The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001
Thomas J. Bruno Physical and Chemical Properties Division National Institute of Standards and Technology Boulder, CO
Approved for public release; distribution unlimited. Executive Summary: AFOSR-MIPR F1SBAA8022G001
• Characterization of a real fuel: JP-8
– i.e., chemical analysis, VLE, ρ, υ, λ, Cv
• Complete RefProp fluids files for RP-1 and RP-2
• Perform thermal decomposition studies on RP-2: – no additives – with THQ, tetralin, +100 package
Approved for public release; distribution unlimited. NIST Staff:
• Tom Bruno • Arno Laesecke • Stephanie Outcalt • Richard Perkins • Jason Widegren • Marcia Huber • Eric Lemmon
Approved for public release; distribution unlimited. and Students:
• Beverly Smith • Lisa Ott • Kari Brumbeck • Amelia Hadler • Tara Lovestead
Approved for public release; distribution unlimited. First, a bit of history
Approved for public release; distribution unlimited. RP-1:
• Rocket Propellant 1 (refined petroleum 1)
• Kerosene base, used with LOX in rockets such as the Saturn V
• Density 0.81 - 1.02 g/mL
• Oxidizer to fuel ratio = 2.56
• Temperature of combustion = 3,670 K
Approved for public release; distribution unlimited. RP-2
• A highly hydrotreated kerosene • Little or no sulfur • Few if any aromatics • Clear at present, no added dye
Approved for public release; distribution unlimited. NASA RP-1 Project
• We obtained a sample of RP-1, 2002: – P000016660 – Chemical analysis revealed presence of many aromatics and alkenes
• An extensive series of measurements and correlations was done.
• At the December ’03 workshop, it was decided that the lot was “unusual”.
• A follow-on project determined compositional variability.
Approved for public release; distribution unlimited. Our results were summarized in NISTIR 6646, and the preliminary RP-1 fluid file was developed
Approved for public release; distribution unlimited. We start with:
• Comprehensive chemical analysis • Distillation curves (of the advanced variety)
Approved for public release; distribution unlimited. RP-1 Distillation Curves
260.0
250.0 Curve is far more typical of a complex fluid 240.0 RP-1, in spec
RP-1, out of spec 230.0
220.0 Temperature, Tk, C Temperature, Tk,
210.0 Curve is dominated by a few major components 200.0 0 102030405060708090100 Volume Fraction, %
Approved for public release; distribution unlimited. 280.0
270.0
260.0
C) RP-1 and RP-2 are very similar in volatility, while o 250.0 ( k TS-5 is slightly less volatile
240.0
230.0 Temperature, T
220.0
RP-1 210.0 RP-2 TS-5
200.0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Distillate Volume Fraction
Approved for public release; distribution unlimited. Now, complete the property suite:
ρ, υ, λ, Cv,etc.
Approved for public release; distribution unlimited. ρ, kg·m-3 860 Compressed Liquid Density of RP-1 Density: 840
820 Experimental details were discussed earlier 800
780
760
740
720
700
680
660 250 270 290 310 330 350 370 390 410 430 450 470 490 T , K
Approved for public release; distribution unlimited. ρ , kg·m-3 860 Compressed Liquid Density of RP-2
840 And for RP-2: 820
800
780
760
740
720
700
680
660 250 270 290 310 330 350 370 390 410 430 450 470 490 T , K
Approved for public release; distribution unlimited. w / m·s-1 1400
RP-1 Speed of sound of RP-1 and RP-2 as a function of 1350 RP-2 temperature at ambient pressure. 1300
1250
1200
1150
1100 270 280 290 300 310 320 330 340 350 T / K
Approved for public release; distribution unlimited. -1 κs / TPa 1050 Adiabatic compressibility data of RP-1 and RP-2 as 1000 a function of temperature at ambient pressure. 950
900
850
800
750
700
650 RP-1
RP-2 600 270 280 290 300 310 320 330 340 350 T / K
Approved for public release; distribution unlimited. ν / mm2·s-1 2.4
Kinematic viscosity of RP-1 2.2 and RP-2 as a function of temperature at ambient 2 pressure.
1.8
1.6
1.4
1.2 RP-1
RP-2
1
0.8
0.6 280 290 300 310 320 330 340 350 360 370 380 T / K
Approved for public release; distribution unlimited. Thermal Conductivity of RP-1 (New Sample)
0.130
0.120
0.110 -1 K -1 m . 0.100 / W
λ 300 K 0.090 350 K 400 K 450 K 500 K 0.080 550 K
0.070 0 10203040506070 P / MPa Approved for public release; distribution unlimited. Thermal Conductivity of RP-2
0.130
0.120
0.110 -1 K -1 m . 0.100 / W
λ 300 K 0.090 350 K 400 K 450 K 0.080 500 K 550 K
0.070 0 10203040506070 P / MPa Approved for public release; distribution unlimited. In parallel, a study of decomposition was done:
• Decomposition studies have been part of the NIST protocol since we left cryogenics
• With RP-2, the decomposition is important as a measurement. – straight RP-2, RP-2 with additives, corrosivity studies
Approved for public release; distribution unlimited. Explicit consideration of sample decomposition was begun of necessity:
• Straty, G.C., Palavra, A.M.F., Bruno, T.J., PVT Properties of Methanol at Temperatures to 300 oC, Int. J. Thermophys, 7(5), 1077,
1986.
