(Lectures 2, 3 & 4) Energy Resources and Usage; Fuels and Thermochemistry I, II & III A. U.S.

Energy Outlook (Attachment A PowerPoint Presentation) B. International Energy Outlook (Attachment B PowerPoint Presentation) C. Background 1. Combustion and chemical reactions play a very important role in our everyday lives, in many engineering applications, and in the study of energy and environment. 2. Combustion may be defined as the process of burning a substance in the presence of air or oxygen with the liberation of light and heat. 3. An example of an unwanted chemical reaction is shown below:

Smoke from the Station Fire rises over downtown Los Angeles Monday, Aug. 31, 2009. (AP Photo/Jon Vidar)

D. Representative Applications 1. Electric power plants (Coal, Gas) 2. Transportation: Automobiles, Aircraft, Ships, Buses a. Liquid fuels such as Gasoline, Diesel fuel, Jet Fuel, Ethanol, and Biodiesel) b. Gaseous fuels such as propane and natural gas 3. Rocket Motors (Liquid, Solid Propellants) MAE 136 Lectures 2, 3 & 4 Page 1

4. Energy Intensive Industries (Cement Coal, Steel Oil, Gas, Glass Gas, Aluminum Oil, Gas, Pulp and Paper Wood) 5. Household and Industrial Heating (Oil, Gas) 6. Forest Fires 7. Fuel Cells and Other Solid State Devices 8. Chemical Reactions in the Human Body E. Composition of Dry Air

1. Gaseous composition of dry air.

Constituent Nitrogen Oxygen Argon Carbon dioxide Neon Helium Methane Krypton Hydrogen Nitrous oxide Xenon Ozone* Carbon monoxide Sulfur dioxide Nitrogen dioxide Ammonia

Chemical symbol N2 O2 Ar CO2 Ne He CH4 Kr H2 N2O Xe O3 CO SO2 NO2 NH3

Mole percent 78.084 20.947 0.934 0.0350 0.001818 0.000524 0.00017 0.000114 0.000053 0.000031 0.0000087 trace to 0.0008 trace to 0.000025 trace to 0.00001 trace to 0.000002 trace to 0.0000003

* Low concentrations in troposphere; ozone maximum in the 30- to 40-km regime of the equatorial region. Mackenzie, F.T. and J.A. Mackenzie (1995), Our Changing Planet. Prentice-Hall, Upper Saddle River, NJ, p 288-307. (After Warneck, 1988; Anderson, 1989; Wayne, 1991. http://eesc.columbia.edu/courses/ees/slides/climate/table_1.html. 2. For the purpose of simplifying the analyses slightly, it will be assumed that air consists of 21 percent O2 and 79 percent N2 by volume. Thus, each mole of oxygen will be accompanied by MAE 136 Lectures 2, 3 & 4 Page 2

Furthermore 1 kmol O2 + 3.76 knol N2 = 4.76 kmol of air F. Chemical Reactions A + Reactants G. Burning of Hydrogen in Oxygen 1 H2 + a O2 b H2O Conservation of Species: H Balance: 2 + 0 = 2b O Balance: 0 + 2a = b b=1 a = b/2 = a= B C Products

Therefore, the chemical reaction is 1 H2 + O2 1 H2O The coefficients a and b are referred to as stoichiometric coefficients, i.e., the coefficients in the theoretical equation. Most real reactions are not stoichiometric and depend on the quantity of reactants as well as pressure and temperature. Such situations require the study of chemical equilibrium. H. Burning of Hydrogen in Air When hydrogen burns in air 1 H2 + (O2 + 3.76 N2) 1 H2O + d N2 N2 Balance: (3.76) = d and 1 H2 + (O2 + 3.76 N2) 1 H2O + 1.88 N2 Although nitrogen remains inert in chemical reactions, it plays an important role in First Law calculations as will be seen. I. Role of Air in Combustion Processes 1. The theoretical air is the minimum amount of air that supplies sufficient oxygen for the complete combustion of all the carbon, hydrogen, and any other elements in the fuel that may oxidize. When complete combustion is achieved, there is no free oxygen in the products. MAE 136 Lectures 2, 3 & 4 Page 3 d = 1.88

