U.S. patent number 3,883,376 [Application Number 05/357,748] was granted by the patent office on 1975-05-13 for high reactivity fuels for supersonic combustion ramjets.
This patent grant is currently assigned to The United States of America as represented by the Secretary of the Navy. Invention is credited to Frederick S. Billig, Stephen E. Grenleski, Jr., James C. Pirkle, Jr..
United States Patent |
3,883,376 |
Billig , et al. |
May 13, 1975 |
High reactivity fuels for supersonic combustion ramjets
Abstract
The invention relates to highly reactive fuel compositions
primarily inted for supersonic combustion ramjet engines. In
particular, the invention provides highly reactive fuel
compositions capable of efficient oxidation and thrust production
even within the low combustor residence time of a supersonic
combustion ramjet engine. The fuel compositions comprise specific
blends of a major fuel component and an additive which, on
pyrophoric combustion thereof, produces sufficient heat energy to
spontaneously ignite and burn the major fuel component at a
substantially increased rate.
Inventors: |
Billig; Frederick S.
(Rockville, MD), Pirkle, Jr.; James C. (Wheaton, MD),
Grenleski, Jr.; Stephen E. (Silver Spring, MD) |
Assignee: |
The United States of America as
represented by the Secretary of the Navy (Washington,
DC)
|
Family
ID: |
26776870 |
Appl.
No.: |
05/357,748 |
Filed: |
May 7, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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87344 |
Nov 5, 1970 |
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Current U.S.
Class: |
149/22; 44/316;
44/358; 149/87; 149/109.4 |
Current CPC
Class: |
C10L
1/30 (20130101); C10L 1/301 (20130101); C10L
1/00 (20130101) |
Current International
Class: |
C10L
1/30 (20060101); C10L 1/10 (20060101); C10L
1/00 (20060101); C10l 001/30 () |
Field of
Search: |
;149/22,87,109.4
;44/57,68,76 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Miller; E. A.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of U.S. patent
application, Ser. No. 87,344 now abandoned, of the same title,
filed Nov. 5, 1970, by the same inventors; the aforesaid
application being hereby abandoned.
Claims
We claim:
1. A fuel composition capable of ignition within the low residence
times occurring in a supersonic ramjet combustion engine
comprising:
a hydrocarbon selected from the group consisting of n-dodecane,
methylcyclopentadiene dimer, and tetra-hydro methylcyclopentadiene
dimer, the hydrocarbon being present in the fuel composition in a
proportion equal to at least 50 percent and not more than 87.5
percent by weight thereof; and, a pyrophoric additive component
selected from the group consisting of respective mixtures of
trimethylaluminum and ethyldecaborane; trimethylaluminum and
pentaborane; triethylaluminum, ethyldecaborane, and
diethyldecaborane; and, trimethylaluminum, ethyldecaborane, and
diethyldecaborane; the additive component being present in the fuel
composition in a proportion equal to not more than 50 percent by
weight thereof and wherein the first-named constituent of each
mixed additive component constitutes at least 20 percent of the
additive component by weight.
2. A fuel composition capable of ignition within the low residence
times occurring in a supersonic ramjet combustion engine
comprising:
methylcyclopentadiene dimer having a weight percent of at least 80
percent of the total composition; and,
a pyrophoric additive component selected from the group consisting
of respective mixtures of trimethylaluminum and pentaborane having
relative weight percents of at least 8 percent and at least 9
percent respectively of the total composition; triethylaluminum,
diethyldecaborane, and ethyldecaborane having relative weight
percents of at least 6 percent of the total composition for
triethylaluminum and at least 6 percent of the total composition
for the mixture of diethyldecaborane and ethyldecaborane; and
trimethylaluminum, diethyldecaborane, and ethyldecaborane having
relative weight percents of at least 6 percent of the total
composition for trimethylaluminum and at least 8 percent of the
total composition for the mixture of diethyldecaborane and
ethyldecaborane.
Description
BACKGROUND AND SUMMARY OF THE INVENTION
In recent years increased interest has developed in the use of
liquids for fuels in a supersonic combustion ramjet engine, known
in the art as a "scramjet" engine. Although the static temperatures
and pressures in the "scramjet" combustor are often similar to
their subsonic counterparts, the typical residence time for
ignition and combustion are considerably shorter. In the scramjet
engine the effects of a higher vehicle velocity coupled with the
exclusion of baffles, turbulence generators, etc., produce
substantially lower fuel residence times in the supersonic
combustor. Thus, in general, the fuel for a supersonic combustion
ramjet must be more reactive than that for a subsonic combustion
ramjet. Scramjet fuel compositions should also have a high heating
value per unit mass; high density, which in turn defines the
heating value per unit volume; good storage and thermal stability
characteristics; high heat capacity if the fuel is to be used for
regenerative cooling; low cost; and low toxicity. However, for
scramjet engines with low takeover Mach numbers, e.g., M.sub.0 =
4-6, the requirement for high reactivity is of greatest
importance.
