n),
• iii) Napthenes (cyclo-alkanes, C_nH_2n ),
• iv) Aromatics (having benzene ring, C_nH_{2n - 6}).

It is then refined by fractional distillation in oil refinery to obtain a large number of consumer products, from petrol or gasoline, diesel to kerosene, heavy oil, fuel oil, asphalt, chemical reagents, plastics etc.

Most of the derivatives of the petroleum have been used as fuel or heating purpose. The major products of a petroleum refinery are:

• (i) Gasoline,
• (ii) Kerosene,
• (iii) Diesel Oil,
• (iv) Fuel oil,
• (v) Heavy Oil,
• (vi) Lubricating Oil,
• (vii) Asphalts

INTRODUCTION: 

As the demands for gasoline, kerosene/ jet fuel and diesel oil are maximum, refineries around the world have started to convert heavy fuels and other higher hydrocarbons into gasoline, kerosene and diesel oil. To perform this, refineries have adopted several thermo-chemical processes those can convert high molecular weight hydrocarbons into lighter ones by breaking them.

GENERAL REFINERY PROCESSES:

Petroleum refining has evolved continuously in response to changing consumer demand for better and different products. The original requirement was to produce kerosene as a cheaper and better source of light than whale oil. The development of the internal combustion engine led to the production of gasoline and diesel fuels. The evolution of the airplane created an initial need for high-octane aviation gasoline and then for jet fuel, a sophisticated form of the original product, kerosene. Present-day refineries produce a variety of products including many required as feedstock for the petrochemical industry.

a) Distillation Processes:

The first refinery, opened in 1861, produced kerosene by simple atmospheric distillation. Its by-products included tar and naphtha. It was soon discovered that distilling petroleum under vacuum could produce high-quality lubricating oils. However, for the next 30 years kerosene was the product consumer wanted. Two significant events changed this situation. The invention of the electric light decreased the demand for kerosene and the invention of the internal combustion engine created a demand for diesel fuel and gasoline (naphtha). 

b) Thermal Cracking Processes:

With the advent of mass production and World War I, the number of gasoline-powered vehicles increased dramatically and the demand for gasoline grew accordingly. However, distillation processes produced only a certain amount of gasoline from crude oil. In 1913, the thermal cracking process was developed, which subjected heavy fuels to both pressure and intense heat, physically breaking the large molecules into smaller ones to produce additional gasoline and distillate fuels. Visbreaking, another form of thermal cracking, was developed in the late 1930's to produce more desirable and valuable products. 

c) Catalytic Processes:

Higher-compression gasoline engines required higher-octane gasoline with better antiknock characteristics. The introduction of catalytic cracking and polymerization processes in the mid- to late 1930's met the demand by providing improved gasoline yields and higher octane numbers.   Alkylation, another catalytic process developed in the early 1940's, produced more high-octane aviation gasoline and petrochemical feedstock for explosives and synthetic rubber. Subsequently, catalytic isomerization was developed to convert hydrocarbons to produce increased quantities of alkylation feedstock. Improved catalysts and process methods such as hydrocracking and reforming were developed throughout the 1960's to increase gasoline yields and improve antiknock characteristics. These catalytic processes also produced hydrocarbon molecules with a double bond (alkenes) and formed the basis of the modern petrochemical industry. 

d) Treatment Processes:

Throughout the history of refining, various treatment methods have been used to remove non-hydrocarbons, impurities, and other constituents that adversely affect the properties of finished products or reduce the efficiency of the conversion processes. Treating can involve chemical reaction and/or physical separation. Typical examples of treating are chemical sweetening, acid treating, clay contacting, caustic washing, hydrotreating, drying, solvent extraction, and solvent dewaxing. Sweetening compounds and acids desulfurize crude oil before processing and treat products during and after processing. 

Following the Second World War, various reforming processes improved gasoline quality and yield and produced higher-quality products. Some of these involved the use of catalysts and/or hydrogen to change molecules and remove sulfur. 

 Basics of Hydrocarbon Chemistry:

Crude oil is a mixture of hydrocarbon molecules, which are organic compounds of carbon and hydrogen atoms that may include from one to 60 carbon atoms. The properties of hydrocarbons depend on the number and arrangement of the carbon and hydrogen atoms in the molecules. The simplest hydrocarbon molecule is one carbon atom linked with four hydrogen atoms: methane. All other variations of petroleum hydrocarbons evolve from this molecule. 

 

Hydrocarbons containing up to four carbon atoms are usually gases, those with 5 to 19 carbon atoms are usually liquids and those with 20 or more are solids. The refining process uses chemicals, catalysts, heat, and pressure to separate and combine the basic types of hydrocarbon molecules naturally found in crude oil into groups of similar molecules. The refining process also rearranges their structures and bonding patterns into different hydrocarbon molecules and compounds. Therefore it is the type of hydrocarbon (paraffinic, naphthenic, or aromatic) rather than its specific chemical compounds that is significant in the refining process. 

