Hydrodesulfurization of diesel in a slurry reactor

The need for more complete removal of sulfur from fuels is due to the lower allowable sulfur content in gasoline and diesel, which is made difficult by the increased sulfur contents of crude oils. This work reports an experimental study on the hydrodesulfurization (HDS) of diesel in a slurry reactor. HDS of straight-run diesel using a NiMoS/Al₂O₃ catalyst was studied in a high-pressure autoclave for the following operating conditions: 4.8–23.1 wt% catalyst in the reactor, 320–360 °C, 3–5 MPa pressure, and 0.56–2.77 L/min hydrogen flow rate. It was found that the reaction rate was proportional to the catalyst amount and increased with temperature, pressure and hydrogen flow rate. The reaction kinetics for the HDS reaction in the slurry reactor was obtained. As compared with HDS in a fixed bed reactor, HDS in a slurry reactor is promising because of the uniform temperature profile, high catalyst efficiency, and online removal and addition of catalyst.     

Redox features in the catalytic mechanism of the “standard” and “fast” NH3-SCR of NOx over a V-based catalyst investigated by dynamic methods

The redox mechanism governing the selective catalytic reduction (SCR) of NO/NO₂ by ammonia at low temperature was investigated by transient reactive experiments over a commercial V₂O₅/WO₃/TiO₂ catalyst for diesel exhaust aftertreatment. NO + NH₃ temperature-programmed reaction runs over reduced catalyst samples pretreated with various oxidizing species showed that both NO₂ and HNO₃ were able to reoxidize the V catalyst at much lower temperature than gaseous O₂: furthermore, they significantly enhanced the NO + NH₃ reactivity below 250 °C via the buildup of adsorbed nitrates, which act as a surface pool of oxidizing agents but are decomposed above that temperature. Both such features, which were not observed in comparative experiments over a V-free WO₃/TiO₂ catalyst, point out a key catalytic role of the vanadium redox properties and can explain the greater deNO_x efficiency of the “fast” SCR (NO + NH₃ + NO₂) compared with the “standard” SCR (NO + NH₃ + O₂) reaction. A unifying redox approach is proposed to interpret the overall NO/NO₂–NH₃ SCR chemistry over V-based catalysts, in which vanadium sites are reduced by the reaction between NO and NH₃ and are reoxidized either by oxygen (standard SCR) or by nitrates (fast SCR), with the latter formed via NO₂ disproportion over other nonreducible oxide catalyst components.     

Characterization and optimization of an autothermal diesel and jet fuel reformer for 5 kWe mobile fuel cell applications

The present paper describes the characterization of an autothermal reformer designed to generate hydrogen by autothermal reforming (ATR) from commercial diesel fuel (～10 ppm S) and jet fuel (～200 ppm S) for a 5 kW_e polymer electrolyte fuel cell (PEFC). Commercial noble metal-based catalysts supported on 900 cpsi cordierite monoliths substrates were used for ATR with reproducible results. Parameters investigated in this study were the variation of the fuel inlet temperature, fuel flow and the H₂O/C and O₂/C ratios. Temperature profiles were studied both in the axial and radial directions of the reformer. Product gas composition was analyzed using gas chromatography.It was concluded from the experiments that an elevated fuel inlet temperature (≥60 °C) and a higher degree of fuel dispersion, generated via a single-fluid pressurized-swirl nozzle at high fuel flow, significantly improved the performance of the reformer. Complete fuel conversion, a reforming efficiency of 81% and an H₂ selectivity of 96% were established for ATR of diesel at P = 5 kW_e, H₂O/C = 2.5, O₂/C = 0.49 and a fuel inlet temperature of 60 °C. No hot-spot formation and negligible coke formation were observed in the reactor at these operating conditions. The reforming of jet fuel resulted in a reforming efficiency of only 42%. A plausible cause is the coke deposition, originating from the aromatics present in the fuel, and the adsorption of S-compounds on the active sites of the reforming catalyst.Our results indicate possibilities for the developed catalytic reformer to be used in mobile fuel cell applications for energy-efficient hydrogen production from diesel fuel.     

