ARTVILLE

ALTERNATIVES TO PETROLEUM-BASED ENERGY FOR TRANSPORTATION

il refineries in the United States process almost 17 million barrels (Bbl) of oil each day, producing over 9 million barrels (380 million gal) of gasoline and 2 million Bbl (84 million gal) of diesel fuel. Gasoline and total petroleum expenditures were U.S.$186 billion and U.S.$336 billion, respectively, in 2001. Total petroleum consumption is over 20 million Bbl/day as shown in Figure 1. B. WAYNE Since the known reserves of crude oil are expected to peak and decrease in the near future, alternative transportation fuels must be developed. The term hydrogen economy, coined by General Motors in 1970, has recently become widely used, with renewed concerns about our current oil-based economy. In a hydrogen economy, fuel cells are expected to play a critical role in transportation as well as in household electric power and heating (see Small-Scale Hydrogen Units). A change to a hydrogen infrastructure from petroleum for transportation and natural gas for home heating will take many years and substantial capital investment. A major short-term challenge is that over 80%

of all hydrogen is produced using natural gas as a feedstock. Like petroleum, the supply of natural gas is limited. Ethanol and biodiesel are alternative fuels that enable the use of internal combustion engines and an existing fuel delivery infrastructure. In the United States, most ethanol-based fuels use a mix of 10% ethanol and 90% gasoline, while many automobile manufacturers are producing engines capable BEQUETTE of burning a blend of 85% ethanol and 15% gasoline. Biodiesel fuel, produced from soybean and other vegetable oils, can be combusted in diesel engines without major engine modification. Transportation fuel prices have increased substantially over the past year and are expected to remain high with increased demand from growing economies, such as those in China and India, enabling ethanol and biodiesel fuels to become competitively priced with petroleumbased gasoline and diesel fuel. In this article we review petroleum economics and describe the large-scale manufacturing processes currently used to produce hydrogen. We then discuss efforts to

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produce hydrogen on a smaller scale for fuel cells and provide an overview of processes for ethanol and biodiesel fuel production.

PETROLEUM SUPPLY AND DEMAND

Variations in petroleum supply and product demand have led to swings in gasoline prices and availability over the past three decades. For example, the gasoline shortages in 1973 and 1979 were due to the reduced output of oil from OPEC. A drop in crude oil prices in 1982 put several independent oil refiners out of business, since they were left with millions of barrels of crude oil whose value had suddenly decreased by $10/Bbl. Although the total U.S. petroleum product consumption rate increased from 16.7 to 20.5 million Bbl/day from 1974 to 2004, the U.S. per capita daily consumption actually decreased from 3.28 to 2.93 gal/person, peaking at 3.56 gal/person in 1978. The average fuel economy of cars increased by 45% between 1974 and 1990, with an additional 10% increase through 2004. The average fuel economy of tractor-trailer trucks, however, has remained constant at 5 m/gal for over 30 years. A detailed analysis of the nations energy supply is available in the Annual Energy Review 2004 [1]. Hurricanes Katrina and Rita in August and September, 2005 disrupted the supply of petroleum from oil production rigs in the Gulf of Mexico, which were forced to shut

down, leading to calls for a release of oil from the strategic petroleum reserve. The impact on gasoline prices, however, was not due to the reduced crude supply. U.S. refineries have been operating at over 90% of refining capacity, so the forced shutdown of at least eight to ten major refineries along the Gulf Coast restricted the supply of refined products. While crude and product costs are inherently interrelated, gasoline prices are largely affected by constraints on refining capacity. Since 1974 the number of refineries operating in the United States has decreased from 273 to 149. However, expansion of the remaining refineries has enabled U.S. refiners to barely keep up with the demand. One major new refinery construction project, currently under way, is a small 150,000 Bbl/day refinery in Yuma, Arizona, which is due to come online in 2010. The operation of petroleum refineries is discussed in [2].

LARGE-SCALE HYDROGEN PRODUCTION

Hydrogen has several industrial uses, including the production of ammonia and methanol, the treatment of refinery streams [2], and the hydrogenation of vegetable oils. Although hydrogen is the most abundant element in the universe, the molecular form of hydrogen is available on Earth in only extremely small quantities. Hydrogen is typically manufactured by the steam reforming of natural gas, which is composed largely of methane (CH4 ).

