Combined pre-reforming-desulfurization of high-sulfur fuels for distributed hydrogen applications

A major challenge facing the future Hydrogen Economy is the issue of hydrogen fuel delivery and distribution. In the near term, it may be necessary to deliver high-density hydrocarbon fuels (e.g., diesel fuel) directly to the end-user (e.g., a fueling station) wherein it is reformed to hydrogen, on demand. This approach has the advantages of utilizing the existing fuel delivery infrastructure, and the fact that more energy can be delivered per trip when the tanker is filled with diesel instead of liquefied or compressed hydrogen gas. Reforming high-sulfur hydrocarbon fuels (e.g., diesel, JP-8, etc.) is particularly challenging due to rapid deactivation of conventional reforming catalysts by sulfurous compounds. A new on-demand hydrogen production technology for distributed hydrogen production is reported. In this process, first, the diesel fuel is catalytically pre-reformed to shorter chain hydrocarbons (C₁-C₆) before being fed to the steam reformer, where it is converted to syngas and further to high-purity hydrogen gas. In the pre-reformer, most sulfurous species present in the fuel are converted to H₂S. Desulfurization of the pre-reformate gas is carried out in a special regenerative redox system, which includes an iron-based scrubber coupled with an electrolyzer. The integrated pre-reformer and sulfur-scrubbing unit operated successfully for 100 h at desulfurization efficiency of greater than 95%.     

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.     

Diffusion coefficients of diesel fuel and surrogate compounds in supercritical carbon dioxide

Facilitating a new concept of clean diesel combustion using supercritical fluids requires a better understanding of thermophysical properties of the diesel fuel/diluent system. Mass diffusivity is one such property that is important to understand diesel fuel/diluent mixing and spray and combustion of supercritical fuel mixtures. In this work, diffusion coefficients of diesel fuel and surrogate compounds in supercritical carbon dioxide were experimentally determined by the Taylor dispersion method at temperatures from 313.15 to 373.15 K and pressures up to 30 MPa. Difficulties were encountered to measure diffusion coefficients using the Taylor dispersion method near the critical region of CO₂ which resulted in curve-fitting errors greater than 5%. Predictive correlations including Wilke-Chang, Scheibel, and He-Yu were examined. Diffusivity data were also fitted by D₁₂/T − η and correlations. Results showed that the He-Yu correlation has the best prediction performance while the D₁₂/T − η correlation best fits the data with AAD% < 8%.     

Flow properties of vegetable oil-diesel fuel blends

Straight vegetable oils provide cleaner burning and renewable alternatives to diesel fuel, but their inherently high viscosity compared to petroleum based diesel is undesirable for diesel engines. Lowering the viscosity can be simply achieved by either increasing the temperature of the oil or by blending it with diesel fuel, or both. In this work the rheological properties of diesel fuel and vegetable oil mixtures at different compositions were studied as a function of temperature to determine a viscosity-temperature-composition relationship for use in design and optimization of heating and fuel injection systems used in diesel engines. The vegetable oils used were corn, canola, olive, peanut, soybean and sunflower oils which are of commercial food grade. All the vegetable oils and their blends with No. 2 diesel fuel showed time-independent Newtonian behaviour within the test temperatures between 20 °C and 80 °C. Viscosities of the pure oils and diesel were satisfactorily correlated with temperature by means of the Arrhenius typed relationship. The Arrhenius blending rule was found applicable to describing the composition dependence of viscosity all vegetable oils-diesel blends at a fixed temperature. These relations were combined to develop a simple mixture viscosity model to predict the viscosity of the vegetable oil-diesel blends as functions of temperature and composition based on properties of the pure components.     

Effects of ethyl tert-butyl ether addition to diesel fuel on characteristics of combustion and exhaust emissions of diesel engines

The effects of ethyl tert-butyl ether (ETBE) addition to diesel fuel on the characteristics of combustion and exhaust emissions of a common rail direct injection diesel engine with high rates of cooled exhaust gas recirculation (EGR) were investigated. Test fuels were prepared by blending 0, 10, 20, 30 and 40 vol% ETBE to a commercial diesel fuel. Increasing ETBE fraction in the fuel helps to suppress the smoke emission increasing with EGR, but a too high fraction of ETBE leads to misfiring at higher EGR rates. While the combustion noise and NO_x emissions increase with increases in ETBE fraction at relatively low EGR rates, they can be suppressed to low levels by increasing EGR. Though there are no significant increases in THC and CO emissions due to ETBE addition to diesel fuel in a wide range of EGR rates, the ETBE blended fuel results in higher aldehyde emissions than the pure diesel fuel at relatively low EGR rates. With the 30% ETBE blended fuel, the operating load range of smokeless, ultra-low NO_x (<0.5 g/kWi h), and efficient diesel combustion with high rates of cooled EGR is extended to higher loads than with the pure diesel fuel.     

