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Synthetic and alternative fuels have been considered good energy sources to power engines since the early years of engine development. The original engine developed by Rudolf Diesel, for example, was designed to be fueled by powdered coal. Henry Ford considered ethanol to be a good fuel source because it was renewable and because of its benefit toward agriculture. Since that time, a variety of alternatives to refined petroleum products have been evaluated and used as fuels for internal combustion engines. Reasons for considering synthetic and alternative fuels stem from two primary motivating factors: the need to ensure an adequate supply of low-cost fuel, and the desire to use fuel that burns completely and cleanly without undesirable exhaust emissions. The terms "synthetic fuel" and "alternative fuel" are closely related, but not truly synonymous. Synthetic fuel was coined as a term in the middle of the twentieth century to include gaseous, liquid and solid fuels produced from coal, oil shale, tar sands, and biomass. Alternative fuel appeared as a popular phrase during the latter years of the twentieth century which referred to fuels that were not totally based on petroleum and held potential as clean-burning, low-polluting, commercially viable fuel resources. A. COAL Coal is a rich source of carbon and has been a valuable source of fuel for centuries. It is classified by both coal type and coal rank. Coal type is determined by the nature of the original biomass that led to the formation of the coal. Coal rank signifies the degree of maturation or chemical change in coal and usually determines coal quality. The calorific value, moisture content, elemental analysis, volatile matter, ash, and fixed carbon content are important qualities of coal. The carbon in coal can exist in two forms, volatile carbon and base carbon. Volatile carbon is released by pyrolysis while base carbon remains as a residual char or coke. Both forms of carbon in coal have been utilized in the development of synthetic fuel. In 1792, Murdoch, a Scottish engineer, distilled coal in an iron oven and used the coal gas to fuel lamps in his home. This discovery led to the development of the coal gas industry, and by 1812, distilled coal gas was being used to fuel street lamps in London. Use of distilled coal gas quickly spread throughout Europe and remained an important source of domestic and industrial heating and lighting into the early twentieth century.
Distilled coal gas contained about 50% hydrogen, 20 to 30% methane, with the remainder being principally carbon monoxide. The calorific value of coal gas served as a benchmark for the "town gas" industry that was to follow. The solid coke by-product produced from coal gas processing was a source of further fuel development during the later years of the nineteenth century. Complete gasification of coke was achieved by blasting hot coke with alternating amounts of steam and air to produce a "blue water gas." This fuel burned with a distinct blue flame and was composed of about 50% hydrogen, 40% carbon monoxide, with the remainder being carbon dioxide and nitrogen. Coal, as a primary source for gaseous fuel, was eventually replaced when large quantities of low-cost natural gas were discovered and commercialized in the twentieth century. 1. Coal Gasification In 1868 Siemens suggested the use of an underground gasification process to derive gas from coal remaining in the ground after mining. This type of underground coal gasification process was developed and used commercially in parts of Europe and Asia for several years and involved blowing air or oxygen into a coal seam through an injection well and then igniting the system. Through a second production well, the resulting coal gas could be withdrawn and used. Underground coal gasification processes, however, have since given way to more favorable and highly developed aboveground processes. Aboveground coal gasification has undergone extensive technological development over the years and has experienced cyclic periods of commercial viability and decline. Reactors for use in aboveground coal gasification are usually one of three designs: packed bed, fluidized bed, or entrained (cocurrent) flow. Depending on the process, gasification temperatures can range from 98O0F to 2,25O0F (5270F to 1,2320C). Product composition can be controlled by reaction temperature, reaction pressure, and the feed rates of carbon, oxygen, and steam. Carbon is usually in the form of either pulverized coal or a coal-water slurry. The following examples are provided to illustrate the effect of gasification reaction conditions on product yield: - Hydrogen and carbon monoxide product yield increases with increased temperature, decreased pressure, and decreased oxygen in the feed. - Methane product yield is increased with low temperature and high pressure. Feed composition has less impact on yield. - Carbon dioxide increases with high pressure and increased oxygen in the feed. Even after its replacement by the natural gas industry, aboveground coal gasification processes continued to be developed and maintain commercial interest today. FIGURE 12-1 provides a schematic view of various coal gasification processes developed. Hydrogenation and catalytic gasification processes produce large quantities of synthetic natural gas from coal and yield clean burning fuel. Steam-oxygen and steam-air gasification processes produce a carbon-monoxide-
and hydrogen-rich "synthesis gas." This gas is a valuable raw material for chemical syntheses such as Fischer-Tropsch fuel production and methanation reactions that yield synthetic natural gas and methanol. FIGURE 12-1. Coal Gasification Process
H 2 S, NH3 CO2
Gasification Steam Air Gasification
CO, H2, N2 CO 2 , H 2 S, NH3
H 2 S, NH3 CO2
Low-CV gas Medium-CV gas Upgrading and methanation
CO, H2 Purification CO 2 , H 2 S, NH3
CH4, H2, CO Hydrogasification CO 2 , H 2 S, NH3
H 2 S, NH3 CO2
High-CV gas Light methanation
H 2 S, NH3 CO2
CH4, CO, H2 Purification Catalytic cryogenic gasification CO 2 , H 2 S, NH3 & separation
(From Probstein, Ronald F. and Edwin R. Hicks. 1990. Synthetic Fuels. Cambridge, Ma.: pH Press.)
For Fischer-Tropsch gasoline production, the desired mole ratio yield of hydrogen:carbon monoxide ranges from 0.5:1 to 1:1. For methane production, a hydrogen:carbon monoxide ratio of 3:1 is desired. An additional processing step termed the gas shift reaction or water-gas shift incorporating steam is sometimes required to produce the desired product ratio yield of hydrogen:carbon monoxide. The production of methanol from coal gasification was described in a 1913 German patent issued to Badisch Anilin und Soda Fabrik, or BASF. The process has since gone through numerous technological advances and stages of commercial development. Today, however, most methanol plants use natural gas rather than coal gas as the carbon feedstock, but some coal gas plants are still operational. One large-scale plant operating in South Africa using a Texaco/Koppers-Totzek process utilizes a fixed bed reactor to process coal gas into methanol. In this process, carbon monoxide and hydrogen from gasification are fed into the top of a reactor held at a temperature of 48O0F to 52O0F (25O0C to 27O0C) and pressures ranging from 725 psig to 1,450 psig. Produced methanol vapors are collected
from the bottom of the reactor and are separated. The reaction is represented by the following equation: CO2 + 3H2 -> CH3OH + H2 As a general summary, three principal gasification reactions of carbon from coal are oxygenolysis, hydrogenolysis, and hydrolysis. These reactions are shown by the following simplified examples: Oxygenolysis: C + O2 JE CO2
C + CO2 -> 2CO
Hydrogenolysis: C + 2H2 JE CH4 Hydrolysis: C + 2H2O JE CO2 + 2H2 2C + 2H2O -> CO2 + CH4 2. Coal Liquefaction Liquid coal products were first developed and produced in Germany by Bergius in the years between 1912 and 1926. In 1931, he received the Nobel Prize in chemistry for his work. The liquefaction process involved reacting either pulverized coal or coal-oil slurries with hydrogen at high temperatures and pressures to produce a liquid product. This liquid was suitable for further refinement into motor fuels. During World War II, Germany greatly expanded the production of liquid fuels, mostly aviation fuel, from the direct liquefaction of coal. At the height of production, 12 plants were operational. a. Fischer-Tropsch Process After World War II, direct liquefaction of coal became uneconomical as the use of lower-cost petroleum products became more widespread. However, the German process of indirect coal liquefaction, the Fischer-Tropsch process, continued to hold some interest. The Fischer-Tropsch process first involved production of a carbon monoxide and hydrogen-rich "synthesis gas" by the controlled gasification of coal followed by a catalytic reaction process to yield a valuable mixture of hydrocarbon products. Simplified Fischer-Tropsch reactions are shown by the following equations:
CO + 2H2 -> (-CH2-) + H2O nCO + 2nH,^CH, +nH.O 2 n 2n 2 CO + 2H2 —> (hydrocarbons, alcohols, acids) + H2O The Fischer-Tropsch indirect coal liquefaction process was developed into commercial-scale production by the South African Coal and Gas Corporation. The production facility, termed the Sasol facility, first began producing Fischer-Tropsch liquid fuels from coal in 1955. Several Sasol plants are operational today producing a range of hydrocarbon fuels as well as other products from coal. Fischer-Tropsch reaction products are primarily olefinic hydrocarbons with lower percentages of paraffins, aromatics, and oxygenated compounds. Both gaseous and liquid hydrocarbons are produced. Low-carbon-number alcohols and acids are the primary oxygenates. TABLE 12-1 lists representative products from the Sasol FischerTropsch process. TABLE 12-1. Typical Sasol Fischer-Tropsch Reaction Products
Gases Methane Ethylene Ethane Propene Propane Butene Liquids C 5 IoC 7 Light oils Heavy oils Alcohols Acids Total
CH4 C2H4 C2H6 C3H6 C3H8 C4H8
11 4 6 11 2 8
8 33 6 9 _2 100
The desired products are hydrocarbons in the C5 to C10 range that can be used in gasoline production. Iron-, cobalt- and nickel-based catalysts plus the proper selection of reaction temperatures and pressures are used to control product output. Increasing residence time in the reactor yields more paraffinic products and reduces the formation of alcohol and acid.