Effects of diesel particulate trap and addition of di-methoxy-methane,di-methoxy-propane to diesel on emission characteristics of a diesel engine

The objective of this investigation was to improve the performance of a diesel engine by adding oxygenated fuel additives of known percentages. The fuel additives di-methoxy-methane (DMM) and di-methoxy-propane (DMP) were separately blended with diesel fuel in proportions of 1 ml, 3 ml and 5 ml. The experimental study was carried out on a single cylinder DI diesel engine. The result showed an appreciable reduction of emissions such as smoke density, particulate matter and marginal increase in the performance when compared with normal diesel run. The same engine was employed with diesel particulate trap (DPT) in the exhaust pipe to study its influence on the emission analysis.     

Polyoxometalate as effective catalyst for the deep desulfurization of diesel oil

Aiming at the deep desulfurization of the diesel oil, a comparison of the catalytic effects of several Keggin type POMs, including H₃PW_xMo_12?xO₄₀ (x = 1, 3, 6), Cs_2.5H_0.5PW₁₂O₄₀, and H₃PW₁₂O₄₀, was made, using the solution of DBT in normal octane as simulated diesel oil, H₂O₂ as oxidant, and acetonitrile as extractant. H₃PW₆Mo₆O₄₀ was found to be the best catalyst, with a desulfurization efficiency of 99.79% or higher. Hence, it is promising for the deep desulfurization of actual ODS process. The role of the main factors affecting the process including temperature, O/S molar ratio, initial sulfur concentration, and catalyst dosage, was investigated, whereby the favourable operating conditions were recommended as T = 60 °C, O/S = 15, and a catalyst dosage of 6.93 g (H₃PW₆Mo₆O₄₀)/L (simulated diesel). With the aid of GC–MS analysis, sulfone species was confirmed to be the only product after reaction for 150 min. Furthermore, macro-kinetics of the process catalyzed by H₃PW₆Mo₆O₄₀ was studied, from which the reaction orders were found to be 1.02 to DBT and 0.38 to H₂O₂, and the activation energy of the reaction was found to be 43.3 kJ/mol. Moreover, the catalyst recovered demonstrated almost the same activity as the fresh.     

Selective catalytic reduction of NOx by NH3 on Fe/HBEA zeolite catalysts in oxygen-rich exhaust

This paper deals with the systematic study of Fe/HBEA zeolites for the selective catalytic reduction (SCR) of NO_x by NH₃ in diesel exhaust. The catalysts are prepared by incipient wetness impregnation of H-BEA zeolite (Si/Al = 12.5). The SCR examinations performed under stationary conditions show that the pattern with a Fe load of 0.25 wt.% (0.25Fe/HBEA) reveals pronounced performance. The turnover frequency at 200 °C indicates superior SCR activity of 0.25Fe/HBEA (8.5 × 10⁻³ s⁻¹) as compared to commercial Fe-exchanged BEA (0.99 × 10⁻³ s⁻¹) and V₂O₅/WO₃/TiO₂ (1.0 × 10⁻³ s⁻¹). Based upon powder X-ray diffraction (PXRD), temperature programmed reduction by H₂ (HTPR), diffuse reflectance UV–vis spectroscopy (DRUV–VIS) and catalytic data it is concluded that the pronounced performance of 0.25Fe/HBEA is substantiated by its high proportion of isolated Fe oxo sites. Furthermore, isotopic studies show that no association mechanism of NH₃ takes place on 0.25Fe/HBEA, i.e. N₂ is mainly formed from NO and NH₃.The evaluation of 0.25Fe/HBEA under more practical conditions shows that H₂O decreases the SCR performance, while CO and CO₂ do not affect the activity. Contrary, SCR is markedly accelerated in presence of NO₂ referring to fast SCR. Moreover, hydrothermal treatment at 550 °C does not change SCR drastically, whereas a clear decline is observed after 800 °C aging.     