2. When the amount of air supplied is less than the theoretical air required, the combustion is incomplete. The result is CO and hydrocarbons in the products of combustion. 3. When the amount of air supplied is greater than the theoretical air required, there is free oxygen in the products. 4. Although the nitrogen remains inert (except at very high temperature reactions), its temperature does change and must be taken into consideration. J. Air-Fuel Ratio, AF 1. For the reaction in Part H, the air-fuel ratio on a molar basis is =

On a mass basis

2. The equivalence ratio is defined as the ratio of the actual fuel-air ratio to the fuel-air ratio for complete combustion with the theoretical amount of air. The reactants are said to form a lean mixture when the equivalence ratio is less than unity, and a rich mixture when it is greater than unity. K. Burning of Hydrogen with 150 Percent Theoretical Air Note that 150 percent theoretical air also corresponds to 50 percent excess air: 1 H2 + 1.5 (1/2) (O2 + 3.76 N2) H2O + e O2 + f N2 O Balance: N Balance: The reaction in this case is

and the molar air-fuel ratio is =

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L. Fossil Fuels 1. Organic All compounds of carbon. Example: Coal. 2. Hydrocarbons (Liquid or Gas): Made up only of carbon & oxygen, CxHy .

Coal
Sedimentary Rock

Anthracite coal

Composition

Primary

Carbon

Secondary

hydrogen, sulfur, oxygen, nitrogen

3. Coal Coal is a combustible black or brownish-black sedimentary rock usually occurring in rock strata in layers or veins called coal beds or coal seams. The harder forms, such as anthracite coal, can be regarded as metamorphic rock because of later exposure to elevated temperature and pressure. Coal is composed primarily of carbon along with variable quantities of other elements, chiefly hydrogen, sulfur, oxygen, and nitrogen.

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Classification of Coal (U.S. Department of Energy, http://fossil.energy.gov/education, March 15, 2012) Lignite: The largest portion of the world's coal reserves is made up of lignite, a soft, brownish-black coal that forms the lowest level of the coal family. You can even see the texture of the original wood in some pieces of lignite that is found primarily west of the Mississippi River in the United States. Subbituminous: Next up the scale is subbituminous coal, a dull black coal. It gives off a little more energy (heat) than lignite when it burns. It is mined mostly in Montana, Wyoming and a few other western states. Bituminous: Still more energy is packed into bituminous coal, sometimes called "soft coal." In the United States, it is found primarily east of the Mississippi River in midwestern states like Ohio and Illinois and in the Appalachian mountain range from Kentucky to Pennsylvania. Anthracite: Anthracite is the hardest coal and gives off a great amount of heat when it burns. Unfortunately, in the United States, as elsewhere in the world, there is little anthracite coal to be mined. The U.S. reserves of anthracite are located primarily in Pennsylvania

Throughout history, coal has been a useful resource for human consumption. It is primarily burned as a fossil fuel for the production of electricity and/or heat, and is also used for industrial purposes such as refining metals. Coal forms when dead plant matter is converted into peat, which in turn is converted into lignite, then anthracite. This involves biological and geological processes that take place over a long period of time. Coal, a fossil fuel, is the largest source of energy for the generation of electricity worldwide, as well as one of the largest worldwide anthropogenic sources of carbon dioxide releases. Gross carbon dioxide emissions from coal usage are slightly more than those from petroleum and about double the amount from natural gas. Coal is extracted from the ground by mining, either underground by shaft mining through the seams or in open pits. The energy density of coal, i.e. its heating value, is roughly 24 MJ/kg. 4. Petroleum (Energy Choices: A Guide to Facts and Perspectives, ASME, NY 2010) Petroleum or crude oil is a naturally occurring, dark, viscous flammable liquid consisting of a complex mixture of hydrocarbons of various molecular weights and other liquid organic compounds, that are found in geologic formations beneath the Earth's surface. Several fuels are obtained by refining petroleum and these include but are not limited to gasoline, Diesel fuel, propane, and other fuels. Sour crude oil is crude oil containing the impurity sulfur. It is common to find crude oil containing some impurities. When the total sulfur level in the oil is > 0.5 % the oil is called "sour". The impurities need to be removed before this lower quality crude can be refined into petrol, thereby increasing the cost of processing. This results in a higher-priced gasoline than that made from sweet crude oil. Thus sour crude is usually processed into heavy oil such as diesel and fuel oil rather than gasoline to MAE 136 Lectures 2, 3 & 4 Page 6

