Fuel Processing Technology 85 (2004) 727 742 www.elsevier.

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Evaluation of soot particulate mitigation additives in a T63 engine

Edwin Corporan a,*, Matthew DeWitt b, Matthew Wagner c
Air Force Research Laboratory, AFRL/PRTG 1790 Loop Rd N, WPAFB OH 45433-7103, USA b University of Dayton Research Institute, 1790 Loop Rd N, WPAFB OH 45433-7103, USA c Air Force Research Laboratory, AFRL/PRTM 1790 Loop Rd N, WPAFB OH 45433-7103, USA
a

Abstract The performance of fuel additive candidates to mitigate soot particulate emissions in turbine engines was assessed in a T63 helicopter engine. Seventeen additives, including commercial compounds to reduce emissions in internal combustion engines, diesel cetane improvers, and experimental/proprietary additives, were evaluated. The additives were individually injected into the JP-8 fuel feed to the engine, and evaluated at a minimum of three concentration levels. The engine was operated at two conditions, idle and cruise, to investigate additive effects at different power settings or equivalence ratios. Particulate samples were collected from the engine exhaust using an oil-cooled probe, and analyzed using a suite of particulates instrumentation, which included a condensation nuclei counter (CNC), scanning mobility particle sizer (SMPS), laser particle counter (LPC) and a tapered element oscillating microbalance (TEOM). Results indicate that the diesel cetane improvers and commercial smoke abatement additives tested had minimal impact on particulate emissions in the T63 turboshaft engine. One proprietary additive was shown to reduce particle number density (PND) by up to 67% at the relatively high concentration of 3000 mg/l. These benefits were observed only at cruise condition, which may provide some insight into the mechanisms by which the additive suppresses the formation or enhances the oxidation of soot particles. Test results with blends of JP-8 and Norpar-13 (normal paraffins) show significant reductions in particulate emissions for both idle and cruise conditions demonstrating the potential environmental benefits of using blends of clean (low aromatic and low sulfur) fuels with JP-8. Comparisons of mass determination with different instruments and preliminary results of chemical characterization of particulate emissions with and without additives are also presented. D 2004 Elsevier B.V. All rights reserved.
Keywords: Additives; Particulate; Engine

* Corresponding author. Tel.: +1-937-255-2008; fax: +1-937-255-3893. E-mail address: edwin.corporan@wpafb.af.mil (E. Corporan). 0378-3820/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2003.11.016

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1. Introduction The United States consumes approximately 26 billion gallons of jet fuel per year [1]. Based on the International Civil Aviation Organization (ICAO) Emissions Index for particulate matter (PM), it is estimated that 7.0 million pounds of solid particulate are emitted each year by US aircraft. PM may either be emitted directly or formed in the atmosphere by transformations of gaseous emissions of compounds including nitrogen oxides (NOx), volatile organic compounds (VOCs), and sulfur oxides (SOx). Studies have shown that these airborne particles pose both health and environmental risks. The National Ambient Air Quality Standards (NAAQS) have a health-based regulation for particulate matter with diameters less than 10 Am (PM10). Research indicates that exposure to coarse particles (larger than 2.5 Am diameter) is associated with aggravation of asthma and increased respiratory illness [2]. Additionally, chronic health effects have been linked with long-term exposure to these coarse particles. However, there is increasing evidence that the PM10 regulation (annual arithmetic mean of 50 Ag/m3, 24-h average of 150 Ag/m3) is insufficient to eliminate serious health and environmental problems for particulate matter with diameters smaller than 2.5 Am (PM2.5). As a result, the EPA has adopted a revision of the particulate matter regulation to regulate PM2.5 particles (arithmetic annual average of 15 Ag/m3, 24-h average 65 Ag/m3) [3]. Recently, the U.S. Supreme Court upheld the constitutionality of the Clean Air Act and the EPAs decision on setting the new health-protective PM2.5 regulation. The health effects associated with PM2.5 can range from aggravation of respiratory and cardiovascular disease to premature mortality [4]. Most particulate matter from aircraft engines is PM2.5. Since these fine particles contain high amounts of carbon, they are usually referred to as soot in the combustion community. However, there is evidence that harmful polycyclic aromatic hydrocarbons (PAH) are present in these carbon-laden particles.