The micro-reactor testing of catalysts and fuel delivery apparatuses for diesel autothermal reforming

This study investigated two factors affecting the performance of diesel autothermal reforming (ATR): the reforming activity of selected catalysts and the effect of devised fuel delivery apparatuses. When fluorite and perovskite-structured ceramic materials were used as substrates, H₂ yields were higher than when an inert Al₂O₃ substrate was used at 700–800 °C. Gadolinium (Gd)-doped CeO₂ (CGO) had the highest H₂ production rate in the selected substrates. Platinum (Pt) showed better performance than rhodium (Rh) and ruthenium (Ru) when CGO was used as the substrate. Although the nickel (Ni)-added Pt catalyst (Pt–Ni) showed high H₂ yield, carbon deposition over this catalyst was more severe than with Pt. Oxygen ion (O²⁻) vacancies generated by Gd dopants can enhance the reforming activity of CeO₂. When using a microchannel catalyst bed, the performance degradation at high gas flowrates can be compared to a packed catalyst bed of pellet type. For effective fuel delivery, we have introduced an ultrasonic injector (UI) and a plasma injector (PI). The UI-reforming showed greater long-term stability than non-UI reforming because the generation of carbon precursors was suppressed. On the other hand, the PI-reformer had low conversion efficiency, although it had high H₂ selectivity.     

Low temperature exhaust gas fuel reforming of diesel fuel

The application of exhaust gas assisted fuel reforming in diesel engines has been investigated. The process involves hydrogen generation by direct catalytic interaction of diesel fuel with engine exhaust gas. Using a laboratory reforming mini reactor incorporated in the exhaust system of a diesel engine, up to 16% hydrogen in the reactor product gas was achieved at a reactor inlet temperature of 290 °C. The results showed that such levels of hydrogen can be produced with appropriate control of the reaction parameters at temperatures typical of exhaust gas temperatures of diesel engines operating at part load without any requirement for external heat source or air and steam supply. The use of simulated reformed fuel was shown to be beneficial in terms of engine exhaust emissions and resulted in reduction of NO_X and smoke emissions.     

Syngas production from liquid fuels in a non-catalytic porous burner

This paper investigates rich combustion of n-heptane, diesel oil, kerosene and rapeseed-oil methyl ester (RME) bio-diesel for the purpose of producing syngas ready for the clean-up stages for fuel-cell applications or for traditional combustor enrichment. Rich flames have been stabilised in a two-layer inert porous medium combustor and a range of equivalence ratios and porous materials have been examined. n-heptane was successfully reformed up to an equivalence ratio of 3, reaching a conversion efficiency (based on the lower heating value of H₂ and CO over the fuel input) up to 75% for a packed bed of alumina beads. Similarly, diesel, kerosene and bio-diesel were reformed to syngas in a Zirconia foam burner with conversion efficiency over 60%. A preliminary attempt to reduce the content of CO and hydrocarbons in the reformate has been also conducted using commercial steam reforming and water-gas shift reaction catalysts, obtaining encouraging results. Finally, soot emission has been assessed, demonstrating particle formation for diesel oil above φ = 2, whereas bio-diesel showed the lowest soot formation tendency among all the fuels tested.     

The influence of operating parameters on the performance and emissions of a DI diesel engine using methanol-blended-diesel fuel

In this study, the effects of injection pressure and timing on the performance and emission characteristics of a DI diesel engine using methanol (5%, 10% and 15%) blended-diesel fuel were investigated. The tests were conducted on three different injection pressures (180, 200 and 220 bar) and timings (15°, 20°, and 25° CA BTDC) at 20 Nm engine load and 2200 rpm. The results indicated that brake specific fuel consumption (BSFC), brake specific energy consumption (BSEC), and nitrogen oxides (NO_x) emissions increased as brake thermal efficiency (BTE), smoke opacity, carbon monoxide (CO) and total unburned hydrocarbon (THC) decreased with increasing amount of methanol in the fuel mixture. The best results were achieved for BSFC, BSEC and BTE at the original injection pressure and timing. For the all test fuels, the increasing injection pressure and timing caused to decrease in the smoke opacity, CO, THC emissions while NO_x emissions increase.     