reduce processing cost. Sour oil can be toxic and corrosive, especially when the oil contains high levels of hydrogen sulfide Tar Sands are a mixture of sand, clay, and bitumen which is a heavy crude oil. The oil is difficult and expensive to produce because mining and retorting or steam assisted heating of the reservoirs where it is found. 5. Gasoline C8H18 Gasoline is a transparent petroleum-derived liquid that is primarily used as a fuel in internal combustion engines. It consists mostly of organic compounds obtained by the fractional distillation of petroleum, enhanced with a variety of additives. (Some gasolines also contain ethanol as an alternative fuel; for example, E10 contains 10 percent ethanol). In North America, the term "gasoline" is often shortened in colloquial usage to "gas", whereas most current or former Commonwealth nations use the term "petrol". Under normal ambient conditions its material state is liquid, unlike liquefied petroleum gas or "natural gas". Spark ignition engines are designed to burn gasoline in a controlled process called deflagration. But in some cases, the unburned mixture can autoignite, which results in rapid heat release and can damage the engine. This phenomenon is often referred to as engine knocking or end-gas knock. One way to reduce knock in spark ignition engines is to increase the resistance to autoignition, which is expressed by its octane rating. Octane rating is measured relative to a mixture of 2,2,4-Trimethylpentane (an isomer of octane) and n-heptane. In the US, octane ratings in unleaded fuels can vary between 86 and 87 AKI (91-92 RON) for regular, through 89-90 AKI (94-95 RON) for mid-grade (European premium), up to 90-94 AKI (95-99 RON) for premium (European super). Energy is obtained from the combustion of gasoline, the conversion of a hydrocarbon to carbon dioxide and water. The combustion of octane in air follows this reaction: 2 C8H18 + 25 (O2 + 3.76 N2) 16 CO2 + 18 H2O + 94 N2 Gasoline blends differ, and therefore actual energy content varies according to the season to season and producer by up to 4% more or less than the average, according to the US Environmental Protection Agency (EPA). On average, about 19.5 US gallons of gasoline are available from a 42-US-gallon (35 imp gal; 160 L) barrel of crude oil (about 46% by volume), varying due to quality of crude and grade of gasoline. The remaining residue comes off as products ranging from tar to naphtha. The EIA (2010) has recently posted on the Internet a detailed list of the contributors to the cost of a gallon of gasoline. 6. Kerosene - C12H26 Today, kerosene is mainly used in fuel for jet engines (more technically Avtur, Jet A and Jet A-1, Jet B, JP-4, JP-5, JP-7 or JP-8). One form of the fuel known as RP-1 is burned with liquid oxygen as rocket fuel. These fuel grade kerosenes meet specifications for MAE 136 Lectures 2, 3 & 4 Page 7

