Читать книгу Encyclopedia of Renewable Energy - James Speight G., James G. Speight - Страница 62

Ethanol is the predominant fuel produced form crops that, because of favorable properties, has been used as fuel in the United States since at least 1908, along with methanol and gasoline (Table A-10).

Table A-10 Selected physical and chemical properties of methanol, ethanol, and gasoline.

	Methanol	Ethanol	Gasoline
Property	CH3OH	C2H5OH	C4-C12
Molecular weight (g/mol)	32	46	~114
Specific gravity	0.789 (25oC, 77oF)	0.788 (25oC, 77oF)	0.739 (16oC, 60oF)
Vapor density rel. to air	1.10	1.59	3.0 (-40)
Liquid density (g/cm-3 at 25oC, 77oF)	0.79	0.79	3.0 to 4.0
Vapor pressure, 38oC (100oF)	4.6	2.5	8-10
Heat of evaporation (Btu/lb)	472	410	135
Heating value (kBtu gal-1)
Lower (LHV)	58	74	111
Upper (UHV)	65	85	122
Viscosity (cp)	0.54	1.20	0.56
Flash point (oC, oF)	11 (52)	14 (57)	-36 (-33)
Flammability/explosion limits
(%) Lower (LFL)	6.7	3.3	1.3
(%) Upper (UFL)	36	19	7.6

Although early efforts to sustain an ethanol program failed, oil supply disruptions in the Middle East and environmental concerns over the use of lead as a gasoline octane booster renewed interest in ethanol in the late 1970s. At present, extending the volume of conventional gasoline is a significant end use for ethanol, as is its use as an oxygenate. To succeed in these markets, the cost of ethanol must be close to the wholesale price of gasoline, currently made possible by the federal ethanol subsidy. However, in order for ethanol to compete on its own merit,s the cost of producing it must be reduced substantially.

The production of ethanol from corn is a mature technology that holds much potential. Substantial cost reductions may be possible, however, if cellulose-based feedstocks are used instead of corn. Producers are experimenting with units equipped to convert cellulose-based feedstocks, using sulfuric acid to break down cellulose and hemicellulose into fermentable sugar. Although the process is expensive at present, advances in biotechnology could decrease conversion costs substantially. The feed for all ethanol fermentations is sugar - traditionally a hexose (a six-carbon or “C6” sugar) such as those present naturally in sugar cane, sugar beet, and molasses. Sugar for fermentation can also be recovered from starch, which is actually a polymer of hexose sugars (polysaccharide).

Biomass, in the form of wood and agricultural residues such as wheat straw, is viewed as a low cost alternative feed to sugar and starch. It is also potentially available in far greater quantities than sugar and starch feeds. As such, it receives significant attention as a feed material for ethanol production. Like starch, wood and agricultural residues contain polysaccharides. However, unlike starch, while the cellulose fraction of biomass is principally a polymer of easily fermented hexose (C6) sugars, the hemicellulose fraction is principally a polymer of pentose (C5) sugars; with quite different characteristics for recovery and fermentation, the cellulose and hemicellulose in biomass are bound together in a complex framework of crystalline organic material known as lignin.

These differences mean that recovery of these biomass sugars is more complex than recovery of sugars from a starch feedstock. Once recovered, fermentation is also more complex than a simple fermentation of hexose sugars. The current focus focuses on the issues of releasing the sugars (hydrolysis) and then fermenting as much of the C6 and C5 sugars as possible to produce ethanol.

There are several different methods of hydrolysis: (i) concentrated sulfuric acid, (ii) dilute sulfuric acid, (iii) nitric acid, and (iv) acid pretreatment followed by enzymatic hydrolysis.

Ethanol is produced from the fermentation of sugar by enzymes produced from specific varieties of yeast. The five major sugars are the five-carbon xylose and arabinose and the six-carbon glucose, galactose, and mannose. Traditional fermentation processes rely on yeasts that convert six-carbon sugars to ethanol. Glucose, the preferred form of sugar for fermentation, is contained in both carbohydrates and cellulose. Because carbohydrates are easier than cellulose to convert to glucose, the majority of ethanol currently produced in the United States is made from corn, which produces large quantities of carbohydrates. Also, the organisms and enzymes for carbohydrate conversion and glucose fermentation on a commercial scale are readily available.

The conversion of cellulosic biomass to ethanol parallels the corn conversion process. The cellulose must first be converted to sugars by hydrolysis and then fermented to produce ethanol. Cellulosic feedstocks (composed of cellulose and hemicellulose) are more difficult to convert to sugar than are carbohydrates. Two common methods for converting cellulose to sugar are dilute acid hydrolysis and concentrated acid hydrolysis, both of which use sulfuric acid.

Dilute acid hydrolysis occurs in two stages to take advantage of the differences between hemicellulose and cellulose. The first stage is performed at low temperature to maximize the yield from the hemicellulose, and the second, higher temperature stage is optimized for hydrolysis of the cellulose portion of the feedstock. Concentrated acid hydrolysis uses a dilute acid pretreatment to separate the hemicellulose and cellulose. The biomass is then dried before the addition of the concentrated sulfuric acid. Water is added to dilute the acid and then heated to release the sugars, producing a gel that can be separated from residual solids. Column chromatographic is used to separate the acid from the sugars.