Characteristics of the simultaneous removal of PM and NOx using CuNb-ZSM-5 coated on diesel particulate filter

The purpose of this study is to investigate the characteristics of the simultaneous removal of PM and NOx on the CuNb-ZSM-5 SCR/DPF catalysts coated onto DPF substrate. NOx conversion by the CuNb-ZSM-5 catalyst was higher than those by Cu- or Fe-ZSM-5 catalysts. NOx conversion of the SCR/DPF catalyst with a wall-flow (plugged) was considerably lower under 450 °C than that of the SCR/DPF catalyst with a channel-flow (unplugged). The de-NOx performance of the SCR/DPF catalyst coated with CuNb-ZSM-5 was highest among the catalysts examined. SCR/DPF catalyst coated with CuNb-ZSM-5 had superior PM oxidation performance compared to the other SCR/DPF catalysts.     

Phosphorus-containing activated carbon as acid support in a bifunctional Pt–Pd catalyst for tire oil hydrocracking

A bifunctional Pt–Pd catalyst supported on phosphorus-containing activated carbon has been prepared, characterized and tested in the hydrocracking of a hydrotreated tire pyrolysis oil. The product has a very interesting composition: 48–78 wt% naphtha and 19–42 wt% diesel fractions, with moderate amounts of aromatics (< 40 wt%) and sulfur (< 250 ppm). The challenge was to prepare a stable, porous, selective and acid carbonaceous catalyst from a waste (olive stone), which has been confirmed from the catalytic properties and product distribution point of view. In fact, phosphate groups in the activated carbon are stable hydrocracking sites, with comparable performance to that of the acid sites present in amorphous SiO₂–Al₂O₃.     

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.     

Preparation of phosphate promoted Na2WO4/Al2O3 catalyst and its application for oxidative desulfurization

Phosphate promoted Na₂WO₄/Al₂O₃ catalyst with 10 wt.% tungsten was prepared by simple impregnation method. Analytical characterization results showed that tungstate and phosphate were uniformly dispersed in alumina matrix and its structural properties were preserved. The effect of phosphate as promoter in catalyst activity was studied using dibenzothiophine (DBT) as model oil and the results reveal that it plays an important role in oxidation activity of Na₂WO₄/Al₂O₃ catalyst, in addition, the catalytic activity of Na₂WO₄/Al₂O₃ was increased gradually with increasing phosphorus contents up to 2.5 wt.%. The catalyst was recycled and the results show that no significant decrease in catalyst activity was observed even after five recycled runs. We also applied our catalyst in oxidative desulfurization (ODS) of FCC diesel oil (with sulfur contents 4100 ppm), and more than 92% of sulfur was removed from diesel oil under mild reaction conditions.     

SO42−–Mn–Co–Ce supported on TiO2/SiO2 with high sulfur durability for low-temperature SCR of NO with NH3

The catalysts SO₄^2 − Mn–Co–Ce/TiO₂/SiO₂ were investigated for the low-temperature SCR of NO with NH₃ in the presence of SO₂. An excellent SO₂ durability at low temperature was obtained with the catalyst used TiO₂/SiO₂ as support and modified with SO₄^2 −. The catalyst sulfated with 0.1 mol/L H₂SO₄ solution and then calcined at 300 °C exhibited the best NO_x conversion efficiency of 99.5% at 250 °C in the presence of 50 ppm SO₂. The conversion efficiency did not decrease after repeatedly used for 8 times.     