smoke points and freeze points. The combustion reaction can be approximated as follows, with the molecular formula C12H26 (Dodecanese): C12H26 + 18.5 (O2 + 3.76 N2) 12 CO2 + 13 H2O + 69.56 N2 7. Diesel Fuel C10H20 to C15H28 Diesel fuel in general is any liquid fuel used in diesel engines. The most common is a specific fractional distillate of petroleum fuel oil, but alternatives that are not derived from petroleum, such as biodiesel, biomass to liquid (BTL) or gas to liquid (GTL) diesel, are increasingly being developed and adopted. Diesel fuel is very similar to heating oil, which is used a fuel to heat homes and apartments and in central heating. Petroleumderived diesel is composed of about 75% saturated hydrocarbons (primarily paraffins including n, iso, and cycloparaffins), and 25% aromatic hydrocarbons (including naphthalenes and alkylbenzenes). The average chemical formula for common diesel fuel is C12H23, ranging approximately from C10H20 to C15H28. 8. Ethane C2H6 Ethane is a chemical compound with chemical formula C2H6. At standard temperature and pressure, ethane is a colorless, odorless gas. Ethane is isolated on an industrial scale from natural gas, and as a byproduct of petroleum refining. Its chief use is as petrochemical feedstock for ethylene production. The complete combustion of ethane releases 1559.7 kJ/mol, or 51.9 kJ/g, of heat, and produces carbon dioxide and water according to the chemical equation C2H6 + 3.5 (O2 + 3.76 N2) 2 CO2 + 3 H2O + 13.16 N2 9. Propane C3H8 Propane is a three-carbon alkane with the molecular formula C3H8, normally a gas, but compressible to a transportable liquid. A by-product of natural gas processing and petroleum refining, it is commonly used as a fuel for engines, oxy-gas torches, barbecues, portable stoves, and residential central heating. A mixture of propane and butane, used mainly as vehicle fuel, is commonly known as liquefied petroleum gas (LPG or LP gas). It may also contain small amounts of propylene and/or butylene. An odorant, such as ethanethiol or thiophene, is added so that people can easily smell the gas in case of a leak. Propane undergoes combustion reactions in a similar fashion to other alkanes. In the presence of excess oxygen, propane burns to form water and carbon dioxide. C3H8 + 5 (O2 + 3.76 N2) 3 CO2 + 4 H2O + 18.8 N2 When not enough oxygen is present for complete combustion, incomplete combustion occurs when propane burns and forms carbon monoxide and carbon as well as carbon MAE 136 Lectures 2, 3 & 4 Page 8

dioxide and water. Unlike natural gas, propane is heavier than air (1.5 times as dense). In its raw state, propane sinks and pools at the floor. Liquid propane will flash to a vapor at atmospheric pressure and appears white due to moisture condensing from the air. When properly combusted, propane produces about 50 MJ/kg. The gross heat of combustion of one normal cubic meter of propane is around 91 MJ. 10. Butane C4H10 Butane is a gas with the formula C4H10 that is an alkane with four carbon atoms. Butanes are highly flammable, colorless, easily liquefied gases. When oxygen is plentiful, butane burns to form carbon dioxide and water vapor; when oxygen is limited, carbon (soot) or carbon monoxide may also be formed. 2 C4H10 + 13 (O2 + 3.76 N2) 8 CO2 + 10 H2O + 48.88 N2 The maximum adiabatic flame temperature of butane with air is 2,243 K (1,970 C or 3,578 F).

Butane lighter in use

Butane lighter, showing liquid butane reservoir

The most common use of butane is as lighter fuel for a common lighter or butane torch. Butane gas is sold bottled as a fuel for cooking and camping. When blended with propane and other hydrocarbons, it is referred to commercially as LPG, for liquefied petroleum gas. It is also used as a petrol component, as a feedstock for the production of base petrochemicals in steam cracking, as fuel for cigarette lighters and as a propellant in aerosol sprays such as deodorants.

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11. Natural Gas (Primarily Methane CH4 with lesser amounts of ethane, propane, and nitrogen). [Reference: Energy Choices: A Guide to Facts and Perspectives, ASME, New York 2010] Natural Gas is a clear gas that is found in formations in the earth and most of the time with crude oil and produced through wells drilled into the formations in the earth and most of the time with crude oil and produced through wells drilled into the formation. Pressures, depths, composition heating value, and corrosiveness vary with each source. Natural gas is typically found associated with oil at depths of about a mile or greater. Natural gas is primarily methane, and a typical composition is methane CH4 70-90 percent, ethane C2H6, propane C3H6, and Butane C4H10. The gas must be processed before it can be used. The produced gas may also contain hydrogen sulfide H2S, which is highly toxic, and is referred to as sour gas. Production of sour gas requires special processing and safety procedures. Natural Gas from Shale (http://chevron.com, March 17, 2012). According to Chevron, natural gas is an efficient energy source and the cleanest-burning fossil fuel. Natural gas extracted from dense shale rock formations has become the fastest-growing source of gas in the United States and could become a significant new global energy source. Although the energy industry has long known about huge gas resources trapped in shale rock formations in the United States, it is over the past decade that energy companies have combined two established technologieshydraulic fracturing (fracking) and horizontal drillingto successfully unlock this resource. Methane is the main primary constituent in natural gas, and probably the most abundant organic compound on earth. The relative abundance of methane makes it an attractive fuel. However, because it is a gas at normal conditions, methane is difficult to transport from its source. Main reactions with methane are: combustion, steam reforming to syngas, and halogenation. In general, methane reactions are difficult to control. Partial oxidation to methanol, for example, is challenging because the reaction typically progresses all the way to carbon dioxide and water even with incomplete amounts of oxygen. Like other hydrocarbons, methane is a very weak acid. The combustion of methane may be written as CH4 + 2 (O2 + 3.76 N2) CO2 + 2 H2O + 7.52 N2 Natural gas is a cleaner burning fuel than either coal or gasoline, and with plentiful supplies in the United States at the present time, it is a very popular fuel. In fact, Bennett (2012) in a recent article in the Wall Street Journal has written about U.S. automakers moving toward equipping pickup trucks powered by natural gas.