2. Experimental 2.1. T63 engine and fuel system A T63-A-700 turboshaft engine, used primarily in helicopter applications, was used in this additive evaluation. The engine is located in the Engine Environment Research Facility (EERF) in the Propulsion Directorate at Wright-Patterson Air Force Base, and is used to evaluate turbine engine lubricants, fuels, and sensors in an actual engine environment. A schematic of the engine as installed in the EERF is shown in Fig. 1. The compressor draws atmospheric air through the inlet, compresses it via six axial stages and one centrifugal stage, and discharges it to two tubes which carry it to the combustor inlet on the aft end of the engine. The combustion gases flow forward through the combustor to two uncoupled two-stage turbine sections. The gas producer turbine drives the compressor, and the power turbine drives the output shaft, which is connected to a hydraulic dynamometer. After the power turbine, the exhaust gases turn 90j to enter two exhaust collectors to route the gases out of the test cell. Particulate emissions were taken

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Fig. 1. Engine environment research facility setup.

via an oil-cooled sampling probe installed parallel to the flow into the exhaust duct 10 in. from the engine centerline. JP-8 fuel was supplied to the T63 from an external tank, and the fuel flow rate was measured with a flow meter (FLfuel). The additives were diluted to a predetermined concentration in JP-8 to improve their flowability, and injected via two ISCO Model 1000D syringe pumps immediately downstream of the fuel flow meter. The required additive flow was computed from the measured fuel flow rate and the desired additive concentration. The syringe pump displacement was adjusted via a computer-controlled feedback loop to provide the required additive flow rate. The fuel/additive passed through a static mixer (to ensure a homogeneous mixture) and entered the engines fuel filter, fuel pump and the engine fuel control. The fuel control (CF1), in conjunction with the governor (CF2), metered the required amount of fuel/additive to the engines pressure atomizing fuel nozzle and circulated the remaining fuel back through the fuel pump. For a given engine operating condition, the combined fuel/additive flow was held constant. The engine was operated at two conditions, designated as Ground Idle (GI) and Normal Rated Power (NRP) (also referred to as cruise condition). Nominal values for operating parameters at these conditions are listed in Table 1. GI was attained by a fixed fuel control setting and no load on the dynamometer. NRP was attained by adjusting the governor control and dynamometer load to maintain the intra-turbine temperature (T5) at 1280 jF and output shaft speed at 6000 rpm. For all tests, the total flow of fuel plus additive was computer-feedback controlled to maintain a constant T5. This approach assured the best run-to-run repeatability between tests conducted with and without the additives.

Table 1 Engine operating conditionsWP standard day (850 ft, 14.25 psia, 77 jF) Power Idle Cruise (NRP) P3 (psia) 35 80 T3 (jF) 251 498 T5 (jF) 750 1280 SHP (hp) 8 238 Fuel flow (lb/min) 0.89 2.92 Air flow (lb/min) 95 169 Overall F/A ratio 0.009 0.017 Burner F/A ratio 0.040 0.075

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2.2. Particulate measurement methodology and instrumentation Currently, there is no standard methodology or instrumentation for measuring mass and particle number density (PND) for PM2.5 emissions from gas turbine engines. The EPA has a standard method for measuring particulate emissions from stationary sources called Method 5. The method consists primarily of collecting and weighing the carbon from the engine exhaust deposited on a quartz filter. The EPA Method 5 is very labor intensive, extremely slow (about 3 h per sample) and is susceptible to significant uncertainty from filter handling. An industry standard used for engine emissions certification is the smoke number. In this method, a known volume of engine exhaust is passed through a filter, and the change in filter optical reflectance is correlated to the quantity of particulate matter collected. However, it has been found that smoke number is largely the result of a few large diameter particles, and that the contribution of fine particles to the smoke number is minimal. As such, smoke number is considered an unsuitable method for measuring PM2.5 exhaust from turbine engines. The methodology used in this effort was based on that used by the University of Missouri-Rolla (UMR). [5] Particulate emissions from the T63 engine were characterized using mainly commercially available particle counters and electrostatic classifiers. Precision errors of less than 5% (2r) in the particle number measurements were observed for both engine conditions due to the steady operation of the engine. Particulate emissions were captured and transported to the analytical instruments (described in Table 2) via an oil-cooled probe. The probe design, shown in Fig. 2, was based on an AEDC/NASA/UMR design and consisted basically of three concentric tubes with three fluid passages. The outermost passage carried the recirculating cooling oil, the middle passage provided particle free dilution air, and the center passage transported the diluted sample to the instruments. The probe was installed facing the flow in the center and near the exit of the engine to help capture a representative sample of the engine exhaust and avoid diluting or contaminating with surrounding air. The exhaust sample was diluted with dry air at the tip of the probe to prevent water condensation and particulate loss to the wall due to high wall-sample temperature gradients, and to prevent saturation of the particulate instrumentation. Due to the high particle count from this engine, dilution rates of 94 98% were used (analyzed sample consisted only 2 6% of the exhaust). The corrected particle count was calculated for various dilution rates and found to be in excellent agreement ( < 5% error). The diluted sample was drawn into the analytical instruments via a vacuum pump, and the air dilution and sample flows were controlled with high precision Brooks 5850 (0 10 SLPM) flow controllers. Dilution flows were initially set to 100% (only particle-free air through the system) and subsequently adjusted to the desired dilution ratio based on engine condition. 2.3. Description of additives The additives evaluated are listed in Table 3. These include: diesel cetane improvers, detergent/dispersants for jet fuels, commercial additives for gasoline and diesel engines, and various research additives. The additives were nominally tested at 1 , 5 and 10 the recommended concentrations. They were diluted in JP-8 (to improve additive