Fischer–Tropsch synthesis over a Co/SiO2 catalyst modified with Mn- and Zr under practical conditions

Fischer–Tropsch (FT) synthesis activity and the stability of a Co/SiO₂ catalyst modified with Mn- and Zr were examined under various practical conditions. Dependence of FT synthesis on reaction pressure and bench-scale FT synthesis were investigated. Evaluating catalyst lifetime during continuous FT reactions was conducted. The Co + Mn + Zr/SiO₂ catalyst exhibited relatively greater activity and stable reactivity for 168 h. Sulfur resistance of catalysts were investigated and results showed that the presence of 4 ppm H₂S drastically affected catalytic activity. The Co + Mn + Zr/SiO₂ catalyst exhibited greater activity even with H₂ presence and the sulfur poisoning rate was almost similar on both Co + Mn + Zr/SiO₂ and Co/SiO₂ catalysts.     

NO reduction over nanostructure M-Cu/ZSM-5 (M: Cr,Mn, Co and Fe) bimetallic catalysts and optimization of catalyst preparation by RSM

The selective catalytic reduction (SCR) of NO with NH₃ in the presence of oxygen over a series of H-ZSM-5 supported transition metal oxides (Co, Mn, Cr, Cu and Fe) was investigated. Among them, Cu/ZSM-5 nanocatalyst was found to be the most promising catalyst based on activity. The modification of Cu/ZSM-5 by adding different transition metals (Co, Mn, Cr and Fe) to improve the efficiency of NO conversion was studied. The results indicated that the Fe–Cu/ZSM-5 bimetallic nanocatalyst was the highest active catalyst for NO conversion (67% at 250 °C and 93% at 300 °C). Response surface methodology (RSM) involving central composite design (CCD) was employed to evaluate and optimize Fe–Cu/ZSM-5 preparation parameters (Fe loading, calcinations temperature, and impregnation temperature) in SCR of NO at 250 °C. The optimum condition for maximum NO conversion was estimated at 4.2 wt.% Fe loading, calcinations temperature of 577 °C and impregnation temperature of 43.5 °C. Under these condition, experimental NO conversion efficiency was 78.8%, which was close with the predicted value (79.4%).     

Selective catalytic reduction of NO by ammonia using mesoporous Fe-containing HZSM-5 and HZSM-12 zeolite catalysts: An option for automotive applications

Mesoporous and conventional Fe-containing ZSM-5 and ZSM-12 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnation method and tested in the selective catalytic reduction (SCR) of NO with NH₃. It was found that for both Fe/HZSM-5 and Fe/HZSM-12 catalysts with similar Fe contents, the activity of the mesoporous samples in NO SCR with NH₃ is significantly higher than for conventional samples. Such a difference in the activity is probably related with the better diffusion of reactants and products in the mesopores and better dispersion of the iron particles in the mesoporous zeolite as was confirmed by SEM analysis. Moreover, the maximum activity for the mesoporous zeolites is found at higher Fe concentrations than for the conventional zeolites. This also illustrates that the mesoporous zeolites allow a better dispersion of the metal component than the conventional zeolites. Finally, the influence of different pretreatment conditions on the catalytic activity was studied and interestingly, it was found that it is possible to increase the SCR performance significantly by preactivation of the catalysts in a 1% NH₃/N₂ mixture at 500 °C for 5 h. After preactivation, the activity of mesoporous 6 wt% Fe/HZSM-5 and 6 wt% Fe/HZSM-12 catalyst is comparable with that of traditional 3 wt% V₂O₅/TiO₂ catalyst used as a reference at temperatures below 400 °C and even more active at higher temperatures.     

Detection of hydrogen using multi-walled carbon-nanotube yarns coated with nanocrystalline Pd and Pd/Pt layered structures

Robust and flexible chemiresistors fabricated from multi-walled carbon nanotube yarns decorated with nanocrystalline Pd (Pd-MWCNTs) were used to detect hydrogen from 20 parts per million (ppm) and above in nitrogen at room temperature. With the chemiresistors fabricated by introducing a layer of Pt on Pd (Pt–Pd-MWCNTs), the lower limit of detection (LLD) was found to extend down to 5 ppm. It is shown that the observed response to hydrogen is a resultant of two mechanisms, namely, the formation of the hydrides of Pd and nanoscopic gap closing which leads to opposing changes in resistance in the composite yarns. A deviation from the Sievert’s law is observed at concentrations above 100 ppm and is attributed to the presence of these competing mechanisms. In air, the LLD was found to be 2000 ppm for the Pd-MWCNT chemiresistor and 400 ppm for the Pt–Pd-MWCNT chemiresistor. The Pt–Pd-MWCNT chemiresistor showed excellent response and recovery characteristics in air. For Pd-MWCNT chemiresistor, the nanoscopic gap-closing mechanism became prominent at concentrations below ～1000 ppm and allowed the detection of hydrogen down to 200 ppm in air using negative changes in resistance.     