Both the dilute and concentrated acid processes have several drawbacks. Dilute acid hydrolysis of cellulose tends to yield a large amount of by-products. Concentrated acid hydrolysis forms fewer by-products, but for economic reasons, the acid must be recycled. The separation and concentration of the sulfuric acid add more complexity to the process. The concentrated and dilute sulfuric acid processes are performed at high temperatures (100 and 220°C, 212 and 430°F) which can degrade the sugars, reducing the carbon source and ultimately lowering the ethanol yield. Thus, the concentrated acid process has a smaller potential for cost reductions from process improvements such as acid recovery and sugar yield for the concentrated acid process could provide higher efficiency for both technologies.

Another approach involves countercurrent hydrolysis, a two-stage process. In the first stage, cellulose feedstock is introduced to a horizontal co-current reactor with a conveyor. Steam is added to raise the temperature to 180°C (355°F; no acid is added at this point). After a residence time of approximately 8 minutes, during which some 60% of the hemicellulose is hydrolyzed, the feed exits the reactor. It then enters the second stage through a vertical reactor operated at 225°C (435°F). Very dilute sulfuric acid is added to the feed at this stage, where virtually all of the remaining hemicellulose and, depending on the residence time, anywhere from 60% w/w to all of the cellulose is hydrolyzed. The countercurrent hydrolysis process offers higher efficiency (and, therefore, cost reductions) than the dilute sulfuric acid process. This process may allow an increase in glucose yields to 84% w/w, an increase in fermentation temperature to 55°C (131°F), and an increase in fermentation yield of ethanol to 95% w/w.

The greatest potential for ethanol production from biomass, however, lies in enzymatic hydrolysis of cellulose. The enzyme cellulase, now used in the textile industry to stone wash denim and in detergents, simply replaces the sulfuric acid in the hydrolysis step. The cellulase can be used at lower temperatures, 30 to 50°C (86 to 122°F), which reduces the degradation of the sugar. In addition, process improvements now allow simultaneous saccharification and fermentation (SSF). In the saccharification and fermentation process, cellulase and fermenting yeast are combined, so that as sugars are produced, the fermentative organisms convert them to ethanol in the same step. Once the hydrolysis of the cellulose is achieved, the resulting sugars must be fermented to produce ethanol. In addition to glucose, hydrolysis produces other six-carbon sugars from cellulose and five-carbon sugars from hemicellulose that are not readily fermented to ethanol by naturally occurring organisms. They can be converted to ethanol by genetically engineered yeasts that are currently available, but the ethanol yields are not sufficient to make the process economically attractive. It also remains to be seen whether the yeasts can be made hardy enough for production of ethanol on a commercial scale.

A large variety of feedstocks is currently available for producing ethanol from cellulosic biomass. The materials being considered can be categorized as agricultural waste, forest residue, and energy crops. Agricultural waste available for ethanol conversion includes crop residues such as wheat straw, corn stover (leaves, stalks, and cobs), rice straw, and bagasse (sugar cane waste). Forestry waste includes underutilized wood and logging residues; rough, rotten, and salvable dead wood; and excess saplings and small trees. Energy crops, developed and grown specifically for fuel, include fast-growing trees, shrubs, and grasses such as hybrid poplars, willows, and switchgrass.

Briefly, corn stover is the leaves and stalks of field crops, such as corn (maize), sorghum, or soybean that are commonly left in a field after harvesting the grain. Corn stover is similar to straw, which is the residue left after any cereal grain or grass has been harvested at maturity for its seed and can be directly grazed by cattle or dried for use as fodder; stover has attracted some attention as a potential fuel source, and as a biomass feedstock for fermentation or as a feedstock for ethanol production from cellulose.

Although the choice of feedstock for ethanol conversion is largely a cost issue, feedstock selection has also focused on environmental issues. Materials normally targeted for disposal include forest thinnings collected as part of an effort to improve forest health, and certain agricultural residues, such as rice straw. Also, forest residues represent an opportunity to decrease the fire hazard associated with the dead wood present in many forests. Small quantities of forest thinnings can be collected at relatively low cost, but collection costs rise rapidly as quantities increase.

Agricultural residues, in particular corn stover, represent a tremendous resource base for biomass ethanol production. Agricultural residues, in the long term, would be the sources of biomass that could support substantial growth of the ethanol industry. At conversion yields of around 60 to 100 gal per dry ton, the available corn stover inventory would be sufficient to support 7 to 12 billion (7 to 12 x 10⁹) gal of ethanol production per year.

Dedicated energy crops such as switchgrass, hybrid willow, and hybrid poplar are another long-term feedstock option. Switchgrass is grown on a 10-year crop rotation basis, and harvest can begin in year 1 in some locations and year 2 in others. Willows require a 22-year rotation, with the first harvest in year 4 and subsequent harvests every 3 years thereafter. Hybrid poplar requires 6 years to reach harvest age in the Pacific Northwest, 8 years in the Southeast, Southern Plains, and South Central regions, and 10 years in the Corn Belt, Lake States, Northeast and Northern Plains regions.

The use of cellulosic biomass in the production of ethanol also has environmental benefits. Converting cellulose to ethanol increases the net energy balance of ethanol compared to converting corn to ethanol. The net energy balance is calculated by subtracting the energy required to produce a gallon of ethanol from the energy contained in a gallon of ethanol (approximately 76,000 Btu). Corn-based ethanol has a net energy balance of 20,000 to 25,000 Btu per gallon, whereas cellulosic ethanol has a net energy balance of more than 60,000 Btu per gallon. In addition, cellulosic ethanol use can reduce greenhouse gas emissions. Cellulosic ethanol can produce an 8 to 10% reduction in greenhouse gas emissions when used in E10 and a 68 to 91% reduction when used in E85.

See also: Agricultural Residue, Agricultural Waste, Biomass, Alcohols.