Transient N.SUB.2.O decomposition process and reactor

Abstract

A N.sub.2O decomposition reactor and a method of its use to produce an effluent suitable for use in an ignition device or in the main fuel injection system in high speed aircraft. N.sub.2O decomposition is an exothermic reaction and produces a high temperature product containing high concentrations of O.sub.2. Combination of fuel with this effluent ignites quickly and is an effective ignition source for the aircraft combustor. Reactor performance is adjusted to meet the conditions required for a selected application by changing the relative concentrations of CO.sub.2 and N.sub.2O, modifying the reactor length, and varying the quantity of catalyst in the reactor. For use in a pilot ignition device, the desired effluent temperature is between 500? C. and 1200? C. in order to ignite and combust the fuel within the design residence time, between 0.5 and 10 ms. For application as a barbotage gas generator in a fuel injection system, the temperature of the effluent can range from 300? C. up to 800? C. and it is desirable that the effluent temperature remains within this range for periods of up to two minutes.

Claims

1. A catalytic N.sub.2O decomposition process to generate an effluent containing oxygen which comprises: introducing a N.sub.2O feed mixture into a decomposition reactor to contact a N.sub.2O decomposition catalyst; preheating the N.sub.2O feed mixture introduced into the reactor prior to contact of the N.sub.2O feed mixture with the N.sub.2O decomposition catalyst; and contacting the N.sub.2O decomposition catalyst with the preheated N.sub.2O feed mixture to generate the effluent containing oxygen; where the mass flow of the N.sub.2O feed mixture per minute introduced into and flowing through the N.sub.2O decomposition catalyst equals or exceeds the weight of the decomposition reactor, thereby requiring control of reaction temperature; and where the N.sub.2O feed mixture is diluted with CO.sub.2 to control reaction temperature to prevent exceeding maximum operating temperature of the reactor.

2. The process of claim 1, where the reactor is operated in pulsed mode, wherein the N.sub.2O feed mixture flow is stopped before the reactor temperature exceeds maximum operating temperature of the reactor.

3. The process of claim 1, further comprising monitoring the temperature of the heated effluent containing oxygen generated in the reactor and stopping the flow of N.sub.2O feed mixture into the reactor when the temperature of the effluent exceeds a selected maximum operating temperature of the reactor.

4. The process of claim 3, wherein the maximum operating temperature is controlled to a temperature between 492? C. and 1263? C.

5. The process of claim 1, wherein the heated effluent containing oxygen reaches a temperature between 800? C. and 1200? C. in less than 20 seconds and maintains that temperature range for up to 20 seconds.

6. The process of claim 1, wherein the heated effluent containing oxygen reaches a temperature between 400? C. and 800? C. and maintains that temperature range for up to two minutes.

7. The process of claim 1, wherein the maximum operating temperature is controlled to a temperature between 492? C. and 1263? C.

8. The process of claim 1, wherein the N.sub.2O feed mixture is adjusted to comprise 40 to 75 mole % CO.sub.2.

9. The process of claim 1, wherein the N.sub.2O decomposition catalyst comprises rhodium oxide, ruthenium oxide, zirconium oxide, silica oxide, strontium hexaaluminate or lanthanum hexaaluminate.

10. A catalytic N.sub.2O decomposition reactor for generating a heated effluent comprising oxygen, which comprises an inner and an outer annulus in flow communication and a reactor exit fitting in the inner annulus, wherein a N.sub.2O feed mixture introduced into the outer annulus passes into the inner annulus and the heated effluent leaves the reactor through the exit fitting in the inner annulus, wherein the inner annulus comprises a N.sub.2O decomposition catalyst, and wherein the N.sub.2O feed mixture is preheated to a selected temperature in the outer annulus prior to contacting the N.sub.2O decomposition catalyst in the inner annulus, wherein: a. at least a portion of the walls forming the outer annulus are ribbed, finned or wrapped with wire, b. the reactor further comprises a choke flow venturi valve at the exit fitting in the inner annulus to maintain pressure in the reactor and wherein the heated effluent containing oxygen exits the reactor through the choked flow venturi valve; and/or c. the reactor further comprises a flow controller for adjusting the CO.sub.2 content in the N.sub.2O feed mixture and at least one thermocouple for monitoring temperature of the heated effluent containing oxygen exiting the reactor.

11. The reactor of claim 10, which further comprises a heater in thermal contact with the inner annulus and wherein the outer annulus is in thermal contact with the inner annulus and heat produced in the inner annulus by N.sub.2O decomposition reaction and heat generated by the heater function to preheat the feed in the outer annulus.

12. The reactor of claim 10, wherein at least a portion of the walls of the outer annulus are ribbed.

13. The reactor of claim 12, which further comprises a choked flow venturi valve at the exit fitting in the inner annulus to maintain pressure in the reactor and wherein the heated effluent containing oxygen exits the reactor through the choked flow venturi valve.

14. The reactor of claim 13, which further comprises a frit at the exit of the choked flow venturi valve through which the heated effluent containing oxygen is dispersed on exiting the reactor.

15. The reactor of claim 10, which further comprises a choked flow venturi valve at the exit fitting in the inner annulus to maintain pressure in the reactor and wherein the heated effluent containing oxygen exits the reactor through the choked flow venturi valve.

16. The reactor of claim 10, wherein the reactor further comprises an outer shell in which the outer annulus and the inner annulus are formed by insertion of a liner into the outer shell and wherein an outer surface of the liner is finned, ribbed or wrapped with wire.

17. The reactor of claim 16, which further comprises a choked flow venturi valve at the exit fitting in the inner annulus to maintain pressure in the reactor and wherein the heated effluent containing oxygen exits the reactor through the choked flow venturi valve.

18. The reactor of claim 10, which further comprises a flow controller for adjusting the CO.sub.2 content in the N.sub.2O feed mixture and at least one thermocouple for monitoring temperature of the heated effluent containing oxygen exiting the reactor, wherein the CO.sub.2 content in the N.sub.2O feed mixture is adjusted to control reaction temperature to prevent exceeding maximum operating temperature of the reactor.

19. The reactor of claim 18, which further comprises a choked flow venturi valve at the exit fitting in the inner annulus to maintain pressure in the reactor and wherein the heated effluent containing oxygen exits the reactor through the choked flow venturi valve.