Crude Oil Other Liquidsa Exports 0.03 Refinery Input 0.86

Refined Refined Productsc Productsc Imports 1.90 Exports 0.96

Other Liquidsa for Reprocessingd 0.05 Residential 0.89

merc ial 0. 40

Com

Crude Oil Imports 10.04 Crude Oil Supply 15.47 Crude Oil Production 5.43

Motor Gasoline 9.06 Crude Oil Refinery Input 15.48 Refinery Refinery Input Output 16.75 17.77 _ _ _ _ _ Petroleum Distillate Consumption Fuel Oil 20.52 _ 4.05_ _ __ Liquefied 2.14 Petroleum Gases _ _ _ _ _ Jet Fuel_ _ _ _ _ 1.62 Residual _ 0.60_ _ __ Fuel Oil Other 2.83

Industrial 5.08

Transportation 13.52

Crude Oil Crude Oil e Adjustments Stock NGPL Change Refinery 0.19 0.15 Input 0.41

e Refined Productsc Processing NGPL Stock Change 0.01 Gain 1.02 Direct Use 1.40 Fuel Ethanol and Motor Gasoline Blending Components 0.45

Electric Power 0.53

FIGURE 1 U.S. petroleum energy flows, in millions of barrels per day. Due to net processing gains (products have a lower density than the feedstock) and imports of refined products, the volumetric petroleum output is significantly greater than the domestic and imported crude oil. From the DOE Annual Energy Review 2004 [1].

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Steam-Reforming Reaction
The steam-methane reforming reaction combines methane and water to form carbon monoxide and hydrogen according to CH4 + H2 O CO + 3H2 . (1)

This reaction is endothermic, meaning that energy must be added to convert the reactants to products and maintain a constant temperature. Equilibrium thermodynamics

can be used to find the conversion that occurs at a given temperature but provides no information about the reaction rate. For endothermic reactions, operation at a high temperature favors a higher conversion of the reactants to products. In this reaction two molecules react to form four molecules; this expansion favors product formation at low pressures and a reduced conversion of the reactants to products at high pressures. Low pressure operation,

Small-Scale Hydrogen Units

uel cells for automobiles can either have an onboard reformer to produce hydrogen (from gasoline, for example) or store hydrogen for direct use in the fuel cell. In recent years most automobile manufacturers have assumed that hydrogen will be the primary fuel and that an onboard reformer will not be available, thus requiring hydrogen fueling stations. Several companies are developing residential fuel-cell systems that use a reformer to produce roughly 5 kW of electric power, with natural gas as the feedstock. While the primary objective of the reformer is to produce hydrogen for the fuel cell for electricity production, it is possible to produce hydrogen for a fuel cell vehicle. Each household could then serve as a refueling station, with safety a paramount consideration. CATALYTIC PARTIAL OXIDATION While some systems have a steam reformer-based reactor with the same reactions that occur in manufacturing-scale processes, others are based on the catalytic partial oxidation reaction CH4 + 1 O2 CO + 2H2 , 2 (S1)

AUTOTHERMAL REFORMING An autothermal reforming reactor (ATR) uses a balanced combination of an exothermic catalytic partial oxidation reaction and an endothermic steam-reforming reaction to produce hydrogen without requiring external heating or cooling. The carbon monoxide can be removed by either the preferential oxidation (S3) or the watergas-shift reaction (2). ANODE TAIL-GAS CATALYTIC BURNER Since not all of the hydrogen reacts with oxygen to form water and electricity in a fuel cell stack, residual hydrogen remains in the tailgas stream leaving the anode. This hydrogen, along with any unconverted methane from the reformer, is combusted in a catalytic burner. This energy is then used in other parts of the process, including steam generation, to supply the steam-reforming reactor. FUEL-CELL SYSTEM CONTROL Each new large-scale process plant control system development is usually substantially different from similar plants due to the use of different feedstocks, product mixes, and plant operating cultures. Small-scale reforming and fuel-cell systems make process control more similar to other control fields, where a controller is imbedded in a consumer or commercial product. As the demand for fuel cell systems increases, these systems can benefit from standardized control strategies. Robustness to feed variability remains an issue, since natural gas composition varies depending on the source. A major consideration in the design of a fuel cell system is whether the system is operated as grid connected or off grid. This distinction dictates the amount of battery or capacitance necessary, for example, to handle rapid swings in the household electric power demand. Similarly, for combined heat and power (CHP) systems it is important to consider heat load characteristics. A CHP fuel-cell system for a house in Florida must have characteristics that are different from a system in the Adirondack Mountains of New York. Another consideration is that large-scale manufacturing plants can economically justify numerous sensors and actuators and have maintenance personnel to keep these devices calibrated and working properly. Since reliability is an important consideration in a residential-scale fuel-cell system, most designs seek to minimize the number of sensors and actuators.

