Liquid phase desulfurization of jet fuel by a combined pervaporation and adsorption process

Since the conventional hydrodesulfurization process employed in the refinery industry is not suitable for mobile fuel cell applications (e.g. auxiliary power units, APUs), the present study aims at developing an alternative process and determining its technical feasibility. A large number of processes were assessed with respect to their application in fuel cell APUs. The results revealed that a two-step process combining pervaporation and adsorption is a suitable process for the on-board desulfurization of jet fuel. Therefore, a pervaporation process with subsequent adsorption was selected for detailed investigation. Six different membrane materials and ten sorbent materials were screened to choose the most suitable candidates. Further laboratory experiments were conducted to optimize the operating conditions and to collect data for a pilot plant design. Different jet fuel qualities with up to 1675 ppmw of sulfur can be desulfurized to a level of 10 ppmw. The aim of developing a suitable process for the desulfurization of jet fuel in fuel cell APUs was thus achieved.     

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.     

Diesel fuel desulfurization with hydrogen peroxide promoted by formic acid and catalyzed by activated carbon

Desulfurization of diesel fuels with hydrogen peroxide was studied using activated carbons as the catalysts. Adsorption and catalytic properties of activated carbons for dibenzothiophene (DBT) were investigated. The higher the adsorption capacity of the carbons is, the better the catalytic performance in the oxidation of DBT is. The effect of aqueous pH on the catalytic activities of the activated carbons was also investigated. Oxidation of DBT is enhanced when the aqueous pH is less than 2, and addition of formic acid can promote the oxidation. The effect of carbon surface chemistry on DBT adsorption and catalytic activity was also investigated. Adsorption of DBT shows a strong dependence on carboxylic group content. The oxidative removal of DBT increases as the surface carbonyl group content increases. Oxidative desulfurization of a commercial diesel fuel (sulfur content, 800 wt. ppm) with hydrogen peroxide was investigated in the presence of activated carbon and formic acid. Much lower residual sulfur content (142 wt. ppm) was found in the oxidized oil after the oxidation by using the hydrogen peroxide-activated carbon-formic acid system, compared with a hydrogen peroxide-formic acid system. The resulting oil contained 16 wt. ppm of sulfur after activated carbon adsorption without any negative effects in the fuel quality, and 98% of sulfur could be removed from the diesel oil with 96.5% of oil recovery. Activated carbon has high catalytic activity and can be repeatedly used following simple water washing, with little change in catalytic performance after three regeneration cycles.     

Deep hydrodesulfurization of diesel fuel: Design of reaction process and catalysts

Deep hydrodesulfurization (HDS) of diesel fuel oil was designed based on the recognition that alkyl dibenzothiophenes such as 4-methyl-and 4,6-dimethyldibenzothiophenes were the main target for deep HDS. Multi-stage and fractional HDS were very effective to achieve satisfactory HDS in terms of both sulfur level and fluorescent color of desulfurized oil. Catalysts with the selective hydrogenation of refractory sulfur species in major aromatic partners and isomerization-disproportionation of their alkyl groups prior to HDS were also designed to promote the desulfurization of such sulfur species.     

Desulfurization of Transportation Fuels by Adsorption

This paper is a review on sorbents for desulfurization of transportation fuels (gasoline, diesel, and jet fuel). Since the π-complexation sorbents are the most promising, they are the focus of the discussion. During π-complexation, the thiophenic compounds can bind selectively to the sorbents, especially the substituted ones. The later remain highly unreacted in hydrodesulfurization (HDS) (i.e., “refractory” sulfur). Molecular orbital (MO) calculations and experiments have shown that these refractory compounds [(e.g., 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene (DMDBT)] bind strongly with the π-complexation sorbents because of a better electron donation/back-donation ability. The sorbents reviewed include Ag-Y, Cu(I)-Y, Ni(II)-Y, and Ni(II)-X zeolites prepared using various ion-exchange techniques. The techniques included vapor and solid-state ion exchanges, which are suitable for obtaining high loadings of transition metals. The best sorbent, Cu(I)-Y [vapor-phase ion-exchanged (VPIE)], is capable of producing almost 38 cm³ of desulfurized fuel per g of sorbent with a sulfur concentration of less than 0.2 ppmw. Using these π-complexation sorbents in layered bed matrices further increases the desulfurization capacity.     