20. The reactor of claim 18, wherein at least a portion of the walls forming the outer annulus are ribbed, finned or wrapped with wire.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1A-1C show exploded diagrams of the components of an exemplary pulsed torch reactor. FIG. 1A is the outer shell which shows the location of the ceramic liner on the inside of the outer shell. FIG. 1B shows the tube liner with a flared end on one side that is used to seal the outer annulus on assembly. FIG. 1C shows the cartridge heater which is inserted into the reactor on assembly. See FIG. 4A for an exemplary assembled pulsed torch. Exemplary dimension and relative dimensions for the OD of the elements and the length of the elements are given.

(2) FIGS. 2A-2C show exploded diagrams of the components of an exemplary reactor for the barbotage application. FIG. 2A is the outer shell, which in contrast to the outer shell of the torch reactor does not have a ceramic insulating layer. FIG. 2B shows the liner with a flared end on one side that is used to seal the outer annulus on assembly. FIG. 2C shows the cartridge heater which is inserted in the reactor on assembly. See FIG. 4B for an exemplary assembled barbotage reactor.

(3) FIGS. 3A and 3B illustrate an exemplary finned tube liner for increased heat transfer surface area which can be employed in the pulsed torch reactor or the barbotage reactor. FIG. 3A illustrates the finned circumference of the tube liner giving exemplary dimensions of the fins and diameter of the tube liner. FIG. 3B illustrates a longitudinal view of an exemplary finned tube liner, with exemplary dimensions.

(4) FIGS. 4A and 4B show diagrams of the assembled reactors. FIG. 4A is the reactor for the pulsed torch application, while FIG. 4B is a diagram of the reactor for the barbotage application. In both reactor drawings, the N.sub.2O reaction gas flows (shown as arrows) from right to left in the outer annulus and then from left to right in the inner annulus are shown as arrows.

(5) FIGS. 5A and 5B show diagrams of the exemplary assembled reactors and include the exemplary location of the catalyst beds. In both reactors, the catalyst is packed in the inner annulus, between the cartridge heater and the inner surface of the liner. FIG. 5A is a diagram of the reactor for the torch application. The exemplary catalyst was Rh supported on ZrO.sub.2. FIG. 5B is a diagram of the reactor for the barbotage application. The exemplary catalyst was Rh supported on SiO.sub.2. In each case, a portion of the inner annulus is packed with inert inorganic packing material, such as crushed reticulated alumina foam, which holds the catalyst in place. In embodiments, the inert packing material can be coated with catalyst to provide a catalyzed foam.

(6) FIGS. 6A-6C illustrate three different types of temperature measurements that were made. Thermocouples (FIG. 6A) were spot welded on the outer surface of both torch and barbotage reactors at the locations shown in FIG. 1A and FIG. 2A and described as Wall TCs. Thermocouples were also inserted into the outer annular paths of both reactors, preferably spaced evenly between the outer shell and the liner as shown in FIG. 6B. The locations of the ports installed in the reactors for these measurements are shown in FIG. 1A and FIG. 2A. Finally, for the barbotage reactor, thermocouples were spot welded on the outside of the liner as illustrated in FIG. 5C. Locations for these measurements are shown in FIG. 2A.

(7) FIG. 7A illustrates an exemplary choked venturi valve useful in the reactors herein. FIGS. 7B and 7C show assembled reactors with the approach tubes (69) and the choked flow venturi valves (61) on the ignition reactor and the barbotage reactor, respectively. As illustrated in FIG. 7A, the choked venturi valve is adapted from an AN fitting. An internal portion of each choked flow venturi is cast with a ceramic material that is designed to handle high temperatures and rapid changes in temperature (thermal shock). The diameter of the throat of the venturi valve is sized to generate the desired pressure inside the N.sub.2O decomposition reactor. For these applications, mass flow rate through the valve can range from 0.5 to 5.0 lb/min. In a specific embodiment, the mass flow rate ranges from 0.7 to 4.0 lb/min. In an embodiment, a pressure of approximately 400 psig is achieved at a mass flow rate of 1.47 lb/min.

(8) FIG. 8 shows the adiabatic temperature that can be reached from N.sub.2O decomposition as a function of CO.sub.2 concentration in the N.sub.2O/CO.sub.2 feed mixture, starting with a compressed liquid at 25? C.

(9) FIG. 9 shows the maximum temperatures reached in tests with various concentrations of N.sub.2O. This shows that the maximum temperature reached can be controlled by adjusting the relative concentrations of N.sub.2O and CO.sub.2 in the mixture. These temperatures are higher than those shown in FIG. 8, which shows that significant energy can be added to the mixture by quenching the preheated catalyst and reactor mass over short periods of time.

(10) FIG. 10 shows the different transient behaviors with similar amounts of N.sub.2O in the mixture. With 7.5 grams of catalyst, the fluid exit temperature reached a maximum in 12,500 ms. With 15 grams of catalyst, the maximum was reached at 25,000 ms and the temperature was stable, remained between 800 and 900? C. between runtimes of 20,000 and 30,000 ms or for 10 seconds.

(11) FIG. 11 shows temperatures measured at the far end of the outer annulus, just before the flow was directed into the inner annulus (at TC location 2a in FIGS. 2B and 4B) during barbotage tests. In all cases, the temperature was rising as the flow entered the inner annulus which is the requirement for stable reactor performance in the barbotage application. If the temperature is falling at this location, then the reaction rate will drop rapidly and stop.

(12) FIG. 12A shows CO.sub.2 and N.sub.2 solubility in a kerosene-based fuel, JP-7, at two temperatures 68? F. and ?4? F. as a function of exposure pressure.

(13) FIG. 12B shows the viscosity of JP-7, at two temperatures 68? F. and ?4? F. as a function of CO.sub.2 and N.sub.2 exposure pressure.

(14) FIGS. 13A and 13B compare the effect of dissolved CO.sub.2 on fuel spray. FIG. 12A is a photograph of a spray field generated with RP-2 that was saturated with CO.sub.2 whereas, FIG. 12B is a photograph of spray field generated under identical conditions using RP-2 that did not contain dissolved CO.sub.2. Note that the size bar represents 5000 microns. The photograph in FIG. 12A with CO.sub.2 saturated fuel shows that there are larger areas of a fine mist and fewer ligament structures particularly in the bottom half of the spray field compared to the photograph in FIG. 12B with neat RP-2.

DETAILED DESCRIPTION OF THE INVENTION

(15) U.S. patent application Ser. No. 14/272,273 filed May 7, 2014 and Ser. No. 15/587,643, filed May 5, 2017 relate to catalytic heat exchanger reactors, particularly for N.sub.2O decomposition and application to ignition for jet engines. These applications and in addition U.S. provisional application 61/820,324, filed May 7, 2013 are each incorporated by reference herein for descriptions of the reactor and its operation.