which is mildly exothermic. Some methane is also converted through the total oxidation (combustion) reaction CH4 + 2O2 CO2 + 2H2 O , (S2)

which is highly exothermic. Multiple reactions involving a single reactant comprise another common characteristic of chemical processes. The ratio of methane converted in the first reaction (S1) to that in the second reaction (S2) is known as the selectivity. Judicious choice of operating conditions, oxygen/methane ratio, and catalyst to promote the partial oxidation reaction is necessary to improve the selectivity. Since pure oxygen is too expensive to be used as a reactant, air (21% oxygen, 79% nitrogen) is used. Nitrogen is an inert (nonreacting) component that has a major impact on thermal and compression requirements since it is such a large component of the air feedstream. Carbon monoxide can damage fuel cell catalysts, so it must be further reacted in a preferential oxidation reactor before it is sent to the fuel cell stack. The exothermic carbon monoxide oxidation reaction is CO + 1 O2 CO2 . 2 (S3)

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however, results in larger equipment sizes, so the design operating pressure of modern steam reforming units is 12 atm. Reactants are rarely supplied in exact stoichiometric ratios; one limiting reactant is usually present with all other reactants supplied in excess of the stoichiometric ratio. For this reaction, methane is the limiting reactant, and water is supplied in excess to shift the equilibrium to increase the conversion of methane to hydrogen.

Feed Fuel Combustion Air Reformer Catalyst Reformer Tubes Process Steam HighVelocity Burner Export Steam

Adsorbents

High-Purity Hydrogen

Flue Gas

Steam Reforming Process

A typical process flow sheet for steam reforming of natural gas is shown in Figure 2 [3]. Note that there are three reactors, several heat exchangers, and a pressure-swing adsorption (PSA) unit; pumps and compressors are not shown. The natural gas feed stream is preheated before entering the desulfurization reactor by exchanging heat with the flue gas leaving the reformer furnace. Heat from the flue gas is also used to generate steam, some of which mixes with the natural gas feed to the reforming reactor. The reactor is much like a vertical firedfurnace, as shown in Figure 3 [4], with feed passing through tubes packed with catalyst, and with heat transferred from the combustion side of the furnace. The 250300 tubes are roughly 40 ft long and 5 in in diameter, spaced several inches apart in six or seven rows. The steam-to-methane ratio is maintained above a minimum value to improve conversion to hydrogen and minimize coking (formation of carbon deposits). The product stream from the reactor contains carbon monoxide, hydrogen, excess water, and unreacted methane. The carbon monoxide (CO) left in the product stream is further reacted with steam in the water-gas-shift reaction to form carbon dioxide and more hydrogen according to CO + H2 O CO 2 + H2 . (2)

4-Tower PSA-Unit Desulfurizer

Boiler Feedwater

CO-Shift Syngas Tailgas Buffer Tank

Tailgas

Condensate

FIGURE 2 Steam reforming flow sheet [3]. The feed natural gas is preheated and passed through a desulfurizer before entering the reformer. The product stream, combining hydrogen, residual methane, and carbon monoxide, is cooled by heat exchange with the boiler feedwater before passing through the CO-shift reactor. Hydrogen is separated from the other gases in the pressure swing adsorption (PSA) unit, while the residual gases are recycled for combustion in the reformer furnace. (Printed with permission from Hydrocarbon Processing Magazine.) Inlet Manifold Effluent Chamber Valve Fuel Gas Reader