Because of the low-sulfur, -nitrogen, and -aromatic content of Fischer-Tropsch fuels, there is renewed interest in these products. In two recent studies, FischerTropsch diesel was evaluated and compared to an ultra-low sulfur California diesel and to a 49 cetane number, low-sulfur diesel. In the two studies, carbon monoxide, nitrogen oxide, hydrocarbon, particulate, and carbon dioxide emissions were reduced in vehicles fuels by Fischer-Tropsch diesel. The fuel economy, however, was also reduced. The low aromatic content and high concentration of waxlike hydrocarbons in Fischer-Tropsch diesel can lead to the need for special handling and treatment of the fuel to prevent gelling when used in cold-temperature conditions. Other processes have been developed in recent years, especially during the decades of the 1960s and 1970s, to produce liquid fuels from coal. Examples include the H-Coal, Mobil M, Solvent Refined Coal, and Exxon Donor Solvent processes. b. H-Coal Process The H-Coal process is a direct liquefaction procedure that utilizes a fluidized, high-velocity, ebullated bed reactor. Crushed, powderlike coal particles, 0.2 mm or less in diameter, are mixed with recycle oil to form a slurry. The coal-oil slurry is injected along with hydrogen and a cobalt-molybdenum catalyst into the reactor at a temperature of 85O0F (4550C) and pressures ranging from about 3,000 to 3,500 psi. The products produced are highly aromatic, contain about 0.5% nitrogen, and primarily range from C4 to >975°F (5250C) in character. The H-Coal process can be operated in either the "fuel oil" or the "syncrude" modes to produce higher percentages of heavier residual oil or naphtha-distillate type streams. c. Mobil M Process The Mobil M process is an indirect liquefaction process. Compared with a direct liquefaction process, such as the H-Coal process, indirect liquefaction offers the advantage of heteroatom removal as gaseous hydrogen sulfide, ammonia, and water vapor. The resulting hydrocarbon liquid product remains relatively free of sulfur, nitrogen, and oxygen. A special ZSM-5 alumino-silicate zeolite catalyst is used in the Mobil M process to selectively limit maximum molecule carbon number size to C9 to C10 range compounds. The two-stage process first converts methanol to dimethyl ether before final conversion to hydrocarbon molecules having a boilingpoint range, octane number, and other properties appropriate for gasoline production. Feedstock methanol can originate from coal gasification or other processes such as steam reforming of methane or biomass production. In this process, light olefins are produced that subsequently polymerize to form heavier olefins, paraffins, and aromatics. Hydrocarbon products range in size from C1 to C10. Extensive upgrading of the final product is not required. High-octane gasoline is the primary product produced.
d. Solvent Refined Coal (SRC) Process A direct liquefaction technique, the SRC process involves mixing dried and finely pulverized coal with a hydrogen donor solvent, such as tetralin, to form a coalsolvent slurry. The slurry is pumped together with hydrogen into a pressurized, vertical flow reactor. The reactor temperature is about 8250F (44O0C) and pressures range from 1,450 to 2,000 psi. A residence time in the reactor of about 30 minutes is required for the carbonaceous material to dissolve into solution. From the reactor, the product passes through a vapor/liquid separation system. The slurry solids remaining in the reactor are then removed and filtered. Various filtration techniques have been developed to remove solids from recoverable oil. An SRC-II process was subsequently developed to operate at a higher temperature, longer reactor residence time, and increased hydrogen consumption rates. The filtration step was replaced with a gasification step effective at generating hydrogen-rich synthesis gas from slurry solids. Further hydroprocessing is needed to upgrade the liquid naphtha and fuel oil products into usable fuels. e. Exxon Donor Solvent Process Similar in several respects to the SRC process, the Exxon Donor Solvent process incorporates an additional catalytic hydrogenation step to further enrich the hydrogen donor solvent. Once enriched, the donor solvent is mixed with finely pulverized coal and fed with hydrogen into an upward flow reactor. Reactor temperatures range from about 80O0F to 90O0F (4250C to 48O0C) and pressure from 2,000 psi to 2,500 psi. After a residence period of about 45 minutes, the product is removed from the reactor, flashed, and distilled by atmospheric and vacuum distillation. Aportion of the distillate boiling in the 3950F to 80O0F (20O0C to 4250C) range is collected and used to produce additional donor solvent. The vacuum bottoms are processed by gasification or flexicoking. 3. Upgrading of Coal Liquids Depending upon the intended use, coal liquids typically require some degree of hydroprocessing to remove heteroatoms of sulfur, nitrogen, and oxygen. Further saturation of aromatic compounds may also be required. The resulting product is lighter in color, has better long-term storage stability, and burns more efficiently. Also, hydroprocessing helps to remove the carcinogenic polycyclic aromatic compounds that are often present in the raw liquid product. B. BIOMASS Biomass for fuel production could be considered material that is either directly or indirectly derived from biological sources such as products of agriculture and forestry. As a fuel source, biomass is considered renewable and one that does not
contribute to an imbalance in the overall atmospheric carbon dioxide concentration. Carbon dioxide produced when biomass carbon is burned is subsequently utilized in photosynthesis by plant cells. The conversion of carbon dioxide and water to carbohydrate and oxygen by photosynthetic plant cells is represented by the following equation: Sunlight -> -^ -> Crc(H2O)ra + nO2 Chlorophyll
^zCO2 + mH2O
Carbon dioxide is present in the atmosphere at about 0.03 vol.% and also in water as dissolved gas or carbonate. It is estimated that carbon dioxide follows a 350-year life cycle as it passes from air and water, into organic compounds, and then returns. The use of biomass as fuel will keep this carbon dioxide balance in check if the use:replacement ratio of biomass remains equally balanced. Burning fossil fuels, by comparison, does not provide the immediate opportunity or option for replacement. Fuel biomass production, though, requires a commitment of land, a consistent supply of water, energy input to develop and maintain, and can directly compete with food production. Raw material for biomass fuel can come from various sources such as wood, legumes, grains, sugar crops, animal waste, municipal waste, aquatic plants, and food and cotton production waste. TABLE 12-2 provides examples of biomass raw materials. Converting biomass into fuel grade products such as gases, alcohols, and oils can be accomplished by processes such as fermentation, anaerobic digestion, thermal conversion, and oil extraction. The fuel grade products produced from these processes can be utilized directly as alternative fuel or, if appropriate, serve as components for blending into existing petroleum-based fuels. TABLE 12-2. Typical Biomass Raw Materials, Products, and Use
Wood paper-pulping waste Grains, legumes, tubers Sugar crops Agricultural waste
Sawdust, logging residues, tannins, waxes Corn, soybeans, rice, wheat, barley, rapeseed, potatoes Sugar cane, sugar beets, sweet sorgum, grapes Cheese whey, cotton, and cane bagasse
Oils, resins, gums, Vegetable oils, fermentable starch and sugar Fermentable sugars Fermentable sugar, on-site combustion
Animal and municipal waste
Manure, sewage treatment plant sludge
Kelp, algae, water hyacinth
Anaerobic digestion to methane, on-site combustion, mixing with coal to form solid fuel Direct combustion, can utilize carbon dioxide from industrial flue gas, can grow in municipal waste facilities
1. Fermentation Fermentation is the anaerobic decomposition of organic compounds, basically carbohydrate, into alcohols by the action of bacterial enzymes. Ethanol is the desired product of carbohydrate fermentation, but other alcohols, acids, ketones, and aldehydes can form as by-products. One common example of ethanol production from biomass is the fermentation of corn. For illustration, this process will be summarized. Traditionally, corn is dry-milled and suspended in boiling water to free the carbohydrate-rich starch compound from the nonstarch, cellulose biomass. The starch and cellulose components at this stage carry through the process. The nonconvertible cellulose biomass is later separated. The milled corn-water slurry, called "mash," is boiled for about 1 hour. Enzymes such as oc-amylase can be added to the process to help prevent gellation of starch. Enzymes are also added to catalyze the hydrolysis or saccharification of starch. Malt produced by the germination of barley grain contains the enzymes that catalyze this hydrolysis. Sometimes called diastase, the enzymes are primarily a- and Bamylase. Glucoamylase is a pure enzyme that can now be used. Both diastase and glucoamylase hydrolyze starch polysaccharide to the disaccharide, maltose. For fuel grade ethanol production, hydrolysis takes place at temperatures ranging from about 12O0F to 14O0F (5O0C to 6O0C) for about 1 hour. The final product of hydrolysis is called a "wort." Solids can be filtered from the wort before continuing. Prior to fermentation, the wort is then cooled to temperatures below 850F (3O0C), and the pH is adjusted to about 5. Yeast such as Saccharomyces cerevisiae, Saccharomyces carlsbergensis or Candida brassicae are added and fermentation proceeds for 2 to 3 days under batch processing conditions. Yeast produces the enzymes maltase, zymase, and invertase. Maltase converts maltose to glucose. Zymase converts glucose to ethanol. Invertase converts any sucrose present to fermentable sugar. The following equations illustrate the enzymatic conversion of starch to ethanol:
Diastase 2(-C6H10O5-)+ H2O -» C12H22On Maltose Maltase 2 C6H12O6 2 0 -» Glucose
Zymase 2C6H12O6 -> 4C2H5OH+ 4CO2 Ethanol Since fermentation takes place in a dilute aqueous solution, the reaction continues until the alcohol concentration approaches about 14%. At higher concentrations, the process becomes self-inhibitory. By-products from starch fermentation to ethanol can include higher-molecular-weight alcohols, glycerine, and ethers. Usually no more than 10% starch is converted to these compounds. Atmospheric distillation, vacuum distillation, and membrane separation techniques can be used to recover ethanol from the final fermented product. The distillate bottoms, called stillage, are recovered as a by-product for animal feed. A biomass fermentation flow diagram is provided in FIGURE 12-2. Steeping and wet-milling processes are also utilized to separate soluble compounds from corn. One process involves removal of soluble starch and protein from corn by steeping corn in a warm sulfurous acid solution for about one to two days. The undissolved corn solids are then coarsely wet-milled and processed to collect the oil-containing germ for corn oil production. Also, for more enzymeresistant cellulose biomass, sulfuric acid or hydrochloric acid can be used to digest the cellulose polysaccharide into fermentable molecules. Countercurrent hydrolysis is a new approach to hydrolyzing cellulose. Feedstock is introduced into a horizontal reactor via a conveyer. Steam is introduced to raise the temperature to 3550F (18O0C). After a residence time of about eight minutes, much of the feedstock is hydrolyzed, and it is then introduced into a vertical reactor heated to 4350F (2250C). Highly dilute sulfuric acid is added at this stage, and most of the remaining cellulose is hydrolyzed. This process has the advantage of minimizing the risk of using more concentrated acids, plus the yield of fermentable raw material is greatly increased. Cellulose hydrolysis by enzymes capable of breaking the B-1,4 linkage between glucose molecules offers great potential as a means to hydrolyze nonfermentable cellulose polymer. The enzyme cellulase, now used in the textile industry and in certain detergents, can be used for cellulose hydrolysis. Enzyme digestion can completely replace acid-type digestion and proceeds at lower temperatures ranging from 850F to 1220F (3O0C to 5O 0 C). In a process termed simultaneous saccharification and fermentation (SSF), both cellulase and yeast are combined to enable single-step hydrolysis and fermentation of biomass to greatly increase ethanol yield.
FIGURE 12-2. Simplified Fermentation Process Diagram Biomass
Sugar crop biomass
Starch or cellulosic biomass
Sugar syrup concentrating
Acids or enzymes
Sugar syrup or "wort" Recycle liquor
Stillage Concentation/ evaporation
Solids to combustion
Spent yeast Distillers grain (From Probstein, Ronald F. and Edwin R. Hicks. 1990. Synthetic Fuels. Cambridge, Ma.: pH Press.) 2. Anaerobic Digestion Biogas or synthetic natural gas production can be accomplished by utilizing the process of anaerobic digestion to convert biomass into methane. This multistage process of anaerobic decomposition involves hydrolysis of complex organic compounds by multiple bacterial species. The bacteria are grouped into the following classes:
Hydrolytic bacterial that break apart complex organic matter Hydrogen-producing acetogenic bacteria that metabolize organic acids Homoacetogenic bacteria that convert formate compounds into acetate Methanogenic bacteria that produce methane and carbon dioxide
Biogas production involves blending pulverized biomass material with water and any added nutrient material to form a mixture known as a "substrate." The substrate is then held in a digester where bacteria begin to propagate and establish conditions necessary for biogas production. The bacteria required to establish the process of anaerobic digestion are usually present naturally in the biomass material. The process of producing a thriving population of microorganisms is termed "acclimation." Sludge from a previous process batch can be used to help inoculate or seed the digestor. To ensure that the anaerobic bacteria thrive, careful control over substrate concentration, pH, temperature, nutrients and toxins must be maintained. For example, acetate concentrations above 2 g/L and ammonia concentrations above 3 g/L will significantly diminish methane production. Oxygen and certain metals and antibiotic contaminants can be harmful. The bacteria are mostly mesophiles, effective between temperatures of 680F and 1120F (2O0C to 450C) and thermophiles, effective between temperatures of 1120F and 15O0F (450C to 650C). Digestor operating temperatures can be adjusted to control bacteria population and reaction time. Mesophilic processing may require digestor residence times ranging from 10 to 15 days. Thermophilic processing may required a 5- to 10-day digestor residence time. Addition of nutrients containing phosphorus, nitrogen, and trace elements, plus maintenance of pH between 6.6 and 7.6, aid the digestion process. A two-stage anaerobic digestor is provided in FIGURE 12-3. FIGURE 12-3. Two-Stage Anaerobic Digestor Digester gas
Gas Active zone
Gas Supernatant Supernatant
Digested sludge Digested sludge
(From Probstein, Ronald F. and Edwin R. Hicks. 1990. Synthetic Fuels. Cambridge, Ma.: pH Press.)
Raw biogas produced from anaerobic digestion contains methane, carbon dioxide, ammonia, hydrogen sulfide, and water vapor. Yield of methane from conversion of biomass is about 30 wt% or 600 pounds for each ton of biomass digested. Liquid or solid adsorption media or catalytic conversion can be used to remove inorganic contaminant gases from methane. Also, it is possible to burn biogas as on-site fuel after removal of hydrogen sulfide. The remaining highwater-content supernatant can sometimes be recycled after proper treatment or, if appropriate, used for irrigation. Residual sludge can have a high nitrogen content and may serve as fertilizer. The typical composition of biogas is outlined in TABLE 12-3. TABLE 12-3. Typical Composition of Biogas
Methane Carbon dioxide Ammonia Hydrogen sulfide Water
Percent of Composition, wt%
50-65 35-50 1 0.1-1.0 5-15
3. Thermal Conversion Pyrolysis, gasification, and combustion are typical thermal conversion processes for biomass. These processes are compared and contrasted in TABLE 12-4. TABLE 12-4. Biomass Thermal Conversion Process Comparison Conversion Process Condition Pyrolysis
Temperature Environment Products
Type of Conversion Process
>2,732°F (UOO0C) 1,472-2,0120F 0 (800-1,10O C) Air No oxygen Oxygen, steam, hydrogen Recoverable Solid char produced High yield of carbon heat can be at low temperatures; monoxide, carbon used to generate liquid and gases at dioxide, hydrogen, higher temperatures methane, ethane, steam and produce electricity nitrogen, and water No synthetic High quantity and Higher yield and quality of liquid and quality of gas produced fuel gas produced than with pyrolysis; gas produced in a hydrogen atmosphere more costly than pyrolysis
<1,1 120F (60O0C)
Wood pyrolysis illustrates a thermal conversion process and demonstrates the impact the heating rate can have on product yield. When heated to temperatures between 16O0F and 1750F (71.10C and 79.40C), a watery distillate is produced called pyroligneous acid. This liquid contains between 5% to 10% acetic acid and 1.5% to 3% methyl alcohol or "wood alcohol." At higher heating temperatures, viscous unstable wood pyrolysis oil is collected. This oil contains useful tall oil and creosote oil, a raw material in resin manufacture. Wood pyrolysis oil has a high oxygen content, low sulfur content, and can serve as an on-site burner fuel to meet energy needs. At much higher pyrolysis temperatures, conversion to water vapor, carbon dioxide, carbon monoxide, hydrogen, methane, and higher-molecularweight hydrocarbons results. See FIGURE 12-4.
FIGURE 12-4. Thermal Conversion of Biomass
[Chars Solid fuels
(From Probstein, Ronald F. and Edwin R. Hicks. 1990. Synthetic Fuels. Cambridge, Ma.: pH Press.)