(16) U.S. provisional application 62/687,747, filed Jun. 20, 2018 and US patent application 16/447,91, filed Jun. 20, 2019 relate at least in part to a pulsed torch application of a reactor as descried herein. U.S. patent application Ser. No. 16/447,913, filed Jun. 20, 2019 also provides additional description of choked venturi valves. The entire description and drawings in this provisional application are incorporated by reference herein.

(17) This disclosure relates to a reactor that comprises two concentric annular flow paths. The inner annulus is bounded on the inside by a cartridge heater and on the outside by a metal or alloy tube made of high temperature metal or alloy, such as nickel-chromium-iron or nickel-chromium-iron-molybdenum alloys, such as those in the Inconel? (Special Metal Corporation) family of alloys and Hastelloy? X (Haynes International). The outer annulus is bounded on the inside by the high temperature metal/alloy tube and on the outside by a metal tube which need not be made of high temperature metal or alloy, for example, 316-SS may be used. In a unique feature of this disclosure, the length of the reactor is varied to meet specific performance objectives in use in scram jet applications. When used to create a hot effluent to be used with the ignition torch, the reactor is shorter, from about 8 inches to 20-in in length. When used to produce an effluent that is mixed with the main engine fuel to improve injection, the reactor is longer, from 15 inches to 30 inches.

(18) FIGS. 1A-1C and 2A-2C show exploded views of the reactor components for the ignition torch and for the barbotage application, respectively. FIGS. 4A and 4B show assembled views of the ignition torch and barbotage torch, respectively. Each reactor comprises three primary components.

(19) FIG. 1A shows the structure of the outer shell (5) which forms a cylindrical reactor. The shell is made from metal tubing with a thin layer of ceramic insulation (7) cast on the inner surface of the outer shell (5) to insulate the metal from the high temperatures in the reactor. The thickness of the ceramic insulator layer (7) is adjusted as known in the art to achieve desired insulation in view of the temperatures involved and the metal and other materials employed. In specific embodiments, the insulation is less than ? inch thick, in other embodiments the insulation is 1/16 to ? inch thick. In a specific embodiment, the insulation is about ? inch thick. The outer shell (5) serves as the pressure boundary for the reactor and it has a maximum operating pressure of 800 psig as long as the maximum wall temperature remains below 800? C. The outer shell (5) is provided with a closed end fitting (4) to facilitate assembly of the reactor components, and formation of an inner annulus (16) and outer annulus (14) (see FIG. 4A). The outer shell (5) is also provided with an open flow exit end fitting (3) through which flow exits the reactor. In FIG. 1A, inlet port (6) is shown coupled through a channel in end fitting (3) into the outer annulus (14). Inlet port (6) may however enter directly through the outer shell (5) into the outer annulus (14).

(20) FIG. 1B shows a high temperature metal or alloy tube liner (13) which is referred to herein as a tube liner with a flared fitting (11). The tube liner fits into the cylinder formed by the outer shell (5). Insertion of the tube liner (13) into the outer shell (5), such that a seal is formed between the flared fitting (11) and the end fitting (3) forms an outer annulus (14) between ceramic layer (7) and the tube liner (13). The inlet port (6) at one end of the outer shell introduces the N.sub.2O reaction feed mixture into the outer annulus (14). Several thermocouples are spot-welded at selected locations (1a-d) on the outer surface of the outer shell (5) to monitor temperatures during preheat and testing (wall TCs). Several ports (2a-d) are provided on the outer shell (5) for thermocouples that measure temperatures in the outer annulus (14) (see also FIG. 6B). These thermocouples are optional, but useful for monitoring reactor operation and/or optimizing such operation. In a specific embodiment, at least one thermocouple is positioned at one end of the outer annulus distal from the inlet (6), e.g., at position 2a, to allow a temperature measurement before the gas mixture contacts the catalyst. For sustained operation the temperature at this location should be constant or increasing. If, in contrast, the temperature in the outer annulus at this point is decreasing then the reaction rate on the catalyst will decrease which will generate less energy to preheat the feed mixture and will cause the reaction to stop. It is important to adequately preheat the feed mixture.

(21) FIG. 1C illustrates the cartridge heater (10) with heater fitting (12) that is inserted into tube liner (13) and defines the inner boundary of the inner annulus (16) of the reactor which is formed between the heater cartridge (10) and the tube liner (13). The heater (10) is used to bring the catalyst and reactor walls up to operating temperature before the N.sub.2O feed mixture flow is started. The outside material of the heater is preferably made of oxidation resistant material. In some examples, the heater comes with a thermocouple located at the far end (flow exit end) of the heater.

(22) FIG. 4A shows the assembled reactor for the ignition torch, where assembly of components form the outer annulus (14) and the inner annulus (16). The figures include arrows that show the direction of the feed flow from the flow inlet (6) through outer annulus (14), through inner annulus (16) to exit through the exit flow fitting (3). The feed flow enters the port on the right side of the reactor and then travels to the other end of the reactor in the outer annulus (14), where it is preheated to the temperature needed to achieve the needed reaction before it contacts the catalyst. The preheat temperature typically used with the Rh catalyst to rapidly initiate the catalytic decomposition reaction at startup is 400 to 500? C., but can vary according to the form and amount of catalyst present, the catalyst metal loading, the intrinsic surface area of the catalyst support (m.sup.2/gram), and other factors. The preheated feed flow then enters the inner annulus (16) and moves back toward the right side where it contacts the catalyst (see FIG. 4A), causing the N.sub.2O decomposition reaction to begin.

(23) FIGS. 2A-2C show the components of an exemplary reactor for the barbotage application. Outer shell (25) is similar in structure and function to outer shell (5) of FIG. 1A, but does not have an insulating ceramic liner. The outer shell is provided with a closed end fitting (4) to facilitate assembly of the reactor components, and formation of an inner annulus (16) and outer annulus (14) (see FIG. 3B). The outer shell is also provided with an open flow exit end fitting (23) through which flow exits the reactor. In FIG. 2A, inlet port (26) is shown coupled directly through the outer shell (25) into the outer annulus (14). Several thermocouples are spot-welded at selected locations (1a-g) on the outer surface of the outer shell (25) to monitor temperatures during preheat and testing. Several ports (2a-f) are provided on the outer shell (25) for thermocouples that measure temperatures in the outer annulus (14).

