1 - kerosene fuels for aerospace propulsion – composition and properties

“Kerosene” Fuels for Aerospace Propulsion – Composition and Properties

Tim Edwards* Air Force Research Laboratory, Propulsion Directorate

Wright-Patterson AFB, OH

ABSTRACT This paper describes the composition and selected properties of kerosene fuels for aerospace propulsion. These petroleum distillate fuels are composed of hundreds-to-thousands of hydrocarbons, with the variations in composition controlled by specifications on boiling range, vapor pressure, contaminants, freeze point, etc. The specific fuels to be discussed include military jet fuels JP-5,7,8 and T-6, commercial jet fuels Jet A, Jet A-1 and TS-1, and kerosene rocket propellants RP-1 and RG-1. Chemical class composition will be discussed, as well as pertinent physical properties. Sources of physical property data and modeling approaches will also be discussed.

INTRODUCTION The discussion of kerosene fuels divides fairly

naturally into two applications: turbine engines and liquid rockets. The term kerosene is used to describe a distillate fraction of petroleum boiling between (roughly) 150-300 C (300-570 F). An illustration of the resulting distribution of the hydrocarbons in various fuels is shown in Figure 1.

Turbine Engine Fuels The early pioneers in gas turbine development, Whittle in England and Von Ohain in Germany, faced a wide variety of options in choosing a fuel for gas turbines. Whittle had considered diesel fuel, but ended up choosing kerosene because of an expected requirement for a lower freeze point than that available with diesel [Martel, 1987]. In contrast, Von Ohain originally decided to use hydrogen, but combustor developmental difficulties led to a switch to liquid fuel [Dukek et al, 1969]. The world’s first turbojet-powered flight was made on August 27, 1939 in a Heinkel 178 aircraft burning aviation gasoline. The first flight of the Whittle engine occurred on May 15, 1941 in a Gloster Meteor aircraft using kerosene as the fuel. Despite their head start in turbojet engine development, Germany did not decide until 1943 to produce jet-powered aircraft. ________________________ *Associate Fellow, AIAA

One of the arguments for development at that time was Germany's shortage of high octane fuel and the expectation that the jet engine could run on diesel fuel [Dukek et al, 1969].

Most of the jet engines developed before the end of World War II utilized conventional kerosene as a fuel. As engines and specifications developed, it became apparent that several fuel properties were key to bounding the envelope of jet fuel characteristics. High altitude operation (with ambient temperatures on the order of -65 F) meant fuel freeze point required attention. However, the lower the freeze point the lower the fraction of crude oil that was suitable, so freeze point had to be balanced against availability. Atomization and altitude relight were aided by higher fuel volatility (vapor pressure), which had to be traded against boiloff and entrainment losses from fuel tanks at altitude (as well as safety concerns from explosive mixtures in tank vapor spaces) [Maurice et al, 2001a]. Two fuels emerged in the late 40’s and early 50’s from this chaotic situation: a “wide-cut” gasoline/kerosene mixture called JP-4 in the U.S. (MIL-F-5624 in 1950) and a kerosene fuel with a -50 C (-58 F) freeze point specified as DERD-2494 in England and Jet A-1 in the U.S. ASTM D-1655 specification. This freeze point was arrived at through a significant research effort. ASTM D-1655 also specified Jet A with a -40 C (-40 F) freeze point. Civil aviation currently uses Jet A-1 (or its equivalent) throughout the world, except for domestic carriers in the U.S., who use Jet A. Military aircraft used JP-4 until converting to JP-8 in the 1980s. JP-8 (MIL-T-83133) is essentially Jet A-1 with a three military-specified additives-fuel system icing inhibitor, corrosion inhibitor/lubricity improver, and static dissipater. The conversion to JP-8 occurred primarily to improve the safety of aircraft, although the “single fuel for the battlefield” concept (and the similarity of jet fuel to diesel fuel) is centered on the use of aviation kerosene in all Air Force and Army aircraft and ground vehicles. The history of the evolution of conventional, widely available jet fuels from the late 1950s to the present is mainly the story of the evolution of test methods and fuel additives to maintain the integrity of the jet fuel supply and to improve safety and correct operational problems.