Design and analysis of a diesel processing unit for a molten carbonate fuel cell for auxiliary power unit applications

Fuel cell-based auxiliary power units (APUs) are a promising technology for meeting global energy needs in an environmentally friendly way. This study uses diesel containing sulfur components such as dibenzothiophene (DBT) as a feed. The sulfur tolerance of molten carbonate fuel cell (MCFC) modules is not more than 0.5 ppm, as sulfur can poison the fuel cell and degrade the performance of the fuel cell module. The raw diesel feed in this study contains 10 ppm DBT, and its sulfur concentration should be reduced to 0.1 ppm. After desulfurization, the feed goes through several unit operations, including steam reforming, water-gas shift, and gas purification. Finally, hydrogen is fed to the fuel cell module, where it generates 500 kW of electrical energy. The entire process, with 52% and 89% fuel cell and overall system efficiencies, respectively, is rigorously simulated using Aspen HYSYS, and the results are input into a techno-economic analysis to calculate the minimum electricity selling price (MESP). The electricity cost for this MCFC-based APU was calculated as 1.57$/kWh. According to predictions, the cost reductions for fuel cell stacks will afford electricity selling prices of 1.51$/kWh in 2020 and 1.495$/kWh in 2030. Based on a sensitivity analysis, the diesel price and capital cost were found to have the strongest impact on the MESP.     

The effect of CO2 dissolved in a diesel fuel on the jet flame characteristics

This paper is concerned with an experimental study of the jet diffusion flame characteristics of fuel containing CO₂. Using diesel fuel containing dissolved CO₂ gas, experiments were performed under atmospheric conditions with a diesel hole-type nozzle of 0.19 mm orifice diameter at constant injection pressure. In this study, four different CO₂ mass fraction in diesel fuel such as 3.13%, 7.18%, 12.33% and 17.82% were used to study the effect of CO₂ concentration on the jet flame characteristics. Jet flame characteristics were measured by direct photography, meanwhile the image colorimetry is used to assess the qualitative features of jet flame temperature. Experimental results show that the CO₂ gas dilution effect and the atomization effect have a great influence on the flame structure and average temperature. When the injection pressure of diesel fuel increased from 4 MPa to 6 MPa, the low temperature flame length increased from 18.4 cm to 21.7 cm and the full temperature flame length decreased from 147.6 cm to 134.7 cm. With the increase of CO₂ gas dissolved in the diesel fuel, the jet flame full length decreased for the jet atomization being improved greatly meanwhile the low temperature flame length increased for the CO₂ gas dilution effect; with the increase of CO₂ gas dissolved in the diesel fuel, the average temperature of flame increases firstly and then falls. Experimental results validate that higher injection pressure will improve jet atomization and then increased the flame average temperature.     

Hydrodesulfurization of JP-8 fuel and its microchannel distillate using steam reformate

A field-deployable process for generation of clean desulfurized fuel from JP-8 feedstock is described. The process employs a compact hydrodesulfurization unit, operated in the vapor phase using steam reformate provided by an integrated steam reformer, as a replacement for hydrogen co-feed gas. The process includes a microchannel distillation unit upstream of the hydrodesulfurizer unit, which allows use of a lighter feed fraction to be processed in place of the full JP-8. The novel microchannel distillation concept is described and performance data for the unit, operating as a rectifier, are provided. Since the generated light fraction fuel from microchannel distillation contains fewer refractory sulfur components, the subsequent HDS process can readily achieve a significant sulfur reduction. The overall process can generate an ultra-clean JP-8 light fraction fuel with approximately 300 ppb sulfur residual. Hydrodesulfurization of full JP-8 fuel without the microchannel distillation unit was also studied. The effect of various operating parameters on the overall hydrodesulfurization performance, as well as the conversion of some individual sulfur components such as 2,3-dimethyl-benzothiophene, 2,3,5-trimethyl-benzothiophene and 2,3,7-trimethyl-benzothiophene, were investigated. Steam content in reformate at 30 mol% or less was found to improve HDS performance compared with dry reformate, despite a decrease in hydrogen partial pressure. However, at even higher concentrations of steam, hydrodesulfurization performance decreased.     

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.     