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M. Biofuels Biomass is produced directly or indirectly from photosynthesis with the basic chemical reaction written in simplified form as CO2 + H2O + Sunlight CH2O (carbohydrate) + O2 In this reaction carbohydrates are produced. As we know, living animals breathe oxygen and give off CO2, while plant life takes in CO2 and gives off O2. Clearly, plant and other organisms need each other to survive and to maintain a balance of O2 and CO2 in the atmosphere. There are two ways to produce biofuels. The first is to use crops that contain high sugar content such as sugar cane, sugar beets, sorghum or starch such as corn, wheat, and barley. Yeast fermentation is then used to produce ethanol. The second way is to grow plants such as oil palms, soybeans, rapeseeds, sunflowers, and other plants that contain a high concentration of vegetable oil to produce biodiesel. Biomass may be defined as living or dead biological material which can be used as a source of energy. Biofuels are made from biomass. 1. Wood Wood is a hard, fibrous tissue found in trees. It has been used for hundreds of thousands of years for both fuel and as a construction material. It is an organic material, a natural composite of cellulose fibers (which are strong in tension) embedded in a matrix of lignin which resists compression. At the present time the most important use of wood in the European Union is for heating. In France more than 40 percent of the individual homes use wood for space heating. Charcoal is usually obtained by heating wood in the absence of oxygen. It is 85-98 percent carbon and has a higher energy density than wood and burns hotter and cleaner than wood. Before the advent of fossil fuels, charcoal was used extensively as a fuel and as a metallurgical reducing agent. Curkeet (2011) presented an overview on the combustion characteristics of Wood. Wood as a fuel goes back to the beginning of recorded history, and it has been used to cook, heat, and in other ways. All wood is made up of primarily Cellulose, Hemi-Cellulose and Lignin: Cellulose (C6H10O5)x Hemi-Cellulose xylose, mannose, galactose, rhamnose, and arabinose (sugars). Lignin - C9H10O2, C10H12O3, C11H14O4

These constituents are all essentially complex hydrocarbons which form chains and MAE 136 Lectures 2, 3 & 4 Page 11

fibers with lignin acting as an adhesive binding it all together. All common wood is made up of roughly 50 3% Carbon, 6 1% Hydrogen, and 443% Oxygen with the rest inorganic ash. Softwoods tend toward higher Carbon and lower Oxygen content than hardwoods. When burned completely about the wood mass is converted to Carbon Dioxide and about to water. This process liberates (heating value) about 8600 Btu per pound (20MJ/kg) of heat energy for hardwoods and 9000 Btu/lb (21MJ/kg) for softwoods. Complete combustion of wood produces only carbon dioxide (CO2) and water (H2O). There is no visible smoke, no creosote, and no harmful emissions. It releases the full heating potential of the fuel. Natural wood has no significant sulfur or metals content. Incomplete combustion results in production of significant levels of CO, and many hydro- carbons. These unburned components represent lost heating value, pollutant emissions, and potential creosote formation. Since ideal combustion is never achieved, 50 100 percent excess air is always required to approach 100% combustion. So the real chemical reaction looks more like A CAHBOC + u (O2 + 3.76 N2) d CO2 + g O2 + h N2 + j H2O + k CXHY When wood is freshly cut it can have very high moisture content. Even trees that have been dead for years can have a moisture content as high as 50% or more. To maximize heating efficiency and minimize poor combustion and emissions, it is essential to properly dry or season fuel wood. Forest fires are undesirable occurrences that involve the burning of trees (wood), brush, and anything in the path of the fire. Such fires can inflict great damage over a larger area and spew pollutants in the environment. Two photos of recent forest fires in the Los Angeles area are shown below.