Autothermal reforming of diesel fuel in a structured porous metal catalyst: Both kinetically and transport controlled reaction

Autothermal reforming (ATR) of diesel fuel into syngas was studied experimentally and theoretically. The experiments were performed in a reactor consisting of two cylindrically shaped monoliths 50 × 55 mm. Different catalytically active components and supports (Co, Mn, Rh, BaO, La₂O₃/Al₂O₃ and SiO₂) were tested. The reactor parameters were as follows: O₂/C = 0.5, S/C = 1.5–1.7, T_in = 350–400 °C. The regularly structured catalytic monoliths were prepared using various metal porous supports. The most active and coke resistant catalyst was determined. The original modeling approach was based on the assumption that ATR involves two parallel reaction routes: (1) complete hydrocarbon oxidation, (2) steam reforming of hydrocarbon. The experimental data and the results of reactor modeling agreed well and allowed a conclusion that the ATR rate is controlled by inter-phase mass transfer. However, the contribution of the reaction routes (1) and (2), i.e., the distribution of hydrocarbon flux between these reactions is determined by the ratio of the reaction rate constants and oxygen concentration near the surface.     

Influence of fuel sulfur on the characterization of PM10 from a diesel engine

To study the effects of fuel sulfur content on the characteristics of diesel particle emitted from a typical engine used in China, two types of diesel fuel with sulfur content of 30 ppm and 500 ppm were used in this engine dynamometer test under six operation conditions corresponding to 20%, 50% and 80% load at 1400 rpm and 2300 rpm engine speeds, respectively. Gaseous pollutants and particulate matter (PM) emissions were sampled with AVL AMA4000 and Model 130 High-Flow Impactor (MSP Corp), respectively. More specifically, the PM mass, total carbon (TC), organic carbon (OC), elemental carbon (EC) and water-soluble ion distribution were also measured. Compared with high sulfur diesel, the application of low sulfur diesel can lower fuel-based PM emissions by 9.2-56.6%. At 1400 rpm, the low sulfur diesel decreased both OC and EC by 5-34% and about 20%; while at 2300 rpm, the low sulfur fuel decreased OC by 33-57% and increased EC emission, resulting in a lower OC/EC ratio. The evidence implicating that OC oxidation was promoted by low sulfur diesel, but the effect on EC oxidation was dependent on engine speed. The linear regression has been conducted between TC and PM₁₀, and the slopes were 0.88 and 0.80 for low sulfur diesel and high sulfur one, respectively. Higher sulfate content was detected in the 0.13 μm particles when using the high sulfur diesel, but the percentage of sulfate was 0.9% for PM₁₀ from both diesel fuels. Comparing with that of 500 ppm, EC increased sharply to a maximum of 114% in particles of 0.13 μm when using 30 ppm sulfur diesel at 2300 rpm.     

On-site low-pressure diesel HDS for fuel cell applications: Deepening the sulfur content to ?1 ppm

This work investigates the feasibility of ultra-deep hydrodesulfurization (i.e. ?1 ppm of sulfur content) of several diesel feedstocks, viz., regular (R), premium (P) and hydrotreated straight-run (HSR) at low pressures, i.e. 10 bar, to lower significantly the operation costs. The premium and regular diesel contain additive packages with several components such as cetane boosters, antioxidants that show to negatively affect the sulfur conversion at low pressures. In the hydrotreated straight-run diesel fuel, which does not contain an additive package, total desulfurization can be obtained at 10 bar, T = 340 °C and LHSV = 1 h⁻¹. As a model for the additive package, FAME (fatty acid methyl ester), an ingredient that encounters the demands of a sustainable future, was added to the hydrotreated straight-run diesel (HSR + FAME) in order to check its influence on the total sulfur conversion. Results show that this biofuel component hindered tremendously the sulfur removal process by lowering the sulfur removal from 98% to zero at 10 bar, probably by competitive adsorption. At higher pressures, e.g. 30 bar, when FAME was present, new sulfur compounds were formed during the HDS process and the effective sulfur removal was very low.     