Catalyst Tube Spring Support Catalyst Loading Flange

Riser Tube

Inlet Pigtail Catalyst Tube

Vertical Firing Burners

Mixed Feed Header

Since (2) is mildly exothermic (releases energy) it is favored at a lower operating temperature than the steam reforming reaction. Hydrogen is separated from carbon dioxide, carbon monoxide, water, and any residual methane using PSA, as shown in Figure 4. In PSA, molecular sieves capture the polar (asymmetric charge distribution) and larger compounds, while allowing the hydrogen to pass through. Eventually, the molecular sieves become filled with the impurities and must be regenerated. The feed is switched to another bed and a sequence of operations is

Flue Gas Tunnels Outlet Manifold

Flue Gas Duct to Convection Section

FIGURE 3 Steam reforming furnace. The natural gas feedstream enters a header and passes downward through tubes packed with catalyst. The outlet stream consists of hydrogen, carbon monoxide, and unconverted natural gas components. The catalyst tubes are heated primarily by radiation heat transfer from the fuel-gas combustion. Control valves manipulate the fuel-gas flow to adjacent sections of the furnace. (Adapted from [4]).

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performed to regenerate the column [5]. A small flow of hydrogen is used to purge the methane and other gases during regeneration; since this purge stream has significant energy content, it is recycled and burned in the reformer furnace. The cycle time is the order of minutes, and PSA systems typically have six to ten beds. Steam reformer capacities range from 0.1 to 100 million standard cubic feet per day (MMSCFD). To put these figures in perspective, if 100 MMSCFD of hydrogen were completely converted to electricity using a perfect fuel cell (83% efficiency based on the higher heating value), the power would be 329 MW. A picture of the Air Products 100 MMSCFD plant in Westlake, Louisiana, is shown in Figure 5 to provide a sense of the scale of the equipment. The reforming furnace and reactor are part of the covered structure, which is 75-ft tall. The PSA beds are the ten white columns to the right of the reformer. This plant supplies hydrogen to ConocoPhillips and other plants in Louisiana.

Control Challenges
Conversion of methane in the reformer reactor is favored by high temperature, whereas high tube temperatures lower the tube lifetime. It is therefore important to control the temperature profile subject to tube skin temperature constraints. Since tube temperatures are affected by adjacent fuel gas flows, a coordinated or multivariable strategy for manipulating the valve positions is necessary to achieve tight temperature control. Oxygen and carbon monoxide sensors in the flue gas are used to regulate the excess combustion air to minimize the furnace energy consumption.

The methane reforming process has several features that are common to chemical manufacturing plants. While heat integration can result in substantial energy savings, it often allows perturbations in the temperature of one stream to propagate and affect other streams. Similarly, recycle streams conserve material but can have a strong effect on process dynamics. The dynamics of a system with recycle can be much longer than single-pass systems, while the positive feedback of some recycle systems can magnify disturbances, sometimes called the snowball effect [6]. In a methane reforming plant, the purge stream is recycled and combusted in the reformer furnace, inducing variability in the fuel-gas quality (heat content). Unlike some separation processes, however, the PSA system largely decouples the product stream purity from reformer furnace operation problems. Like many chemical processes, the natural gas feedstock composition can vary, affecting the plant operating conditions. The reformer tube catalyst decays with time, requiring that the tube temperature setpoints be changed. Model predictive control is used in most new hydrogen plants to enforce constraints and handle multivariable interactions.

Hydrogen Pipeline Operation

Pipelines present challenging control and supply chain management problems, particularly when several hydrogen plants supply a single pipeline to several customers. The Air Liquide Operations Control Center in Houston regulates 1,660 miles of pipelines supplying oxygen, nitrogen, hydrogen, and carbon monoxide to plants on the Gulf Coast and Mississippi River [7]. Every six hours

Hydrogen Product

H2 CO Molecular Sieve CH4 Activated Carbon CO2

Tail Gas

Buffer Drum

Raw Gas [H2, CO, CH4, CO2]

FIGURE 4 Diagram of a PSA unit. The impure hydrogen stream from the steam reformer and CO-shift reactors enters a bed packed with activated carbon and molecular sieve materials. The hydrogen passes through while the remaining components are absorbed by the bed material. After a few minutes the bed sites become depleted and must be regenerated; the raw gas feedstream is switched to a regenerated bed, and a portion of the pure hydrogen stream is used to regenerate the depleted bed. (Adapted from [5].)

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an optimizer determines the equipment configuration and energy supply that minimizes energy costs while satisfying the customer demand. Weather forecasts and electricity supply information are used to predict the effect of possible electricity curtailments and changing feedstock prices during hot weather. Operation during extreme weather events, such as hurricanes, is particularly difficult.

