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Energy Sources
Transportation fuels are but one of the energy demands in the
U.S. that are competing for the various resources available. In
1996, these energy demands were met as follows:1
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Alternative Fuels
The government relations committee of the American Institute of Chemical
Engineers (AIChE) formed the Alternative Fuels Task Force to study this
subject. In the report by this group,3 they state that the U.S. will continue
to depend heavily on petroleum products for the foreseeable future but that
an analysis is warranted of fuels that could supplement or replace conven-
tional gasoline and diesel fuels.
“The study suggests that, while no alternative fuel is a panacea for all
problems, CNG, LPG, and RFG present the best overall alternatives to con-
ventional gasoline based on current technology. These three alternative
fuels (ATFs) provide environmental benefits at a relatively low fuel cost.”
Eight key characteristics were considered for each fuel:
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CHAPTER 5 • ENERGY RESOURCES AND TRANSPORTATION FUELS
The resulting averages fuel performance indices for the fuels studied
were as follows:
Fuel Index
Conventional gasoline 3.7
RFG 3.8
Ethanol 2.6
Methanol 3.1
Electric 3.2
Compressed natural gas (CNG) 4.1
Liquified petroleum gas (LPG) 4.0
Though CNG and LPG have the highest average ranking, they fall short
on availability and customer convenience.
The Energy Information Administration of the Department of Energy
reports estimates of alternative–fueled vehicles in use in the U.S., and their
consumptions in thousands of gallons of equivalent gasoline (Tables 5–1
and 5–2).4
Table 5–3 compares some of the properties of two vegetable oils that
have been studied as substitutes for or extenders of diesel oil.4
Gasoline
Gasoline is the largest volume single material produced by the U.S.
refining industry, equal to about 56% of the crude oil refined. Most of the
research and development efforts of the industry have been devoted, direct-
ly or indirectly, to increasing the yield and quality of gasoline. Therefore, it
is fitting that we dwell awhile on its properties and characteristics.
Octane number. The most familiar property of gasoline, aside from its
flammability, is its antiknock index or octane number. Octane number is a
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R+M
–––––––
2
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and manual transmission. It was found that the resulting DONs correlated
very well with road ratings during low–speed acceleration.
Another attempt at characterizing road performance by laboratory test
is the front–end octane number or FEON that involves the distillation from
the whole gasoline of the more volatile portion up to a certain volume
percent or to a certain vapor temperature. The RON of this lower boiling
material is then determined. The difference between the RON of the whole
gasoline and this portion is referred to as R-100 when the gasoline is dis-
tilled to a vapor temperature of 100˚C.8 It is referred to as R75 when the
RON is determined on the first 75% of the gasoline distilled off.9
Like the DON, FEON appears to correlate well with road octane
performance in representatives of particular segments of the car population.
Figure 5–1 traces average octane values for regular and premium gaso-
lines marketed in the U.S.10
A driveability index has been accepted by the automobile and petroleum
industries as providing a good indication of the driveability performance of
a gasoline:11
It has been shown that the DI increases on average as the RVP of gaso-
line decreases. Auto manufacturers recommend a maximum DI of 1,200 to
provide satisfactory driveability.
Another characteristic of gasoline that is of interest is its sensitivity,
which is defined as RON – MON. A maximum value for sensitivity is some-
times specified for a gasoline. Figure 5–2 illustrates the sensitivities of the
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Class AA A B C D E
RVP Temp F 7.8 9 10 11.5 13.5 15
Max 10% 158 158 149 140 131 122
Min 50% 170 170 170 170 150 150
Max 50% 250 250 245 240 235 230
Max 90% 374 374 374 365 365 365
Max EP 437 437 437 437 437 437
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HYDROCARBONS
Normal Butane 94.4 98.4 96.4
Isobutane 100.8 97.4 99.1
Butylenes 104.1 82.9 93.5
Natural Gasoline 73.5 72.5 73.0
Light Straight Run 59.2 59.9 59.6
Intermed. Straight Run 70.0 70.7 70.4
Heavy Straight Run 80.8 81.5 81.2
Light Naphtha 41.3 42.0 41.7
Reformate (80 RON) 80.7 74.3 77.5
Reformate (90 RON) 90.5 80.4 85.5
Reformate (95 RON) 95.2 83.4 89.3
Reformate (100 RON) 99.9 87.6 93.8
Light FCC Gasoline 94.7 79.3 87.0
Heavy FCC Gasoline 87.0 78.1 82.6
Light Hydrocrackate 86.6 83.0 84.8
Polymer Gasoline 96.0 83.0 89.5
Medium Hydrocrackate 76.5 71.0 73.8
Propylene Alkylate 91.7 92.2 92.0
Butylene Alkylate 94.3 94.5 94.4
Heavy Alkylate 85.4 82.2 83.8
OXYGENATES
Methanol 133.0 99.0 116.0
Ethanol 129.0 96.0 112.5
MTBE 118.0 100.0 109.0
ETBE 118.0 102.0 110.0
TAME 111.0 98.0 104.5
SOURCE: EPA,"Costs and Benefits of Reducing Lead in Gasoline",
March 1984, EPA-230-03-84-005
Straight run (virgin) and thermal (from thermal cracking) stocks are very
minor constituents in today's gasoline having been displaced by components
produced by catalytic processes.