An acceptable supersonic ramjet engine fuel composition must ignite
spontaneously and burn efficiently within the extremely brief
residence time (.about.0.5 msec) available for oxidation in the air
flow through the supersonic combustor. Fuels previously employed in
subsonic ramjet engines, while having desirable cost, handling, and
high heat content characteristics, cannot satisfy the high
reactivity requirement of the scramjet at the combustor static
temperatures and pressures typical of scramjet take-over
conditions. Although heavy hydrocarbon fuels have high heat content
per unit volume and are easily handled and stored, these fuel
compositions often fail even to ignite in the scramjet engine.
Substances capable of acceptable ignition and combustion within the
low residence time in the scramjet engine are generally expensive,
toxic, and difficult to store and handle. Many of these readily
ignitable substances are actually pyrophoric in nature, that is,
the substance ignites spontaneously on exposure to an oxidizing
source. For instance, the boranes and alkaylated boranes meet the
reactivity requirement but are undesirable due to cost, handling,
storage, toxicity, and other considerations. Pentaborane and other
lower boranes are pyrophoric at room temperature and also have a
relatively low density. Aluminum alkyls also meet the reactivity
requirement but are pyrophoric and have low energy densities.
The invention provides fuel compositions combining the desirable
characteristics of the hydrocarbons with an essentially pyrophoric
additive blend. Particularly, the present fuel compositions
substantially exhibit desired cost, handling, storage, and density
properties while being capable of ignition and efficient combustion
within the low residence times encountered in a supersonic
combustor.
Accordingly, it is the primary object of the invention to provide
fuel compositions for supersonic ramjet engines which ignite and
burn efficiently within the low residence times of a supersonic
combustor.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present fuel compositions essentially consist of blends of a
major fuel component usually consisting of a heavy hydrocarbon
component which ordinarily would not ignite under scramjet
conditions, and an additive component present in a relatively low
proportion for initiating ignition and aiding in continued
combustion of the composition. The major fuel component may be
chosen from a large group of suitable hydrocarbons. Primary
considerations for hydrocarbon choice are density, cost, and
storability. Straight-chain alkanes, such as n-dodecane (C.sub.12
H.sub.26), may be chosen but are not generally as desirable as the
highdensity heterocyclic hydrocarbons. In particular fuels such as
methylcyclopentadiene dimer (MCPD, C.sub.12 H.sub.16) and its
hydrogenated derivative, tetra-hydro methylcyclopentadiene dimer
(T-HMCPD, C.sub.12 H.sub.20), have desirable characteristics.
"Shelldyne-H," a proprietary product of Shell Development
Corporation, is a heavier hydrogenated hydrocarbon (C.sub.14
H.sub.18, molecular weight 186.3) having acceptable handling and
density chracteristics. Low molecular weight hydrocarbons have
storage and handling difficulties which usually outweigh any
advantage to their use.
Essentially pyrophoric additives having the high reactivity
necessary to promote rapid ignition of the fuel compositions
include mixtures of the alkylated aluminums, such as
triethylaluminum (TEA) and trimethylaluminum (TMA), and the boranes
and alkylated boranes, particularly pentaborane (B.sub.5 H.sub.9)
and either a mixture of diethyldecaborane and ethyldecaborane
(C.sub.3.2 H.sub.20.3 B.sub.10, HiCal 3-D) or ethyldecaborane
alone. Blends of these additive components, particularly TEA and
"HiCal 3D," are used in a composition including a heavy hydrocarbon
as the major constituent.
Ignition of the present fuel compositions is provided by the
additive mixture. For example, in a fuel composition comprising a
hydrocarbon, an aluminum alkyl, and "HiCal 3-D," the aluminum alkyl
burns initially, the combustion of the aluminum and recombination
of alkyl radicals occurring first and producing a small exothermic
heat release insufficient to ignite the hydrocarbon. However, the
heat released by the rapid aluminum reaction is sufficient to
ignite the "HiCal 3-D" which does produce enough heat to ignite the
hydrocarbon. Although the organic portion of the aluminum alkyl
usually burns subsequent to the combustion of the aluminum portion,
this "second phase" combustion which releases the major portion of
the heat of combustion of the aluminum alkyl is often too slow to
effectively ignite the hydrocarbon.