• Straty, G.C., Ball, M.J., Bruno, T.J., PVT of toluene at temperatures to 673 K, J. Chem. Eng. Data, 33,115,1988.
Approved for public release; distribution unlimited. Experimental effort involves numerous high value, one-of-a kind apparatus:
• VLE Instruments
• Viscometers – torsional crystal – Stabinger – gravitational
• Densimeters – dual sinker – rapid screening
• Thermal Conductivity – low and high temperature hot wire
• Speed of Sound
• Etc.
Approved for public release; distribution unlimited. At only 100 oC, the sample decomposed into
CO, H2, and synthetic products
Approved for public release; distribution unlimited. Samples are thermally stressed in stainless steel ampoule reactors
ampoule reactor thermostat
insulated box
slots for reactors
stainless steel block (one of two)
temperature probe
heaters PID temperature controller
Approved for public release; distribution unlimited. Ampoule reactors:
Temperatures to 450 oC Pressures to 10,000 psi (once, by accident, to 36,000 psi)
6”
Approved for public release; distribution unlimited. Approved for public release; distribution unlimited. Extent of decomposition determined by analysis
GC-FID of RP-2
Unheated sample The light decomposition products are used for the After 10 min at 450 °C kinetic analysis
Emergent suite of decomposition products
Approved for public release; distribution unlimited. Pseudo-first-order kinetics on the emergent suite of decomposition products
k′ A B The assumption of first-order kinetics Ad d B][][ is a necessary ==− ′ Ak ][ approximation for dt dt these complex mixtures. 2ln t = 2/1 k′
Approved for public release; distribution unlimited. Separate phase analysis is performed determine thermal or catalytic mechanisms
Gas-liquid separation device
Liquid and gas phases analyzed by FTIR, GC-FID and GC-MS
Bruno, T.J., Conditioning of multiphase flowing samples for chemical analysis, Sep. Sci. Tech., 40, 1721-1732, 2005.
Approved for public release; distribution unlimited. Decomposition kinetics of RP-2
75 75 375 °C 400 °C
50 50
25 25 Product Suite Area Product Suite Area
500 1000 1500 50 100 150 200 250 Reaction Time / min Reaction Time / min
The rate constant for decomposition, k', is obtained from the fit.
Approved for public release; distribution unlimited. Decomposition kinetics of RP-2
160 200 425 °C 450 °C
120 150
80 100
40 50 Product Suite Area Product Suite Area
50 100 150 10 20 30 40 50 Reaction Time / min Reaction Time / min
The rate constant for decomposition, k', is obtained from the fit.
Approved for public release; distribution unlimited. Decomposition kinetics of RP-2
200 450 °C
150 425 °C
100 375 °C 400 °C
Product Suite Area 50
500 1000 1500 Reaction Time / min
Approved for public release; distribution unlimited. Rate constants for RP-2 decomposition
T / °C (k ′ ± 1σ) / s−1 375 (1.33 ± 0.30)×10−5 400 (9.28 ± 2.01)×10−5 -7 425 (1.33 ± 0.33)×10−4 450 (5.47 ± 0.80)×10−4 -8 -9 ' k
ln -10
-11
-12 1.35 1.40 1.45 1.50 1.55 1000/T
Approved for public release; distribution unlimited. Decomposition kinetics of RP-1
200 RP-1 at 450 °C
150
100
Product Suite Area Suite Product 50
10 20 30 40 50 Reaction Time / min
The decomposition of RP-1 and RP-2 is very similar.
Andersen, P.C., Bruno, T.J., Thermal decomposition of RP-1 rocket propellant, Ind. Eng. Chem. Res., 44, 1670-1676, 2005.
Approved for public release; distribution unlimited. Comparison of RP-1 and RP-2 decomposition
200 450 °C
150
100
Product Suite Area 50 • RP-2 • RP-1
10 20 30 40 Reaction Time / min
Approved for public release; distribution unlimited. Comparison of Jet A with RP-1 and RP-2
-6
-8 k' ln -10
RP-1RP-1 RP-2RP-2 JetJet A A -12
1.35 1.40 1.45 1.50 1.55
1000 / T
Approved for public release; distribution unlimited. Comparison of RP-1 and RP-2 decomposition
RP-1 RP-2 T / °C (k ′ ± 1σ) / s−1 (k ′ ± 1σ) / s−1 375 (1.13 ± 0.04)×10−5 (1.33 ± 0.30)×10−5 400 (1.19 ± 0.33)×10−4 (9.28 ± 2.01)×10−5 425 (3.08 ± 0.77)×10−4 (1.33 ± 0.33)×10−4 450 (5.84 ± 1.33)×10−4 (5.47 ± 0.80)×10−4
Approved for public release; distribution unlimited. Decomposition of RP-2 with additives
• RP-2 with 5% tetralin
• RP-2 with 5% THQ N H
• RP-2 with 256 ppm of the additive mixture in JP-8 +100 - contains a chelator, antioxidant, and surfactant
Hydrogen donors increase thermal stability by interrupting radical decomposition pathways.