E. Corporan et al. / Fuel Processing Technology 85 (2004) 727742 Table 2 Particulate emissions instrumentation Instrument and model number Condensation Nuclei Counter (CNC) CPC TSI Model 3022A Measurement Particle number density (PND) (#/cm3) Description

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Scanning mobility particle sizer (SMPS) TSI model 3936 Differential mobility analyzer (DMA) TSI model 3081 Condensation Nuclei Counter CPC TSI Model 3022A Tapered element oscillating microbalance (TEOM) Rupprecht & Patashnick Series 1105 diesel particle monitor

Particle size distribution

Direct particulate mass concentration (mg/m3)

Laser particle counter (LPC) MetOne

Particulate count for particles larger than 300 nm

Real-time count of particles per cm3. Uses principle of condensing supersaturated vapor on sub-micron size particles. Particles are counted with an optical detector via individual pulses ( < 104 particles) or by photometric means. Capability up to 107 particles per cm3. Consists of an electrostatic classifier to determine particle size according to mobility through an electric field. A CNC is used to determine particle concentrations in a size bin. Particle diameter size range of 7 300 nm. Collects particles on a filter attached to an oscillating tapered element. The mass on the filter is determined based on the change in natural frequency of the tapered element. Used only when significant changes in PN observed. Number of particles determined via light scattering. Count of larger particles found to be negligible in T63.

flowability) before entering the syringe pumps and then injected into the fuel flow to the engine. Due to nondisclosure agreements between the Air Force and the additive companies, the chemical composition of proprietary and commercial additives cannot be disclosed. Nonetheless, this study evaluates the performance of these research compounds, diesel cetane improvers, and commercial additives in a turbine engine burning

Fig. 2. Particulate matter probe design.

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Table 3 Additives evaluated on the T63 combustor Additive (1) Enviro max (EMP) (2) Enviro max (EMD) biodiesel (3) Wynns emissions control + plus + (4) Kleen fuel (5) Fuel fix (6) RXP biodiesel (7) Viscon (8) Isobutyl nitrate (9) 2-Ethylhexyl nitrate (10) Norpar-13 (11) Betz Dearborn 8Q462 (12) PA-1 (13) PA-2 (14) PA-3 (15) PA-4 (16) PA-5 (17) PA-6 Concentration tested (mg/l) 780 20 000 780 3900 3000 60 000 3900 78 000 205 822 780 15 620 780 3900 200 8000 500 5000 10 30% by vol. 256 10 240 200 8000 400 10 000 200 4000 200 2000 200 10 000 200 2000 Additive type fuel catalyst for gasoline and diesel fuel catalyst for gasoline and diesel with biodiesel emissions reducer combustion enhancer high molecular weight polymer emissions reducer gasoline and diesel high molecular weight polymer cetane improver cetane improver solvent (normal paraffins) detergent/dispersant similar to thermal cracking initiator detergent (PA-5 and PA-6 blend) thermal stability (contains PA-4) detergent type detergent type detergent type Company Maxma LC Maxma LC Wynns oil company Green fuel Fuel Fix RXP Products GTA Technologies Aldrich Aldrich Exxon-Mobil Betz Dearborn Synthesized Lubrizol Lubrizol Lubrizol Lubrizol Lubrizol

JP-8. Furthermore, it provides the additive companies an assessment of their additives in a jet engine and the opportunity to reformulate their products for jet fuel.