4. Oil Seed Processing Vegetable oil based fuels were used as diesel fuel in some Asian and African countries during World War II. Raw materials appropriate for use in producing oils suitable for combustion in a diesel engine include soybeans, cottonseed, rape seed, peanuts, safflower, canola, sunflower, and corn. Processed cooling oil and beef tallow have also been used as raw material sources. Oils derived from these sources are rich in molecules ranging from C10 to C24 in carbon number. The most valued oils have high concentrations of molecules in the C16 to C18 carbon number range. Both saturated and unsaturated molecules are found, but the major portion of the molecules contain one or two double bonds. The molecules are linear without branching or cyclization. These properties provide for good combustion characteristics in the diesel engine. In their raw, natural state, these oils exist in the form of a triglyceride or fat. In order to derive the useful oil from the raw material, the triglyceride must be separated from protein bodies and sterols also present within the oil seed. To illustrate this process, soybean oil production will be briefly described. Soybeans grow on a bushy, annual plant ranging in height from about 30 to 50 inches (75 to 125 cm). Stems have a hairlike covering and leaves are trifoliated. Flowers range in color from white to purple with variations in-between. Seedpods usually contain three spherical to oval seeds weighing 0.1 to 0.2 g. Most seeds have a yellow coat containing two oil- and protein-rich cotyledons. Argentina, Brazil, China, and the United States produce the worlds largest supply of soybeans. In the United States, the midwestern soybean harvest begins in September and October when the moisture content of the soybean is 13%. These beans can be stored for about one year. Soybeans with less than 12% moisture can be stored for two years or more. Higher-moisture-content beans must be aerated and dried in bins before being shipped by truck, rail, or barge for storage in elevators or silos. Traditional processing involves cleaning and drying the beans to a 10% to 11% moisture content to help loosen the hull or seed coat. The beans are then cracked, dehulled, and conditioned with steam to help facilitate flaking. The conditioned beans are flaked and then mixed with hexane in a Rotocel vat. The oil in the flake is extracted by hexane. The oil-hexane solution is then separated from the residual flake. The hexane is removed from the oil by evaporation and the hexane is reused. The residual flake is treated with steam in the desolventizer-toaster to remove the remaining hexane. Steam also deactivates hard to digest compounds in the flake to improve its value as protein meal. Collected soybean oil is usually degummed to remove phospholipid, wax, and nontriglyceride impurities before further processing.
More efficient procedures utilize expanders and extruders to convert the flakes into collets, or porous, spongelike material. Collets are larger and less fragile than soybean flakes aiding in the oil extraction and drainage process. This also minimizes the amount of hexane that needs to be recovered in the desolventizer. On average, a ton of soybeans yields about 18% oil, 72% protein meal, 7% hulls, and 3% loss. A listing of the primary fatty acids found in soybean oil is provided in TABLE 12-5.
TABLE 12-5. Fatty Acid Composition of Soybean Oil
Carbon Number: Number of Double Bonds
12 4 24 53 7
Palmetic Stearic Oleic Linoleic Linolenic
16:0 18:0 18:1 18:2 18:3
To produce biodiesel grade methyl esters, the oil must be trans-esterified with methyl alcohol. This process cleaves the triglyceride to yield glycerol and the individual methyl ester compounds. Most biodiesel trans-esterification is base catalyzed and has the operational advantage of low temperature, low pressure, and high conversion rates. The process involves reacting the degummed oil with an excess of methyl alcohol in the presence of an alkaline catalyst such as sodium or potassium methoxide, reaction products between sodium or potassium hydroxide and methyl alcohol. The reaction is carried out at approximately 15O0F under pressure of 20 psi and continues until trans-esterification is complete. Glycerol, free fatty acids and unreacted methyl alcohol are separated from the methyl ester product. The methyl ester is purified by removal of residual methyl alcohol and any other low-boilingpoint compounds before its use as biodiesel fuel. From 7.3 Ib of soybean oil, 1 gallon of biodiesel fuel can be produced. See FIGURE 12-5.
FIGURE 12-5. Schematic for Processing Soybeans into Oil and Meal Beans Bean cleaner Bean dryer Natural gas
Flakes Feed scalper Trash Scale Cracking nills Dehuller Hulls Bean conditioner
Liquid hexane Hexane vapor Hexane and steam vapor Hexane scrub Desolventizertoaster Meal dryer Steam
Condensate Flaking mills
>ir To meal - grinder
(From Kirk-Othmer Encyclopedia of Chemical Technology: 4th ed. 1997. Soybeans and Other Oilseeds. New York. John Wiley & Sons.)
C. SYNTHESIS GAS TO METHANOL
Methanol was first produced commercially in 1830 by the pyrolysis of wood to produce "wood alcohol." Almost a century later, a process was developed in Germany by BASF to produce synthetic methanol from coal synthesis gas. The first synthetic methanol plant was introduced by BASF in 1923 and in the United States by DuPont in 1927. In the late 1940s, natural gas replaced coal synthesis gas as the primary feedstock for methanol production. In 1966, ICI announced the development of a copper-based catalyst for use in the low-pressure synthesis of methanol. Passage of Clean Air Act legislation helped to spur the development of a number of alternative fuels, and methanol became one of the preferred liquid fuels for further investigation. The fuel oxygenate mandate also helped maintain the growth of the methanol industry. Methanol is used in the synthesis of methyl tertiarybutyl ether (MTBE), a high-octane gasoline blending component and primary oxygenate used in reformulated gasoline. Currently, the use of MTBE as the preferred oxygenate for fuel blending is being replaced by use of ethanol in many reformulated fuel blends.
Although methanol can be produced from a variety of industrial processes including pyrolysis of wood, coal gasification, and anaerobic digestion of biomass, steam reforming of natural gas is the most common means of producing methanol today. A typical process involves feed pretreatment, steam reforming, waste heat recovery, synthesis gas compression, methanol synthesis, and distillation. The steam reforming process is briefly described. 1. Methanol Feed Pretreatment Residual sulfur compounds present in the methanol feed must be removed before reforming. Sulfur severely degrades and poisons the CuZn reforming catalyst. In this step, natural gas is heated with steam to 50O0F (26O0C), mixed with a small amount of hydrogen and passed through a CoMo or NiMo catalyst bed. Sulfur is converted to H2S and then absorbed onto a ZnO catalyst bed. This process reduces sulfur to less than 0.1 ppm. If feedstock contains a significant amount of hydrocarbons heavier than methane, and adiabatic reformer, or pre-reformer, can be used. After desulfurization, the feedstock is heated to 93O0F to 1,02O0F (50O0C to 55O0C) and passed through a special nickel-alumina catalyst bed. Highermolecular-weight hydrocarbons are then converted to methane. 2. Steam Reforming A steam reformer is a large process furnace possessing a series of externally heated, catalyst-filled reaction tubes. The principal reaction taking place in the steam reformer produces a synthesis gas represented by the following equation:
C R , + nRO <-» nCO + (2/i + I)H, n 2n+2 2 ^ ' 2
Special high-strength metallurgy is used in the construction of reformer tubes to help ensure longer life and better efficiency. 3. Waste Heat Recovery Process gases leaving the steam reformer are at temperatures of about 158O0F to 1,62O0F (86O0C to 88O0C). This heat is recovered in heat exchange systems for use in boilers and overall process applications. 4. Compression Synthesis gas is compressed to pressures of about 250 psig before entering the methanol synthesis reactor and conversion to methanol. Also, after methanol synthesis, any unreacted synthesis gas is again compressed and recycled back through the reactor.
5. Methanol Synthesis Compressed synthesis gas is passed through a CuZn catalyst to yield crude methanol, water, and low quantities of ethanol, acetone, and other impurities. Noncondensable gases from the process such as hydrogen, carbon monoxide, and carbon dioxide are recycled, recompressed, and again passed across the CuZn catalyst. 6. Distillation Depending on the grade of methanol being produced, up to four separate distillation steps may be required to produce the purest grade of methanol, Grade AA. For fuel grade methanol, one distillation step is usually required.
D. OIL SHALE Oil shale deposits are found throughout the world. In 1838, the first oil shale industry was developed in France to distill oil shale for use as lamp fuel. In 1862, production began in Scotland. The oil shale industry in France was operational until the 1950s, but the Scottish industry continued for about 100 years until the high-grade oil shale reserves were depleted. Other processes were later developed in Estonia, China, and the United States. The Oil Shale Corporation, or TOSCO, processed over 900 tons of shale per day during the 1970s to yield over 35,000 gallons per day of raw shale oil. At the same time Union Oil and other companies were highly involved in developing the Colorado shale oil industry with a goal of producing between 1,700,000 to 2,500,000 gallons of synthetic shale oil per day. Compared to coal as a potential raw material for synthetic fuel development, oil shale differs substantially. Coal, for example, can be burned directly as a practical fuel source. Oil shale is less practical for direct burning because of its higher concentration of inorganic material and lower percentage of readily combustible organic compounds. Kerogen is a high-molar-mass organic material found in oil shale and is insoluble in most organic solvents. Bitumen is a soluble organic fraction of oil shale, but is in low concentration in oil shale. 1. SHALE OIL EXTRACTION Pyrolysis of oil shale kerogen, or the decomposition of kerogen by heat in the absence of air, converts kerogen into a synthetic shale oil. Kerogen pyrolysis begins at about 70O0F (37O0C) and is essentially complete by 93O0F (50O0C). Pyrolysis is carried out by a process called "retorting." Both surface retorting and in- situ retorting processes have been developed.