Future Hydrogen Sources

In the long term it is important to develop additional major sources of hydrogen. Electrolytic methods to split water into hydrogen and oxygen are extremely energy intensive and hard to justify if hydrocarbons FIGURE 5 Natural gas steam reforming hydrogen production plant in Westlake, Louisiana. are used to generate the electric This 100 million standard cubic feet per day plant serves ConocoPhillips and extends the Air energy. On the other hand, wind or Products hydrogen pipeline approximately 40 mi to Lake Charles, Louisiana. The reforming solar energy can supply a renew- furnace is under the roof at the left center, and the PSA columns are toward the right center. able source of energy for electrolyt- The flue gas stack is at the extreme left. (Printed courtesy of Air Products, Inc.) ic production of hydrogen. In addition, research efforts are developing thermochemical cycle processes [8], where a heat efficiency (mi/gal) as conventional gasoline when operatsource, such as residual heat from a nuclear power plant, ed at higher compression rates, due to the higher comis combined with coupled reversible chemical reactions bustion efficiency of ethanol. The United States currently has 95 fuel ethanol to yield a net reaction of the decomposition of water to refineries, with a total production capacity of 4.3 billion form hydrogen and oxygen. gal/year of ethanol [11], with most using corn as the feedstock. Plant capacities range from around 20 milETHANOL PRODUCTION Ethanol, also known as ethyl alcohol, can be produced lion100 million gal/year (55,000275,000 gal/day or from a petroleum source (ethylene) but is more widely 1,30006,500 Bbl/day). Approximately 3% by volume of manufactured using the fermentation of sugars. Fermen- gasoline needs in the United States is met using fuel tation processes have a long history, dating back Sumer- ethanol. In Brazil, sugar cane is used to produce 3 bilian and Babylonian beer making, which is about 5% lion gal/year of ethanol. Glucose is fermented, using yeast, to produce ethanol ethanol, over 8,000 years ago [9]. Henry Ford planned to use ethanol fermented from corn in the 1880s when he and carbon dioxide. The stoichiometric equation designed early Model Ts, but petroleum-based fuels grew C6 H12 O6 2C2 H5 OH + 2 CO 2 , quickly in the early 20th century [10], leading to the use of gasoline engines. Ethanol has a road octane number of 99, which is substantially higher than the 87-octane value indicates that one molecule of glucose forms two moleof regular gasoline. The traditional market in the United cules each of ethanol and carbon dioxide. From the molecStates has been gasohol, which is 10% ethanol and 90% ular weights of each compound, 1 g of glucose is converted gasoline, but there are now 5 million cars on the road that to 0.51 g of ethanol and 0.49 g of carbon dioxide. can run on E85 (85% ethanol, 15% gasoline) as well as A conventional corn milling and fermentation 100% gasoline (and any combination in between). With a process flow sheet is shown in Figure 6 [12]. The front reduction in additives such as methyl tertiary-butyl ether end of the process involves the preparation of corn to (MTBE), due to environmental concerns, ethanol will play provide glucose and other sugars for the fermentation a more important role as a partially oxygenated fuel addi- reactors. The fermentation product stream is concentrattive to improve combustion efficiency. Although the heat ed using distillation columns, similar to those discussed of combustion of ethanol is 30% less than that of gasoline, in [2]. A thermodynamic equilibrium nonideality, ethanol-gasoline blends can yield almost the same fuel known as an azeotrope, limits the purity to 95.5%

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ethanol and 4.5% water (by volume). Anhydrous (waterfree) ethanol is produced by using molecular sieves (in PSA columns) that adsorb water and allow the ethanol to pass through. Because of liquor laws, the resulting 200-proof ethanol must be denatured so that it cannot be consumed as a beverage; in this case, 5% gasoline is added to denature the alcohol. A second product stream is the dry distillers grains and solubles (DDGSs), which can be sold for use as livestock feed. A third product in large-scale plants is carbon dioxide, which can be pressurized and used to carbonate beverages or as an inert gas for industrial use; a portion can be solidified and sold as dry ice. The product split is roughly equal amounts of ethanol, DDGSs, and carbon dioxide.

this heat energy is removed by heat exchange with cooling water in the overhead condenser. Excess energy is consumed if the DDGS solids are too dry or if the molecular sieves are regenerated too frequently. Model predictive control has been used to reduce plant steam usage by 35% and natural gas usage by 1% [13].