3. Results and discussion 3.1. Commercial additives Commercial additives used in gasoline and diesel engines were evaluated. The companies supplied additives that have undergone testing in independent laboratories and have reportedly shown to be effective in reducing gaseous emissions and improving fuel economy. It has been proposed that the additives reduce emissions by improving the combustion process by chemical and/or physical means. A brief description of these commercial additives and their proposed function to reduce emissions is given below. The Fuel Fix and Viscon additives employ a very similar approach; high molecular weight polymers are used to change the fuels physical characteristics to modify the fuels atomization and vaporization behavior. The proposed function of the additive is to prevent the rapid vaporization of the fuels higher volatility components in the combustion

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chamber and, therefore, promote the vaporization and combustion of all fuel components uniformly. Both additive manufacturers have observed significant reductions in gaseous emissions (CO, HC and NOx) and fuel consumption with increased engine power with their additives in internal combustion engines. Test results in the T63 show that neither additive was effective in reducing particle number density (PND) or changing particle size distribution. However, both additives appeared to change the surface tension of JP-8 since the resultant treated fuel had an elastic-like consistency. The additives were blended at relatively high concentrations with JP-8 before entering the syringe pumps, and were noticeably more difficult to draw into the pumps. The negligible effects observed by these additives on the T63 emissions may indicate that this engine or its injection system (1960s technology) is fairly insensitive to changes in certain physical properties of the fuel. The additives will be tested in a high performance turbine engine combustor to investigate if physical changes in the fuel can impact emissions in newer engines. If benefits are observed with this class of additive, its pumping characteristics will be addressed. Several commercial additives evaluated were expected to reduce emissions by chemically changing the combustion process. Kleen Fuel is a blend of aliphatic nitro compounds, which reportedly has active components that break down to release oxygen. The oxygen released from these nitroparaffin groups is used to burn the remaining unburned hydrocarbon components in the combustion chamber to improve engine performance and reduce emissions. RxP is a hydrocarbon blend that reportedly contains a molecule that absorbs a large portion of the infrared radiation emitted during the combustion process. The unburned fuel is preheated (producing higher combustion temperatures) and the heat loss to the combustor chamber wall is reduced to produce more efficient engine operation and lower emissions. Enviro Max is a combination of a heterogeneous catalyst and a combustion promoter. The homogenous catalyst consists of micron-sized particles of solid zinc oxide/peroxide suspended in selected solvents, which are blended with the proprietary combustion promoter and tert-butyl hydroperoxide (TBH). Two formulations of the Enviro Max additives were tested in this study, the EMP and EMD biodiesel. It should be noted that in the pre-mixed EMP/JP-8 blend a significant amount of the additive separated from the fuel and settled in the bottom of the fuel reservoir. This characteristic most likely prevented a homogenous fuel/additive mixture, and obviously makes the present formulation of EMP an undesirable additive for jet fuel. Wynns Emissions Control + Plus + additive is also reported to be an emissions reduction additive; however, specific details about its functionality were not defined. Tests results show that these commercial additives were all relatively ineffective in reducing PND or altering particle size distributions in the T63. Only the Kleen additive had a measurable effect by reducing PND by 19% at the cruise condition; however, it was added at a relatively high concentration of 7.8% by volume. Additionally, preliminary test results in an atmospheric combustor showed that Kleen (at f 1.5% by volume in JP-8) produced measurable reductions in PND with the combustor operating at fuel rich conditions (phi = 1.1). Differences in combustor pressure, fuel nozzle characteristics, and equivalence ratios may explain the differences in additive effectiveness between the two combustors. During the preparation of this paper, additional experiments with the Kleen additive were being conducted to help explain its superior performance in the atmospheric combustor compared to the T63.