a. Surface Retorting Surface retorting or aboveground retorting involves mining, crushing, and heating raw oil shale to release kerogen liquids for processing. One successful surface retorting process was named the Paraho process after the Portuguese phrase "para homen" meaning "for mankind." The process involves first crushing raw shale to particles ranging in size from 5 to 75 mm and feeding the shale particles into the top of a retort column where hot gases pyrolyze the kerogen. The oil vaporizes into a mist of organic compounds and volatile gaseous products. The vaporized mist and gases are recovered from the retort and condensed into a liquid product. Organics remaining bound to the shale descend through the retort column and are ignited in an oxygen-containing and air-recycle gas mixture to provide heat required for further pyroly sis. The spend shale falls to the bottom of the retort and is removed. The oil yield from the Paraho process is about 90%. See FIGURE 12-6. Examples of other surface retorting include the Union Oil, TOSCO II, and Lurgi-Ruhrgas processes. FIGURE 12-6. Paraho Surface Retort Raw shale Oil mist separators Mist formation and preheating Retorting zone Combustion zone Recycle gas blower Spent shale cooling and gas preheating
Spent shale (From Probstein, Ronald F. and Edwin R. Hicks. 1990. Synthetic Fuels. Cambridge, Ma.: pH Press.)
b. In-Situ Retorting In- situ, or in-place, retorting involves fracturing the shale in place or mining out a portion of the shale to provide a means to ignite the shale in the ground. Once ignited, air is systematically fed into the underground formation to maintain combustion. Heat from combustion radiates through the in-situ retort bed and drives oil and gas from the kerogen. Piping connections are made and the oil and gas are pumped from the underground retort and separated. Although some shale oil is combusted and lost by in-situ processing, the costs associated with continuous mining and disposal of spent shale are eliminated. Care must be take to ensure that in-situ processing does not contaminate groundwater.
2. SHALE OIL PROPERTIES Shale oils are dark-brown, viscous, waxy liquids that usually contain higher concentrations of nitrogen and oxygen heteroatoms than coal liquids or crude oil. Oils can often have high pour point temperatures and may have trace concentrations of arsenic. Nitrogen levels of 2% and oxygen concentrations of 1.5% are typical. The sulfur content averages about 1%. Liquid shale oil can be upgraded by hydroprocessing to yield a useful organic product for synthetic fuel production. Shale oil liquids, compared with coal liquids, are highly paraffinic and significantly less aromatic. Typically shale oil liquids have fewer than 25% aromatic compounds compared with coal liquids that contain from 60% to 75% or more aromatic compounds. Hydroprocessing with CoNi catalyst to remove the high percentage of nitrogen from shale oil is common. Distillation of shale oil into process fractions can be completed either before or after hydroprocessing. If hydroprocessed before distillation, the naphtha yield increases to provide higher quantities of gasoline grade blendstock. Distilled synthetic shale oil yields about 50% to 60% middle distillate range fractions, 10% to 20% naphtha, with the remainder as residual oil. Light naphtha collected is very paraffinic and has a low octane number. The middle distillate fraction can be upgraded by conventional means to produce specification grade jet fuel and diesel fuel. The residual oil yields a high-quality, hydrogen-rich #6 fuel oil. Residual oil treatment by delayed or fluid coking can yield additional liquid or gaseous products.
E. TAR SANDS OR OIL SANDS Reserves of tar sands or oil sands are found in Venezuela, the Uinta Basin of Utah, and extensively in the Athabasca deposits in Alberta, Canada. In the late 1940s, Sidney Ellis and Karl Clark developed processes to enable valuable oil to be
extracted from tar sands. Pilot plant operations initiated in the 1950s led to commercial scale construction of a synthetic oil facility in the Athabasca region in 1965 by Great Canadian Oil Sands, Ltd. The plant went into operation in 1968. Syncrude Canada, Ltd., began operating a commercial facility in 1978. Synthetic oil production from oil sand processing in Canada has developed into the largest industry of its type in the world. The oil sands from the Athabasca deposits are a mixture of sand grains, water, and high-viscosity crude hydrocarbon called bitumen. At room temperature, bitumen is a semisolid, but will convert to a viscous liquid at about 30O0F (1490C). Sand grains are about 0.075 to 0.25 mm in diameter with small amounts of attached clay. The grains are all in direct contact and wet with a thin continuous sheetlike layer of water. Bitumen fills the void between the wetted sand grains and forms a continuous phase through the pores. Bitumen is about 17% to 18% of the mass. The composition of Athabasca oil sand bitumen is provided in TABLE 12-6. TABLE 12-6. Composition of Athabasca Oil Sand
Carbon Hydrogen Nitrogen Sulfur Oxygen
83.2 10.2 0.4 4.6 1.6
Canadian oil sand processing plants have been developed by Syncrude and Suncor for extraction and upgrading of tar sand bitumen into fuel. Aboveground surface mining and in-situ methods have been developed to recover raw material. Bitumen recovery from surface mined oil sand requires "conditioning" in order to free the bitumen from the sand matrix. 1. Bitumen Recovery from Surface Mining Raw oil sand is collected in open-pit mines using massive bucket wheel excavators and electric drag lines. To obtain one barrel of recoverable, synthetic crude oil from oil sand, about 1.6 tons of oil sand must be mined and processed. It is estimated that 10% of the energy obtained from the final synthetic crude is required for oil sand mining. Once mined, methods such as hot water extraction, cold water extraction, solvent extraction, direct coking, and fluid coking are employed to recover the oil sand hydrocarbon for fuel processing. Hot water processing and direct coking are described in the following sections.
a. Hot Water Processing Hot water processing requires mixing the sand with water at a temperature of about 1950F (9O0C) to form a pulp containing 60% to 85% solids. Sodium hydroxide and other conditioners can be added to control pH and aid in separation. Conditioning is carried out in a rotating, steam heated drum. Large quantities of water are added and the layers disintegrate. The conditioned pulp is pumped to separation cells where the sand settles and the bitumen oil froths to the surface on the rising bubbles. The sand is separated, and the bitumen oil mixture is collected for further upgrading. b. Direct Coking Direct coking is a pyrolysis process utilizing a fluidized bed reactor to distill and remove bitumen from the oil sand matrix. By direct coking, oil sand is pyrolyzed by heating in a coker to about 90O0F (4820C). At this temperature, the volatile synthetic oil separates from the sand matrix and is recovered from the coker as a condensed liquid. Coke deposits form on the sand as a result of thermal cracking of bitumen. The coke bearing sand is then fluidized with air and transferred to a burner operating at 1,40O0F (76O0C) to drive coke from the sand producing flue gas and hot, clean sand. A portion of this sand supplies heat for additional coking. 2. Bitumen Recovery from In-Situ Processing In regions where tar sand deposits are covered by dense rock or other formations, in-situ recovery may be more practical. Steam injection and underground combustion processes may be used for oil recovery. a. Steam Injection or Flooding Recovery of oil sand bitumen by steam injection involves either cyclic or continuous injection of steam at high pressure into a well. In cyclic injection, steam is injected into the oil sand formation for a period of time ranging from weeks to months. The steam spreads or floods the formation creating heat or pressure. The steam is then turned off, and the well is sealed for weeks to months. When the well is reopened, a mixture of water and bitumen can be withdrawn. Continuous injection is accomplished by drilling two wells into the oil sand deposit, one injection well and one recovery well. Into the injection well, air is pumped at high pressure, and bitumen at the base of the well is ignited. Air injection continues and moves the combustion process along as temperatures of 66O0F to 94O0F (35O0C to 45O0C) are attained. The bitumen is thermally cracked and vaporized. The cracked oils, gases, and vapors are driven toward the production well by injected air and recovered.
b. Underground Combustion The process of recovering bitumen by underground combustion is accomplished by drilling two wells into the oil sand deposit for injection and for recovery. Through one well, air is injected at high pressure, and the deposit is ignited by heating bitumen at the base of the well. Injected air feeds the combustion process and moves it along as temperatures of 66O0F to 84O0F (35O0C to 45O0C) are attained. The bitumen is thermally cracked and vaporized. The cracked oils, gases, and vapors are driven toward the production well by injected air and collected. 3. Upgrading Bitumen to Produce Synthetic Fuels After hot water extraction, crude bitumen is upgraded into synthetic oil fractions by either delayed coking or fluidized coking. A representative product yield from direct coking of Athabasca oil sand bitumen is provided in TABLE 12-7. TABLE 12-7. Product Yield from Direct Coking of Athabasca Bitumen
C1-C4; H2S Naphtha Kerosene Gas oil - diesel Heavy fuel oil Coke
Mass % Yield
7.9 12.7 15.0 36.2 6.0 22.2
Liquid products contain sulfur and nitrogen and must be hydroprocessed to improve quality. Separate hydroprocessing units for upgrading the naphtha, kerosene, and gas oil fractions can be used to optimize the overall process. Refined gas oil or diesel fuel is aromatic in character and contains more cycloparaffins than conventional crude oil. The resulting fuel is low in cetane number, high in density, and typically has very good low-temperature handling properties. A 1998 Canadian study was issued comparing the engine exhaust emissions of diesel fuel derived from oil sand and diesel fuel derived from conventional crude oil. The study was completed using a Ricardo Proteus single-cylinder engine that replicates one cylinder of a Volvo TD 123 heavy-duty truck engine. The engine is direct-injected and has a displacement volume of 2 L. From this study it was found that the higher density of oil sand diesel contributed to greater particulate emissions when compared to conventional diesel fuel of the same cetane number, sulfur content, and total aromatic content. The NO exhaust emission levels of the two fuels were comparable.