Rhodium supported on thermally enhanced zeolite as catalysts for fuel reformation of jet fuels

Autothermal reformation of military jet fuel (1096 ppmw sulfur) was investigated with rhodium supported on thermally stabilized Y zeolite catalysts. The zeolite catalysts were thermally stabilized by ion exchanging with nitrate solutions of rare-earth metals (La, Ce, Sm, Gd, Dy and Er). Surface area analyses indicated that the exchanged zeolite could maintain its porous structure as high as 950 °C instead of 800 °C for a commercial NaY zeolite. The structure of the exchanged zeolite was characterized by X-ray diffraction (XRD). Rh-SmNaY zeolite reforming catalysts were prepared by incipient wetness and organometallic synthesis. The JP8 reforming experiments were performed in a short contact time adiabatic reactor with a monolithic catalyst with the addition of air and steam at a temperature below 920 °C. The effects of steam and fuel-to-air ratio (C/O ratio) were studied. Hydrogen and carbon monoxide were produced as the main products. Durability tests were performed with Rh/SmNaY-zeolite catalysts. This work shows that zeolite based catalysts can convert transportation fuels such as high sulfur jet fuel (over 1000 ppmw S) to syngas for solid oxide fuel cell applications.     

Desulfurization of petroleum residues and their carbonization properties

The desulfurization of petroleum residues of high sulfur content was carried out using three kinds of Lewis acids under a nitrogen flow of atmospheric pressure at 150–330°C. Considerable amounts of sulfur were eliminated from the residue as hydrogen sulfide with the aid of aluminum chloride at 150°C or higher temperatures. Ferric or zinc chloride was found also to eliminate sulfur from the residue in the form of the corresponding metal sulfides at 330°C without the evolution of hydrogen sulfide.Effects of such desulfurization on the coking properties were observed by means of optical microscopy and X-ray diffraction. Although the original residues gave cokes with a mosaic arrangement of anisotropic domains, benzene-soluble fractions of the desulfurized residue gave a graphitizable needle coke. The desulfurized residues were further analyzed by chemical techniques to study the structural change brought about by acidic desulfurization. This kind of desulfurization was revealed to be carried out without decreasing the aromaticity of the residue, being different from the hydrodesulfurization with cobalt-molybdena catalysts.     

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.     

燃料油吸附脱硫的研究进展

与传统的加氢脱硫技术相比,吸附脱硫技术在超低硫燃料油生产方面具有明显优势,近年来得到了迅速发展。综述了吸附法脱除燃料油中有机硫化物的研究进展,重点介绍了反应吸附脱硫和选择性吸附脱硫两种类型的吸附脱硫方法以及分子筛基吸附剂、金属氧化物基吸附剂、活性炭基吸附剂和粘土基吸附剂在吸附脱硫方面的应用。指出选择性吸附脱硫技术是近期最有希望实现零硫目标的脱硫技术。     

Energy-efficient ultra-deep desulfurization of kerosene based on selective photooxidation and adsorption

Selective photooxidation and adsorptive desulfurization of kerosene was investigated for fuel cell applications. Photooxidation was conducted using a 5 W low-pressure mercury lamp at 25 °C in the presence of O₂. It was found for the first time that the rates of photooxidation of dominant sulfur compounds remaining in commercial kerosene after hydrogenation were at least 100 times higher than those of benzothiophenes (BTs) and dibenzothiophenes (DBTs), although their molecular forms were not clarified. The photooxidation of these highly reactive sulfur compounds was completed within 30 min and made them removable by adsorbents such as molecular sieves. On the other hand, non-reactive sulfur compounds such as DBTs were removed by adsorbents such as activated carbon. Using this proposed method, which combines selective photooxidation of highly reactive sulfur compounds and adsorptive desulfurization of reactive and non-reactive sulfur compounds, the total sulfur content in kerosene can be efficiently reduced to less than 0.1 μg g⁻¹ (ppm) under mild conditions.     

Oxidative Desulfurization of Hydrocarbon Fuels

New requirements for very low sulfur content (10 ppm) in liquid motor fuels demand novel approaches for ultra-deep desulfurization. For production of near-zero-sulfur diesel and low-sulfur fuel oil, removal of refractory sulfur compounds, like 4,6-dimethyldibenzothiophene and other alkyl-substituted thiophene derivatives, is necessary. Elimination of these compounds by hydrodesulfurization (HDS) requires high hydrogen consumption, high pressure equipment, and new catalysts. Various oxidative desulfurization processes, including recent advances in this field for diesel fuels, and the drawbacks of this technology in comparison with HDS are examined and discussed. It is shown that the oxidation of sulfur compounds to sulfones with hydrogen peroxide allows for production of diesel fuels with a sulfur content of 10 ppmw or lower at atmospheric pressure and room temperature. The gas phase oxidative desulfurization of sulfur compounds with air or oxygen is feasible at atmospheric pressure and higher temperatures: 90–300 °С and offers better economic solutions and incentives.     