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Further testing of these commercial additives on other engines is necessary to generalize their performance on all turbine engines. There are many reasons why an additive that is effective in reducing emissions on an IC engine may be ineffective in a jetfueled turbine engine. In general, turbine engines operate at higher combustion efficiencies than their IC counterparts, and jet fuels have lower aromatics (proposed soot precursors) than both diesel and gasoline fuels. Furthermore, diesels (which produce considerably higher particulate exhaust than gasoline engines) operate at higher pressures and temperatures than jet engines, and the fuel distribution within its cylinders is nonuniform, which increases the fuel-rich zones and promotes the formation of soot particulate. The nonsteady operation of the reciprocating engines is also likely to adversely impact emissions. Overall, jet-fueled turbine engines burn cleaner than IC engines, and therefore, the challenge of reducing harmful PM2.5 emissions from aircraft turbine engines is significantly greater. 3.2. Research additives Additives used to increase fuel thermal stability (ability of fuel to resist carbon formation upon heating) were also investigated for their ability to reduce particulate emissions. The Betz Dearborn 8Q462 ( + 100 additive) is a commercially available additive package with a detergent/dispersant added at only 256 mg/l (about one quart per 1000 gal of fuel) to increase the thermal stability of JP-8 by 100 jF (JP-8 + 100) [6]. JP-8 + 100 is currently used in over 3000 Air Force aircraft (mostly fighters and trainers). Experience has demonstrated that JP-8 + 100 significantly reduces unscheduled maintenance, maintains engine components cleaner, and drastically reduces soot buildup on hot engine components [7 9]. The reduced soot buildup on engine turbine blades prompted an investigation into the potential of + 100 to reduce soot particulate emissions. Unpublished, limited field data on a fighter aircraft engine showed significant reductions in PND emission index using JP-8 + 100 compared to operation with JP-8. Additionally, in recent tests at the United Technologies Research Center (UTRC), significant reductions in particle size, PND and smoke number were observed in an F119 single-nozzle combustor operated with JP-8 + 100 [10]. The PA-2 to PA-6 research additives were similar to the Betz + 100 as they contained detergent-type active ingredients. PA-2 is composed of detergents PA-5 and PA-6 diluted in a hydrocarbon carrier. PA-1 is an oxygen-containing additive with similar chemical structure as a proprietary compound used to accelerate fuel thermal cracking at high temperatures. The original compound could not be evaluated because it is no longer produced. Results show that the + 100, PA-1 and PA-6 additives had negligible effects on particulate emissions. The PA-3 and PA-4 additives actually increased PND by 10% to 25% at concentrations of 200 4000 mg/l with the largest increases occurring at cruise condition at the highest additive levels. Although the + 100 additive was tested at up to 40 times the recommended dose, minimal effects on particulate emissions were observed. Differences in injector design, combustor pressure and geometry, and JP-8 fuel batches between the T63 and the UTRC F119 single nozzle tests are believed to contribute to the significantly different results obtained in the two tests. Further studies on the effects of

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+ 100 on the emissions of various aircraft and engines are underway under several Air Force programs [11]. It is believed that detergent-type additives may have long-term beneficial effects on emissions as fuel nozzles become cleaner and fuel atomization is improved. However, two detergent-type additives were shown to have an immediate positive effect on particulate emissions. The PA-2 additive reduced PND by up to 45%; however, undesirably high concentrations of 10,000 mg/l (f 1.0% by volume) were required. In addition, the improvement was only observed at the cruise condition. Based on the reductions observed with PA-2, its two active ingredients (PA-5 and PA-6) were evaluated. As mentioned above, PA-6 had negligible effects on particulate emissions; however, significant reductions in PND were observed with PA-5. Fig. 3 displays the immediate reduction in PND as the PA-5 additive was added to the fuel, and the return to baseline PND upon removal of the additive. A maximum PND reduction of 67% at 3000 mg/l (f 0.30% volume) was observed. As shown, the effectiveness of PA-5 decreased as the additive concentration was increased (e.g., 63% reduction at 2000 mg/l and 67% reduction at 3000 mg/l). Consistent with PA-2 these improvements were observed only at cruise conditions. Assuming a chemical interaction, we infer that the additive has a high activation energy, thus requiring higher flame temperatures to break down and produce radicals or other species that react to reduce the formation of soot and soot precursors. Further studies are needed to verify this hypothesis. In addition, studies on potential physical effects of additives on fuel atomization will be pursued. The particle size distribution for the T63 using PA-5 is shown in Fig. 4. PA-5 was observed to increase the concentration of particles in the 7 10 nm diameter range. These smaller particles are believed to be products formed via breakdown of the additive or smaller soot particles from reduced soot surface growth and coagulation. Future detailed studies will be conducted on PA-5 and similar chemistry additives in the T63 and in a high

Fig. 3. Effects of PA-5 additive at various concentrations on particle number density (PND) in the T63 engine.