The addition of an aluminum alkyl to an alkylated borane can
shorten t.sub.ig of the alkylated borane by as much as 50 percent.
For example, 20 percent by weight of triethylaluminum to "HiCal
3-D" shortens the ignition delay of the alkylated borane by nearly
50 percent, due to ignition of the "HiCal 3-D" by the rapid heat
release of the aluminum in the TEA as described generally
hereinabove. The optimum amount of TEA added to "HiCal 3-D" appears
to be near 20 percent. Since the alkylated borane is thereby
ignited much more readily, the large exothermic heat release thus
produced causes a proportionally more rapid ignition of the
hydrocarbon component of the present fuel compositions.
The present fuel compositions were tested to measure ignition time,
t.sub.ig, and combustion efficiency, .eta..sub.c. Ignition delay
tests were conducted using air supplied at 2000.degree.R at 15-20
psia to a plenum attached to a converging nozzle having a nominal
Mach number of 0.75 exiting into a rectangular test section. The
components were injected from a 2mm diameter hole in the tip of a
tube located on the axis of the nozzle. In order to evaluate
performance of the compositions, static pressures were measured in
the plenum, at the nozzle exit, and at several locations in the
test section. Parameters affecting performance are found to include
the initial air static temperature T.sub.a, and the initial fuel
temperature T.sub.f, both of which cause reduction in t.sub.ig as
they increase. Overall fuel/air ratio does not seem to affect
t.sub.ig. Mach 1.6 and Mach 2.5 nozzles were also used in the test
arrangement described. The results of these tests are summarized in
Tables I, II, and III reproduced below.
TABLE I
__________________________________________________________________________
Results of Subsonic Ignition Tests of Pyrophoric-Hydrocarbon
Mixtures Fuel Air Combustion Combustion Fuel Total Total Static
Mach Static Flow Flow Fuel Velocity Delay Delay Temp. Pressure
Pressure Number Temp. Temp. Dist. Time (.degree.R) (psia) (psia)
(.degree.R) (lb/sec) (lb/sec) (.degree.R) (ft/sec) (inches) (msec)
__________________________________________________________________________
50.0%NDD 1927 19.25 13.92 0.695 1757 0.0280 0.843 730 1427 17.0
0.99 12.0%TEA 37.5%HiCal-3D 50.0%SDH 1953 22.97 19.79 0.465 1871
0.0256 0.777 714 985 6.0 0.51 12.5%TEA 37.5%HiCal-3D 75.0%SDH 1945
24.57 20.54 0.512 1848 0.0268 0.892 775 1078 7.0 0.54 12.5%TEA
12.5%HiCal-3D 87.50%SDH 1940 23.47 19.87 0.493 1851 0.0259 0.830
808 1043 7.0 0.56 6.25%TEA 6.25%HiCal-3D Shelldyne-H 1959 25.52
21.44 0.505 1863 0.0140 0.916 868 1068 no ignition 10.0%TEA 1959
17.19 11.03 0.823 1725 0.0250 0.823 821 1670 no 90.0%SDH ignition
Shelldyne-H 1937 19.78 13.13 0.790 1722 0.0844 0.913 847 1606 no
ignition 12.5%TEA 1944 27.07 23.14 0.480 1858 0.0400 0.941 766 1014
6.0 0.50 12.5%HiCal-3D 75.0%SDH MCPD 1944 13.05 19.36 0.773 1736
0.0420 0.884 787 1578 no ignition 6.25%TEA 1943 23.86 20.35 0.482
1854 0.0476 0.831 739 1017 5.0 0.41 6.25%HiCal-3D 87.50%MCPD
__________________________________________________________________________
TABLE II
__________________________________________________________________________
Mach Initial Air Initial Fuel Ignition Delay Fuel Number
Temperature,.degree.R Temperature,.degree.R Time, msec
__________________________________________________________________________
6.7 % TMA 8.9 % HiCal 3-D 87.50% MCPD 2.5 1535 710 0.20 12.5 % TEA
12.5 % HiCal 3-D 2.5 1535 710 0.15 75.0 % Shelldyne-H
__________________________________________________________________________
TEA = Triethyl aluminum TMA = Trimethyl aluminum MCPD =
Methylcyclopentadiene dimer THMCPD =
Tetrahydro-methylcyclopentadiene dimer
TABLE III
__________________________________________________________________________
Fuel M.sub.ci ER T.sub.t T.sub.ci P.sub.t T.sub.f P.sub.ci
Combustion % by weight (psia) efficiency (.degree.R) (.degree.R)
(psia) (.degree.R) .eta..sub.c
__________________________________________________________________________
8.2 TMA 3.23 0.53 4020 1527 459 723 7.63 0.41 9.0 HiCal 3-D 82.8
MCPD 12.5 TEA 3.24 0.58 3876 1457 448 711 7.37 0.32 12.1 HiCal 3-D
75.4 Shelldyne-H
__________________________________________________________________________
Other tests indicate that the following fuel compositions according
to the present invention ignite within 0.2 msec for T .gtoreq.