(24) These thermocouples are in general optional, but useful for monitoring reactor operation and/or optimizing such operation. In a specific embodiment, at least one thermocouple is positioned at one end of the outer annulus distal from the inlet (26), e.g., at position 2a in FIG. 2A, to allow a temperature measurement before the gas mixture contacts the catalyst. For sustained operation the temperature at this location should be constant or increasing. If, in contrast, the temperature in the outer annulus at this point is decreasing then the reaction rate on the catalyst will decrease which will generate less energy to preheat the feed mixture and will cause the reaction to stop. It is important to adequately preheat the feed mixture, particularly for the barbotage application.

(25) FIG. 2B shows high temperature metal or alloy tube liner (13) again with flared fitting (11). The tube liner fits inside of the cylinder formed by the outer shell. Insertion of the tube liner (13) into the outer shell (25) with flared fitting (11) engaged with end fitting (23) forms an outer annulus (14) between the outer shell (25) and the tube liner (13). The inlet port (26) at one end of the outer shell (25) introduces the N.sub.2O reaction feed mixture into the outer annulus (14). Outer shell (25) is also provided with several ports (22a-e) for thermocouples to measure temperatures of the outside of liner (13).

(26) FIG. 2C shows the cartridge heater (10) with heater fitting (12) that is inserted into tube liner (13) and defines the inner boundary of the inner annulus (16) of the reactor which is formed between the heater cartridge (10) and the tube liner (13). The heater (10) is used to bring the catalyst and reactor walls up to operating temperature before the N.sub.2O feed mixture flow is started. In some examples, the heater comes with a thermocouple located at the far end (flow exit end) of the heater. FIGS. 2A-2C give exemplary OD and length dimensions of the components.

(27) The tube liner (13) of the reactor is made of a high temperature metal alloy that is preferably oxidation-corrosion resistant. Stainless steel or other metals or alloys may be used. Nickel-chromium-iron alloys, such as those in the Inconel? (Special Metal Corporation) family of alloys are useful for tube liners herein. Nickel-chromium-iron-molybdenum alloys, such as that commercially available as Hastelloy? X (Haynes International), are also useful for tube liners. A number of high temperature alloys which exhibit oxidation-corrosion resistance are known in the art and one of ordinary skill in the art can chose from among the alternatives available those that are appropriate for use in the reactors of this invention.

(28) In an embodiment, fins (34) can be added to the outside of the liner (13), as illustrated in FIGS. 3A and 3B to increase surface area and improve heat transfer. In FIG. 3A, the spacing between fins (35) the width of a fin (36) and the height of a fin (37) are shown and exemplary dimensions are given. Also shown are the outside diameter (38) of the finned tube, the inside diameter of the finned tube (39) and the thickness (40) of the tube liner without fin and exemplary dimensions are given. FIG. 3B provides a longitudinal view of the finned tube liner (33) carrying a plurality of fins (34). Stainless steel, among other materials, can be used for the finned tube liner. High temperature alloys, such as nickel-chromium-iron alloys or nickel-chromiun-iron-molybdenum alloys, such as those in the Inconel? (Special Metal Corporation) family of alloys, or Hastelloy? X are desirable because they are more oxidation resistant than stainless steel. Oxidation resistance is desirable because high temperature oxygen is produced by the N.sub.2O decomposition reaction in the inner annulus.

(29) In specific embodiments, the high temperature alloy employed is Inconel?600, Inconel?625, Iconel?800 or Hastelloy?-X. The composition of these commercially available alloys is known in the art.

(30) In specific embodiments, the heater cartridges employed in the reactors herein have an outer shell which is made from a high temperature alloy which is corrosion resistant, such as Iconel? 800.

(31) In specific embodiments, the heater surface, and the inside surface of the tube liner is coated with a layer of a suspension of fine ZnO.sub.2 particles as an added barrier to oxidation. More specifically, a Pryo-Paint? 634-ZO (Aremco Products, Inc.) product can be used to provide an oxidation-protection layer on the internal metal, alloy or ceramic surfaces of the reactors herein. It will be appreciated by those of ordinary skill in the art that other products can be employed to provide refractory coatings (Zn oxide, alumina, etc.) on internal surfaces of the reactors herein. The barbotage reactor outer shell of FIG. 2A was not provided with a ceramic liner in exemplary embodiments herein because heat loss was not believed to be a significant issue. However, in an embodiment, the barbotage reactor can be provided with a ceramic liner similar to that shown and described in FIG. 1A.

(32) FIGS. 4A and 4B show the assembled reactors for the ignition torch and barbotage reactors, respectively. The figures include arrows that show the direction of the feed flow. The feed flow (46) enters the port on the right side of the reactor and then travels to the other end of the reactor in the outer annulus (14), where it is preheated to the temperature needed to achieve the needed reaction before it contacts the catalyst. The preheat temperature typically used with Rh catalyst to rapidly initiate the catalytic decomposition reaction at startup is 400 to 500? C., but can vary according to the form and amount of catalyst present, the catalyst metal loading, the intrinsic surface area of the catalyst support (m.sup.2/gram), and other factors. The preheated feed flow then enters the inner annulus (16) and moves back toward the right side where it contacts the catalyst, causing the N.sub.2O decomposition reaction to begin. Gas products then exit the reactor (47). The plurality of TC's (22a-22e) for measurement of the outside of the tube liner are not shown in FIG. 4B.

(33) FIGS. 5A and 5B show exemplary locations of the catalyst in the reactor for the ignition torch and barbotage reactors, respectively. The catalyst can be contained in the packed bed as shown here or it can also be coated on the inside wall of the tube liner (13) and/or outside wall of the cartridge heater (10). In the illustrated embodiment, the catalyst is packed in the inner annulus (16), between the outer surface of the cartridge heater (10) and the inner surface of the liner (13). Catalyst (50) is positioned in portion of the inner annulus (16). Another portion of the inner annulus (16), contains inert inorganic foam or any inert diluent (51). In embodiments not specifically shown, a portion of the uncatalyzed foam can be replaced with catalyzed foam. Catalyzed foam is a catalytically inert inorganic foam coated with active catalyst. A final portion of the inner annulus just proximal to the exit is optionally packed with uncatalyzed foam (52). Uncatalyzed or catalyzed foam is employed in part to maintain catalyst in selected positions in the inner annulus. FIG. 5A shows an exemplary catalyst configuration for the torch application where the catalyst (50) is loaded in a back portion of the inner annulus proximal to the flow exit (47). A front portion of the inner annulus distal to the flow exit is loaded with inert inorganic foam (uncatalyzed filler/foam) (51), such as crushed reticulated alumina. In specific examples, catalyst 50 varies between 7.6 grams mixed with 27.6 grams of ZrO.sub.2 diluent to 15.0 grams mixed with 55 grams of ZrO.sub.2 diluent with the front of the reactor packed with crushed alumina foam. In an optional embodiment, a small portion of the inner annulus proximal to the flow exit (47) (back of the reactor) also contains uncatalyzed foam.

