Selection and performance comparison of jet fuel surrogates for autothermal reforming

Three fuel mixtures were investigated as possible surrogates for low-sulfur JP-8. The selected fuel mixtures were chosen based on a desire to match hydrocarbon chemical composition classes found in real jet fuels. The surrogate fuels selected consisted of single, binary and tertiary-component mixtures of n-dodecane, decalin and toluene in liquid volume ratios of 10:0:0, 9:1:0 and 7:1:2. The hydrocarbon components selected represented the largest chemical classes within JP-8 of normal paraffin, cyclo-paraffin and aromatic. The surrogate fuels and individual surrogate fuel components were reacted in an atmospheric pressure autothermal reformer with noble metal catalysts under conditions of steam-to-carbon ratio of 2.0, fuel equivalency energy flow of 3.3 kW thermal, space velocities of 21,000-28,000 h⁻¹ and variable oxygen-to-carbon ratios of 0.8-1.2. For all fuels investigated fuel conversion of greater than 96% could be achieved. The single component n-dodecane proved to be the least reactive resulting in lower hydrogen yields, lower reforming efficiency and increased olefin products in the reformate. The binary mixture of n-dodecane and decalin resulted in a closer match with JP-8, but did not correlate well in terms of fuel conversion and hydrogen yield. Aliphatic mixtures also exhibited greater olefin production. The three-component mixture of n-dodecane/decalin/toluene provided the best correlation to JP-8 and appears to be a good three-component surrogate fuel, particularly over the operating range of oxygen to carbon ratio of 0.95-1.10.     

Laminar flame speeds and extinction limits of conventional and alternative jet fuels

Experimental results of laminar flame speeds and extinction stretch rates for the conventional (Jet-A) and alternative (S-8) jet fuels are acquired and compared to the results from our earlier studies for neat hydrocarbon surrogate components, including n-decane and n-dodecane. Specifically, atmospheric pressure laminar flame speeds are measured using a counterflow twin-flame configuration for Jet-A/O₂/N₂ and S-8/O₂/N₂ mixtures at preheat temperatures of 400, 450, and 470 K and equivalence ratios ranging from 0.7 to 1.4. The flow field is recorded using digital particle image velocimetry. Linear extrapolation is then applied to determine the unstretched laminar flame speed. Experimental data for the extinction stretch rates of the nitrogen diluted jet fuel/oxidizer mixtures as a function of equivalence ratio are also obtained. In addition, the experimental data of Jet-A are compared to the computed values using a chemical kinetic mechanism for a kerosene surrogate reported in literature. A sensitivity analysis is further performed to identify the key reactions affecting the laminar flame speed and extinction stretch rate for this kerosene surrogate.     

Determination of sulfur contaminants in military jet fuels

Military jet fuel samples have been characterized by gas chromatography with a sulfur chemiluminescence detector and a mass spectrometer (GC-SCD-MS). Sixteen distinct organosulfur compounds were quantified in the jet fuel samples. The structures and the concentrations for seven of them are determined in this study. Although the total sulfur content of jet fuel varies from sample to sample, the individual organosulfur distribution remains unchanged for six jet fuel samples obtained over a 4-year period. The two major sulfur compounds are determined to be 2,3-dimethylbenzothiophene and 2,3,7-trimethylbenzothiophene. These two major compounds are determined to be good representative compounds in jet fuel surrogates for computational studies of jet fuel catalysis such as JP-8 reformation.     

Characteristics of jet fuels produced from hydrogenated shale oils

Shale oils from the United States (Geokinetics, Occidental, Paraho and Tosco II) were hydrotreated, fractionated into jet fuel cuts (boiling range 121–300°C), then characterized to evaluate their suitability as jet fuels. Nitrogen content was considerably higher, though the amount of hydrogen was relatively lower, than in typical petroleum jet fuels. Sulfur content was significantly below the acceptable limit. Trace metal contents in shale oil jet fuels were below the maximum levels for those in petroleum jet fuels. Vanadium, copper, lead and alkali metals were not present. Physical properties, except freezing points, were comparable to those of standard jet fuels.     