1 American Institute of Aeronautics and Astronautics

38th AIAA/ASME/SAE/ASEE Joint Propulsion Conference & Exhibit7-10 July 2002, Indianapolis, Indiana

AIAA 2002-3874

This material is declared a work of the U.S. Government and is not subject to copyright protection in the United States.

Specialty fuels were developed for various applications throughout the second half of the 20th century. JP-5 (included in MIL-F-5624) is a high-flash (140 F) kerosene used on-board U.S. Navy ships to enhance safety. The development of higher Mach aircraft led to several specialty fuels. As flight velocity increases, aerodynamic heating leads to larger amounts of heat being rejected to the fuel, both in the tanks and in the engine, leading to vapor pressure and thermal stability concerns. The cutoff point between the use of conventional Jet A-1/JP-8 fuels and specially-produced fuels is between Mach 2.2 and 3. Thus, the Mach 2.2 Concorde uses Jet A-1, while the Mach 3 XB-70 and SR-71 used specialty fuels. JP-6 (MIL-F-25656) was a low-volatility kerosene developed for the Mach 2+ XB-70 [Freschl and Steele, 1965]. The Mach 3 SR-71 required JP-7 (MIL-T-38219), a low-volatility/high-thermal-stability, highly-processed (low sulfur and aromatics) kerosene [Martel, 1987]. The U-2 high-altitude reconnaissance aircraft required both improved thermal stability and lower freeze point in its fuel (JP-TS, MIL-T-25524) because of its high altitude, long duration cruise. These specialty fuels gave higher performance than conventional aviation kerosenes, at the expense of higher fuel and logistical costs (JP-7 and JP-TS are roughly 3X the cost of JP-8/Jet A-1). The temperature limits of these various fuels are approximately 325 F for Jet A/Jet A-1/JP-8, 425 F for JP-TS, and 550 F for JP-7 [Croswell and Biddle, 1992]. Just for completeness, it should be noted that JP-9 and JP-10 are high density missile fuels, not kerosene fuels, and consist of one (JP-10) and three (JP-9) hydrocarbons. Typical kerosene fuel properties are shown in Table 1.

Russian jet fuels underwent a parallel evolution throughout this period [Ragozin, 1961; Pustyrev, 1993]. In most properties, current Russian fuels TS-1 and RT and Russian specifications (GOST 10227) are interchangeable with Jet A-1/JP-8. The main difference between fuels TS-1 and RT is in the area of thermal stability: TS-1 is a straight run fuel, while RT is hydrotreated. By comparison with Jet A-1/JP-8, TS-1 and RT are “lighter” (have a lower initial boiling point and 10% recovery point in distillation) and have a correspondingly lower flash point and freeze point. For example, recent unpublished surveys of Russian jet fuel at Moscow airport have shown an average flash point of 97 F (vs 127 F for Jet A-1 shown in Table 1). Pustyrev discusses two specialty Russian fuels specified in GOST 12308: T-8V, a higher density/higher flash kerosene and T-6, a high density kerosene (specific gravity 0.84 vs 0.8 for Jet A-1/JP-8) which has no commercial or military counterpart in Europe or the U.S. [Pustyrev, 1993]. U. S. Air Force programs in the 1980s demonstrated the production of fuels similar to T-6 [Hanson, 1989; Smits, 1986], but no

specification was published in the absence of user requirements.

Beyond Mach 5, flight speeds are considered hypersonic (vs supersonic). The high heat loads encountered by vehicles in hypersonic flight leads inevitably to regenerative cooling of (at least) the combustor. The heat loads and fuel flows are such that high levels of fuel heat sink are required. This heat sink can be obtained from sensible heating of high heat capacity fuels such as liquid hydrogen or the use of endothermic (hydrocarbon) fuels. For many applications, hydrocarbon fuels are preferred due to their greater density [Lewis and Gupta, 1997] and ease of handling. Endothermic fuels achieve heat sink by deliberate reactions of the bulk fuel, such as dehydrogenation or cracking [Maurice et al, 2001b; Lander and Nixon, 1971; Sobel and Spadaccini, 1997; Ianovski, 1993]. Engine concepts for hypersonic aircraft are currently under development in several programs.