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Fig. 4. Effects of PA-5 additive at various concentrations on particle size distribution of T63 engine exhaust at cruise condition.

performance single-nozzle combustor equipped with advanced laser diagnostics instrumentation. These studies will help elucidate mechanisms by which the additive reduces PND and alters particle size distribution. In addition, soot samples will be chemically characterized to ensure that the additive is not producing additional/other harmful pollutants. Norpar-13, an Exxon solvent consisting mostly of normal paraffins averaging a carbon number of 13, was blended (10 30% by vol.) in JP-8 and evaluated in the T63. The objective was to reduce the aromatic concentrations (also increase the hydrogen-to-carbon ratio) in JP-8 to investigate their effect on particulate emissions. Also, the blend of Norpar13 in jet fuel is expected to have similar emissions benefits as blends of synthetic (coal or natural gas) and petroleum derived jet fuels. As shown in Fig. 5 Norpar-13 dramatically reduced PND at both idle and cruise engine conditions. At idle, reductions of up to 52% were observed at Norpar-13 concentrations of 30% by volume. These results are consistent with previous studies that have found aromatics to be strong contributors to soot formation in hydrocarbon-fueled combustion systems. [12] Previous research has shown that at the range of temperatures found in the T63 combustor (f 2000 2800 jF), hydrocarbon aromatics produce soot via a fast route that involves condensation of the aromatic rings into soot nuclei [13]. The proposed mechanism begins with the transformation of the initial aromatic hydrocarbon into macromolecules via gas-phase reactions. The partial pressure of these macromolecules grows to supersaturation levels causing their condensation into liquid microdroplets, which eventually become soot nuclei. Subsequently formed gaseous macromolecules then contribute to nuclei growth. The addition of Norpar13 reduced the relative aromatic-to-aliphatic ratio, thus reducing particle nucleation. As shown in Fig. 5, the benefits of Norpar-13 were more pronounced at idle than at cruise. The increased F/A ratio, and thus higher combustor temperatures and pressures, at the cruise condition, increased the reaction rates of soot production, which appear to slightly

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Fig. 5. Reduction in particle number density in the T63 engine as a function of percent of Norpar-13 in JP-8.

offset the benefits of reducing the overall aromatic concentration in the fuel. The size distribution curves in Fig. 6 show that Norpar-13 has only minor effects on the particle size distribution (peak particle diameter about 18 nm with or without Norpar-13). Apparently, reducing the aromatics in JP-8 mainly reduces soot particle nucleation, and has less of an

Fig. 6. Size distribution of particle emissions from T63 engine at idle for various JP-8/Norpar-13 blends.

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impact on the surface growth and coagulation stages, which are the processes that affect particle size. 3.3. Cetane number improvers Alkyl nitrates have been found to be effective cetane number improving additives. Increased cetane number diesel fuels have a lower ignition delay time, which result in improved engine performance and reduced emissions. Based on the dramatic improvements in diesel engine emissions with the ignition promoters, two cetane improvers were evaluated. The most widely used cetane-improving additive is 2-ethylhexyl nitrate (2EHN). The additive is thermally unstable and decomposes at high temperatures to release radicals that accelerate oxidation, and thus, promote combustion. Isobutyl nitrate was also evaluated to assess effects of nitrates with different alkyl groups. Results show that the nitrate compounds were ineffective in reducing PND or affecting particle size in the T63. These results are consistent with previous research on a J79 combustor fueled with JP-5, which showed alkyl nitrates to be ineffective in reducing particulate emissions. [14] Furthermore, results in shock tube experiments have shown the ineffectiveness of 2-EHN in reducing ignition delay time of JP-8 even when added at 50% by volume [15]. Development of additives that reduce the ignition delay time of jet fuels are of interest since they may have similar beneficial effects on emissions as cetane improvers have on diesels. 3.4. Calculation of particulate matter (PM) mass emissions and identification of polycyclic aromatic hydrocarbon (PAH) chemical composition In addition to measuring the PND and size distribution, it is important to consider the mass concentration and chemical composition of PM when characterizing the emissions from a combustion source. Since the total mass of PM emissions has both regulatory and health implications and the value is not easily inferred from the particle size data, direct measurement of the total mass is necessary. In addition, it is possible that alterations to the PND and size distribution may not directly correlate to changes in the total PM mass. Identification of the chemical composition of the PM is desirable since certain PAH species have been recognized as carcinogens. Therefore, it would be beneficial to determine how a chemical additive alters the total concentration of these species. Furthermore, quantitative information about the PAH composition may provide valuable insight into the mechanism of soot formation as these species have been identified as important precursors. There are three methods for the measurement of PM mass emissions that can be employed in our laboratory: (1) collection of PM via flow-through filtration with subsequent off-line quantification, (2) on-line measurement using a tapered element oscillating microbalance (TEOM), and (3) calculation using particle size distribution data. During collection via a sample filtration, a quantified volume of undiluted combustor exhaust is sampled with a Roseco engine smoke emissions sampler, and PM is collected using Whatman QMA-type quartz filters. Quantification of the sample mass is conducted by off-line analysis with a LECO Multiphase Carbon Analyzer (assumes PM is primarily