Effective supports to moderate H2S inhibition on cobalt and nickel molybdenum sulfide catalysts in deep desulfurization of gas oil

Deep desulfurization of gas oil was attempted in the presence of H₂S over commercially available catalysts. Hydrotreated gas oil containing 340 ppm of sulfur (ppmS) was successfully desulfurized to less than 10 ppmS under the presence of 1.67% H₂S over CoMoS and NiMoS supported on acidic supports. Such supports are believed to enhance the sulfur release from active sites and the hydrogenation of refractory sulfur species to accelerate their deep desulfurization.     

Desulfurization of Transportation Fuels by Adsorption

Abstract

This paper is a review on sorbents for desulfurization of transportation fuels (gasoline, diesel, and jet fuel). Since the π‐complexation sorbents are the most promising, they are the focus of the discussion. During π‐complexation, the thiophenic compounds can bind selectively to the sorbents, especially the substituted ones. The later remain highly unreacted in hydrodesulfurization (HDS) (i.e., “refractory” sulfur). Molecular orbital (MO) calculations and experiments have shown that these refractory compounds [(e.g., 4‐methyldibenzothiophene and 4,6‐dimethyldibenzothiophene (DMDBT)] bind strongly with the π‐complexation sorbents because of a better electron donation/back‐donation ability. The sorbents reviewed include Ag‐Y, Cu(I)‐Y, Ni(II)‐Y, and Ni(II)‐X zeolites prepared using various ion‐exchange techniques. The techniques included vapor and solid‐state ion exchanges, which are suitable for obtaining high loadings of transition metals. The best sorbent, Cu(I)‐Y [vapor‐phase ion‐exchanged (VPIE)], is capable of producing almost 38 cm³ of desulfurized fuel per g of sorbent with a sulfur concentration of less than 0.2 ppmw. Using these π‐complexation sorbents in layered bed matrices further increases the desulfurization capacity.     

Two-step adsorption process for deep desulfurization of diesel oil

An integrated adsorption process for deep desulfurization of diesel fuel was proposed and examined. Conventionally hydrodesulfurized straight run gas oil (HDS-SRGO) having less than 50 ppm sulfur was also adsorptively treated with activated carbon fiber (ACF) to attain the ultra low sulfur gas oil having less than 10 ppm sulfur. The ACF, used in cleaning-up HDS-SRGO, was successively examined in straight run gas oil (SRGO) treatment to enhance its hydrodesulfurization (HDS) reactivity over conventional CoMo catalyst by removing the nitrogen and refractory sulfur species contained in SRGO. Such integrated adsorption–reaction process makes it possible to utilize the maximum adsorption capacity of ACF and achieve ultra deep desulfurization og SRGO. Regeneration of used ACF with a conventional solvent was proved very effective in restoring its adsorption capacity.     

清洁燃料的非加氢脱硫技术进展

日益严格的环保法规,对生产低硫、超低硫清洁燃料技术提出了更高要求。介绍了汽柴油脱硫的相关技术,包括加氢脱硫和非加氢脱硫。着重介绍了吸附、氧化和生物脱硫技术进展,同时简要介绍了萃取、膜分离及络合脱硫等工艺。与加氢脱硫相比,非加氢脱硫技术具有操作条件温和、投资及操作费用低等优点,具有更加广阔的发展前景。     

Influence of nitrogen-containing components on the hydrodesulfurization of 4,6-dimethyldibenzothiophene over Pt, Pd, and Pt–Pd on alumina catalysts

Pyridine and piperidine inhibited the hydrodesulfurization of 4,6-dimethyldibenzothiophene (4,6-DM-DBT) over alumina-supported Pt, Pd, and Pt–Pd catalysts. The Pd catalyst was least sensitive and the Pt–Pd catalysts were most sensitive to the nitrogen-containing compounds. Pyridine was a stronger inhibitor than piperidine at low initial pressure, but the reverse was true at high initial pressure. Hydrogenation of the tetrahydro to the hexahydro and on to the perhydro sulfur-containing intermediate as well as the removal of sulfur from these intermediates was slowed down by piperidine and pyridine. The hydrogenation pathway in the hydrodesulfurization of 4,6-DM-DBT was inhibited much more than the direct desulfurization pathway. The hydrogenation of the desulfurized products 3,3′-dimethylcyclohexylbenzene and 3,3′-dimethylbiphenyl over the Pt–Pd catalysts was suppressed by piperidine and pyridine. Piperidine and pyridine substantially decrease the ability of noble metal particles to convert refractory molecules like 4,6-DM-DBT and diminish the advantage of bimetallic Pt–Pd over monometallic Pt or Pd catalysts.