Approved for public release; distribution unlimited. Decomposition of RP-2 with additives
80 • RP-2 375 °C • RP-2 + 100 additive
60 • RP-2 + 5% tetralin 5% THQ lowers • RP-2 + 5% THQ the rate of 40 decomposition by about an order of
Product Suite Area 20 magnitude.
400 800 1200 1600 Reaction Time / min
Approved for public release; distribution unlimited. Decomposition of RP-2 with additives
160 • RP-2 425 °C • RP-2 + 100 additive
120 • RP-2 + 5% tetralin
• RP-2 + 5% THQ The stabilizing 80 effect is smaller at higher temperature.
Product Suite Area 40
30 60 90 120 Reaction Time / min
Approved for public release; distribution unlimited. Concentration of THQ during decomposition
375 °C 425 °C
6 6
5 5
4 4 as%Mass THQ M ass % THQ
3 3
2 2
1 1
0 0
Approved for public release; distribution unlimited. 0 400 800 12000 1600 50 100 150 200 250
Time / min T im e / m in Parallels results430.0 with B100 (biodiesel): 430.0
420.0 430.0 420.0 B100 + 1% THQ B100 + 1% tetralin B100 + 1% t -decalin 410.0 420.0 410.0 410.0 400.0 400.0 400.0 C) C) C) o o 390.0 o ( ( ( k k k 390.0 390.0 380.0 380.0 380.0
370.0 370.0 370.0 Temperature, T Temperature, T T Temperature, 360.0 360.0 360.0
350.0 350.0 0.0 0.2 0.4 0.6 0.8 1. 350.0 0.0 0.2 0.4 0.6 0.8 1.0 340.0 340.0 340.0 0.0 0.2 0.4 0.6 0.8 1.0 0 Distillate Volume Fraction Distillate Volume Fraction Distillate Volume Fraction
Approved for public release; distribution unlimited. Lower is better! A clear high-temperature stabilization effect occurs.
Approved for public release; distribution unlimited. Stabilization of RP-2:
>> >>>>
tetrahydroquinoline tetralin +100
Stabilization of B100: > ≈ >> tetrahydroquinoline t-decalin tetralin
Approved for public release; distribution unlimited. Corrosivity of decomposed RP-1
An improved copper strip corrosion test, developed at NIST, was used to determine the corrosivity of four liquids based on RP-1: (1) RP-1 (2) RP-1 + 0.14 % allyl sulfide (3) RP-1 after 2 h at 400 °C (4) RP-1 + 0.14 % allyl sulfide after 2 h at 400 °C
Approved for public release; distribution unlimited. ETP copper 1018 steel coupons coupons
Approved for public release; distribution unlimited. Corrosivity of decomposed RP-1
GC analysis with a flame ionization detector RP-1 + 0.14 % allyl sulfide, decomposed RP-1 + 0.14%allylsulfide RP-1 +
RP-1
RP-1 + 0.14 % allyl sulfide
Decomposed RP-1 RP-1, decomposed
Decomposed RP-1 + 0.14 % allyl sulfide RP-1
Decomposition greatly increased the corrosivity of the mixture, and slightly increased the corrosivity of RP-1.
Approved for public release; distribution unlimited. Corrosivity of decomposed RP-1
Sample CSCT L* [sulfur] / ppm RP-1 + 0.14 % allyl sulfide, decomposed 4a 160 3.1 RP-1 + 0.14 % allyl sulfide 1a 199 28.8 RP-1, decomposed 1b 189 not detected RP-1 untarnished 197 not detected
Approved for public release; distribution unlimited. Rocket and Hypersonic Vehicle Propellant Workshop:
Place: NIST Boulder Laboratories
Time: Sept. 25 - 26, 2008
“ Rollout of RP fluid files”
Approved for public release; distribution unlimited. Acknowledgements:
• AFRL-EAFB
• Matt Billingsley, Ron Bates and Steve Hanna
• Tim Edwards, AFRL-WPAFB
Approved for public release; distribution unlimited. Decomposition of RP-2 with additives
160 • RP-2 425 °C • RP-2 + 100 additive • RP-2 + 5% decalin 120 • RP-2 + 5% tetralin • RP-2 + 5% THQ
80 Product Suite Area 40
30 60 90 120 Reaction Time / min
Approved for public release; distribution unlimited. Thermal Conductivity of RP-1 (2003)
0.130 300 K 350 K 400 K 0.120 450 K 500 K 547 K 0.110 608 K
-1 650 K K -1
0.100 / W m λ
0.090
0.080
0.070
0.45 0.50 0.55 0.60 0.65-3 0.70 0.75 0.80 0.85
ρ / g cm Approved for public release; distribution unlimited.