Approved for public release; distribution unlimited.
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.
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
200.0
210.0
220.0
230.0
240.0
250.0
260.0
0 10 20 30 40 50 60 70 80 90 100
Volume Fraction, %
Tem
pera
ture
, Tk,
C
RP-1, in spec
RP-1, out of spec
Curve is dominated by a few major components
Curve is far more typical of a complex fluid
Approved for public release; distribution unlimited.
200.0
210.0
220.0
230.0
240.0
250.0
260.0
270.0
280.0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Distillate Volume Fraction
Tem
pera
ture
, Tk (
o C)
RP-1RP-2TS-5
RP-1 and RP-2 are very similar in volatility, while TS-5 is slightly less volatile
Approved for public release; distribution unlimited.
Now, complete the property suite:
ρ, υ, λ, Cv, etc.
Approved for public release; distribution unlimited.
660
680
700
720
740
760
780
800
820
840
860
250 270 290 310 330 350 370 390 410 430 450 470 490
T , K
ρ, kg·m-3
Compressed Liquid Density of RP-1
Density:
Experimental details were discussed earlier
Approved for public release; distribution unlimited.
660
680
700
720
740
760
780
800
820
840
860
250 270 290 310 330 350 370 390 410 430 450 470 490
T , K
ρ , kg·m-3
Compressed Liquid Density of RP-2
And for RP-2:
Approved for public release; distribution unlimited.
1100
1150
1200
1250
1300
1350
1400
270 280 290 300 310 320 330 340 350
RP-1
RP-2
w / m·s-1
T / K
Speed of sound of RP-1 and RP-2 as a function of temperature at ambient pressure.
Approved for public release; distribution unlimited.
600
650
700
750
800
850
900
950
1000
1050
270 280 290 300 310 320 330 340 350
RP-1
RP-2
T / K
κs / TPa-1
Adiabatic compressibility data of RP-1 and RP-2 as a function of temperature at ambient pressure.
Approved for public release; distribution unlimited.
0.6
0.8
1
1.2
1.4
1.6
1.8
2
2.2
2.4
280 290 300 310 320 330 340 350 360 370 380
RP-1
RP-2
ν / mm2·s-1
T / K
Kinematic viscosity of RP-1 and RP-2 as a function of temperature at ambient pressure.
Approved for public release; distribution unlimited.
Thermal Conductivity of RP-1 (New Sample)
0.070
0.080
0.090
0.100
0.110
0.120
0.130
0 10 20 30 40 50 60 70
P / MPa
λ /
W. m
-1K
-1
300 K350 K400 K450 K500 K550 K
Approved for public release; distribution unlimited.
Thermal Conductivity of RP-2
0.070
0.080
0.090
0.100
0.110
0.120
0.130
0 10 20 30 40 50 60 70
P / MPa
λ /
W. m
-1K
-1
300 K350 K400 K450 K500 K550 K
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
PID temperature controller
insulated box
heaters
temperature probe
stainless steel block (one of two)
slots for reactors
ampoule reactor thermostat
Approved for public release; distribution unlimited.
Ampoule reactors:
6”
Temperatures to 450 oC
Pressures to 10,000 psi
(once, by accident, to 36,000 psi)
Approved for public release; distribution unlimited.
Extent of decomposition determined by analysis
The light decomposition products are used for the
kinetic analysis
GC-FID of RP-2
Unheated sample
Emergent suite of decomposition products
After 10 min at 450 °C
Approved for public release; distribution unlimited.
Pseudo-first-order kinetics on the emergent suite of decomposition products
A Bk′
][][][ AkdtBd
dtAd ′==−
kt
′=
2ln2/1
The assumption of first-order kinetics
is a necessary approximation for
these complex mixtures.
Approved for public release; distribution unlimited.
Separate phase analysis is performed determine thermal or catalytic mechanisms
Liquid and gas phases analyzed by FTIR, GC-FID and GC-MS
Gas-liquid separation
device
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
The rate constant for decomposition, k', is obtained from the fit.
50 100 150 200 250
75
50
25
Reaction Time / min
Prod
uct S
uite
Are
a
400 °C
500 1000 1500
75
50
25
Reaction Time / min
Prod
uct S
uite
Are
a
375 °C
Approved for public release; distribution unlimited.
Decomposition kinetics of RP-2
The rate constant for decomposition, k', is obtained from the fit.
10 20 30 40 50
Reaction Time / min
200
150
100
50
Prod
uct S
uite
Are
a
450 °C
50 100 150
Reaction Time / min
160
120
80
40
Prod
uct S
uite
Are
a
425 °C
Approved for public release; distribution unlimited.
Decomposition kinetics of RP-2
500 1000 1500Reaction Time / min
Prod
uct S
uite
Are
a
200
150
100
50
450 °C
375 °C400 °C
425 °C
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
425 (1.33 ± 0.33)×10−4
450 (5.47 ± 0.80)×10−4
1000/T
ln k
'
1.35 1.40 1.45 1.50 1.55
-11
-10
-9
-8
-7
-12
Approved for public release; distribution unlimited.