F. PROPERTIES AND PERFORMANCE OF ALTERNATIVE FUELS
Synthetic and alternative fuels such as synthetic hydrocarbons, alcohols, biodiesel, compressed gases, fuel-water emulsions, diether-type fuels, P-series fuels, hydrogen, and other potential energy sources are being investigated and developed. Even though no direct replacement for petroleum-based hydrocarbon fuel exists, a significant amount of technical and performance information has been collected on some of these alternate energy sources. 1. Gaseous Fuels The abiogenic theory suggests that very large quantities of natural gas exist deep within the Earth and migrate upward through cracks and fissures. "Deep gas" is believed to lie at depths of 15,000 to 30,000 ft. Natural gas is a mixture of hydrocarbon and nonhydrocarbon gases found in porous underground formations. Raw natural gas may be subclassified as follows: - Nonassociatedgas. Free gas not in contact with significant amounts of crude oil in the reservior - Associated gas. Free gas in contact with crude oil in the reservoir - Dissolved gas. Gas in solution with crude oil in the reservoir Methane is the main constituent of natural gas with ethane, carbon dioxide, nitrogen, hydrogen, water vapor, hydrogen sulfide, helium, argon, and natural gas liquids comprising the remainder. Compared to other synthetic and alternative fuels, little processing is required to make natural gas suitable for use as fuel. After removal of water vapor, hydrogen sulfide, and natural gas liquids, the gas is ready for shipment and use. As an alternative transportation fuel, natural gas exists in two forms, liquefied natural gas (LNG) for long-distance transportation and distribution, and compressed natural gas (CNG) for short-distance transport and cylinder storage. Sophisticated CNG storage and pumping systems are required to maintain cryogenic temperatures needed to maintain safe use of the fuel. Fueling hoses and dispensing units must be carefully maintained to ensure complete and accurate pressure regulation, leak detection, flow regulation, and vapor recovery. In vehicles, CNG is stored at 3,000 to 3,600 psig in double-walled, vacuum-insulated cryogenic containers and then vaporized by engine heat to produce usable fuel. The vaporizer utilizes engine heat to help expand the cold liquid into a gaseous form. Some designs utilize an expansion tank or buffer to provide additional space for expansion of cold CNG when engine demand for fuel is suddenly reduced. This buffer also stores expanded gas for engine starting. Stainless steel is the recommended material for tank construction. Welded joints, compression fittings, and Teflon gaskets are
used in assembly because of their pressure strength and compatibility under cryogenic conditions. Liquefied petroleum gas (LP gas or LPG) refers to mixtures of three- and fourcarbon hydrocarbons such as propane, propene, butane, butene, and isobutane. Low amounts of ethane may also be present. Natural gas liquids and petroleum refining processes are the primary sources of LPG. LPG from petroleum refining often contains significant quantities of olefinic compounds. Important uses include heating residential and commercial buildings, fuel for cooking, chemical feedstock, and a natural gasoline blendstock. For use as a motor vehicle fuel, LPG containing mostly propane is required. Vehicle LPG storage tanks are cylindrical with rounded ends and are capable of holding fuel at pressures of 240 to 250 psig. The tanks are much stronger than those used to hold conventional liquid fuels, but less sophisticated than CNG storage tanks. Carbon steel or aluminum can be used for tank construction. Because propane can dissolve plasticizers used in elastomer production, only propaneresistant elastomers such as neoprene, nitrile, or Teflon should be used. Except for the need for a gas-tight connection, LPG can be dispensed in the same manner as gasoline or diesel fuel. To ensure that adequate vapor space is available for gas expansion, automatic limiters are incorporated to maintain an 80% maximum fill rate. In many respects, LPG engines resemble conventional spark ignition engines. Engine conversion kits utilize a digital stoichiometric air-fuel ratio control system with feedback control via an oxygen sensor to minimize emissions while manitaining good fuel economy. The combustion properties of gaseous fuels flowing through engine system orifaces can vary depending upon the gas composition. Pure gases will possess different combustion properties than mixed gases. Stoichiometric air-fuel control systems utilized on compressed gas engines must be able to account for these differences in fuel quality to provide accurate fuel metering. This is accomplished by determining the Wobbe Index of fuel being metered. The Wobbe Index (W) is determined by the following equation:
W = H/p
where H is the volumetric heating value of the gas and p is the specific gravity of the gas. A change in the Wobbe Index of gaseous fuel will result in a nearly proportional change in the rate of energy flow, and thus in the air-fuel ratio. A lower Wobbe Index results in a leaner air-fuel ratio, while a higher Wobbe Index provides a richer mixture. Stiochiometric engine control systems are able to compensate for reasonable variations in fuel Wobbe Index and provide appropriate air-fuel metering adjustments. Without this adjustment mechanism, problems such as low power,
increased exhaust emissions, knock, or engine overheating could result. Wobbe Index values for compressed gases typically range between 1,300 and 1,420 BTU per standard cubic foot (scf) (48.5 and 52.9 MJ/m3). A primary reason for interest in the use of gaseous fuels is the production of lower levels of engine exhaust emissions and air pollutants than conventional fuels. When used to fuel newly designed low-emission vehicles capable of operating on either gasoline or CNG, the emission levels were found to be significantly lower after 50,000 miles for CNG-fueled vehicles. Results using Chrysler Minivans meeting California ultra-low emission vehicle (ULEV) emission standards are provided in TABLE 12-8. Similar low levels of exhaust emission have been reported using specially designed heavy-duty compression-ignition engines from Cummins, Detroit Diesel, Hercules, and Volvo. TABLE 12-8. Exhaust Emission Values After 50,000 Miles Comparing Gasoline and CNG in a Flexible Fueled Chrysler Engine
Emissions, g/mi Fuel
1 2 3
Nonmethane organic gases Formaldehyde Not available
Primary environmental benefits of using compressed gases as alternative fuel sources can be summarized as follows: - Inherently low exhaust emission levels of nonmethane hydrocarbons and air pollutants such as benzene - Low fuel emission levels on cold-starting; engine starting is not significantly impacted by temperature - Less complex emission control system is required due to overall lower exhaust levels - Minimal fugitive emission levels from storage and refueling facilities due to tightly sealed gas tanks and handling hardware
2. Ethanol As an automotive fuel, ethanol has been utilized throughout the world. Brazil, Scandinavia, France, the United States, Germany, Japan, New Zealand, and other countries have found ethanol to be an effective alternative fuel for transportation vehicles. The Ford Model T, as an example, could be modified to run on either ethanol or gasoline. Ethanol blended fuels were marketed in the United States during the 1920s and 1930s, and by 1938, an ethanol facility in Atchison, Kansas, was producing 18 million gallons of ethanol annually. During this era, one fuel blend called Agrol was proposed that contained 78% ethanol, 7% other alcohols, and 15% coal distillates. After World War II, interest in fuel ethanol production declined significantly, primarily because of the low cost of petroleum-based fuels. The world energy crisis of the 1970s, however, spurred interest once again in ethanol as a transportation fuel source. Brazil adopted the widespread production and use of "Alcool," hydrated ethanol, and "Gasolina" a 78:22 ratio blend of gasoline:ethanol as a motor fuel. Other countries developed policies to maintain a fuel grade ethanol industry by conversion of biomass. Also, clean air and reformulated fuel policies have helped to promote the use of ethanol as a viable alternative fuel. a. Ethanol Fuel Grades Ethanol can be readily produced by industrial processes such as the sulfonationhydrolysis process and the direct catalytic hydration process as outlined by the following equations: Sulfonation-Hydrolysis Process
2CH2=CH2 + H2SO4 -+ (CH3CH2)2S04 Ethylene Diethyl Sulfate (CH3CH2)2S04 + 2H2O -^ 2CH3CH2OH + H2SO4 Diethyl Sulfate Ethanol
Direct Catalytic Hydration Process CH2=CH2 + H2O -> CH3CH2OH Catalyst Biomass fermentation, however, yields the greatest supply of fuel grade ethanol. As a transportation vehicle fuel, ethanol can be used directly, blended with conventional fuel, or used as an oxygenate in reformulated fuels. Before use, fuel grade ethanol is denatured by blending with gasoline at volumes ranging from 1 % to 10%. Requirements for denatured fuel grade ethanol are fully described in