(34) FIG. 5B shows an exemplary catalyst configuration used in the barbotage application. The catalyst in this example application comprises Rh supported on SiO.sub.2. In the illustrated example catalyst configuration of FIG. 5B a front portion of the inner annulus 16 (distal from the flow exit 47) is packed with supported catalyst (50) and a back portion of the inner annulus proximal to the flow exit 47 is packed with uncatalyzed foam (51). In an embodiment not shown, a portion of the uncatalyzed foam can be replaced with catalyzed foam. A small portion of the inner annulus proximal to the flow exit is optionally packed with uncatalyzed foam (52). In an embodiment of the reactor of FIG. 5B, 18.8 g of supported catalyst is packed in the front end of the annulus (distal from the flow exit), resulting in a bed length of 9.1-inches. In this embodiment, the catalyst was followed by 9.1 inches of crushed alumina foam, and the final 2.875-in of the annulus was filled with uncoated, crushed alumina foam. The catalyst configurations illustrated in FIGS. 5A and 5B are illustrative and not limiting.

(35) In embodiments, the ignition reactor (torch reactor) is shorter than the barbotage reactor. The barbotage reactor generally is operated at lower temperature than the ignition reactor. Typically, more CO.sub.2 is mixed with the N.sub.2O in the barbotage reactor compared to the ignition reactor. Adding more CO.sub.2 generally reduces the temperature in the catalyst bed, which in turn reduces the rate that the flow of feed is preheated in the outer annulus. In this case, a longer path is typically required to for the incoming feed to reach the temperature needed to be active when the feed contacts the catalyst.

(36) In generally, the amount catalyst incorporated into a reactor, and the ratio of catalyst to inert diluent is adjusted to achieve a desired temperature profile. With addition of more catalyst, it was generally observed that the gas temperature exiting the reactor was somewhat lower and more consistent which is better for barbotage. Using less catalyst the temperature of gas exiting was generally hotter more quickly but then decrease which was preferred for the ignition torch reactor.

(37) In a preferred embodiment, the feed entering the reactor is in a two-phase state at a pressure of at least 600 psig. In another preferred embodiment, the feed mixture enters the outer annulus at a location directly across from the catalyst in the inner annulus and the heat of reaction is used to provide the enthalpy to vaporize the feed mixture. This configuration limits the maximum temperature reached in the inner annulus and limits damage to the catalyst. After being fully vaporized the mixture continues to flow and heat up along the length of the outer annulus to the far end of the reactor, where it transfers into the inner annulus. Once inside the inner annulus, the flow reverses direction and contacts the catalyst.

(38) FIGS. 6A-6C show the locations of the thermocouples (TC) on the outer wall and inside the outer annulus for the ignition torch and barbotage reactors. The temperature measurements on the outer wall, with TC spot welded (1) to the outer wall of the outer shell (5, 35) of the reactors as shown in FIG. 6A, can be monitored during transient operation and if they exceed set values, the reaction can be stopped. During transient operation, temperatures measured at these locations can also be used to evaluate the effectiveness of preheating. FIG. 6B illustrates a TC positioned in the outer annulus through TC port 2 to measure temperatures therein. FIG. 6C illustrates a TC positioned at the outer wall of the tube liner (13, 33). A TC is introduced through port 22 (see FIG. 2A) and spot welded to the outer wall of liner (13, 33). In a preferred embodiment for the barbotage application, the temperature measured at 2a in FIG. 2A must be constant or rising to achieve sustained operation for the necessary time period. If the temperature at this location is decreasing, the reaction will stop prematurely.

(39) FIG. 7A illustrates an exemplary choked venturi valve (61) for use in reactors of this invention. FIGS. 7B and 7C show the assembled reactor with the flow exiting though the choked flow venturi for the ignition torch and barbotage reactors, respectively. In a preferred embodiment, the flow through the venturi has a velocity equal to the speed of sound. In another embodiment, the flow restriction of the venturi maintains a pressure of between 400 and 650 psig in the reactor. The venturi valve (61) illustrated in FIG. 7A is adapted from a conventional AN fitting. The shaped channel (62) through the fitting is shaped to provide the venturi valve by casting a ceramic material (63) in the desired shape to form the valve throat (64) and valve exit (65). The shaped channel (62) is symmetrical with respect to the center line of the valve (66) (i.e., the center line of the AN fitting). One of ordinary skill in the art understands that a variety of shaped channels can be used to provide the choked venturi effect. One of ordinary skill in the art can select a valve shape appropriate for use in the reactors herein in view of the descriptions herein and what is well-known in the art.

(40) FIG. 7B illustrates a reactor as in FIG. 4A or 5A adapted to have a choked venturi valve (61) coupled to the end fitting (3) through which flow exits the reactor (77). FIG. 7C illustrates a reactor as in FIG. 4B or 5B adapted to have a choked venturi valve (61) coupled to the end fitting (23) through which flow exits the reactor (77). The choked venturi valve is coupled to the respective end fitting through an approach tube (69). The approach tube is a tube of selected length matched in OD with the open end fitting (3). Exemplary length of the approach tube is 5 inches with an OD of 0.75 in. Use of this tube facilitates connection of the reactor to the choked flow venturi valve. The tube which is made of stainless steel or high temperature alloy (as described herein) has a ceramic lining as illustrated for ceramic lining 7 in FIG. 1A. The approach tube can be provided with one or more ports for introduction of one or more thermocouples, which allow measurement of the temperature of the gas leaving the reactor before it enters the venturi valve. The approach tube can also be provided with a gas sample port for sampling the gas exiting the reactor.

