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ME 422 Introduction to Combustion Fall 2013 Instructor: Dr. Elisa Toulson

Lecture 3-Fuels

Homework
Due September 12th: Chapter 17 Questions 17.1, 17.2, 17.3, 17.8

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Natural Gas
Primarily methane with smaller quantities of other light (C2-C8) hydrocarbons,N2, CO2, He, hydrogen sulfide, water, O2 also present. Natural gas usually forms underground and rises towards the surface until it gets trapped by some geological formation such as layers of porous sedimentary rock with a denser impermeable layer of rock on top. Gas in these reservoirs is generally under pressure so once a hole is made in the impermeable rock the gas will escape on it own.

Natural Gas Uses

In the U.S. natural gas is mostly used in the transportation sector for fleets but as of 2008 there were 9.6 million natural gas vehicles worldwide, led by Pakistan (2.0 million), Argentina (1.7 million), Brazil (1.6 million), Iran (1.0 million), and India (650,000)

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Typical Composition of Biogas

Biogas
Biogas: a gas produced by the biological breakdown of organic matter in the absence of oxygen Biogas is produced by the anaerobic digestion or fermentation of biodegradable materials such as biomass, manure, sewage, municipal waste, green waste, plant material, and crops. Biogas comprises primarily methane (CH4) and carbon dioxide (CO2) and may have small amounts of hydrogen sulphide (H2S).

Compound Methane Nitrogen Hydrogen Hydrogen sulfide Oxygen

Chem CH4 N2 H2 H2S O2

% 5075 2550 010 01 03 00

Carbon dioxide CO2

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Synthetic Gas (Syngas)

Gasification process for syngas production

C + H2O CO + H2 H298 = 175.3 kJ/mol C + O2 CO2 H298 = -393.5 kJ/mol CO2 + C 2CO H298 = 172.5 kJ/mol

More than a million Wood Gas Vehicles were used when fuel was rationed during World War 2.

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Fisher Tropsch Liquid Fuels

Interest in gas-to-liquid or Fischer-Tropsch diesel fuels has increased in recent years because of their potential to displace imported petroleum. Fisher-Tropsch process was invented in the 1920s in Germany and during World War 2 production accounted for an estimated 9% of German war production of fuels and 25% of the automobile fuel. The price of oil determines whether Fisher-Tropsch synthesis fuels are viable as capitol costs are high. Commercial Fisher-Tropsch synthesis plants have been in operation in South Africa for more than 50 years where an abundance of coal and government policy makes them viable.

Fisher Tropsch Liquid Fuels

Synthetic Liquid Fuels can be generated from the syngas derived from various feedstocks using the Fisher-Tropsch synthesis process. The FischerTropsch process involves a series of chemical reactions that produce a variety of hydrocarbons molecules . The more useful reactions produce alkanes as follows: (2n+1) H2 + n CO CnH(2n+2) + n H2O Most of the alkanes produced tend to be straight-chain, suitable as diesel fuel. In addition to alkane formation, competing reactions give small amounts of alkenes, as well as alcohols and other oxygenated hydrocarbons.

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Fisher-Tropsch Reactor

Hydrogen
Hydrogen gas is highly flammable and will burn in air at a very wide range of concentrations between 4% and 75% by volume When hydrogen combusts in air, the products are water and nitrogen, but there is potential to form nitrogen oxides (NOx). The main advantages of hydrogen are that it burns easily, it can be used almost directly in systems that are well developed and reliable, and it can significantly reduce fossil fuel consumption. Hydrogen can be produced two ways: by the decomposition of water through electrolysis or by the reformation of fossil fuels

The Space Shuttle Main Engine burnt hydrogen with oxygen, producing a nearly invisible flame at full thrust.

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Considerations for the Choice of Fuels

For most combustion processes, air is used as the oxidizer because air is free and available almost everywhere on earth. Choice of fuel depends on purpose of the combustion process and is subject to local safety and emission regulations:
Energy content per volume or per mass Safety Combustion and fuel properties Cost

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Identification of Fuel by Molecular Structure: IUPAC

The identification of a fuel can be best defined by its molecular structure. For organic chemistry, the convention adopted by International Union of Pure and Applied Chemistry (IUPAC) is well established and should be used.