A vehicle travels past a wall of flames at the Station Fire in the Acton, California area north of Los Angeles, August 30, 2009. (REUTERS/Gene Blevins) #

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Spot fires glow after the Station Fire burned through August 30, 2009 in Acton, California. (Justin Sullivan/Getty Images) #

2. Biodiesel Biodiesel can be produced from soybeans, algae, jatrophra curcas, sunflowers, rapeseed, mahua trees, and other biomass. Algae grows in almost any damp or wet environment, and ponds, canals, trenches, and other objects that hold water provide an ideal environment for algae growth. Japtropha trees/bushes are native to Africa, Asia, and the Americas but are now grown worldwide. The mahua tree is native to the Indian subcontinent.

Pure biodiesel (B-100) from soybeans (Wikipedia, April 3, 2012)

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Hansen (2008) has presented some interesting data on Diesel and Biodiesel fuels. His technical definition of Biodiesel is Biodiesel a fuel comprising mono-alkyl esters of long chain fatty acids derived from vegetable oils or designated B100, and meeting the requirements of ASTMD 6751. It takes one bushel of soybeans to produce about 1.5 gallons of Biodiesel or 100 kg soybeans to produce about 10 liters of Biodiesel. (As an interesting data point, the Wall Street Journal listed the Cash Price of soybeans at $ 14.24 per bushel on April 12, 2012). Hansen represents Diesel fuel as C16H34. Thus, burning Diesel fuel in air the stoichiometric chemical reaction gives C16H34 + 24.5 (O2 + 3.76 N2) 17 H2O + 16 CO2 + 92.12 N2 1kg 14.9 kg 3.1 kg

The stoichiometric air-fuel ratio 14.9 to 1. Now, Hansen states that the soybean Biodiesel fuel molecule is C19H36O2 Thus, 1 kg Biodiesel + 12.5 kg air produces 2.8 kg CO2, i.e., Biodiesel produces about 10 percent less CO2 than does Diesel fuel. Finally Hansen has presented the chart below which compares the energy density (heating value) of various fuels including both Biodiesel and Ethanol.

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3. Ethanol C2H5OH Ethanol, Halperin (2006), is formed when an H atom in ethane, C2H6, is replaced by an OH radical to produce C2H5OH. Halperin (2006) has discussed the characteristics of ethanol. It is a clear colorless liquid with a pleasant smell. Except for alcoholic beverages, nearly all the ethanol used industrially is a mixture of 95% ethanol and 5% water, which is known simply as 95% alcohol. Although pure ethyl alcohol (known as absolute alcohol) is available, it is much more expensive and is used only when definitely required. Ethanol, C2H5OH is the primary biofuel used in the world. Brazil and the United States account for more than two-thirds of the global ethanol production. Brazil uses sugar cane and the United States uses corn. Brazil is able to produce ethanol at a very competitive price, about 40 percent less expensive than that obtained from corn is the U.S., and 70 percent less than the ethanol produced from sugar beets or cereal crops in Europe. Developing crops to produce biofuels requires both land and water. In that regard, Brazil is in a very favorable position with about 18 percent of the worlds freshwater resources. The fuel is derived from plants such as corn, sugarcane, and switch grass among others. In the case of corn, it is first ground into a fine powder, mixed with water, heated, an enzyme is then added to convert the mixture into sugars before yeast is added to ferment it. The resulting liquid has an alcohol content of 10 percent. A distillation process then separates the alcohol from the rest of the mixture before the remaining water is removed. The result is essentially pure alcohol. At the present time ethanol is more expensive as a fuel than gasoline. At present commercial corn-based ethanol comes from corn in the U.S. One of the more exciting ethanol prospects on the horizon is cellulosic ethanol, which can be made from a number of plant by-products, including cornstalks. Although it's unlikely to be commercially available for at least a few years, cellulosic ethanol eventually could help substantially reduce costs. The stoichiometric reaction of ethanol with air is C2H5OH + 3 (O2 + 3.76 N2) 2 CO2 + 3 H2O + 11.28 N2 and the higher and lower heating values of ethanol are 29, 670 kJ/kg and 26,800 kJ/kg, respectively. Gies (2010) has written about the environmental effects of ethanol in the New York Times.