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Assuming the working fluid to be essentially air, the specific heat ratio
is 1.396. Calculating the efficiencies for a series of compression ratios and
plotting the results yields the curve in Figure 5–6. The significant increase
in theoretical efficiency possible by increasing compression ratio is readily
apparent.
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Figure 5–11 depicts the average car fuel economy in miles per gallon of
gasoline versus model year.19
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Diesel fuel
Diesel fuel is second in volume only to gasoline as fuel for
internal–combustion engines. The diesel engine differs from the conven-
tional gasoline engine in the way in which the fuel is ignited. In the gasoline
engine, ignition is initiated by an electric spark—in the diesel, it results from
the heat produced by compression of the fuel–air mixture.
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REGULAR GRADE
1991 1.61 0.038 11.8 28.1 87.1 8.6 1.0
1992 1.70 0.034 12.4 30.0 87.4 7.7 0.4
1993 1.40 0.036 11.8 30.4 87.4 7.7 1.2
1994 1.58 0.035 11.9 30.5 87.3 7.8 1.0
1995 1.33 0.029 11.8 31.0 87.3 8.0 0.8
1996 1.13 0.029 10.2 30.5 87.5 7.9 1.6
PREMIUM GRADE
1991 1.62 0.013 5.5 33.2 92.3 8.6 4.1
1992 1.55 0.012 6.1 34.3 92.3 7.7 2.0
1993 1.33 0.014 6.5 35.5 92.5 7.6 6.7
1994 1.52 0.013 6.5 33.8 82.5 7.8 3.9
1995 1.13 0.007 5.5 33.0 92.4 7.9 2.8
1996 1.04 0.010 4.7 33.1 92.5 7.8 3.0
In the diesel engine, air is drawn into a cylinder and compressed before
fuel is injected into the cylinder. During compression, the air is heated to a
temperature at which the fuel will spontaneously ignite after a short delay.
The length of this delay varies with the types of hydrocarbons making up
the fuel, increasing from paraffin to olefin to naphthene to aromatic.
Cetane number (ASTM Method D 613). The primary measure of diesel
fuel quality is its cetane number. This is a function of the delay before igni-
tion: the shorter the delay, the higher the quality or cetane number. Long
delays cause rough engine operation, misfiring, difficult starting in cold
weather, and smoky exhaust.
The laboratory rating of diesels is similar to the procedure used in
determining the gasoline octane number. The paraffin hydrocarbon cetane
(n–hexadecane) has been assigned the value of 100 cetane. A value of zero
has been assigned to the bicyclic compound alpha methylnaphthalene.
These two compounds are the primary reference fuels. Mixtures of the two
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are used to bracket the quality of the fuel being tested. Recently, the methyl-
naphthalene has been replaced by the highly branched paraffin compound
2,2,4,4,6,8,8–heptamethylnonane with a cetane number of 15. This com-
pound can be produced in very high purity.
The variation of cetane number with carbon number and type of hydro-
carbon is shown in Figure 5–13.21 The alkyl benzenes are obviously unde-
sirable. The low carbon numbers have low cetane numbers and the high
carbon numbers have high freeze points. Cetane numbers of diesels sold in
the U.S. are in the 35 to 65 range, with most engine manufacturers speci-
fying at least 45. The recent trend in cetane index (CI) and sulfur content
of highway diesel is tabulated in Table 5–5.22
The following factors affect the problem of maintaining diesel fuel
quality:
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The relationship between the cetane number and aromatics content of some
diesels is shown in Figure 5–14.23
Volatility. Some volatile compounds are needed in diesel for ease in start-
ing. In general, the heavier compounds have higher heating values than the
lighter compounds and for the same cetane number give better fuel econo-
my. However, in addition to greater starting difficulty, too high a percent of
heavies can cause high formation of deposits in the engine. Therefore, the
refiner blends his available distillates to obtain the desirable volatility.
Diesel fuels usually have an initial distillation point of about 320˚F with a
90% point of about 550˚F to 680˚F depending on the grade.
Pour point (ASTM Method D 97) is the temperature at which flow of the
material ceases. As the temperature of the diesel fuel decreases toward its
pour point, pumping the fuel through supply lines, filters, and injectors
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becomes more difficult. Naphthenes have low pour points, but also low
cetane numbers. Paraffins have high pour points, but high cetane numbers.
