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Hydrogen Donors: Thermal Stabilizers for JP-8+ 100 at High Temperatures

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Hydrogen Donors: Thermal Stabilizers for JP-8+ 100 at High Temperatures THE AMERICAN SOCIETY OF MECHANICAL ENGINEERS Three Perk Avenue, New York, N.Y. 10016-5990 99-GT-56 The Society shall not be responsible for statements or opinions advanced In papers or discussion at meetings of the Society or of its Divisions or Sedans, or printed in its publications. Discussion Is printed only if the paper is published In an ASME Journal. Authorization to photocopy for internal or personal use is granted to libraries and other users registered with the Copyright Clearance Center ICCO provided 53/article is paid to CCC, 222 Rosewood Dr., Danvers, MA 01923. Requests for special permission or bulk reproduction should be ad- dressed to the ASME Technical Publishing Department. Copyright 0 1999 by AS's& All Rights Reserved Printed In U.S.A. Downloaded from http://asmedigitalcollection.asme.org/GT/proceedings-pdf/GT1999/78590/V002T02A008/4218087/v002t02a008-99-gt-056.pdf by guest on 27 September 2021 HYDROGEN DONORS: THERMAL STABILIZERS FOR JP-8+100 AT HIGH TEMPERATURES 11111,10111111111 Edwin Corporan and Donald K. Minus Air Force Research Laboratory Propulsion Directorate Wright-Patterson Air Force Base, Ohio 45433-7103 ABSTRACT temperatures (-150 °C) to prevent the formation of carbon The effectiveness of hydrogen donor compounds as deposits. Thus, there is a need to develop fuels with high additives to reduce pyrolytic deposition in JP-8+100 at high thermal stability (capability) characteristics in order to handle the temperatures was assessed. Decalin and 1,2,3,4 expected increased heat loads. Thermal stability, as defined tetrahydroquinoline (THQ) were added to JP-8+100 at 0.5% here, is the resistance of the fuel to decompose and form (decalin only), 1.0 and 2.5% w/w concentrations and tested in a undesirable carbon deposits. These deposits will foul fuel flow reactor at a fuel exit temperature of 600 °C at 5.2 MPa. system components such as heat exchangers, valves, and Measurements of carbon deposits along the tube and gas nozzles and will be detrimental to aircraft performance. Fuel chromatography/mass spectrometry (GC/MS) analysis of the thermal decomposition (carbon deposition) occurs by two major stressed and unstressed liquid fuel were used to assess processes, thermal oxidative and pyrolytic. Thermal oxidative effectiveness of the additive, and the degree of fuel (or autoxidative) deposits occur when the fuel reacts with decomposition. Additionally, liquid-to-gas conversion was dissolved oxygen present in the fuel (-70 ppm), and begin at determined, and the composition of the gas was determined via temperatures around 150°C for conventional fuels. Pyrolytic GC. Experimental results show significant reductions in deposits occur when the fuel itself begins to thermally pyrolytic deposition in JP-8+100 with the additives relative to decompose at temperatures above 450°C. An additive package the baseline fuel. Tests with decalin showed negligible effects has been developed to significantly reduce the production of on thermal oxidative deposits, while THQ produced significant thermal oxidative deposits in JP-8 (Heneghan et al., 1996). JP- increases in thermal oxidative deposits. The effects of the 8 with the thermal stability package, known as JP-8+100, offers additives on fuel thermal decomposition and conversion rates a 55°C increase in allowable bulk maximum temperature, and are also discussed. increases heat sink capacity by 50% over conventional JP-8. The thermal stability package in JP-8+100 has been very INTRODUCTION effective in suppressing autoxidative deposits. However, for The Air Force Research Laboratory's Fuels Branch fuels operating at higher temperatures, i.e. > 450 °C, pyrolytic (AFRUPRSF), of the Propulsion Directorate has recently deposits become a significant problem. A series of compounds established a program to develop the fundamental technologies known as hydrogen donors have been investigated as which support the development of 'controlled' chemically suppressors of pyrolytic degradation of n-alkanes in static reacting fuels for application to existing and future air and reactors (Yoon et al., 1996, Song et al., 1994). These space vehicles (Maurice et al., 1999). The ultimate goal of this compounds donate hydrogen atoms to alkyl radicals formed program is to develop fuels that effectively meet fuel handling during the thermal decomposition of the parent fuel to yield and combustor needs for advanced propulsion systems. It is more stable molecules, thereby reducing further decomposition. clearly recognized that as propulsion system capabilities for Stabilization of the very reactive alkyl radicals via hydrogen manned and unmanned aircraft increase, the thermal loads abstraction inhibits radical decomposition, cyclization, imposed on combustors, airframe and other subsystems aromatization, and condensation reactions that subsequently become of major concern. Fuel is currently used as the primary form pyrolytic carbon deposits (Song et al., 1992). Several means for direct or indirect cooling of avionics and aircraft