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4. Black Liquor

In the pulp and paper industry black liquor is the spent cooking liquor from the Kraft process when digesting pulpwood into paper pulp removing lignin, hemicelluloses and other extractives from the wood to free the cellulose fibers. Approximately 7 tons of black liquor are produced in the manufacture of one ton of pulp. Black liquor is an aqueous solution of lignin residues, hemicellulose, and the inorganic chemicals used in the process. The black liquor contains 15 percent solids by weight of which 10 percent are inorganic and 5% are organic. Normally the organics in black liquor are 40-45 percent soaps, 35-45 percent lignin and 10-15 percent other organics. The organic matter in the black liquor is made up of water/alkali soluble degradation components from the wood. Lignin is degraded to shorter fragments with sulphur content at 1-2 percent and sodium content at about 6 percent of the dry solids. Cellulose and hemicellulose is degraded to aliphatic carboxylic acid soaps and hemicellulose fragments. The extractives give tall oil soap and crude turpentine. The soaps contain about 20 percent sodium. The residual lignin components currently serve for hydrolytic or pyrolytic conversion or just burning only. Hemicellulosis may undergo fermentation processes, alternatively Current Status New waste-to-energy methods to utilize the energy in the black liquor have been developed. The use of black liquor gasification has the potential to achieve higher overall MAE 136 Lectures 2, 3 & 4 Page 16

energy efficiency than the conventional recovery boiler while generating an energy-rich syngas from the liquor. The syngas can be burnt in a gas turbine combined cycle to produce electricity . The heavy or strong black liquor introduced to the recovery furnace ranges from 60 80 percent solids by weight. The organic fraction of the solids is principally derived from the hemicellulose and the lignin removed from the cellulose strands of the wood chips. The inorganic fraction of the solids is primarily Na2CO3, sodium hydrosulfide (NaHS), and oxidized sulfur compounds. Black liquor also contains various chemical elements which enter the process with the wood, as impurities in makeup limestone and salt cake, and as contaminants in makeup water. These elements include K, Cl, Al, Fe, Si , manganese, Na, Mg, and phosphorous. The heating value of black liquor is a strong function of the carbon content and ranges from about 12,000 to 17,500 kJ/kg, corresponding to carbon content of 28 to 44 percent Carbon, respectively. N. Municipal Solid Waste (MSW) MSW typically consists, as collected, of about 50 percent combustible material such as paper, plastics, wood, and rubber. About 25 percent is noncombustible, and another 25 percent is moisture. The energy content of MSW material is about 5,000 Btu/lb. Waste-toenergy (WTE) plants can significantly reduce the volume of MSW before disposal in landfills. These plants also generate electricity that helps to offset the financial burden on taxpayers who ultimately pay for the waste disposal. WTE plants now incorporate the latest technology to reduce pollutant emissions below the point of endangering public health. Regulatory requirements instituted in 1992 are among the most stringent for any combustion technology because of the variable nature of solid waste. Current operating WTE plants contribute a very small share of the total U.S. energy needs. But if all the MSW were combusted (after recycling 30 percent), plants with the latest technology would contribute 3-4 percent of the total U.S. energy needs. There is significant use of modern waste-to-energy technology to produce electrical power in the U.S. O. Analysis of Combustion Products 1. Dry basis: Fractional analysis of all components, except for water vapor. 2. Wet basis: Fractional analysis of all components including water vapor.