Principal Groups of Hydrocarbon

• Paraffins - The paraffinic series of hydrocarbon compounds found in crude oil have the general formula C_nH_2n+2 and can be either straight chains (normal) or branched chains (isomers) of carbon atoms. The lighter, straight chain paraffin molecules are found in gases and paraffin waxes. Examples of straight-chain molecules are methane, ethane, propane, and butane (gases containing from one to four carbon atoms), and pentane and hexane (liquids with five to six carbon atoms). The branched-chain (isomer) paraffins are usually found in heavier fractions of crude oil and have higher octane numbers than normal paraffins. These compounds are saturated hydrocarbons, with all carbon bonds satisfied, that is, the hydrocarbon chain carries the full complement of hydrogen atoms.
  • Example of simplest hydrocarbon molecule: Methane (CH₄), Examples of straight chain paraffin molecule (Butane) and branched paraffin molecule (Isobutane) with same chemical formula (C₄H₁₀)
    
    
    
    
• Aromatics - Aromatics are unsaturated ring-type (cyclic) compounds which react readily because they have carbon atoms that are deficient in hydrogen. All aromatics have at least one benzene ring (a single-ring compound characterized by three double bonds alternating with three single bonds between six carbon atoms) as part of their molecular structure. Naphthalenes are fused double-ring aromatic compounds. The most complex aromatics, polynuclears (three or more fused aromatic rings), are found in heavier fractions of crude oil.
  • Example of simple aromatic compound: Benzene (C₆H₆), Examples of simple double-ring aromatic compound: Naphthalene (C₁₀H₈)
    
    
    
    
• Naphthenes - Naphthenes are saturated hydrocarbon groupings with the general formula C_nH_2n, arranged in the form of closed rings (cyclic) and found in all fractions of crude oil except the very lightest. Single-ring naphthenes (monocycloparaffins) with five and six carbon atoms predominate, with two-ring naphthenes (dicycloparaffins) found in the heavier ends of naphtha.
  • Example of typical single-ring naphthene: Cyclohexane (C₆H₁₂), Examples of naphthene with same chemical formula (C₆H₁₂) but different molecular structure: Methyl cyclopentane (C₆H₁₂)

Other Hydrocarbons

• Alkenes - Alkenes are mono-olefins with the general formula C_nH_2n and contain only one carbon-carbon double bond in the chain. The simplest alkene is ethylene, with two carbon atoms joined by a double bond and four hydrogen atoms. Olefins are usually formed by thermal and catalytic cracking and rarely occur naturally in unprocessed crude oil.
  • Example of simples Alkene: Ethylene (C₂H₄), Typical Alkenes with the same chemical formula (C₄H₈) but different molecular structures: 1-Butene and Isobutene
    
    
    
    
• Dienes and Alkynes - Dienes, also known as diolefins, have two carbon-carbon double bonds. The alkynes, another class of unsaturated hydrocarbons, have a carbon-carbon triple bond within the molecule. Both these series of hydrocarbons have the general formula CnH2n-2. Diolefins such as 1,2-butadiene and 1,3-butadiene, and alkynes such as acetylene,occur in C5 and lighter fractions from cracking. The olefins, diolefins, and alkynes are said to be unsaturated because they contain less than the amount of hydrogen necessary to saturate all the valences of the carbon atoms. These compounds are more reactive than paraffins or naphthenes and readily combine with other elements such as hydrogen, chlorine, and bromine.
  • Example of simplest Alkyne: Acetylene (C₂H₂), Typical Diolefins with the same chemical formula (C₄H₆) but different molecular structures: 1,2-Butadiene and 1,3-Butadiene

Non-hydrocarbons

• Sulfur Compounds -  Sulfur may be present in crude oil as hydrogen sulfide (H₂S), as sulfur compounds such as mercaptans, sulfides, disulfides, thiophenes, etc. or as elemental sulfur. Each crude oil has different amounts and types of sulfur compounds, but as a rule the proportion, stability, and complexity of the compounds are greater in heavier crude-oil fractions. Hydrogen sulfide is a primary contributor to corrosion in refinery processing units. Other corrosive substances are elemental sulfur and mercaptans. Moreover, the corrosive sulfur compounds have an obnoxious odor.  Pyrophoric iron sulfide results from the corrosive action of sulfur compounds on the iron and steel used in refinery process equipment, piping, and tanks. The combustion of petroleum products containing sulfur compounds produces undesirables such as sulfuric acid and sulfur dioxide. Catalytic hydrotreating processes such as hydrodesulfurization remove sulfur compounds from refinery product streams. Sweetening processes either remove the obnoxious sulfur compounds or convert them to odorless disulfides, as in the case of mercaptans.
  
  
• Oxygen Compounds -  Oxygen compounds such as phenols, ketones, and carboxylic acids occur in crude oils in varying amounts. 
  