The distribution of sulfur compounds in hydrotreated jet fuels: Implications for obtaining low-sulfur petroleum fractions

The mechanism by which jet fuels are hydrotreated to reduce sulfur levels has some important implications in terms of the species and distribution of sulfur compounds remaining in the fuel. The species of sulfur that are most difficult to remove by hydrotreating, such as benzothiophenes and methyl- and dimethyl-benzothiophenes, are concentrated in the higher-boiling fraction of the fuel. Consequently, the lower-boiling fractions of the fuel contain much less sulfur. It may be possible, therefore, to obtain petroleum fractions that contain low levels of sulfur simply by distillation of the jet fuel into low-boiling and high-boiling fractions. A multi-element simulated distillation procedure according to ASTM D-2887, standard test method for boiling range distribution of petroleum fractions by gas chromatography, was coupled with atomic emission detection (GC-AED) and was used to estimate the sulfur concentration in various fractions of jet fuel, namely 20, 50, and 60%. The estimations of sulfur concentration were verified by comparing them to analyzed sulfur concentrations in several fractions of physical distillations of the jet fuels according to a modified ASTM D-86, standard test method for distillation of petroleum products at atmospheric pressure. Sulfur analyses showed that for all fuels analyzed, the initial 20% boiling fraction of the fuel contained no more than approximately 5% of the total sulfur concentration. The initial 50% boiling fraction of the fuel contained no more than 25% of the total sulfur concentration, and in most cases contained significantly less (8-16%). The total concentration of sulfur in the jet fuels tested ranged from 260 to 1380 μg/g, and there did not appear to be a direct relationship between total sulfur concentration and percentage of sulfur in each jet fuel boiling fraction.     

Development of a detailed kinetic model for gasoline surrogate fuels

A detailed chemical kinetic model to describe the autoignition of gasoline surrogate fuels is presented consisting of the fuels iso-octane, n-heptane, toluene, diisobutylene and ethanol. Model predictions have been compared with shock tube ignition delay time data for surrogates of gasoline over practical ranges of temperature and pressure, and the model has been found to be sensitive to both changes in temperature and pressure. Moreover, the model can qualitatively predict the observed synergistic and antagonistic non-linear blending behaviour in motor octane number (MON) for different combinations of primary reference fuels (PRFs) and non-PRFs by correlating calculated autoignition delay times from peak pressures and temperatures in the MON test to experimental MON values. The reasons for the blending behaviour are interpreted in terms autoignition chemistry.     

An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel

This review discusses the problems of sulfur reduction in highway and non-road fuels and presents an overview of new approaches and emerging technologies for ultra-deep desulfurization of refinery streams for ultra-clean (ultra-low-sulfur) gasoline, diesel fuels and jet fuels. The issues of gasoline and diesel deep desulfurization are becoming more serious because the crude oils refined in the US are getting higher in sulfur contents and heavier in density, while the regulated sulfur limits are becoming lower and lower. Current gasoline desulfurization problem is dominated by the issues of sulfur removal from FCC naphtha, which contributes about 35% of gasoline pool but over 90% of sulfur in gasoline. Deep reduction of gasoline sulfur (from 330 to 30 ppm) must be made without decreasing octane number or losing gasoline yield. The problem is complicated by the high olefins contents of FCC naphtha which contributes to octane number enhancement but can be saturated under HDS conditions. Deep reduction of diesel sulfur (from 500 to <15 ppm sulfur) is dictated largely by 4,6-dimethyldibenzothiophene, which represents the least reactive sulfur compounds that have substitutions on both 4- and 6-positions. The deep HDS problem of diesel streams is exacerbated by the inhibiting effects of co-existing polyaromatics and nitrogen compounds in the feed as well as H₂S in the product. The approaches to deep desulfurization include catalysts and process developments for hydrodesulfurization (HDS), and adsorbents or reagents and methods for non-HDS-type processing schemes. The needs for dearomatization of diesel and jet fuels are also discussed along with some approaches. Overall, new and more effective approaches and continuing catalysis and processing research are needed for producing affordable ultra-clean (ultra-low-sulfur and low-aromatics) transportation fuels and non-road fuels, because meeting the new government sulfur regulations in 2006–2010 (15 ppm sulfur in highway diesel fuels by 2006 and non-road diesel fuels by 2010; 30 ppm sulfur in gasoline by 2006) is only a milestone. Desulfurization research should also take into consideration of the fuel-cell fuel processing needs, which will have a more stringent requirement on desulfurization (e.g., <1 ppm sulfur) than IC engines. The society at large is stepping on the road to zero sulfur fuel, so researchers should begin with the end in mind and try to develop long-term solutions.     