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P. Enthalpy of Formation 1. Consider the reaction C + O2 CO2 as shown below:

where the reference or standard temperature and pressure are Tref = 25oC = 298 K Pref = 1 atm = 101.325 kPa = 14.696 psia Apply the First Law to the control volume shown assuming negligible changes in kinetic and potential energies

If we assign a value of zero (0) to the enthalpy of all the elements at the reference state, T = 298 K, P = 1 atm), then

This term is called the enthalpy of formation at Tref = 25oC, Pref = 1 atm with reference to the arbitrary state in which the enthalpy of the elements at 298 K, 1 atm is arbitrarily chosen to be zero. The symbol is . The enthalpy of formation of a substance may be considered to be the enthalpy at a specified state due to its chemical composition. The enthalpy of CO2 at any other temperature T is then

Values of of various substances are given in Table A-25, Page 860 in MSBB. Note that two values are given for water, H2O (g) and H2O (l). The difference between the two values is

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Tables of enthalpy values as a function of temperature for N2, O2, H2O, CO, and CO2 are given in Table A-23, pp 929-932 in MSBB. Values of enthalpies for O, OH, and H2 from Cengel and Boles (2008) are provided as an attachment. Q. First Law Analysis for Reacting Systems Neglecting changes in kinetic and potential energies, application of the steady state First Law to the Control Volume shown yields:

R. Enthalpy of Combustion and Heating Values 1. Definition The enthalpy of combustion RP is defined as the difference between the enthalpy of the products and the enthalpy of the reactants when complete combustion occurs at a given temperature and pressure

2. Tabulated values are usually given at T = 298 K, P = 1 atm and the symbol for data at this reference state. 3. Useful for fuel oil and coal, for which data is not available, for which RP is determined experimentally. Such data is obtained using a bomb calorimeter 4. Heating Value of a Fuel

is used

a. Definition The amount of energy released when a fuel is burned completely in a steady-flow process and the products are returned to the state of reactants, i.e. Heating Value = | i. Higher Heating Value (HHV) Water in the products is in the liquid form ii. Lower Heating Value (LHV) Water in the products is in the vapor form MAE 136 Lectures 2, 3 & 4 Page 19 |

HHV = LHV + (n fg)H2O S. Adiabatic Flame Temperature, TP Assumptions: 1. Steady state 2. Adiabatic combustion process 3. KE = 0 4. PE = 0 5. cv = 0 Under these assumptions the steady state First Law of Thermodynamics is

which may be written as

The resulting outlet temperature is known as the adiabatic flame temperature, Tp. 1. For a given fuel and given T, P of the reactants, the maximum adiabatic flame temperature which can be achieved is with a stoichiometric mixture. 2. Therefore, the adiabatic flame temperature can be controlled by the amount of excess air. 3. Because of the nature of the problem, an iterative solution is generally required

T. References Jeffrey Bennett, Natural Gas to Power Pickups, Wall Street Journal, March 2, 2012. Gene Blevins, Reuters, August 30, 2009. Y. A. Cengel and M. A. Boles, Thermodynamics: An Engineering Approach, Ideal-Gas Properties of H2, H, and OH, 6th Edition, McGraw-Hill, New York, 2008, pp. 946 & 949. Rick Curkeet, Wood Combustion Basics, EPA Workshop, March 2, 1011. Fuels. Wikipedia, (http://en.wikipedia.com, March 17, 2012.

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Erica Gies, As Ethanol Booms, Critics Warn of Environmental Effects, New York Times, June 24, 2010. Alex Halperin, Ethanol: Myths and Realities, Business Week, May 19, 2006. A.C. Hansen, Combustion and Emissions Characteristics of Biodiesel Fuel, CABER, Department of Agricultural and Biological Engineering, University of Illinois, CABER Seminar, Department Mackenzie, F.T. and J.A. Mackenzie (1995), Our Changing Planet. Prentice-Hall, Upper Saddle River, NJ, p 288-307. (After Warneck, 1988; Anderson, 1989; Wayne, 1991. http://eesc.columbia.edu/courses/ees/slides/climate/table_1.html. Michael J. Moran, Howard N. Shapiro, Daisie D. Boettner, and Margaret B. Bailey, Fundamentals of Engineering Thermodynamics, Seventh Edition, John Wiley, New York, 2011. Pure Biodiesel (B-100) from Soybeans, Wikipedia, April 3, 2012 of Agriculture, May 5, 2008. Justin Sullivan, Spot fires Glow after the Station Fire Burned Through, Getty Images, August 30, 2009. Jon Vidar, AP Photo, August 31, 2009. U. Example Problems

Attachments A. U.S. Energy Outlook B. International Energy Outlook C. Ideal Gas Properties of H2, O, and OH

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