(41) In a preferred embodiment of the invention, the temperature of the effluent can be controlled by adjusting the relative concentrations of N.sub.2O and CO.sub.2 in the mixture. Higher concentrations of N.sub.2O will produce higher temperatures. FIG. 8 shows the ideal adiabatic temperature that is reached with N.sub.2O decomposition as a function of N.sub.2O concentration in an ideal gas N.sub.2O/CO.sub.2 feed mixture. At 100% N.sub.2O, the adiabatic decomposition temperature for N.sub.2O gas starting with a compressed liquid at 25? C. and forming N.sub.2 and O.sub.2 is 1452? C. This temperature is high enough to damage the catalyst and reactor components. With the reactor size and flow rates specified herein, the reactor temperature can reach high temperature quickly, which will damage the both the reactor and the catalyst. However, when CO.sub.2 is added to the N.sub.2O feed, the maximum temperature decreases linearly with CO.sub.2 concentration and the reactor can operate for the needed time before exceeding safe operation temperatures. For example, with a mixture of 60% N.sub.2O and 40% CO.sub.2 (mole percent) the ideal gas adiabatic decomposition temperature is 822? C. and with a mixture containing 40% N.sub.2O and 60% CO.sub.2, the ideal gas adiabatic decomposition temperature is 504? C.

(42) FIG. 9 shows that adding CO.sub.2 to the N.sub.2O in the feed tank to reduce the N.sub.2O concentration does in fact control temperature in the reactor. The figure shows the maximum temperatures reached in laboratory tests with various concentrations of N.sub.2O in CO.sub.2 for mixtures starting in the compressed liquid state at 1150 psig and 70 F. This figure shows that the maximum reactor exit temperatures ranged from 492? C. at an N.sub.2O concentration of 34.2% up to 1263? C. at 56.9% N.sub.2O with a reactor exit pressure near 500 psig. The fact that the maximum measured exit temperatures exceed the adiabatic decomposition temperature is due to the addition of heat stored in the reactor during preheating.

(43) In another embodiment, the transient behavior of the reactor can also be controlled by the quantity and the location of the catalyst that is contained in the reactor. FIG. 10 shows the fluid exit temperatures in two tests with the reactor described in this invention. In one case, with 7.5 grams of catalyst and a bed length of 3.75-in, the temperature rose quickly and reached a maximum value of 936? C. in 12,690 ms (12.69 s). In another test where the quantity of the catalyst and bed length were increased to 15 grams catalyst and 10 inches respectively, the temperature rose more slowly, reached a maximum temperature of 731? C. at 22500 ms (22.5 s), and maintained a constant temperature for 30,000 ms (30 s). FIG. 10 also shows that the transient thermal storage and heat transfer process can increase the effluent temperature significantly above the adiabatic decomposition temperature for short periods of time.

(44) The ability to adjust the transient behavior of the reactor is an important feature of the present reactor device. When the reactor is used with an ignition torch, the temperature of the effluent must rise quickly and reach its operating temperature quickly, for example in less than 20 seconds from the start of the N.sub.2O flow, but it is only necessary to maintain the desired temperature range between 800? C. and 1100? C. for a short time, less than 20 seconds. On the other hand, for the barbotage application, the operating temperature can be as low as 400? C., but the flow should last for up to two minutes. In this embodiment, the behavior of the reactor can be modified for each application by changing the reactor length, the quantity of catalyst and the location of the catalyst.

(45) In embodiments, both the amount of CO.sub.2 added to the N.sub.2O reactor feed and the amount and location of catalyst can be adjusted to achieve the desired reactor behavior.

(46) In a separate embodiment, a coating of fuel can be applied to the catalyst prior to use. During the heating process, the fuel will combust and provide sufficient heat to preheat the catalyst and initiate the N.sub.2O decomposition reaction, thereby reducing the power and energy supplied by the cartridge heater.

(47) In embodiments, the invention provides a catalytic N.sub.2O decomposition process conducted in a reactor, where the rate of heat generated by the decomposition reaction causes the reactor temperature to rise rapidly and exceed its maximum allowable temperature, thereby requiring methods to control the reaction temperature. In embodiments, the mass flow of feed mixture introduced into the reactor and flowing through the catalyst equals or exceeds the weight of the decomposition reaction each minute. In embodiments, the reaction temperature is controlled and the reactor is prevented from exceeding its maximum operating temperature by operating the reactor for a short period and stopping the feed flow before the reactor temperature exceeds its safe limits. In an embodiment, reaction temperature is controlled by comprises diluting N.sub.2O with CO.sub.2 in the feed into the reactor. In an embodiment, the reactor size, catalyst quantity, and catalyst location are selected to provide an effluent from the reactor that reaches a temperature range of between 800? C. and 1200? C. in less than 20 seconds and maintains that temperature range for up to 20 seconds. In an embodiment, reactor size, catalyst quantity, and catalyst location are selected to provide an effluent that can be used to ignite fuel in a pilot ignition torch. In an embodiment, reactor size, catalyst quantity, and catalyst location are selected to provide an effluent that reaches a temperature range of between 400? C. and 800? C. and maintains that temperature range for up to two minutes.

(48) In an embodiment, the catalyst provided in the reactor comprises rhodium oxide. In an embodiment, the catalyst provided in the reactor comprises rhodium oxide supported on zinc oxide. In an embodiment, the catalyst provided in the reactor comprises rhodium oxide supported on silica.

(49) In embodiments, the invention provides a catalytic N.sub.2O decomposition reactor where changing the size of the reactor, the quantity of catalyst, and the location of the catalyst is used to control the temperature profile of the effluent of the reactor. In embodiments, the invention provides a catalytic N.sub.2O decomposition reactor where diluting N.sub.2O with O.sub.2 is used to control the temperature profile of the effluent from the reactor. In an embodiment, the reactor size, catalyst quantity, and catalyst location are selected to provide an effluent from the reactor that reaches a temperature range of between 800? C. and 1200? C. in less than 20 seconds and maintains that temperature range for up to 20 seconds. In an embodiment, reactor size, catalyst quantity, and catalyst location are selected to provide an effluent that can be used to ignite fuel in a pilot ignition torch. In an embodiment, reactor size, catalyst quantity, and catalyst location are selected to provide an effluent that reaches a temperature range of between 400? C. and 800? C. and maintains that temperature range for up to two minutes. In an embodiment, reactor size, catalyst quantity, and catalyst location are selected to provide an effluent that can be used to mix with the main fuel supply to reduce viscosity and improve fuel atomization. In an embodiment, the catalyst in the reactor comprises rhodium oxide. In an embodiment, the catalyst in the reactor comprises rhodium oxide supported on zinc oxide. In an embodiment, the catalyst in the reactor comprises rhodium oxide supported on silica.