Artificial neural network approaches on composition-property relationships of jet fuels based on GC-MS

The relationships of composition-properties of 80 jet fuels concerning chemical compositions and several specification properties including density, flashpoint, freezing point, aniline point and net heat of combustion were studied. The chemical compositions of the jet fuels were determined by GC-MS, and grouped into eight classes of hydrocarbon compounds, including n-paraffins, isoparaffins, monocyclopraffins, dicyclopraffins, alkylbenzens, naphthalenes, tetralins, hydroaromatics. Several quantitative composition-property relationships were developed with three artificial neural network (ANN) approaches, including single-layer feedforward neural network (SLFNN), multiple layer feedforward neural network (MLFNN) and general regressed neural network (GRNN). It was found that SLFNNs are adequate to predict density, freezing point and net heat of combustion, while MLFNNs produce better results as far as the flash point and aniline point prediction are concerned. Comparisons with the multiple linear regression (MLR) correlations reported and the standard ASTM methods showed that ANN approaches of composition-property relationships are significant improvement on MLR correlations, and are comparable to the standard ASTM methods.     

Experimental investigation of a pilot-scale jet bubbling reactor for wet flue gas desulphurisation

In the present work, an experimental parameter study was conducted in a pilot-scale jet bubbling reactor for wet flue gas desulphurisation (FGD). The pilot plant is downscaled from a limestone-based, gypsum producing full-scale wet FGD plant. Important process parameters, such as slurry pH, inlet flue gas concentration of SO₂, reactor temperature, and slurry concentration of Cl⁻ have been varied. The degree of desulphurisation, residual limestone content of the gypsum, liquid phase concentrations, and solids content of the slurry were measured during the experimental series.The SO₂ removal efficiency increased from 66.1% to 71.5% when the reactor slurry pH was changed from 3.5 to 5.5. Addition of Cl⁻ (in the form of CaCl₂·2H₂O) to the slurry increased the degree of desulphurisation to above 99%, due to the onset of extensive foaming, which substantially increased the gas-liquid contact area. An increase in the inlet flue gas SO₂ concentration from 502 to led to a decrease in the SO₂ removal efficiency from 80.1% to 69.4%. A temperature increase from 296 to caused a reduction in the degree of desulphurisation from 69.4% to 68.1%, but this result is almost within the experimental uncertainty. The residual limestone level in the gypsum formed increased with increasing values of reactor slurry pH, inlet flue gas SO₂ concentration, and slurry concentration of Cl⁻.     