Naming Conventions for Hydrocarbon Fuels Commonly used for Combustion

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Naming Conventions
Prefixes for Hydrocarbon Fuels

Naming Conventions
The word endings ane, -ene, yne indicate how the carbon atoms are bound in the molecule Saturated is used to denote hydrocarbon molecules in which the maximum number of hydrogen atoms is associated with carbon atoms (i.e. the molecule has no double or triple bonds) Alkanes are saturated, Alkenes and Alkynes are unsaturated

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Naming Conventions
Alkanes with 3 or more carbons can have branches, and such alternative fuel structures are called isomers. Straight chains are denoted as normal (n-) Isomers are molecules with the same chemical formula and often the same kinds of chemical bonds between atoms, but in which the atoms are arranged differently Larger molecules tend to have more isomers. Many isomers share similar if not identical properties in most chemical contexts. Combustion characteristics of isomers, particularly their ignition properties, may be quite different.

Octane has 18 isomers

n-octane C8H18

iso-octane C8H18 2,2,4-trimethylpentane

Example
What is the structural formula for: 2,2,4-trimethyl pentane (iso-octane)

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Question
What is the structural formula for 2-2 dimethylpropane ?

Answer

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Question
What is the structural formula for 2-4-5-trimethyl-3-ethyloctane?

Answer

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The basic molecular structure of Cyclanes is a closed ring, with all carbon atoms singly bonded.

Cyclanes

More complex cyclanes are formed by the substitution of parraffinic groups for H atoms

Methylcyclohexane: most common cycloalkane found in petroleum

Aromatic or benzene family is based on a ring of 6 carbons but with only one hydrogen atom associated with each carbon atom. The resulting 6 free valence electrons from resonance hybrid bonds among the six carbon atoms in the ring so that all of the bonds are equivalent, with the bonding electrons delocalized over several atoms

Aromatics

The term 'aromatic' was assigned before the physical mechanism determining aromaticity was discovered, and was derived from the fact that many of the compounds have a sweet scent.
Napthalene Asprin ethylbenzene

or Toluene or methylbenzene

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Alcohols (ROH)
Common alcohols are formed by the substitution of a hydroxyl group (OH) for an H atom in an alkane molecule. Alcohols are generically designated as ROH, where R is the hydrocarbon radical

Aldehyde
Aldehydes can be emitted from diesel engines and those fueled with alcohols. Aldehydes contribute to photochemical smog
Formaldehyde, Volatile Organic Compound (VOC)

SMOG

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Ketones
Ketones are used as solvents and are formed as intermediate species of Hydrocarbon combustion Acetone is a common Ketone

Ether (R-O-R)
The general structure of an ether is

or

Dimethyl ether

Diethyl ether or

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Esters
Esters are chemical compounds consisting of a carbonyl adjacent to an ether linkage which are derived by reacting an oxoacid with a hydroxyl compound such as an alcohol or phenol Ester names are derived from the parent alcohol and the parent acid Most naturally occurring fats and oils are the fatty acid esters of glycerol

Esters- Important constituents of biodiesel

Methyl linoleate a methyl ester produced from soybean or canola oil and methanol

Ethyl stearate an ethyl ester produced from soybean or canola oil and ethanol

The five primary methyl esters found in biodiesel fuels produced from soy and rapeseed

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Relative amounts of various chemical classes in diesel fuel and possible compounds to represent these chemical classes in a diesel surrogate fuel

General Distribution of Hydrocarbons in Gasoline

Gasoline can consist of more that 500 different types of hydrocarbons between 5 and 12 carbons.

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Properties of Fuels
Ignition Characteristics Volatility Energy Density Flash Point Pour Point Cloud Point

Spark Ignition Engine Ignition

Ignition Quality refers to the prevention of Knock Knock is the spontaneous ignition (auto-ignition or detonation)of the endgas (unburned mixture) ahead of the flame. Detonation is characterized by an instantaneous, explosive ignition of at least one pocket of fuel/air mixture outside of the flame front. A local shockwave is created and the cylinder pressure may rise sharply beyond its design limits and cause engine damage. Pre-ignition is when the mixture in the cylinder ignites before the spark plug fires. Preignition is initiated by an ignition source other than the spark

Engine damage due to knock

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Normal Combustion

Pre-Ignition

Knock

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