燃料油中硫化物的选择性吸附研究进展

综述了不同吸附剂脱硫和选择性吸附两方面的机理及研究进展。在燃料油选择性吸附脱硫研究的吸附剂中,使用最多的是金属阳离子改性的Y型分子筛,以Cu、Ni和Ce改性的Y型分子筛最为成熟。其吸附脱硫机理主要包括π-络合吸附和金属S—M键作用。燃料油（以汽油和柴油为主）组成复杂,含大量烯烃、芳烃、烷烃及少量的氮化物、氧化物、水及胶质,影响吸附剂的吸附脱硫效果,而烯烃和芳烃严重影响吸附剂的选择性吸附脱硫性能。各种吸附剂对富含烯烃或芳烃的燃料油中的硫化物选择性和硫容量不同,但都不高。研究吸附剂与燃料中的硫化物的选择性吸附机理,对研发具有高选择性和高吸附容量的吸附剂起推动作用。     

Enhanced stability of a direct-methane and carbon dioxide protonic ceramic fuel cell with a PrCrO3 based reforming layer

Dry reforming of methane (CH₄ + CO₂ = 2CO + 2H₂) is a very interesting approach both to reduce the overall carbon footprint of the increasing worldwide fossil-based methane consumption as well as to cut emission greenhouse gas of CO₂. Utilizing the produced syngas as fuel directly in protonic ceramic fuel cell can further kill two birds with one stone: obtain power output and high purity CO. However, the drawback of the coking deposition limits the process of the above strategy. Here, we synthesis a Ni-based catalyst with high conversion rates (∼88% for CO₂ and ∼89% for CH₄) and excellent stability (>160 h at 700 °C) proceeded by Ce doping, and further employ it as reforming layer on solid oxide fuel cell. The results demonstrate that the Ce substitution plays an important role for homogenous Ni nanoparticles exsolution, benefiting for the coking resistance of the catalyst then the stability of the cell using CH₄ and CO₂ as fuel directly.     

Fuel composition effects on transportation fuel cell reforming

This work examines the effect of various hydrocarbons on fuel processor light-off and reforming. Major hydrocarbon fuel constituents, such as aliphatic compounds, napthanes, and aromatics have been compared with the fuel processing performance of blended fuel components and reformulated gasoline to examine synergistic or detrimental effects the fuel components have in a real fuel blend.

Short chained aliphatic hydrocarbons tend to have favorable light-off and reforming characteristics for catalytic autothermal reforming compared with longer-chained and aromatic components. Oxygenated hydrocarbons have lower light-off requirements than do pure hydrocarbons. Gas phase oxidation favors higher cetane # fuels, which tend to be longer chained hydrocarbons. Energy consumption during the start-up process shows a large fuel effect. Methanol and dimethylether (DME) show lower start-up energy demands for the fuel processor start-up than do high temperature reforming hydrocarbon fuels such as methane, gasoline and ethanol. Aromatics and longer chained hydrocarbons show a higher tendency for carbon formation, increasing the amount of carbon formed during the light-off phase while the addition of oxygenates tends to lower the carbon formed during the start-up process.     

Evaluation of the economic and environmental impact of combining dry reforming with steam reforming of methane

Lately, there has been considerable interest in the development of more efficient processes to generate syngas, an intermediate in the production of fuels and chemicals, including methanol, dimethyl ether, ethylene, propylene and Fischer–Tropsch fuels. Steam methane reforming (SMR) is the most widely applied method of producing syngas from natural gas. Dry reforming of methane (DRM) is a process that uses waste carbon dioxide to produce syngas from natural gas. Dry reforming alone has not yet been implemented commercially; however, a combination of steam methane reforming and dry reforming of methane (SMR + DRM) has been used in industry for several years.     

A multi-function compact fuel reforming reactor for fuel cell applications

A multi-function compact chemical reactor designed for hydrocarbon steam reforming was evaluated. The reactor design is based on diffusion bonded laminate micro-channel heat exchanger technology. The reactor consists of a combustor layer, which is sandwiched between two steam reforming layers. Between the two function layers, a temperature monitor and control layer is placed, which is designed to locate the temperature sensors. The combustor layer has four individually controlled combustion zones each connected to a separate fuel supply. The reactor design offers the potential to accurately control the temperature distribution along the length of the reactor using closed loop temperature control. The experimental results show that the variance of temperature along the reactor is negligible. The conversion efficiency of the combustor layer is approximately 90%. The heat transfer efficiency from combustion layer to reforming layers is 65-85% at 873 K and 673 K, respectively. The heat transfer rate to the reforming layers is sufficient to support a steam reformation of propane at a rate of 0.7 dm³/min (STP) with a steam to carbon ratio of 2 at 873 K.     