Property-composition relationships for diesel and kerosene fuels

A range of 18 diesel fuels and 21 kerosene fuels from mainly Australian petroleum and synthetic fuel sources, including coal, shale and peat, was investigated. Compositional details were defined as the weight per cent abundances of n-alkanes, branched plus cyclic saturates, single-ring aromatics, doublering aromatics and polynuclear aromatics, using both h.p.l.c. and ¹³C n.m.r. techniques. Relationships between fuel composition and a range of fuel properties were sought. Simple linear relationships between property values and compositional data were used. Explicit correlative expressions were derived using multiple linear regression analysis, with the coefficient of multiple determination, R², indicating the quality of the fit between observed and calculated property values. In most cases good correlations were achieved. For diesels the properties investigated, with R² values in parentheses, were: inverse specific gravity (0.99); ¹³C n.m.r. aromaticity (0.99); ¹H n.m.r. aromaticity (0.88); cetane index (0.97); aniline point (0.96); diesel index (0.98); and FIA-measured aromatics content (0.77). For kerosenes the properties, with R² values in parentheses, were: ¹³C n.m.r. aromaticity (0.98); ¹H n.m.r. aromaticity (0.97); smoke point (0.88); and FIA-measured aromatics content (0.94). The results are shown to be of value in assessing the potential and limitations of hydrotreating as a process for upgrading synfuels.     

Deposition characteristics of diesel and bio-diesel fuels

The aim of this study is to investigate the deposition characteristics of different types of fuels by using the hot surface deposition test (HSDT) as a substitute procedure for real engine deposit tests. Deposit development, deposit compositions and deposit surface temperature fluctuation for diesel fuels and bio-diesel fuels (palm oil based and coconut oil based) are discussed. Deposit development depended on hot surface temperature, overlapping conditions, fuels, deposit properties, initial stage of deposition and competition phenomena during deposit formation. Results show DFP having 1% B100C in composition, showed a greater deposit development rate compared to DF, which resulted in a relatively large amount of deposits for DFP. However, for bio-diesel fuels, B100C obtained a slower deposit development rate compared to B100 although the test conditions were changed. Due to the lower value of MEP and shorter droplet lifetime before MEP, utilization of B100C had a greater potential in reducing deposit formation compared to B100.     

Modeling of wet jet in fluidized bed

A wet jet zone is established in many applications wherever feeding and dispersing a liquid, solution or slurry into fluidized bed by gases is needed. In the present study, a simple mathematical model has been developed to simulate the wet jet in fluidized bed. The different stages involved inside the jet zone have been estimated and analyzed.The evaporation stage of traveling droplets through the jet flare has been treated. The rates of evaporation of each size at all positions along the jet flare have been estimated according to the velocities and surrounding conditions. The final droplet sizes have been determined. Moreover, the total evaporation rate from traveling droplets, before collision either with entrained sand particles or flare boundaries, has been estimated. The traveling droplets, partially evaporated, may collide and settle on entrained sand particles. The model predicts the settlement rates of liquid droplets on entrained sand particles. The total part evaporated from settled liquid has been estimated as well.The study has been applied to the pneumatic feeding of liquid fuel into fluidized bed combustors operating at . The model has been utilized to predict the ratio of fuel vapor that releases inside the jet flare. The remaining part is assumed to evaporate inside the emulsion phase. Three different liquid fuels have been considered: a heavy oil, diesel fuel and gasoline. The main independent variables are those related to the injection conditions including the initial velocity of dispersing air, u₀, and air-to-liquid mass ratio, ALR.The model results demonstrate that only very small droplets completely evaporate inside the flare. The liquid settling over the entrained sand particles plays an essential role in the fuel evaporation inside the flare. The phenomenon is dominant at conditions that result in generation of droplets of larger sizes, i.e., heavier fuel, lower u₀, and greater ALR. The ratio of vapor fuel released in jet flare increases with lighter fuel, higher u₀ and lower ALR. At and ALR=1.0 nearly all-liquid fuel evaporates inside the flare.     