World-wide jet fuel consumption was 177 million gallons/day in 1997, with about 40% of the consumption in the United States [Bacha, 2000].

Kerosene Rocket Propellants Oxygen/hydrogen is the highest performing

operational propellant family. Of course, the low temperatures (20 K) and explosion hazards of hydrogen impose significant launch cost penalties. The low density of liquid hydrogen (4 lb/ft3) is also a drawback. For these reasons, Russian launch vehicles and many U.S. vehicles have used various types of liquid hydrocarbons as a fuel. Although Goddard’s initial 1926 flight test used gasoline, operational hydrocarbon-fueled rockets since then have used kerosene. Jet fuels, as described earlier, are kerosenes; naturally, jet fuels like JP-4 were the initial kerosenes used in rocket tests (although JP-4 does not strictly fit the definition of a kerosene because of its low initial boiling point). However, it was found that jet fuel did not have tight enough specification properties to serve as an effective propellant. The U.S. developed Rocket Propellant 1 (RP-1) in the mid 1950s as MIL-P-25576. In comparison to jet fuel, RP-1 has a much narrower allowable density range, and lower limits on fuel components that were thought to cause deposits during regenerative cooling, such as sulfur, olefins, and aromatics [Sutton, 1992]. Deposit formation (“coking”) led to a maximum fuel-wetted surface temperature limit quoted as 600 F [Cook and Quentmeyer, 1980], 600-700 F [Wagner and Shoji, 1975], 580 F [Rosenberg and Gage, 1991], 710 F [Liang et al, 1998], and 850 F [Van Huff, 1972]. The amount of coking is very dependent upon the fuel-wetted surface, with copper causing more deposition than steel. Russian kerosene (“RG-1”,


“naphthyl”) is somewhat different from RP-1, notably with a higher density (0.832 vs 0.806 at 22 C) [Mehta et al, 1995]. RG-1 has been chilled before use to increase its density (and thus the mass of propellant that can be loaded onto the rocket). Engine applications include

the RD-180, RD-170, and NK-33. Aircraft fuel T-6 has been used in engine tests in place of RG-1 because of its similar physical properties and greater availability. Typical kerosene propellant properties are shown in Table 2.

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RP-1��JP-7Jet A��

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Weight %

Carbon number

Figure 1. Carbon number distribution for several kerosene fuels [Edwards, 2001], diesel [Briker et al, 2001] and avgas [Bacha et al, 2000].

Table 1. Typical aviation fuel properties [Coordinating Research Council, 1983; Martel,

1988; Martel, 1978; ; Goodger and Vere, 1985; Sobel and Spadaccini, 1997; Yu and Eser, 1995; Mehta et al, 1995; Defense Energy Supply Center, 1997; Wood et al, 1989; Hanson, 1989;

Favorskii and Kurziner, 1990]

Property JP-4 JP-5 JP-7 JP-8 (Jet A/ Jet A-1)

T-6

Approx. Formula* C8.5H17 C12H22 C12H25 C11H21 C16H33 H/C ratio 2.00 1.92 2.07 1.91 1.91 Boiling Range, F 140-460 360-495 370-480 330-510 350-600 Freeze point, F -80 -57 -47 -60 JP-8/Jet A-

1; -50 Jet A -77

Flash point, F -10 147 140 127 178 Net heating value, BTU/lb

18,700 18,500 18,875 18,550 18560

Specific gravity ,60 F 0.76 0.81 0.79 0.81 0.84 Critical T, F 620 750 750 770 Critical P, psia 450 290 305 340 *For illustration of average carbon number—not designed to give accurate H/C ratios


Table 2. Typical kerosene propellant properties [Mehta et al, 1995]

Property RP-1 RG-1 Approx. Formula* C12H23.4 C12H23.4 H/C ratio 1.952 1.946 Boiling Range, F 350-525 380-525 Freeze point, F -56 -52 Flash point, F 155 160 Net heating value, BTU/lb 18,650 18560 Specific gravity ,70 F 0.806 0.832 Critical T, F 770 Critical P, psia 315