(50) In an embodiment, the invention provides a catalytic N.sub.2O decomposition reactor which comprises an inner and an outer annulus in flow communication with each other, wherein feed is introduced into the outer annulus and passes into the inner annulus, wherein the inner annulus comprises catalyst, and wherein feed entering the reactor into the outer annulus is preheated to a selected temperature in the outer annulus prior to contacting the catalyst in the inner annulus.

(51) In an embodiment, the catalytic reactor comprises a heater in thermal contact with the inner annulus, the outer annulus is in thermal contact with the inner annulus and heat produced in the inner annulus by reaction and heat generated by the heater function to facilitate reaction in the inner annulus and preheat the feed in the outer annulus. In an embodiment, at least a portion of the walls of the outer annulus are ribbed to enhance heat transfer from the inner annulus to the outer annulus and the feed therein. In an embodiment, the catalytic reactor comprises a choke venturi at the exit from the reactor.

(52) In embodiments, the reactor is constructed by providing an outer shell of selected inner and outer diameter, a tube liner of selected inner and outer diameter, a cylindrical heater of selected outer diameter wherein an inner annulus and an outer annulus are formed by inserting the tube liner into the outer shell and inserting the cylindrical heater into the tube liner, the inner annulus is formed between the heater surface and the inner surface of the tuber liner, the outer annulus is formed between the outer surface of the tube liner and the inner surface of the outer shell. In an embodiment, reactor has a proximal and distal end wherein feed enters and effluent exits the reactor at the proximal (feed entry/effluent exit end) and the distal end of the reactor is sealed externally, but allows passage of feed from the outer annulus to the inner annulus. At the proximal end of the reactor, the outer annulus and inner annulus are not in fluid communication. At the proximal end of the reactor feed enters the inner annulus. At the proximal end of the reactor, effluent gas exits the rector after catalytic reaction of feed with catalyst. Catalyst for decomposition of N.sub.2O is provided in the inner annulus, in one or more packed beds or as a coating on at least a portion of the walls forming the inner annulus. In an embodiment, no catalyst is provided in the outer annulus. In an embodiment, feed enters the outer annulus, passes into the inner annulus where the feed contacts catalyst and decomposition reaction occurs and effluent exits the inner annulus and exits the reactor. In an embodiment, gas effluent from the reactor exits the reactor through a choked venturi valve. In an embodiment, one or more thermocouples are provided in the reactor to measure temperature in the reactor. In an embodiment, at least one thermocouple is provided at the point where feed exits the outer annulus and enters the inner annulus. In an embodiment, temperature at the point where feed exits the outer annulus and enters the inner annulus is monitored. In an embodiment, temperature at the point where feed exits the outer annulus and enters the inner annulus is controlled such that it is constant or increasing rather than decreasing by adjustment of feed flow, relative concentration of N.sub.2O to O.sub.2 in the feed, and/or heater temperature.

(53) Barbotage Application

(54) In a preferred embodiment, the concentration of N.sub.2O in the mixture is maintained at a level of about 30%, which keeps the temperature of the exit fluid low, equal to or less than 600? C.

(55) In a preferred embodiment, the reduced temperature in the catalyst bed reduces the temperature difference between the inner and outer annulus so a longer reactor, between 15 and 30 inches, is required to preheat the incoming flow to the needed temperatures. The reduced temperature also generates a need to increase the quantity of the catalyst to between 10 and 15 grams resulting in a bed length of 5 to 15 inches.

(56) Using a longer catalyst bed results in a lower, but more stable, temperature in the fluid exit compared to a shorter catalyst bed, which is a desirable condition for this application.

(57) In a preferred embodiment for the barbotage application, the temperature of the preheated mixture measured at 2a in FIG. 2A, must not be decreasing during the test in order to achieve the needed operation time. This embodiment has been demonstrated. FIG. 11 shows the gas temperatures measured at this location during a series of tests for the barbotage application. In all cases, the temperatures measured at that location were increasing during the test.

(58) In another embodiment the percent N.sub.2O conversion must be increasing or level at 100% during the test in order to reach the needed operating time. If the temperature reaching the catalyst is increasing as described in the previous embodiment, then the percent N.sub.2O conversion will be increasing as long as the catalyst is not deactivating.

(59) In addition to controlling the N.sub.2O reactor temperature, the addition of CO.sub.2 has an additional advantage for barbotage because CO.sub.2 is very soluble in fuel and therefore can improve fuel atomization. FIG. 12A shows CO.sub.2 and N.sub.2 solubility in a kerosene-based fuel, JP-7, at two temperatures 68? F. and ?4? F. as a function of exposure pressure. At 68? F. and 300 psig, the solubility of CO.sub.2 is 35 SL per liter of fuel and at ?4? F., the solubility is 61 SL/L almost two times higher. On the other hand, N.sub.2, which is also considered for use as a barbotage gas has solubility of 4 SL/L at 68? F. and 3 SL/L at ?4? F. FIG. 11B shows that the high solubility of CO.sub.2 also has a strong effect on the viscosity of the fuel. At 300 psig, the increased solubility of CO.sub.2 at ?4? F. causes the viscosity of the fuel at that temperature to be lower than the viscosity at 68? F. Over all conditions, the viscosity is less with CO.sub.2 compared to N.sub.2.

(60) The very high solubility of CO.sub.2 makes the N.sub.2O decomposition reactor described herein even more useful when used in the barbotage application. Based on the above solubility data, the quantity of CO.sub.2 that would be contained in JP-7 or an equivalent fuel (such as Rocket Propellants, RP1 and RP-2) at expected injection pressures and gas to liquid ratios is about 17.1 SL/L at 68? F. and 29.0 SL/L at ?4? F. When the fuel reaches the combustor, where the total pressure is much lower than in the injectors, the dissolved CO.sub.2 will rapidly come out of solution, forming rapidly growing bubbles inside the fuel droplets, which help break the droplets up and atomize the fuel. It will be appreciated by one of ordinary skill in the art that various jet and rocket fuels are known in the art and can be employed in the reactors of this invention.

(61) This embodiment has also been demonstrated as shown in FIGS. 13A and 13B. FIG. 13A shows a spray field generated with CO.sub.2 saturated RP-2 whereas FIG. 13B shows a spray field generated under identical conditions with neat RP-1. The most notable difference in the images is that there are far fewer fuel ligament structures in FIG. 13A with the CO.sub.2 saturated fuel compared to FIG. 13B. Although there are ligaments present in FIG. 13A, they are located closer to the fuel nozzle exit whereas in FIG. 12B (neat RP-1) a larger number of fuel ligaments are observed all the way to the bottom of the image. Another notable difference is that the image in FIG. 13A shows larger dark areas that appear to have a misty or out-of-focus quality compared to FIG. 13B. These dark, out-of-focus areas are caused by droplets that are too small to be resolved by the camera and end up blocking the backlighting from the flash, causing the unique, dark appearance.