Therefore, the pour point specification for a given locale should be set as high
as is compatible with expected winter temperatures, usually about 10˚F below
the expected low. There are additives available to improve pour point.
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Flash point (ASTM Method D 93) is the temperature to which the fuel must
be heated to generate sufficient vapors for ignition to occur in the presence
of a flame. Flash point specification varies with the grade of the diesel.
Sulfur content (Various ASTM Methods) can cause corrosion and engine
wear. Of greater concern today is the emission of SO 2 into the atmosphere
as result of combustion of the sulfur content.
Jet fuel
Jet fuel is another very important transportation fuel. Though a minor
amount is used in stationary engines, the bulk of jet fuel is used to power
commercial and military aircraft.
Gas turbine fuel is a more general designation, since the stationary
engines develop shaft power to turn electric generators, compressors or other
equipment as contrasted with aircraft engines that develop thrust from
exhaust gases passing through a nozzle at high velocity. In either case, useful
work is obtained by expanding hot combustion gases. In this respect, the gas
turbine is much like a steam turbine, but with a different working fluid.
Each type of gas turbine consists of three basic steps, with two of the
steps common to both types:
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• Air compression
• Fuel combustion
The third step is the jet nozzle for thrust in the case of the aircraft turbine—
the expansion turbine for shaft power in the stationary turbine.
The principal specifications for gas turbine fuels and the corresponding
ASTM test methods include the following:
D 1355 D 2880
Property Aviation Stationary
Aromatics D 1319 —
Flash D 56 D 93
Density D 1298, 4052 —
Freeze point D 2386 —
Smoke point D 1322 —
Viscosity D 445 D 445
Carbon residue — D 524
Pour point — D 97
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Fig. 5–15a Quick Measure of Jet Fuel Properties (©ASTM; reprinted with permission) 14
PETROLEUM REFINERY P ROCESS ECONOMICS
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Fig. 5–15b Quick Measure of Jet Fuel Properties cont’d (©ASTM; reprinted with permission) 14
CHAPTER 5 • ENERGY RESOURCES AND TRANSPORTATION FUELS
Notes
1. EIA, Renewable Energy Annual, Vol. 1, 1997
2. Dye, R. F., in Flashpoint, AIChE Fuels and Petrochemicals
Division Newsletter
3. AIChE, “Alternative Transportation Fuels: A Comparative
Analysis,” September, 1997
4. EIA, “Alternatives To Traditional Transportation Fuels,” DOE/
EIA–0585(95)
5. Morris, W.E., Rogers, J.D., Jr., and Pockitt, R.W., “1971 Cars
and the New Gasolines,” Society of Automotive Engineers,
Mid–Year Meeting, Montreal, June, 1971
6. Foster, J.M., Goodacre, C.L., Griffith, S.T., and Lamarque, P.V.,
Gasoline Antiknock Quality—Are Road Ratings Necessary?, The
Associated Octel Company Limited, London, July, 1964
7. Gerard, P.L., and Di Perna, C.J., “Multifaceted Octane Numbers
for Diverse Engine Requirements,” SAE International
Automotive Engineering Congress, Detroit, January, 1965
8. Roselius, R.R., Gibson, K.R., Ormiston, R.M., Maziuk, J., and
Smith, F.A., “Rheniforming and SSC—New Concepts and
Capabilities,” NPRA Annual Meeting, San Antonio, April, 1973
9. DuPont Technical Memorandum No. 357, Wilmington,
February, 1962
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10. Dickson, C.L., and Sturm, G.P., Jr., NIPER 178, 180, 188, 190,
198, 200
Shelton, E.M., Whisman, M.L., and Woodward, P.W., Oil & Gas
Journal, August 2, 1982, pp. 95–99
Unzelman, G.H., Oil & Gas Journal, April 7, 1986, pp. 88–95
11. Colucci, J., Harts Fuel Technology & Management, March, 1997,
p.12
15. Nelson, W.L., Oil & Gas Journal, March 29, 1971, p. 79
Smith, L.D., Oil & Gas Journal, June 24, 1985, pp. 95–97
Unzelman, G.H., Oil & Gas Journal, April 4 and 17, 1988, pp.
35–41, 48–49
16. Anon., Oil & Gas Journal, June 18, 1990, pp. 49, 50
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CHAPTER 5 • ENERGY RESOURCES AND TRANSPORTATION FUELS
21. Tilton, J.A., Smith, W.M., and Hockberger, W.G., Industrial and
Engineering Chemistry, July, 1948, p. 1,271
22. Dickson, C.L., and Sturm, G.P., Jr., NIPER 187 and 195
23. Unzelman, G.H., Oil & Gas Journal, June 29, 1987, ff 55
25. Dickson, C.L., and Sturm, G.P., Jr., NIPER 184 and 199
75