ASTM D-4806, Standard Specification for Denatured Fuel Ethanol for Blending with Gasolines for Use in Automotive Spark-Ignition Engines. The common grades of ethanol blended fuels available in the United States are briefly described. Similar grades are available in other countries. Gasohol or ElO is a blend of gasoline with ethanol. Gasohol can contain up to 10% ethanol by volume and is one of the most common uses for fuel grade ethanol. E85 contains 85% ethanol by volume and 15% gasoline. E95 contains 95% ethanol by volume and 5% gasoline. Ed75-Ed85 is as defined by ASTM D-5798, Standard Specification for Fuel Ethanol (Ed75-Ed85) for Automotive Spark-Ignition Engines. Reformulated gasoline can contain ethanol. Although reformulated gasoline must contain a minimum of 2.7 wt% oxygen, an EPA waiver for ethanol and certain other alcohols allows as much as 3.7 wt% oxygen in fuel or about 10.5 wt% ethanol. Diesel-ethanol formulations are being marketed that contain other blended components to enhance fuel performance. These recently developed diesel blends contain ethanol at volumes ranging from 7.5% to as high as 30%. Additive concentrations in these blends average 5% or more. This fuel technology is in the early stages of field application. b. Ethanol Handling and Storage Since ethanol is a single, highly polar organic molecule, it can provide performance different from traditional nonpolar hydrocarbon fuels that contain numerous organic molecules. Because of this fact, handling, storage, use, and performance of ethanol and ethanol blended fuels can differ from conventional fuels. Water is completely soluble in ethanol. Water that may be present in storage tanks, piping systems, transfer lines, or hoses can be solubilized by fuel ethanol. In fuel systems containing adherent deposits, ethanol may dissolve and remove these deposits. If brought into the fuel, these deposits can create problems with filter plugging or fuel discoloration. Water contamination can cause ethanol to separate from gasohol blends. Less than 1% water contamination can increase the specific gravity of a gasohol-ethanol-water solution causing it to separate as a heavier, distinct phase from the lower-specific-gravity gasoline. This problem is more pronounced in cold temperatures. Although the freezing point of ethanol is lower than conventional fuels, when contaminated with water, the freezing point of ethanol rises. The electrical conductivity of ethanol is higher than hydroprocessed, conventional fuels. This theoretical safety advantage is of benefit and can help to prevent static buildup or discharge during transfer and loading of fuel. However, the high electrical conductivity can enhance galvanic and electrolytic corrosion of steel, especially in water-contaminated systems. Compatibility of ethanol with tank and piping materials such as carbon steel, stainless steel, and Fiberglas is good. Zinc linings and epoxy linings are not stable in ethanol systems and are not recommended for use. Also, epoxy adhesives and resins are dissolved by ethanol. Teflon and nylon are compatible elastomers. In
gasohol storage, Kalrez, Ryton, Viton, and other elastomers may be used. Very fine filters are recommended for ethanol dispensers to ensure that waterborne solids do not contaminate vehicle filters or fuel injectors. Dispensing hoses delivering ethanol and other alcohol fuels to vehicles may be green or blue in color to signify their compatibility with alcohol fuels. Also, blending ethanol with conventional fuels helps to minimize compatibility problems with existing fuel system components. Commercial use of ethanol fuel is regulated by NFPA 30, Flammable and Combustible Material Code. For ethanol storage and dispensing systems, the NFPA 3OA, Automotive and Marine Service Station Code, would apply. c. Ethanol Use and Performance When ethanol is used in a standard spark ignition or compression ignition engine designed to burn conventional hydrocarbon-based fuels, ethanol performance varies substantially if no engine modifications are made, and it becomes difficult to rate the value of ethanol as an effective fuel. Consequently, flexible fueled vehicles (FFVs) or variable fueled vehicles (VFVs) have been developed to operate on either gasoline or alcohol-based fuels. These vehicles are equipped with on-board sensors and controls to adjust the spark advance and the fuel injector timing to help correct for the differences in fuel performance. Fuel consumption ratings for engines not specifically designed to operate on alcohol-based fuels can range from 30% to 50% higher compared to conventional fuel use. Consumption ratings vary depending upon the driving cycle. The higher consumption is due to the lower number of carbon atoms available from ethanol fuel compared to an equal volume of hydrocarbon-based fuel. Viewed another way, the high oxygen content of ethanol reduces its heating value compared to an equivalent volume of gasoline. In gasohol blends containing 10% ethanol, this significant increase in fuel consumption is not evident. Lower exhaust emission levels of carbon monoxide, particulate, and hydrocarbons are a primary advantage of burning ethanol-based fuel. The high concentration of oxygen available from ethanol participates in driving combustion to completion yielding carbon dioxide and water. Since ethanol contains no sulfur, particulate emissions are minimized. Levels OfNO x and aldehyde compounds in the exhaust can increase if vehicles set to operate on conventional fuel are not adjusted to compensate for the lower ainfuel ratio requirements of alcohol-based fuels. In this case, higher air and oxygen volumes result in the formation of nitrogen oxides and oxidized low-molecular-weight organic compounds such as formaldehyde and acetaldehyde. The oxygen content and the stoichiometric air:fuel ratio of methanol, ethanol, and gasoline are provided in TABLE 12-9.
TABLE 12-9. Characteristic Properties of Methanol, Ethanol, and Gasoline
Oxygen content, wt% Stoichiometric air: fuel ratio Research octane number (RON) Motor octane number (MON) Lower heating value, MJ/kg
34.8 9.0:1 109 90 26.8
O Approx. 14.6:1 90 - 100 80-90 Approx. 42.7
50.0 6.45:1 109 89 19.9
Octane number ratings for both methanol and ethanol are high, making them good gasoline blending components. Ethanol has a research octane number (RON) of 108.6 and motor octane number (MON) of 89.7. As a component in gasoline, the octane blending values for ethanol become even higher. The blending RON for ethanol ranges from 120 to 135, while the blending MON ranges from 100 to 106. The Reid vapor pressure of gasoline increases moderately when ethanol is blended into fuel as an oxygenate. At a 10% ethanol blend volume, the vapor pressure of gasoline can increase by 0.5 to 1.0 psi. If the pHe of ethanol is below 6.5, the possibility of fuel pump malfunction, fuel injector corrosive wear, and engine cylinder wear increases. These effects are reduced in gasohol blends. The high autoignition temperature of ethanol makes its use as a direct substitute for conventional diesel fuel in compression ignition engines less likely. The autoignition temperature of ethanol is about 1,30O0F (7040C), or more than two times higher than the temperature for conventional diesel fuel. However, newly designed, higher-compression engines have been developed to operate on alcoholbased fuels and are now in limited commercial use. Cold weather starting for ethanol fuels is poor unless blended with gasoline or some other starting fluid such as dimethyl ether or isopentane. The minimum starting temperature for neat ethanol fuel is about 6O0F (15.60F). In E95, E85, and ElO blends, the starting problems are minimized. Cylinder and piston ring wear have been observed when using alcohol fuels. Metal loss could be due to wear caused by removal of the lubricating oil film by liquid alcohol during cold starting or by the corrosive action of formic acid or other acids formed during the combustion process. Use of more corrosion- and wear-resistant metal alloys in engine construction have helped resolve this problem. 3. Methanol Methanol, along with nitromethane and isooctane, has been used as a racing fuel for many years. When used in high compression ratio engines, methanol has good
antiknock properties and can be injected with very rich air:fuel ratios, for example, 4:1. This tends to keep the high compression engine cool, and at this ratio, the specific energy is greater than gasoline. Methanol has undergone extensive evaluation as an alternative fuel source. Its high oxygen content and characteristic production of very low levels of exhaust emissions when used as an internal combustion engine fuel make methanol an attractive alternative to use of other fuels. The good performance of methanol in the various classes of flexible-fueled vehicles and ultra-low emission vehicles is well documented. Also, blends of methanol with other alcohols have been accepted as oxygenates for blending into reformulated fuel. However, over the past few years, use of methanol for oxygenate blending has declined. Grades of methanol fuel include the following: - MlOO or neat methanol - M85 containing 85 percent methanol by volume and 15% gasoline - M70-M85 as defined by ASTM D-5797, Standard Specification for Fuel Methanol (M70-M85) for Spark-Ignition Engines Methanol has many of the same advantages and disadvantages as ethanol as an alternative fuel source. Listed in TABLE 12-10 is a comparison of methanol and ethanol as alternative fuels. TABLE 12-10. Various Handling and Performance Properties of Methanol and Ethanol as Alternative Fuels
Carbon steel compatibility Galvanized (zinc-coated) steel compatibility Aluminum compatibility Copper, brass, and bronze compatibility Teflon compatibility Epoxy resins and adhesive compatibility Buna-N, Viton, neoprene, natural rubber compatibility Cork compatibility Heating value per unit volume compared with conventional fuel Octane number compared to conventional gasoline Cetane number compared to conventional diesel fuel Cold weather starting performance compared to conventional fuel
Good Poor Poor Poor Good Poor Poor Poor
Good Poor Good, > if ethanol is pure Poor Good Poor Good Poor
Approx. 50% Approx. 70% Higher Much lower Poor Higher Much lower Poor
Aldehyde emissions compared to conventional fuel CO, HC, and participate exhaust emissions compared to conventional fuel Electrical conductivity compared to conventional fuel Lubricity compared to conventional fuel
Much higher Much higher Poor Poor