The Net Energy Debate

There has been a debate about whether the amount of fuel energy required to grow crops and produce ethanol is greater than the energy content of the ethanol fuel. Some recent studies, including [14], show that when the coproducts from ethanol manufacturing are included in the analysis, there is a positive energy contribution from fuel ethanol. While there has been rapid growth in ethanol production capacity using corn as a feedstock, additional feedstock sources are necessary for ethanol to become a

Ethanol Process Optimization and Control

The multicolumn distillation process is energy intensive, using a large amount of steam in the reboilers; much of

Grain Receiving Storage

Fresh and Recycled Water Steam

CO2 Enzymes Mesh Cooling Jet Cooker

Whole Com Hammer Mill Slurry Tank 5% Gasoline

Liquefaction Yeast Saccharification Fermentation

200-Proof Denatured Ethanol Final Product

200 Proof Ethanol

Molecular Sieves

Atmosphere Beer Thermal Oxidizer 190 Proof Ethanol

DDGS Product To Storage/ Loadout

Exhaust Drum Dryer

Syrup Wet Grain

Distillation System

Condensate to Wastewater Treatment Syrup to Wet Grain

Evaporator Centrifuge

Whole Stillage

Thin Stillage

Backset

FIGURE 6 Conventional ethanol process. The corn is first processed mechanically, followed by a cooking step in which enzymes break starches into glucose and other sugars for fermentation to ethanol. The dilute ethanol stream is distilled to 190 proof (95%), followed by water removal in the molecular sieve columns. The 200-proof (100%) ethanol is denatured with gasoline to prevent sale as beverage alcohol. (Printed with permission from [12].)

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major contributor to engine fuels. During the past decade, the processes for cellulose-based feedstocks, such as switchgrass and wood wastes, have improved. The potential ethanol production rate for these sources is an order of magnitude higher than corn-based processes [10], [15].

Vegetable oils (triglycerides) are reacted with methanol or ethanol to yield methyl or ethyl esters (biodiesel) and glycerine according to Triglyceride + 3 methanol 3 methyl ester + glycerine, where methanol or ethanol is supplied in excess to improve the biodiesel yield. Also, a catalyst, such as sodium hydroxide, is needed to promote the reaction. Most small-scale production facilities are batch processes, while large scale are continuous. A continuous process flow sheet, used for simulation studies, is shown in Figure 7 [17]. Raw vegetable oil is the feedstock, but similar processes are used for waste cooking-oil feedstreams. The oil is reacted with catalyst and excess methanol in the reactor, which is often a continuously stirred tank reactor (CSTR). For batch operation the main challenge is that the reaction is initially mass-transfer limited because the methanol and oil form two distinct phases; it is thus particularly important to have vigorous mixing for batch operation. Two products, biodiesel and glycerol, are formed along with excess methanol in the reactor product stream. Glycerol has a higher specific gravity than biodiesel and is easily separated using a centrifuge. Individuals producing biodiesel in their garage often let the mixture settle in a vessel for several days and decant the biodiesel layer. The biodiesel stream (methyl esters) contains methanol, which is removed in an evaporator operated at a vacuum. A water wash is then used to remove any remaining catalyst, soap, salts, and methanol. Any water remaining in the biodiesel product is removed in a vacuum evaporator.

BIODIESEL PRODUCTION
Diesel engines are more efficient than gasoline engines because they operate at higher combustion ratios and temperatures. In an interesting parallel to Henry Fords plan to use ethanol in internal combustion engines, Rudolf Diesel developed an engine to run on peanut oil. Once again, the supply of cheap oil resulted in the use of petroleum diesel fuel in diesel engines. Over the past decade there has been increasing interest in biodiesel fuel, which can be produced from vegetable oils or animal fats, including waste frying oil. One performance measure for diesel fuel is the cetane number, which is related to the ability to self-ignite at the conditions of the engine cylinder [16]. Depending on the source oil, biodiesel has a higher cetane index (4852) than petroleum diesel (typically 4347). The exhaust of an engine burning biodiesel fuel is said to smell like french fries. Biodiesel is much safer than petroleum diesel, with a higher flash point and lower volatility. The gel and pour points of biodiesel are higher than petroleum diesel, however, limiting its use in cold weather, especially below 25 F. To reduce the gel and pour points, biodiesel is often mixed with petroleum diesel. Common blends include B5 and B20, which represent 5% and 20% biodiesel, respectively.