compounds were identified as effective thermal stabilizers in mechanical systems for military aircraft. The heat sink of reducing the thermal decomposition of the alkane sample in conventional liquid hydrocarbon fuels is limited to moderate static reactors. Recently, several of these additives were Presented at the International Gas Turbine & Aeroengine Congress & Exhthition IndianapoEs, Indiana — June 7-June 10, 1999 investigated in a flow reactor as thermal stabilizers to reduce hydrocarbons, and then installed in the furnace. The reactor is pyrolytic deposition in JP-8 (Corporan and Minus, 1998). Two of initially purged with nitrogen to displace the oxygen in the the additives, 1,2,3,4 tetrahydroquinoline (THQ) and decalin, system and provide an inert environment. The fuel flow is demonstrated very high potential as thermal stabilizers in initiated and the pressure is regulated with the back pressure reducing both thermal decomposition and pyrolytic deposits in control valve to the desired testing pressures. The furnace is JP-8 at high temperatures. THQ was the more effective of the turned on, and the temperature adjusted to the test exit fuel two, however, it also increased thermal oxidative deposition. By temperature. Minor adjustments are made to the back pressure contrast, only moderate increases in autoxidative deposits were valve during the run to maintain a relatively constant pressure observed with decalin. throughout the test. The liquid products are collected for Downloaded from http://asmedigitalcollection.asme.org/GT/proceedings-pdf/GT1999/78590/V002T02A008/4218087/v002t02a008-99-gt-056.pdf by guest on 27 September 2021 The present effort assesses the potential of THQ and chemical analysis two hours after the desired fuel temperature decalin to suppress the formation of pyrolytic deposits in JP-8+ is achieved, and the percent liquid-to-gas conversion, is 100 at 600°C. It also provides insight into the synergy between determined as: the thermal oxidative suppressing package, and the hydrogen donor compounds to mitigate both pyrolytic and oxidative % conversion = Vol. flow inlet - Vol. flow exit X 100 deposits. Vol. flow inlet EXPERIMENTAL Liquid samples are analyzed using a Hewlett Packard The experimental apparatus consists primarily of a fuel 5890/5971 GC/MS. The percent change in n-C10 - n-C15 reservoir, fuel pump, reactor tube, a furnace and a fuel cooler. alkanes and Cr - Cg alkyl benzenes is determined with the The fuel is pumped through the system at a relatively constant GC/MS trace of the liquid samples using the selected ion volumetric rate with a SSI high performance liquid monitoring (SIM) mode with mass ions of 57 and 91 for the chromatography (HPLC) pump. A 0.5 pm sintered filter is used alkanes and substituted benzenes respectively. Due to the to remove any small particulate in the fuel before entering the complexity of the fuel sample, the concentration change of each system. The fuel flow rate is measured with a MAX positive component is approximated semi-quantitatively based on the displacement flow meter. A needle valve, installed downstream peak areas rather than the absolute amounts (per calibration of the pump, is adjusted to dampen the pressure fluctuations curves). The peak area of each component in the stressed inherent in the reciprocating pump. The fuel passes through the sample is reduced by the fraction of liquid converted to gas to reactor, which consists of a 3.18 mm OD, 1.40 mm ID, 107 cm account for the reduction in the liquid product. The gas samples long 316 stainless steel tube. The reactor tube is enclosed in a are analyzed using a Hewlett Packard 5890 GC equipped with a Lindbergh fumace where the fuel is heated to about 600 °C exit thermal conductivity detector (TCD) for hydrogen analysis and a bulk temperature. The heated fuel is cooled and partially flame ionization detector (FID) for CI-C6 alkane and alkene condensed in a water-cooled section, and filtered through a 2.0 analysis. um sintered filter to capture the solid carbon products. The two- After test completion the reactor tube is removed from the phase fuel products are directed to the facility's vent hood and furnace, cut into 5.08 cm sections, rinsed with heptane, and fuel drain. The fuel pressure is regulated to approximately 5.2 dried for a minimum of two hours in a vacuum furnace. The MPa with a needle valve (back pressure valve) installed tube samples are subsequently analyzed for carbon deposition downstream of fuel cooler. Liquid and gaseous samples are in a LECO RC-412 Multiphase Carbon Determinator. collected at the vent hood for off-line analysis. Gas samples are collected in bags and analyzed by GC, and liquid samples Fuel Additives are analyzed by GC/MS. The densities of the unstressed and Pyrolytic alkane degradation proceeds through a free stressed liquid are determined by weighing a measured volume radical initiated and propagated mechanism (Rice, 1933). This of the sample on a laboratory scale. Temperature thermal degradation is initiated by cleavage of a carbon-carbon measurements on the tube surface are made every 17.8 cm bond then continues through the abstraction of atoms from using spot welded K-type thermocouples.
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