(62) In a preferred embodiment, the CO.sub.2 containing barbotage gas is particularly useful with fuel that is cold, less than 0? F. because the high-speed vehicle can be capture carried on aircraft for long periods of time at high altitude before it is deployed, causing the fuel to become very cold before the vehicle is activated.

(63) In a preferred embodiment of the invention, the barbotage gas from the reactor will be dispersed into the fuel using a fine frit that allows the CO.sub.2 to dissolve rapidly and also leaves small bubbles of N.sub.2 and O.sub.2, which are much less soluble, dispersed in the fuel. The small bubbles of dispersed N.sub.2 and O.sub.2 inside the droplets will serve as nucleation sites for CO.sub.2 and increase the rate of CO.sub.2 gas evolution.

(64) In another preferred embodiment, N.sub.2O also has a high solubility in liquid hydrocarbons that comprise kerosene-based jet fuels. Therefore, any unreacted N.sub.2O that exits the reactor will also dissolve in the fuel like CO.sub.2 at high pressure and decrease the fuel viscosity, then it will evolve as bubbles and improve atomization when the pressure decreases in the combustor.

(65) In a preferred embodiment, the concentration of unreacted N.sub.2O in the effluent can be increased by installing a small port on the outer shell of the reactor at the end opposite the inlet port, which draws some fraction of the preheated N.sub.2O/CO.sub.2 mixture out of the reactor before it contacts the catalyst. The flow by-passes the catalyst and then is recombined with the main flow before it passes through the choked flow venturi. This modification permits higher concentrations of N.sub.2O to be fed into the fuel injectors while avoiding the hazards of flowing higher N.sub.2O concentrations through the catalyst by decreasing the overall rate of N.sub.2O decomposition.

(66) In exemplary embodiments of the barbotage reactor;

(67) The volume of the inner annulus is 109 cm.sup.3 and that of the outer annulus is 34 cm.sup.3;

(68) The wall thickness of the outer shell is 0.065 inch;

(69) Mass flow ranges from 5.3 g/s up to 30 g/s;

(70) Surface area on the finned side of the liner is 660 cm.sup.2;

(71) Surface area on the inside of the liner is 294 cm.sup.2; and

(72) The residence time ranges from 11.5 to 65.3 milliseconds (assuming ideal gas at room temperature and 400 psig).

(73) Ignition Torch Application

(74) The application of the N.sub.2O reactor for a pilot ignition torch requires that temperatures of at least 800? C. be reached in the flow exiting the reactor for the fuel injected into the torch to ignite rapidly. Therefore, the N.sub.2O concentration is higher than in the barbotage application, between 40 and 60%, preferably 50%.

(75) In a preferred embodiment, the gas temperature exiting the reactor must rise to 850? C. rapidly after the N.sub.2O flow is started, preferably in less than 20 seconds after the N.sub.2O flow was started, most preferably in less than 10 seconds.

(76) Because the higher N.sub.2O concentrations generate higher temperatures, the incoming N.sub.2O will reach reaction temperatures more rapidly and therefore the reactor for torch application can be shorter than the reactor for the barbotage application, between 8 and 20 inches. The higher reaction rates at the higher temperatures reduce the catalyst requirement so the catalyst weight and bed length can be reduced to between 4 and 11 grams of catalyst and 3 to 10 inches respectively.

(77) In a preferred embodiment, using less catalyst and a shorter bed length produce more rapid temperature increases at the fluid exit, which is the opposite of conventional steady-state reactor design expectations.

(78) In a preferred embodiment after the temperature of the effluent will remain above 800? C., but below 1100? C. for a period of at least five seconds.

(79) In a preferred embodiment, to achieve sustained performance, the percent N.sub.2O decomposition must be increasing or stable at 100% while N.sub.2O is flowing though the reactor.

(80) In exemplary embodiments of the torch reactor:

(81) The volume of the inner annulus is 68.5 cm.sup.3 and the volume of the outer annulus is 33.1 cm.sup.3;

(82) The wall thickness of the outer shell is 0.065 in;

(83) Mass flows range from 11.1 to 30 g/s;

(84) Surface area on the outside of the liner is 210.4 cm.sup.2;

(85) Surface area on the inside of the liner is 182.6 cm.sup.2; and

(86) Residence times range from 8.2 to 22 milliseconds (assuming ideal gas at room temperature and 400 psig).

(87) Either O.sub.2 produced by the decomposition of N.sub.2O or unreacted N.sub.2O can be used as the oxidant for the torch and therefore the percent N.sub.2O decomposition achieve during the test only affects the performance of the device through affecting the temperature of the flow exiting the reactor, not the ability of the mixture to oxidize the fuel entering the pilot torch.

(88) All references cited herein are hereby incorporated by reference to the extent not inconsistent with the disclosure herewith.

(89) Although the description herein contains many specifics, these should not be construed as limiting the scope of the invention but as merely providing illustrations of some of the presently preferred embodiments of the invention. Thus, the scope of the invention should be determined by the appended claims and their equivalents, rather than by the examples given. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and sub-combinations possible of the group are intended to be individually included in the disclosure.

(90) Every combination of components described or exemplified can be used to make and use the devices described herein unless otherwise stated. One of ordinary skill in the art will appreciate that methods and device elements, other than those specifically exemplified can be employed to 10 make and use the devices as described herein without resort to undue experimentation. All art known functional equivalents, of any such methods, and device elements, are intended to be included in this invention. Whenever a range is given in the specification, for example, a temperature range, a time range, a range of pulse rates, a range of pressure or a composition range, all intermediate ranges and subranges, as well as all individual values included in the 15 ranges given are intended to be included in the disclosure.

(91) As used herein, comprising is synonymous with including, containing,, composed of, or characterized by, and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, consisting of does not exclude any element, step, 20 or ingredient not specified in the claim element. As used herein, consisting essentially of does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. Any recitation herein of the term comprising, particularly in a description of components of a composition or in a description of elements of a device, is understood to encompass those compositions and methods consisting essentially of and consisting of the 25 recited components or elements. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.

(92) The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.

(93) In general, the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. The preceding definitions are provided to clarify their specific use in the context of the invention. The examples provided herein are not intended to be limiting.