Combustion and emissions characteristics of compression-ignition engine using dual ammonia-diesel fuel

This study investigated the combustion and emissions characteristics of a compression-ignition engine using a dual-fuel approach with ammonia and diesel fuel. Ammonia can be regarded as a hydrogen carrier and used as a fuel, and its combustion does not produce carbon dioxide. In this study, ammonia vapor was introduced into the intake manifold and diesel fuel was injected into the cylinder to initiate combustion. The test engine was a four-cylinder, turbocharged diesel engine with slight modifications to the intake manifold for ammonia induction. An ammonia fueling system was developed, and various combinations of ammonia and diesel fuel were successfully tested. One scheme was to use different combinations of ammonia and diesel fuel to achieve a constant engine power. The other was to use a small quantity of diesel fuel and vary the amount of ammonia to achieve variable engine power. Under the constant engine power operation, in order to achieve favorable fuel efficiency, the preferred operation range was to use 40-60% energy provided by diesel fuel in conjunction with 60-40% energy supplied by ammonia. Exhaust carbon monoxide and hydrocarbon emissions using the dual-fuel approach were generally higher than those of using pure diesel fuel to achieve the same power output, while NO_x emissions varied with different fueling combinations. NO_x emissions could be reduced if ammonia accounted for less than 40% of the total fuel energy due to the lower combustion temperature resulting in lower thermal NO_x. If ammonia accounted for the majority of the fuel energy, NO_x emissions increased significantly due to the fuel-bound nitrogen. On the other hand, soot emissions could be reduced significantly if a significant amount of ammonia was used due to the lack of carbon present in the combination of fuels. Despite the overall high ammonia conversion efficiency (nearly 100%), exhaust ammonia emissions ranged from 1000 to 3000 ppmV and further after-treatment will be required due to health concerns. On the other hand, the variable engine power operation resulted in relatively poor fuel efficiency and high exhaust ammonia emissions due to the lack of diesel energy to initiate effective combustion of the lean ammonia-air mixture. The in-cylinder pressure history was also analyzed, and results indicated that ignition delay increased with increasing amounts of ammonia due to its high resistance to autoignition. The peak cylinder pressure also decreased because of the lower combustion temperature of ammonia. It is recommended that further combustion optimization using direct ammonia/diesel injection strategies be performed to increase the combustion efficiency and reduce exhaust ammonia emissions.     

Permeation of binuclear, sulphur containing aromatic compounds

Removal of sulphur containing aromatics from fuel is strictly regulated and thus interesting for research as well as for industrial application. Especially difficult is the removal of complex dinuclear thiophenes and their methylated derivatives with conventional hydrotreating technology. Pervaporation could be an alternative separation technology. In order to find out if the separation of the more complex aromatics is possible, especially in low concentrations, variation of separation conditions and development of suitable membrane materials is necessary. The synthesized membrane materials based on 6FDA-4MPD/DABA copolyimides were analyzed by size exclusion chromatography (SEC) and differential thermal analysis (DTA) in combination with thermogravimetric analysis (TGA). In this work temperature-dependent pervaporation experiments were carried out with benzothiophene (about 0.25 wt.%) and n-dodecane as components of a binary feed mixture. The temperature has been varied between 80 °C and 140 °C. Thereby fluxes between 4.1 kg μm m^− 2 h ^− 1 and 32 kg μm m^− 2 h ^− 1 were found. Enrichment factors up to β = 3.3 were reached. In summary, the pervaporation experiments have shown that a significant enrichment of dinuclear aromatic sulphur compounds in combination to an adequate flux is possible.     

Thermodynamic analysis of glycerol dry reforming for hydrogen and synthesis gas production

A thermodynamic analysis of glycerol dry reforming has been performed by the Gibbs free energy minimization method as a function of CO₂ to glycerol ratio, temperature, and pressure. Hydrogen and synthesis gas can be produced by the glycerol dry reforming. The carbon neutral glycerol reforming with greenhouse gas CO₂ could convert CO₂ into synthesis gas or high value-added inner carbon. Atmospheric pressure is preferable for this system and glycerol conversion keeps 100%. Various of H₂/CO ratios can be generated from a flexible operational range. Optimized conditions for hydrogen production are temperatures over 975 K and CO₂ to glycerol ratios of 0-1. With a temperature of 1000 K and CO₂ to glycerol ratio of 1, the production of synthesis gas reaches a maximum, e.g., 6.4 mol of synthesis gas (H₂/CO = 1:1) can be produced per mole of glycerol with CO₂ conversion of 33%.