Decomposition kinetics of RP-1
The decomposition of RP-1 and RP-2 is very similar.
Reaction Time / min
Prod
uct S
uite
Are
a
10 20 30 40 50
50
100
150
200RP-1 at 450 °C
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
Prod
uct S
uite
Are
a
200
150
100
50•
RP-2•
RP-1
10 20 30 40Reaction Time / min
450 °C
Approved for public release; distribution unlimited.
Comparison of Jet A with RP-1 and RP-2
R P - 1R P - 2J e t A
1.35 1.40 1.45 1.50 1.55
1000 / T
-6
-8
-10
-12
ln k
'
RP-1RP-2Jet A
Approved for public release; distribution unlimited.
Comparison of RP-1 and RP-2 decomposition
RP-1 RP-2T / °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
Hydrogen donors increase thermal stability by interrupting radical decomposition pathways.
•
RP-2 with 5% tetralin
•
RP-2 with 5% THQ
•
RP-2 with 256 ppm of the additive mixture in JP-8 +100
-
contains a chelator, antioxidant, and surfactant
NH
Approved for public release; distribution unlimited.
Decomposition of RP-2 with additives
400 800 1200 1600Reaction Time / min
Prod
uct S
uite
Are
a80
60
40
20
375 °C•
RP-2•
RP-2 + 100 additive•
RP-2 + 5% tetralin•
RP-2 + 5% THQ5% THQ lowers
the rate of decomposition
by about an order of
magnitude.
Approved for public release; distribution unlimited.
Decomposition of RP-2 with additives
30 60 90 120Reaction Time / min
Prod
uct S
uite
Are
a
160
120
80
40
425 °C•
RP-2•
RP-2 + 100 additive•
RP-2 + 5% tetralin•
RP-2 + 5% THQThe stabilizing
effect is smaller at higher
temperature.
Approved for public release; distribution unlimited.
Concentration of THQ during decomposition
0
1
2
3
4
5
6
0 5 0 1 0 0 1 5 0 2 0 0 2 5 0T im e / m in
Mas
s%
THQ
0
1
2
3
4
5
6
0 4 0 0 8 0 0 1 2 0 0 1 6 0 0
T im e / m in
Mas
s%
THQ
375 °C 425 °C
Approved for public release; distribution unlimited.
B100 + 1% THQ
340.0
350.0
360.0
370.0
380.0
390.0
400.0
410.0
420.0
430.0
0.0 0.2 0.4 0.6 0.8 1.0
Distillate Volume Fraction
Tem
pera
ture
, Tk (
o C)
B100 + 1% tetralin
340.0
350.0
360.0
370.0
380.0
390.0
400.0
410.0
420.0
430.0
0.0 0.2 0.4 0.6 0.8 1.0
Distillate Volume Fraction
Tem
pera
ture
, Tk (
o C)
Parallels results with B100 (biodiesel):B100 + 1% t -decalin
340.0
350.0
360.0
370.0
380.0
390.0
400.0
410.0
420.0
430.0
0.0 0.2 0.4 0.6 0.8 1.0
Distillate Volume Fraction
Tem
pera
ture
, Tk (
o C)
Approved for public release; distribution unlimited.
Lower is better!
A clear high-temperature stabilization effect occurs.
Approved for public release; distribution unlimited.
tetrahydroquinoline t-decalin tetralin
> ≈ >>
Stabilization of B100:
Stabilization of RP-2:
>>
tetrahydroquinoline tetralin +100
>>>>
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.
Corrosivity of decomposed RP-1
RP
-1, d
ecom
pose
d
RP-1 + 0.14 % allyl sulfide, decomposed
RP-1
RP
-1 + 0.14 % allyl sulfide
Decomposition greatly increased the corrosivity of the mixture, and slightly increased the corrosivity of RP-1.
Decomposed RP-1
RP-1 + 0.14 % allyl sulfide
DecomposedRP-1 + 0.14 % allyl sulfide
RP-1
GC analysis with a flame ionization detector
Decomposed RP-1
RP-1 + 0.14 % allyl sulfide
DecomposedRP-1 + 0.14 % allyl sulfide
RP-1
GC analysis with a flame ionization detector
Decomposed RP-1
RP-1 + 0.14 % allyl sulfide
DecomposedRP-1 + 0.14 % allyl sulfide
RP-1
GC analysis with a flame ionization detector
Decomposed RP-1
RP-1 + 0.14 % allyl sulfide
DecomposedRP-1 + 0.14 % allyl sulfide
RP-1
GC analysis with a flame ionization detector
Approved for public release; distribution unlimited.
Corrosivity of decomposed RP-1
Sample CSCT L* [sulfur] / ppmRP-1 + 0.14 % allyl sulfide, decomposed 4a 160 3.1
RP-1 + 0.14 % allyl sulfide 1a 199 28.8RP-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
30 60 90 120Reaction Time / min
Prod
uct S
uite
Are
a
160
120
80
40
425 °C•
RP-2•
RP-2 + 100 additive•
RP-2 + 5% decalin•
RP-2 + 5% tetralin•
RP-2 + 5% THQ