Storage stability of jet fuels

Storage stabilities of jet fuels derived from petroleum were determined using laser light scattering, sediment formation and oxygen uptake measurements. Fuel degradation was monitored in the presence of the following added specific compounds: 2,5-dimethylpyrrole (DMP), N-methyl pyrrole (NMP), thiophenol, thiophene, decanethanol, dibutyl sulphide, dibutyl disulphide, tetrahydrothiophene, hexadiene, 1-hexene, indene, iron(II), and copper(II)-phthalocyanines (FePc, CuPc) and mixtures of some of these at various temperatures. The light scattering results are correlated with extent of deposit formation, which is an accepted measure of stability, and with oxygen uptake results. Light scattering intensity, weight of deposit and oxygen uptake increase with increase in storage time, concentration of added specific compound and stress temperature. Temperature variations of these measurements give activation energies of the degradation reactions. The first direct evidence has been obtained of the pyrrole radicals in DMP and NMP when a fuel is degraded in the presence of pyrrole. These two pyrrole radicals give different electron paramagnetic resonance parameters: g and linewidth values. The degradation products obtained in the presence of FePc and CuPc show properties which indicate that CuPc interacts with petroleum JP-5 with added DMP more strongly than does FePc.     

A comparative experimental study of the autoignition characteristics of alternative and conventional jet fuel/oxidizer mixtures

Autoignition characteristics of an alternative (non-petroleum) and two conventional jet fuels are investigated and compared using a heated rapid compression machine. The alternative jet fuel studied is known as “S-8”, which is a hydrocarbon mixture rich in C₇-C₁₈ linear and branched alkanes and is produced by Syntroleum via the Fischer-Tropsch process using synthesis gas derived from natural gas. Specifically, ignition delay times for S-8/oxidizer mixtures are measured at compressed charge pressures corresponding to 7, 15, and 30 bar, in the low-to-intermediate temperature region ranging from 615 to 933 K, and for equivalence ratios varying from 0.43 to 2.29. For the conditions investigated for S-8, two-stage ignition response is observed. The negative temperature coefficient (NTC) behavior of the ignition delay time, typical of higher order hydrocarbons, is also noted. Further, the dependences of both the first-stage and the overall ignition delays on parameters such as pressure, temperature, and mixture composition are reported. A comparison between the autoignition responses obtained using S-8 and two petroleum-derived jet fuels, Jet-A and JP-8, is also conducted to establish an understanding of the relative reactivity of the three jet fuels. It is found that under the same operating conditions, while the three jet fuels share the common features of two-stage ignition characteristics and a NTC trend for ignition delays over a similar temperature range, S-8 has the shortest overall ignition delay times, followed by Jet-A and JP-8. The difference in ignition propensity signifies the effect of fuel composition and structure on autoignition characteristics.     

Ethanolamines used for degumming of rapeseed and sunflower oils as diesel fuels

Pure vegetable oils can be used as alternative fuel for standard unmodified diesel engines, provided the oil viscosity has been lowered by heating before they enter the fuel injection system. In its role as diesel fuel, a vegetable oil has to have, among other parameters, a low acidity and low contents of phosphorus and the alkali earth metals Ca + Mg. Such parameters can be achieved by appropriate partial refining of oil by degumming. In this article, three common ethanolamines, monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA), were used as degumming agents for removing non‐hydratable phospholipids from crude rapeseed and sunflower oils. Among the studied ethanolamines, MEA is the most effective for the removal of phosphorus. After degumming with MEA (0.5 wt‐%), the phosphorus content in rapeseed oil was reduced from 445 to 3.5 ppm, and from 163 to 2.2 ppm in sunflower oil. After oil treatment with MEA (1.0 wt‐%), the residual content of Ca and Mg decreased from 136 to 4.2 ppm and from 55.4 to 1.1 ppm in rapeseed oil. In sunflower oil, the values of Ca and Mg decreased from 23.9 to 1.5 ppm and from 24.6 to 1.0 ppm. The acid value of the oils also decreased after degumming with ethanolamines. The advantage of this oil treatment process is that it takes place at ambient temperature, resulting in lower production costs and simpler technology.     

