The Properties of RP-1 and RP-2 MIPR...

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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


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


NIST Staff:

•

Tom Bruno•

Arno Laesecke

•

Stephanie Outcalt•

Richard Perkins

•

Jason Widegren•

Marcia Huber

•

Eric Lemmon


and Students:

•

Beverly Smith•

Lisa Ott

•

Kari Brumbeck•

Amelia Hadler

•

Tara Lovestead


First, a bit of history


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


RP-2

•

A highly hydrotreated kerosene•

Little or no sulfur

•

Few if any aromatics•

Clear at present, no added dye


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.


Our results were summarized in NISTIR 6646, and the preliminary RP-1 fluid file was developed


We start with:

•

Comprehensive chemical analysis•

Distillation curves (of the advanced variety)


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


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


Now, complete the property suite:

ρ, υ, λ, Cv, etc.


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


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:


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.


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.


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.


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


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


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


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.


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.


At only 100 oC, the sample decomposed into CO, H2

, and synthetic products


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


Ampoule reactors:

6”

Temperatures to 450 oC

Pressures to 10,000 psi

(once, by accident, to 36,000 psi)


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


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.


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.


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



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



500 1000 1500Reaction Time / min

Prod

uct S

uite

Are

a

200

150

100

50

450 °C

375 °C400 °C

425 °C


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



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.


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


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


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


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




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.




Prod

uct S

uite

Are

a

160

120

80

40

425 °C•

RP-2•



RP-2 + 5% THQThe stabilizing

effect is smaller at higher

temperature.


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


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


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


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


Tem

pera

ture

, Tk (

o C)


Lower is better!

A clear high-temperature stabilization effect occurs.


tetrahydroquinoline t-decalin tetralin

> ≈ >>

Stabilization of B100:

Stabilization of RP-2:

>>

tetrahydroquinoline tetralin +100

>>>>


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


ETP copper coupons

1018 steel coupons



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


Decomposed RP-1



RP-1


Decomposed RP-1



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


Rocket and Hypersonic Vehicle Propellant Workshop:

Place:NIST Boulder Laboratories

Time:Sept. 25 -

26, 2008

“

Rollout of RP fluid files”


Acknowledgements:

•

AFRL-EAFB

•

Matt Billingsley, Ron Bates and Steve Hanna

•

Tim Edwards, AFRL-WPAFB




Prod

uct S

uite

Are

a

160

120

80

40

425 °C•

RP-2•


RP-2 + 5% decalin•


RP-2 + 5% THQ


Thermal Conductivity of RP-1 (2003)

0.070

0.080

0.090

0.100

0.110

0.120

0.130

0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85

ρ / g cm-3

λ /

W m

-1K

-1

300 K350 K400 K450 K500 K547 K608 K650 K

The Properties of RP-1 and RP-2 MIPR...

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