COMPOSITION

The composition of kerosene fuels is not fixed through specifications. Rather, fuel specifications bound the “envelope” of acceptable compositions. How, then, can the semi-infinitely-variable composition of kerosene fuels be described? Often, the fuels are divided into representative chemical classes. In any case, one simplification that is usually introduced is to approximate the fuel by its average. An example of the variations in JP-8 as given by the Defense Energy Supply Center’s PQIS database is shown in Figure 2 [Defense Energy Supply Center, 1997/98/99]. Figure 3 shows that the property distributions are not necessarily “regular”. Some representative class analyses for aviation kerosenes are shown in Table 3 [Hodgson et al, 1976/1979; Duvall et al, 1985]. In an effort to further distinguish these classes, several analyses of fuels were performed using GC-FIMS [Briker et al, 2001]. The

overall results are shown in Table 4. Examples of the detailed results are shown in Table 5 and 6. Although the aromatic fraction seems to be over-estimated, these data are useful in that the normal- and iso-paraffins are distinguished, and the cycloparaffins (naphthenes) and aromatics are separated by ring size. These analyses and other data were used to generate Table 7, which shows representative average compositions for various kerosene fuels. The JP-7 compositional data is notably scattered, with three analyses giving: 32% naphthenes/65% paraffins [Sobel and Spadaccini, 1997], 56.2% paraffins/41.9 % naphthenes [unpublished 1991 AFRL analysis of a 1984 JP-7], and 37.9% paraffins/59.8% naphthenes [GC-FIMS in Table 2 above]. The RP-1 and RG-1 GC-FIMS composition in Table 2 is closer to published results: RP-1=39% paraffins/58% naphthenes and RG-1=24% paraffins/75% naphthenes [Mehta et al, 1995].

.


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300

350

400 �� 90-96 (18.2±3.1 vol%)��

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Millions of gallons

Aromatics, vol%

259 11 13 15 17 19 21 23

JP-8

Figure 2. Variation in aromatics content of JP-8.

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-40-42-44-46-48-50-52-54-56-58

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Figure 3. Distribution of jet fuel freeze points in U.S airport survey [Davidson, 2001].


Table 3: Hydrocarbon classification ASTM D2784 Jet A-1 JP-8 JP-8 JP-5 Jet A Paraffins 38.3 44.0 46.3 50.7 49.4 (avg

C # = 12) Cycloparaffins 41.6 36.2 39.5 20.9 34.2 (12) Alkyl benzenes 12.6 16.5 7.5 17.7 12.7 (10.7)

Indans/tetralins 4.4 2.3 3.9 9.3 2.1 (11) Indenes/dihydronaphthalenes

0.9 0 0.5 (10)

Naphthalenes 3.0 0.5 1.9 1.1 0.7 (11.5) Average carbon number

10.6

Reference AFWAL-TR-85-2049

unk AFAPL-TR-79-2016

AFAPL-TR-76-26

AFAPL-TR-76-26

Table 4. Preliminary compositional analysis of kerosene fuels from GC/FIMS. Fuel JP-7

3327 RP-1 RG-1 Jet A

96-3219 Jet A-1 95-3136

JP-5 NAPC22

n-paraffins, wt%

8.8 2.1 0.3 8.4 10.3 7.0

i-paraffins 29.1 27.1 8.1 20.8 27.4 21.2 naphthenes 59.8 62.4 86.3 39.6 26.9 50.9 aromatics 2.3 8.4 5.3 31.2 35.4 20.9