An experimental and numerical analysis of the HCCI auto-ignition process of primary reference fuels,toluene reference fuels and diesel fuel in an engine,varying the engine parameters

For a future HCCI engine to operate under conditions that adhere to environmental restrictions, reducing fuel consumption and maintaining or increasing at the same time the engine efficiency, the choice of the fuel is crucial. For this purpose, this paper presents an auto-ignition investigation concerning the primary reference fuels, toluene reference fuels and diesel fuel, in order to study the effect of linear alkanes, branched alkanes and aromatics on the auto-ignition. The auto-ignition of these fuels has been studied at inlet temperatures from 25 to 120 °C, at equivalence ratios from 0.18 to 0.53 and at compression ratios from 6 to 13.5, in order to extend the range of investigation and to assess the usability of these parameters to control the auto-ignition. It appeared that both iso-octane and toluene delayed the ignition with respect to n-heptane, while toluene has the strongest effect. This means that aromatics have higher inhibiting effects than branched alkanes. In an increasing order, the inlet temperature, equivalence ratio and compression ratio had a promoting effect on the ignition delays. A previously experimentally validated reduced surrogate mechanism, for mixtures of n-heptane, iso-octane and toluene, has been used to explain observations of the auto-ignition process.     

Kinetic model for cloud-point blending of diesel fuels

A semi-empirical model, with two adjustable parameters, has been developed for predicting the cloud points following the blending of diesel fuel components. The model is based on a kinetic argument deduced from the cloud-point dependence of the cooling rate. By either using a constant cooling rate or standardizing the cloud point to a constant cooling rate, blended cloud points can be accurately predicted from the equation

where T_j are the component cloud point (K), v_j are the component volume fractions, and T_c is the blended cloud point. The two adjustable parameters, α and β are associated with the concentration of nucleating sites in the components. The contribution of the β term to the prediction is small and is insignificant if component cloud points are evenly distributed. In general, the larger the cloud point the larger the number of nucleating sites, but this also appears to be dependent on the type of molecules involved in the nucleating sites.     

Vegetable oils and animal fats as alternative fuels for diesel engines with dual fuel operation

Vegetable oils and animal fats are applicable as fuels in standard diesel engines after having adapted the fuel system for electronically controlled dual fuel regime oil/fat-fossil diesel. In this contribution, performance and emission characteristics of the engines running on rapeseed oil, lard, or chicken fat are given and compared to those of fossil diesel and fatty acid methyl esters. The results of engine tests of these fuels show a decrease in maximum power and maximum torque in comparison to fossil diesel due to a lower energy content of triacylglycerols. These values are influenced also by a type of the engine used at testing. When compared to fossil diesel, the opacity of oil/fat based fuels is higher for an engine with lower injection pressures while it is lower for an engine with higher injection pressures. The level of both controlled and uncontrolled emissions is low for all tested biofuels and is low also for the reference fossil diesel. The results of performance and emission tests for rapeseed oil containing 3 and 6 vol.% of anhydrous ethanol are comparable to those obtained for pure oil. In this paper, practical experiences based on long-term operation of adapted vehicle fleet fuelled with oil/fat-fossil diesel are mentioned.     

Soot generation of diesel fuels with substantial amounts of oxygen-bearing compounds added

Two-colour pyrometry, thermodynamic analysis, and exhaust emissions analysis have been used to improve understanding of the formation of soot during combustion in a high speed direct-injection automotive diesel engine. Three fuel blends were used: a Base Fuel commercially available in Northern Europe; a blend of the Base Fuel (70%) and esterified rape-seed oil (RME) (30%) and a blend of the Base Fuel (90%) and an ether compound (diglyme) (10%). While the Base Fuel contained no oxygen, both the other two fuels contained equal amounts of oxygen of 3% by mass. The principal results show significant differences in soot generation during combustion between the two oxygenated fuel blends, despite both having the same amount of oxygen.     

燃料油加氢深度脱硫催化剂及工艺技术进展

分析了燃料油中硫化物的形态及加氢脱硫反应机理;介绍了国内外加氢深度脱硫催化剂的研究现状;评述了现有加氢深度脱硫反应工艺及反应器技术。