Standard four-cycle compression ignition engines have been developed to operate on diesel-methanol or neat methanol fuel. In studies using these engines, significantly lower concentrations of hydrocarbon, carbon monoxide, and paniculate exhaust emissions were produced. Some of the modifications made to methanol engines to improve performance include changing the cylinder and piston design, compression ratio adjustment, turbocharger addition, fuel injector enlargement, and use of methanol-resistant materials of construction. Detroit Diesel, Navistar, Volvo, Saab-Scania, and DaimlerChrysler have participated in the development of heavy-duty methanol engines. Results of a study sponsored by the State of California Energy Commission comparing the exhaust emissions from compression ignition engines designed to operate on methanol fuel are shown in TABLE 12-11. The results are compared to typical exhaust emission levels obtained from conventional diesel engines. TABLE 12-11. Comparison of Exhaust Emissions from Methanol Diesel and Conventional Diesel Engines
Exhaust Emission, g/km Methanol Diesel
HC CO NOx Particulates Aldehydes Methanol
1.7-2.5 10-18 14-19 1.7-3.9 Not detected Not detected
0.53 0.48 8.80 0.06 0.10 0.35
Throughout the decades of the 1980s and 1990s, an increasing variety of M85 and MlOO fueled vehicle fleets were operated in California and other regions. In recent years, though, the number of methanol-powered vehicles in California has declined, primarily due to an increase in methanol pricing and changes in retail fuel agreements. A significant proportion of the California methanol fueling facilities have closed, and, for now, the decline in the number of methanol-powered vehicles is expected to continue. The evolving nature of the alternative fuel industry,
however, has resulted in methanol being considered as a viable energy source for automotive fuel cell applications. 4. Biodiesel Methyl ester based biodiesel fuel is commercially produced in Europe as rapeseed methyl ester (RME) and fatty acid methyl ester (FAME). Use in diesel fuel at 5% by volume is the most common application for RME. In the United States, soybean methyl ester (SME or SOME) is typically blended into diesel fuel at 20% by volume and is known as B20. Blends of 5%, B5, 10%, BlO and also neat 100%, BlOO, biodiesel are becoming available. Biodiesel methyl esters blend quite easily into petroleum based conventional diesel fuel. Biodiesel esters typically have better lubricity properties and higher cetane number ratings than conventional diesel fuel, but have poorer water demulsibility and color stability properties. At sub-zero temperatures, the handling characteristics of biodiesel becomes more difficult to control than conventional diesel fuel. As an alternative diesel fuel or fuel blending component, biodiesel is attractive. It is biodegradable, free of sulfur and aromatic compounds and possesses oxygen in its chemical structure. Most engine studies have shown biodiesel exhaust emissions to contain lower concentrations of carbon monoxide, unburned hydrocarbon and SOx than conventional diesel fuel. Values for NOx and particulate emissions vary depending upon engine timing. A brief summary of biodiesel handling and IK performance properties is presented in TABLE 12-12. TABLE 12-12. Physical, Chemica,! and Performance Properties of Biodiesel Fuel and Biodiesel Fuel Blends
Density, g/cm3 @ 15.560C
Typically higher than conventional diesel fuel; values of 0.88-0.89 are expected; blends of biodiesel with conventional diesel fuel will produce densities closer to values of 0.82-0.86. Low limits are similar to conventional diesel fuel; maximum values can be higher. Very low; usually < 50 ppm; emission of SOx in engine exhaust will be proportionally reduced. Approximately 10.5% oxygen aids fuel combustion to help lower exhaust emissions, especially carbon monoxide.
Viscosity @ 4O0C Sulfur, wt% Oxygen content, wt%
Iodine number, g/100 g
Total acid number (TAN), mg KOH/ g Lubricity
Long-term storage stability
Lubricating oil thickening
Approximately 120; iodine number is indicative of double bonds present between carbon atoms; the iodine number for conventional diesel fuel is usually < 1 . Typically higher than conventional diesel fuel; values of 52 or higher are expected; when blended into conventional diesel fuel, the overall cetane number of the blend should increase. Often between 0.4 and 0.8; this value is higher than the average value of 0.05 or less for conventional diesel fuel. Substantially higher than conventional diesel fuel; BOCLE and HFRR values both improve in biodiesel blends. Very poor; biodiesel and biodiesel blends do not shed water as effectively as conventional diesel fuel; fuel haze, gelling, and low-temperature handling problems can develop if biodiesel is contaminated with water in storage and transport. Poor; double bonds present in the methyl ester compounds are active sites for oxidation and condensation reactions; peroxide values can increase; fuel darkening and deposit formation in storage systems can occur; the addition of oxidation inhibitors to biodiesel helps improve storage stability. Usually more difficult to handle at low temperatures than conventional diesel fuel; when blended with conventional diesel fuel, lowtemperature handling of biodiesel improves. On cold starting, liquid methyl ester compounds can pass into the lubricating oil; the higher TAN and the olefinic nature of biodiesel can lead to sludge formation and thickening of the lubricating oil; more frequent oil drain intervals are recommended when biodiesel is used.
5. Fuel-Water Emulsions
Fuel-water emulsion technology has been utilized for several years to improve the combustion properties of heavy residual fuel oils. In the high-temperature combustion environment, water droplets that are finely dispersed in fuel begin to boil and explode into vapor within the fuel drops. As a result, a highly atomized
fuel mist forms, and the fuel burning efficiency improves significantly. This technology has been applied to conventional naphtha- and distillate-based fuels. Studies completed by the United States Army in the 1970s and 1980s confirmed that diesel-water microemulsions could be an effective "fire resistant fuel." It was found that water purity or hardness of 50 ppm or less was required to provide an effective microemulsion. Diesel-water emulsions are being studied extensively worldwide because of the impact these fuels have on reducing engine exhaust emissions, especially NOx and particulates. Although formulations vary, a typical diesel-water emulsion will contain approximately 80% to 90% diesel fuel, 10% to 15% water, and 1% to 5% of an emulsification additive mixture. The resulting fuel blend is transparent in appearance and has the typical appearance of diesel fuel. The high content of water and emulsifier in this fuel creates some differences in handling and application compared to conventional diesel fuel. The surfactant quality of the emulsification additive in the fuel can remove existing deposits from the internal surfaces of fuel handling and storage systems. Problems with fuel discoloration and fuel filter plugging may follow. Compared with conventional diesel, fuel economy ratings per tank of fuel will drop because the overall carbon content per unit volume of fuel is lower. This is due to carbon displacement by water. Diesel-water emulsions are not approved for shipment by finished product pipeline companies. Consequently, the emulsion must be made on-site or near the point of sale. Other issues currently being resolved deal with improving the coldtemperature handling properties of the high-water-content fuel and improving the long-term storage stability of fuel blends
6. Dimethyl Ether Dimethyl ether (DME) is produced as an intermediate compound in the conversion of methanol to gasoline as described in the earlier discussion of the Mobil M process. It can also be produced by various catalytic dehydration reactions. 2CH3OH <-> CH3OCH3 + H2O Dimethyl ether has been used as an effective ignition improver for other alternative fuels such as methanol and ethanol and can be used as an aerosol propellant. Like methanol, DME can be synthesized from fossil fuel sources or frombiomass. Dimethyl ether was first proposed as an alternative fuel for direct-injected (DI) diesel applications in 1995. Since that time, engine testing has shown DME to be as effective as CNG, LPG, and methanol in producing low levels of engine exhaust emissions. Results of an engine study completed in Austria using a Navistar V8 diesel engine are provided in TABLE 12-13.
TABLE 12-13. Alternative Fuel Emission Levels from a Dl Engine Compared to Diesel EURO Il Limits
NO x ,
Diesel EURO II DME CNG LPG Methanol
1.10 0.25 0.20 0.25 0.40
4.0 1.8 0.1 0.1 1.5
0.15 <0.05 <0.05 <0.05 <0.05
7.0 2.5 1.0 1.5 2.5
Problems encountered using DME include: - Fuel leakage past plunger barrel seals - Maintaining proper fuel injection rates due to high DME vapor pressure - Wear of moving parts due to the low lubricity values for DME - Chemical incompatibility with fuel system components Modifications to engine design and fuel system hardware will be needed to effectively evaluate and utilize DME as an alternative fuel source.
7. Hydrogen Fuel cell technology provides the basis for the use of hydrogen as an alternative transportation fuel. Major automotive manufacturers such as DaimlerChrysler, Ford, General Motors, Honda, and BMW are involved in producing fuel cell powered vehicles for commercial sale. By the use of an anode and cathode system to isolate the electron and proton of hydrogen, fuel cell circuits capture the electron flow and generate electricity. The power plant of the fuel cell vehicle utilizes this electricity to operate motor drive mechanisms. Although liquid hydrogen, LH2, can be used as a fuel source, much of the recent fuel cell research is focusing on the partial oxidation of methanol, natural gas, ethanol, or gasoline to produce the necessary hydrogen. Catalysts that aid in the partial oxidation of these fuels yields a readily available, rich source of hydrogen. Water is the primary exhaust emission produced by fuel cell powered vehicles. If a carbon-based fuel source is utilized, then a carbon-containing by-product will also be produced.
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