ASTM D1319

aromatics, vol%

1.1 2.3 2.9 18

Aromatics [Mehta et al 1995], vol %

4.0 3.1

Spec max, vol%

5 5 20* 20* 25

*25 vol% if seller notifies user


Table 5. RP-1 composition by GC-FIMS Isoparaffins n-Paraffins

1-ringcycloparaffins

2-ringcycloparaffins

3-ringcycloparaffins Alkylbenzenes

Benzo-cycloalkanes

Benzo-dicycloalkanes Naphthalenes

c7 0.000 0.000 0.004 0.000 0.000 0.021 0.000 0.000 0.000

c8 0.000 0.011 0.030 0.002 0.002 0.350 0.000 0.000 0.000

c9 0.044 0.063 0.697 0.135 0.013 1.149 0.009 0.000 0.000

c10 0.590 0.244 4.154 2.372 0.113 1.848 0.132 0.000 0.003

c11 4.810 0.817 11.525 7.590 0.607 1.807 0.372 0.005 0.327

c12 8.058 0.687 10.637 6.514 1.167 1.205 0.496 0.014 0.041

c13 7.902 0.052 5.855 3.427 1.117 0.372 0.180 0.006 0.011

c14 4.465 0.136 2.580 1.585 0.608 0.048 0.018 0.000 0.000

c15 1.099 0.039 0.736 0.651 0.150 0.005 0.003 0.000 0.000

c16 0.158 0.016 0.056 0.041 0.002 0.000 0.000 0.000 0.000

sum 27.127 2.064 36.274 22.316 3.778 6.806 1.210 0.025 0.384

Table 6. RG-1 composition by GC-FIMS Isoparaffins n-Paraffins

1-ring cycloparaffins


3-ring cycloparaffins Alkylbenzenes


Benzo-cycloalkanes

Benzo-dicycloalkanes

Naphtho-cycloalkanes

c7 0.009 0 0.034 0 0 0.019 0 0 0 0

c8 0.032 0.003 0.151 0.008 0 0.039 0 0 0 0

c9 0.025 0.002 0.767 0.413 0.014 0.164 0 0.004 0 0

c10 0.166 0.022 2.447 2.428 0.077 0.324 0 0.091 0 0

c11 0.541 0.077 5.258 10.411 0.406 0.62 0 0.288 0.001 0

c12 1.191 0.075 6.727 12.534 1.188 0.609 0 0.61 0.007 0.004

c13 1.515 0.004 5.168 9.345 2.161 0.579 0 0.713 0.035 0.006

c14 2.349 0.058 4.313 6.441 2.739 0.44 0.009 0.412 0.025 0.002

c15 1.696 0.026 2.979 4.741 2.004 0.192 0.002 0.113 0.008 0.001

c16 0.592 0 1.261 1.514 0.55 0.017 0 0.011 0.002 0

c17 0 0 0.091 0.073 0.007 0.001 0 0 0 0

sum 8.116 0.267 29.207 47.914 9.147 3.003 0.011 2.241 0.078 0.014

Table 7. Typical fuel compositions. JP-7 composition uncertain (see text above).

Property JP-5 JP-7 JP-8 (Jet A/A-1) RP-1 Approx. Formula C12H23 C12H25 C11H21 C12H24

H/C ratio 1.92 2.07 1.91 1.98 Avg Composition

Aromatics, vol% 19 3 18 3 Naphthenes 34 42 35 58

Paraffins 45 55 45 39 Olefins 2 2

Sulfur, ppm 470 60 490 20

SURROGATES

For modeling or experimental purposes, it is often useful to approximate the behavior of kerosene fuels using “surrogate” mixtures of 10 or less hydrocarbons [Edwards and Maurice, 2001; Wood, 1989; Wood et al, 1989]. For soot modeling, it is thought that the surrogate must include an aromatic component. GC-FIMS and Table 1 data indicate that

the primary aromatic component in kerosene aviation fuels are alkyl benzenes. The distribution of alkyl benzenes in two Jet A/Jet A-1 fuels [GC-FIMS] is shown in Figure 4, centering roughly around C10. Lindstedt and Maurice [2001] looked at benzene, toluene, and ethylbenzene as aromatic components of a 89% n-decane/11% aromatic surrogate model for kerosene combustion. Good agreement was found with species profiles in a burner-stabilized kerosene flame. These analyses of aviation kerosenes indicates that a


modeling surrogate would match real aviation fuels more accurately if (1) the fraction of aromatics was increased to about 18 vol%, (2) the aromatic was a C10 alkyl benzene, and (3) the non-aromatic component was an iso-paraffin and/or naphthene, as opposed to a n-paraffin. A recent kinetic modeling effort for JP-8 used butyl benzene as the aromatic component, consistent with the data shown in Figure 4 [Montgomery et al,

2002]. Whether these changes would improve the accuracy of the model prediction for aviation kerosene combustion is certainly debatable given the scarcity of experimental data. Surrogates for specialty kerosenes like JP-7, RP-1, and RG-1 should be based primarily on C11-C12 naphthenes and isoparaffins to match the real fuels as closely as possible.