  
• Nitrogen Compounds -  Nitrogen is found in lighter fractions of crude oil as basic compounds, and more often in heavier fractions of crude oil as nonbasic compounds that may also include trace metals such as copper, vanadium, and/or nickel. Nitrogen oxides can form in process furnaces. The decomposition of nitrogen compounds in catalytic cracking and hydrocracking processes forms ammonia and cyanides that can cause corrosion. 
  
  
• Trace Metals -  Metals, including nickel, iron, and vanadium are often found in crude oils in small quantities and are removed during the refining process. Burning heavy fuel oils in refinery furnaces and boilers can leave deposits of vanadium oxide and nickel oxide in furnace boxes, ducts, and tubes. It is also desirable to remove trace amounts of arsenic, vanadium, and nickel prior to processing as they can poison certain catalysts. 
  
  
• Salts -  Crude oils often contain inorganic salts such as sodium chloride, magnesium chloride, and calcium chloride in suspension or dissolved in entrained water (brine). These salts must be removed or neutralized before processing to prevent catalyst poisoning, equipment corrosion, and fouling. Salt corrosion is caused by the hydrolysis of some metal chlorides to hydrogen chloride (HCl) and the subsequent formation of hydrochloric acid when crude is heated. Hydrogen chloride may also combine with ammonia to form ammonium chloride (NH₄Cl), which causes fouling and corrosion. 
  
  
• Carbon Dioxide -  Carbon dioxide may result from the decomposition of bicarbonates present in or added to crude, or from steam used in the distillation process. 
• Naphthenic Acids -  Some crude oils contain naphthenic (organic) acids, which may become corrosive at temperatures above 450° F when the acid value of the crude is above a certain level.

 Major Refinery Products

• Gasoline. The most important refinery product is motor gasoline, a blend of hydrocarbons with boiling ranges from ambient temperatures to about 400 °F. The important qualities for gasoline are octane number (antiknock), volatility (starting and vapor lock), and vapor pressure (environmental control). Additives are often used to enhance performance and provide protection against oxidation and rust formation.
• Kerosene. Kerosene is a refined middle-distillate petroleum product that finds considerable use as a jet fuel and around the world in cooking and space heating. When used as a jet fuel, some of the critical qualities are freeze point, flash point, and smoke point. Commercial jet fuel has a boiling range of about 375°-525° F, and military jet fuel 130°-550° F. Kerosene, with less-critical specifications, is used for lighting, heating, solvents, and blending into diesel fuel.
• Liquified Petroleum Gas (LPG). LPG, which consists principally of propane and butane, is produced for use as fuel and is an intermediate material in the manufacture of petrochemicals. The important specifications for proper performance include vapor pressure and control of contaminants.
• Distillate Fuels. Diesel fuels and domestic heating oils have boiling ranges of about 400°-700° F. The desirable qualities required for distillate fuels include controlled flash and pour points, clean burning, no deposit formation in storage tanks, and a proper diesel fuel cetane rating for good starting and combustion.
• Residual Fuels. Many marine vessels, power plants, commercial buildings and industrial facilities use residual fuels or combinations of residual and distillate fuels for heating and processing. The two most critical specifications of residual fuels are viscosity and low sulfur content for environmental control.
• Coke and Asphalt. Coke is almost pure carbon with a variety of uses from electrodes to charcoal briquets. Asphalt, used for roads and roofing materials, must be inert to most chemicals and weather conditions.
• Solvents. A variety of products, whose boiling points and hydrocarbon composition are closely controlled, are produced for use as solvents. These include benzene, toluene, and xylene.
• Petrochemicals. Many products derived from crude oil refining, such as ethylene, propylene, butylene, and isobutylene, are primarily intended for use as petrochemical feedstock in the production of plastics, synthetic fibers, synthetic rubbers, and other products.
• Lubricants. Special refining processes produce lubricating oil base stocks. Additives such as demulsifiers, antioxidants, and viscosity improvers are blended into the base stocks to provide the characteristics required for motor oils, industrial greases, lubricants, and cutting oils. The most critical quality for lubricating-oil base stock is a high viscosity index, which provides for greater consistency under varying temperatures.

Common Refinery Chemicals

• Leaded Gasoline Additives: Tetraethyl lead (TEL) and tetramethyl lead (TML) are additives formerly used to improve gasoline octane ratings but are no longer in common use except in aviation gasoline.
• Oxygenates: Ethyl tertiary butyl ether (ETBE), methyl tertiary butyl ether (MTBE), tertiary amyl methyl ether (TAME), and other oxygenates improve gasoline octane ratings and reduce carbon monoxide emissions.
• Caustics: Caustics are added to desalting water to neutralize acids and reduce corrosion. They are also added to desalted crude in order to reduce the amount of corrosive chlorides in the tower overheads. They are used in some refinery treating processes to remove contaminants from hydrocarbon streams.
• Sulfuric Acid and Hydrofluoric Acid: Sulfuric acid and hydrofluoric acid are used primarily as catalysts in alkylation processes. Sulfuric acid is also used in some treatment processes.
  
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