1535.degree.R and M .gtoreq. 2.5, conditions corresponding to a
Mach 5 takeover speed at 95,000 feet: Composition No. Components by
weight per cent ______________________________________ I 10%
triethylaluminum 10% HiCal 3-D 80% MCPD II 6.7% trimethylaluminum
8.9% HiCal 3-D 84.4% MCPD III 8% trimethylaluminum 9% pentaborane
83% MCPD ______________________________________
As can be seen in Table I, the additive blends of the present fuel
compositions cause ignition of a heavy hydrocarbon which will not
ignite alone in the available residence time. Triethylaluminum
alone is also shown to be insufficient to ignite the heavy
hydrocarbon, Shelldyne-H.
Direct-connected supersonic combustion testing produced the results
summarized in Tables II and III. Combustion efficiencies,
longitudinal wall static pressure (P.sub.w) distributions, and
radial profiles of properties in the combustor exit plane were
determined at conditions simulating flight at
M.sub..infin..about.7.25 in the tropopause (T.sub..infin.=
390.degree.R) at an altitude of .about. 90,000 ft. These carefully
instrumented tests, with a proven run-to-run reproducibility of
.+-. 3 percent on combustion efficiency, offer a realistic (but
relatively expensive compared to the simpler ignition delay tests)
means for evaluating scramjet fuels. Metered cold air was heated in
a d.c. arc heater to approximately 5000.degree.R and discharged
into a mixing chamber. Unheated secondary air was added to obtain
the desired total temperature, T.sub.t.sbsb.a which is nominally
4000.degree.R. With the nominal plenum pressure of 460 psia the
conditions at the supersonic nozzle-exit plane were M.sub.c.sbsb.i
= 3.23, P.sub.c.sbsb.i = 7.4 psia, and T.sub.c.sbsb.i =
1520.degree.R. To isolate combustor-induced disturbances a 7.27
in.-long cylinder was inserted between the nozzle and the fuel
injector. Fuel was injected perpendicular to the air stream from
ten 0.030-in.-diameter holes that were equally spaced
circumferentially. Immediately downstream of the injector the
combustor had a step increase in diameter from 2.74 in. to 3.28 in.
The 14.4-in.-long cylinder was followed by a
1.4.degree.-half-angle, 14.4-in.-long conical section, which
resulted in an overall combustor exit/injector area ratio of 2.
Pitot and cone-static pressure measurements in the combustor exit
plane provide the data necessary to describe the flow properties in
that plane. Just downstream of the combustor exit, water was
sprayed into the stream to quench the reaction rapidly. The heat
release and combustion efficiency were obtained by making a
calorimetric balance on the exhaust gases, using temperature
measurements from a sixteen-point thermocouple rake in the exit of
the calorimeter together with all of the water-coolant rates. Water
flow to the calorimeter was controlled to yield exit temperatures
between 700.degree.F and 1000.degree.F, and to keep the wall
temperatures at 400.degree.F-800.degree.F in order to guarantee
that all water was vaporized and that reactions were effectively
quenched.
Combustion efficiency is defined as the sum of the total heat
released upstream of the calorimeter exit plus the sensible heat in
the products of combustion when cooled from the colorimeter exit
temperature to 212.degree.F (without condensation of water) divided
by the lowering heating value of the fuel. The total heat release
includes the change in heat flux to the walls with combustion. With
this combustor geometry the total heat loss to the walls is
approximately 110 Btu/sec for the nominal conditions without fuel
flow. With burning, the heat flux increases to about 500 Btu/sec
for ER.sub.eff = 1.0, run lengths between 30 and 45 sec with 10-15
sec for each fuel setting.
* * * * *