27 B14 26 15 26

10 16 B3 B2 1 2 9 B5 7 6 8 B6 12 11 3 B4 4 5 B1 13 14

B8 23 22

B12 29 30 B17 39 34 B11 B15 32 24 25 42 37 41 40

21

17 20 18 B9 B13 31 33 35 36 19 38 B16

FIGURE 7 Biodiesel process simulation flow sheet. Raw vegetable oil is used as the feedstock. The oil is reacted with catalyst and excess methanol in the reactor. Biodiesel and glycerol are formed, with excess methanol in the reactor product stream. Glycerol has a much higher specific gravity than biodiesel and is thus easily separated using a centrifuge. The biodiesel stream (methyl esters) contains methanol, which is removed in an evaporator operated at a vacuum. A water wash is then used to remove any remaining catalyst, soap, salts, and methanol. (Adapted from [17].)

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A typical biodiesel plant has a capacity of up to 30 million gal/year. There are 53 biodiesel plants operating in the United States with a capacity of 354 million gal/year, however, the actual production rate in 2005 was 75 million gal. The market penetration of biodiesel is extremely small; indeed, it has been estimated that, if all the animal fats and vegetable oils currently produced in the United States were converted to biodiesel, the resulting fuel would supply only 15% of diesel needs. For a substantial impact, more acreage needs to be planted with soybeans and similar vegetables. For all renewable fuels, numerous plants distributed throughout farmland can reduce transportation-related costs and energy. Furthermore, with more local and regional cooperatives, farmers can have joint ownership in the fuel-production facilities [18]; this arrangement enables farmers to earn a profit from the final fuel product even when raw material prices decrease. Waste cooking oil is the cheapest biodiesel feedstock since it is available from kitchens that often must pay for disposal, but its use presents many challenges, including the variability of raw material. Biodiesel conversion technology is probably best implemented in small, distributed plants with short travel distances to facilitate the collection of waste cooking oil. For example, several small biodiesel facilities located on college campuses use waste cooking oil to produce biodiesel fuel for campus shuttle buses and maintenance vehicles [19]. Biodiesel from waste cooking oil has become a cottage industry; it is popularized in several books [20] and Web sites [21] and is being produced in many home garages. Since the privately produced fuel is used in a personal vehicle and not sold, the fuel does not need to meet stringent ASTM and related standards. While the combustion of ethanol and biodiesel result in carbon dioxide exhaust, much of this carbon dioxide is recycled to grow more plants. Thus, the impact of biodiesel as a fuel source is a net decrease of carbon dioxide generation of 78% compared to petroleum-based diesel.

AUTHOR INFORMATION
B. Wayne Bequette (bequette@rpi.edu) is a professor of chemical and biological engineering at Rensselaer Polytechnic Institute, with teaching and research interests in process systems and control engineering. Applications of interest include biomedical systems, pharmaceutical processes, and alternative energy, in addition to more traditional chemical processes. He is the author of Process Control: Modeling, Design and Simulation (Prentice-Hall, 2003). He has been actively involved in programming activities of the American Control Conference and is currently president-elect of the American Automatic Control Council. He can be contacted at the Department of Chemical and Biological Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180-3590 USA.

REFERENCES
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FUTURE TRENDS
Transportation fuels are largely petroleum based. At the same time that a hydrogen economy is being developed, the hydrogen source will largely remain hydrocarbon based using natural gas. Substantial effort is required to reach a level of production at which alternative and renewable fuel sources have a major impact on transportation fuel supply. In addition, most alternative fuel sources can benefit from numerous facilities distributed throughout the United States. Bioethanol production facilities may be located closer to the biomass sources, enabling better use and distribution of coproducts, such as livestock feed.

ACKNOWLEDGMENTS
James Kwon, Julie Tran, and Xinqun Huang are gratefully acknowledged for their assistance with several of the drawings.

92 IEEE CONTROL SYSTEMS MAGAZINE

DECEMBER 2006