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comprised of carbon). The exhaust PM mass concentration is determined by normalizing this weight to the total volume of sample gas passed through the filter. Overall, this sampling approach has a high trapping efficiency for compounds of moderate to low volatility, and provides a PM sample that can be subsequently analyzed to determine its elemental and molecular composition. The major drawback of this method is that samples must be collected under a steady-state condition; therefore, data cannot be collected during the addition/removal of an additive to the engine fuel flow. On-line measurement of PM mass emissions is possible using the TEOM. The major advantage to this approach is that PM mass emissions are measured real-time during steady or transient operation of the combustor. Therefore, dynamic changes in the mass emissions due to an additive can be observed (similar to that observed with the PND data shown in Fig. 3). A possible complication with this instrument is that the measurement can be significantly affected by adsorption/desorption of water and volatile organics on the filter element. The third approach is to estimate PM mass using the particle size distribution data; however, assumptions for the particle geometry and density must be made. Typically, soot particles are assumed to have a spherical geometry and a density of approximately 1.8 g/ cm3 [10]. This density value is estimated as a compromise of the value for a representative PAH (e.g., 1.27 g/cm3 for pyrene) and graphitic carbon (f 2.2 g/cm3), which are believed to encompass the range of organic species within the PM. Obviously, the mass estimation is significantly affected by the accuracy of the size distribution data and validity of the assumptions for particle geometry and density. Due to the inherent complexity associated with the measurement of the PM mass emissions, these were not routinely made during initial additive evaluation on the T63. Rather, the measurements were made for additives that were identified to significantly alter PND or particle size distribution. Due to time constraints, only a small number of mass measurements were made during this study, and the results in this section will be limited in scope. As discussed previously, the addition of both PA-5 and Norpar-13 to the baseline JP-8 fuel rendered significant reductions in the measured PND. Therefore, mass emissions were measured during testing with these additives. For testing conducted at the cruise condition with PA-5, reductions in mass emissions measured with the TEOM and calculated using the particle size distribution data are compared to the reduction in the PND in Table 4. As shown in Table 4, the reductions in the measured and calculated mass emissions were significantly lower than those observed for the PND. This indicates that the total
Table 4 Comparison of reduction in mass concentration and PND emissions for testing with various concentrations of PA-5 at cruise Concentration of PA-5 (mg/l) 1000 2000 3000 % Reduction in particle number density 51 63 67 % Reduction in mass concentration using TEOM 21 25 25 % Reduction in mass concentration using size distribution 35 47 51