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Figure 4. Alkyl benzene distribution from GC-FIMS.

HEAT OF FORMATION Unlike pure compounds, the heat of formation of petroleum distillates is not well-defined. For example, the heat of formation is usually given in kcal/mole; what is a mole of “kerosene”? If one requires the heat of formation (for an Isp calculation, for example), usually the heat of formation has to be back-calculated from the heat of combustion and the fuel H/C ratio. If the heat of formation is required per mole, one must be careful to define what the reference “mole” is. Often, the kerosene fuels are defined as (for example) C12H24 or CH.1.9. Table 8 provides the heat of formation (in mass units) for kerosene fuels as calculated from the following equations: Stoichiometry [molar basis] for complete combustion: CaHb + (a+ (b/4)) O2 a CO2 + (b/2) H2O Eq 1

Heat of combustion calculation (lower value) (∆Hc ): a(∆Hf CO2) + (b/2)(∆Hf H2O (gas)) - (∆Hf fuel) – (a+(b/4))(∆Hf O2) = Heat of combustion, in (typically) kcal/mole fuel, ∆Hc Eq 2 where ∆Hf = molar heat of formation {CO2=-94.05 kcal/mole, H2O (gas)=-57.80 kcal/mol, O2=zero (definition)}. The only unknown in Equation 2 is the heat of formation of the fuel. The molar heat of formation can be obtained using the overall formulas from Table 5, or using another user-defined “mole”. Table 8 includes two values of hydrogen content for JP-8, to show the sensitivity of heat of formation to hydrogen content. The higher value of hydrogen content is consistent with the most recent JP-8 data (13.81% in 1999 and 2000). The data in Table 8 was iterated with Mike Zehe of NASA/GRC to compare to


existing kerosene fuel data in the NASA CEA code [McBride and Gordon, 1996]. If one is interested in the variation in heat of formation from lot-to-lot, say for the variable JP-8, the DESC database could be used to calculate heat of formation for each batch of fuel delivered, using the

batch-specific heat of combustion and H/C ratio. Don Penn of AFRL/PRSE did such a calculation several years ago using 1997 data, with the result shown in Figure 5. Note that fuels such as JP-7 and RP-1 are much less variable than JP-8 (Jet A/Jet A-1).

Table 8. Calculated heat of formation for kerosene fuels

Fuel wt% H (meas)

H/C molar (calc)

Mass heat of comb, MJ/kg

(meas)

Mass heat of comb., BTU/lb

Mass heat of comb, kcal/g

Heat of formation

(calc), cal/g

JP-4 14.300 1.9883 43.500 -10397 -413.94 JP-5 13.560 1.8693 43.100 -10301 -355.31 JP-7 14.490 2.0192 43.500 -10397 -453.54 JP-8 13.850 1.9157 43.200 -10325 -391.86 JP-8 13.670 1.8869 43.200 -10325 -354.34

JP-10 1.6000 42.101 18100 -10062 -235.23 RP-1 1.9500 43.357 18640 -10362 -398.83

Heat of Form ation of JP-8, 1997 Buys

0.0

20.0

40.0

60.0

80.0

100.0

120.0

140.0

HF-32.5

-33.5

-34.5

-35.5

-36.5

-37.5

-38.5

-39.5

-40.5

-41.5

-42.5

-43.5

-44.5

-45.5

Heat of Form ation, kcal/100g

JP-8, M Ga

Figure 5. Batch-to-batch variation in calculated heat of formation.


SUMMARY

Almost 200 million gallons of kerosene aviation fuels are burned each day world-wide. This paper has summarized the characteristics and composition of these fuels to a limited extent, and has discussed some of the simplifications that are used to approximate these fuels for various purposes.

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1 - kerosene fuels for aerospace propulsion – composition and properties

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