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mass and particle size emissions are most likely not linearly related, which reiterates the necessity of these mass measurements. It can be observed that the mass emissions were further reduced with increases in PA-5 concentration for the calculated value, while it was independent of concentration for the TEOM measurement. In addition to the differences in the mass reduction values, a discrepancy in the absolute value of the mass concentrations for the various methods used was observed. At the baseline (no additive) cruise condition, the size distribution data rendered a calculated value of approximately 28.3 mg/m3 while the TEOM measured approximately 7.6 mg/m3. When measured using the filtration method and LECO analysis, the mass concentration for this condition was approximately 16.8 mg/m3. The filtration method was also used to measure mass concentrations of PM for testing with various blend percentages of Norpar-13. For testing with 25% Norpar-13 at the idle condition, the PND was reduced by approximately 45% relative to the neat conditions while the reduction in mass via the calculated and filtration methods were approximately 64% and 69%, respectively. Under these conditions, it appeared that blending with Norpar13 was more effective at reducing the total mass of PM emissions than the PND emissions. This is an important observation because it demonstrates that alterations to the mass and PND emissions may not follow the same trends for different additives (i.e., mass always decreases at faster rate than PND). Discrepancies in the absolute mass concentration measurementscalculated value of 2.8 mg/m3 and filtered value of 5.4 mg/m3 for untreated JP-8 at the idle conditionwere also observed. Efforts are underway to explain and minimize these differences in the future. Despite the discrepancies in the absolute value of the mass concentrations, it is reasonable to infer the effect of an additive on the PM mass emissions if the techniques are self-consistent when normalized. There are several possible causes for the discrepancies in the absolute mass values between the various methods. With respect to the value calculated using the size distribution data, the major sources of error are most likely associated with the assumptions of the particle geometry and density. Varying either of these could lead to an increase or reduction in the total mass value and provide for better agreement with the other methods. The assumption that all particles have the same density is also a likely source of error. There may be significant differences in the physical characteristics of the PM depending upon the combustor operating conditions. Variations in the physical properties of the PM may explain the observation that the calculated mass at the cruise condition was higher than the other methods but the opposite was observed at the idle combustor condition. For the TEOM measurements, the major source of variability is most likely adsorption/desorption of moisture (which is high in concentration in the exhaust) and volatile organics on the filter element. This is also a concern for testing with the filtration measurements using the Roseco engine smoke emissions sampler. However, there is the added complication that the quantification for this method is performed off-line (must be transferred for analysis) with the assumption that the PM is primarily carbon; both can increase variability in the data. In addition, the filters were not preconditioned prior to use or analysis. Therefore, the quantity of volatile organics on the filter during analysis could vary depending on the history of the sample. Despite the difficulties with the filtration approach, it is believed to be the most accurate since assumptions regarding the physical characteristics of the particles are not made (e.g., calculation method) and it is

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less affected by sampling artifacts (e.g., moisture adsorption on TEOM filter element) during measurement. Information about the PM chemical composition can be obtained using an analytical method with the samples collected using the filtration method. The procedure involves the thermal desorption of the volatile PM fraction with subsequent identification and quantification using a Gas Chromatograph-Mass Spectrometer. This technique permits for the identification and quantification of a wide range (typically 16 separate species) of PAHs [16]. This method has been used to analyze the PM from a limited number of test conditions, and data analysis is in-progress. As a representative example of the data that can be obtained, the total PAH concentration was reduced from approximately 1.74 10 1 mg/m3 for the neat condition to 6.8 10 2 mg/m3 (61% reduction) for testing with 25% Norpar-13 at idle. Major reductions were observed for a number of individual PAHs, which included fluoranthene (62%) and pyrene (65%). Overall, this analytical approach provides the opportunity for a broader understanding of the effects of the chemical additives on PM emissions. It is anticipated that chemical characterization will be routinely employed during the subsequent evaluation of additives that are found to be effective at reducing PND emissions.

4. Conclusions The first series of tests under a current Air Force program to develop and/or demonstrate fuel additives that reduce particulate emissions from turbine engines was completed. The performance of 17 additive candidates was assessed in a T63 helicopter engine. It was found that diesel cetane improvers and commercially available additives designed to reduce emissions in internal combustion engines were relatively ineffective in reducing particulate emissions from the T63. Tests with blends of JP-8 and Norpar-13 demonstrated the potential environmental benefits of blending JP-8 and a clean (low aromatic and low sulfur) fuel as it reduced PND by 52% when blended at 30% by volume in jet fuel. In addition, preliminary analysis of collected soot particles shows that Norpar13 significantly reduced the concentration of PAHs in the samples. The thermal stability Betz + 100 additive was shown to be ineffective in the T63 even at concentrations up to 40 times the recommended value. One of the proprietary detergent-type additives, PA-5, was the most effective as it reduced PND by 67% at 3000 mg/l (f 0.30% volume). Although detergent-type additives are believed to have positive long-term effects on emissions, it was demonstrated that these could produce immediate reductions in particulate emissions depending on additive chemistry. Additive companies have been informed on the performance of their additives, and several have provided additional formulations for evaluation. Future studies will evaluate these as well as model compounds. Studies will include testing in the T63 engine and in atmospheric and high-pressure combustors. The combustors will have optical access to employ laser-based techniques to investigate the effects of additives on soot formation, flame temperatures and OH radical production. These techniques will aid in understanding the mechanisms by which additives impact soot particulate formation and destruction in advanced and legacy turbine engine combustors.

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Acknowledgements The authors gratefully acknowledge Dr. Mel Roquemore for his technical advice, Mr. Gerald Ewing of AdTech Systems Research for his technical support in operating the T63 engine, and Mr. Joel Everhart for his assistance in reducing test data.

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