Effective parameters for DME steam reforming catalysts for the formation of H2 and CO

Recently, DME has received attention as a clean fuel and is now considered an alternative fuel for diesel engines. DME diesels need de-NOx catalysts such as LNT (Lean NOx Trap) and SCR (Selective Catalytic Reduction) systems. DME is an attractive source of hydrogen because it can be stored easily and is a good transportation fuel. Hydrogen and CO enriched gas as a reductant was used with the LNT catalyst in order to reduce NOx emissions. The steam reforming catalyst of DME was used to formation of hydrogen. It has been reported that Cu-based catalysts have high selectivity and activity in the steam reforming of DME. This research used 600 cPsi cordierite as a catalyst, which was coated with copper. The catalysts were made via a sol–gel and impregnation methods. The formation of H₂ and CO under the prepared catalysts was tested by a model gas. Experimental parameters were considered; the space velocity (SV) and concentrations of H₂O, O₂, and CO₂ were evaluated. The Cu 30%/γ-Al₂O₃ catalyst from the sol–gel method exhibited high and stable activity in the production of hydrogen from the steam reforming of DME. Both DME conversion and the selectivity of hydrogen were affected by SV and the concentrations of H₂O, O₂, and CO₂.     

The catalytic activities and thermal stabilities of Li/Na/K carbonates for diesel soot oxidation

The alkali carbonates displayed a good catalytic activity for soot oxidation and their catalytic performances follow the order K₂CO₃ > Na₂CO₃ > Li₂CO₃ with soot ignition onset temperatures (IOTs) of 310 °C, 320 °C and 320 °C respectively. Na/K and Li/Na/K carbonate catalysts produced by combinations of the three alkali carbonates displayed the lowest IOT of about 320 °C that was higher than that of pure K₂CO₃. It was found that the variation of Li:Na:K molar ratios has very limited effect on the catalytic activity, but considerable effect on the thermal stability of the catalysts.Thermal treatment at 700 °C caused a limited change of IOT, but the deterioration of catalytic performance. In the Li/Na/K catalyst system, the formation of crystalline phases with low melting temperature was observed.     

The effect of natural and synthetic antioxidants on the oxidative stability of palm diesel

Crude and distilled palm oil methyl esters conveniently known as palm diesel have been successfully evaluated as diesel substitute. Crude palm oil methyl esters are produced from transesterification of crude palm oil with minor components such as carotenes and vitamin E still intact and they are reddish in colour. The distilled palm oil methyl esters are obtained after the recovery of minor components (e.g. Carotenes and vitamin E) From the crude palm oil methyl esters. These valuable minor components are preferably to be recovered as they can be sold as value-added products before they are burnt together with the methyl esters as fuel. Although both possesses fuel characteristics which are comparable to those of petroleum diesel, crude palm oil methyl esters are found to exhibit better oxidative stability (rancimat induction period >25 h) than distilled palm oil methyl esters (about 3.5 h). It is attributed to the presence of vitamin E (about 600 ppm), a natural antioxidant in the former. While the distilled palm oil methyl esters contain practically no vitamin E (<50 ppm) and as a result, they exhibit poor oxidative stability. Thus, the crude palm oil methyl esters meet the european standard for biodiesel (EN 14214) which has set a minimum rancimat induction period of 6 h. In the present study, research was conducted to enhance the oxidative stability of distilled palm oil methyl esters in order to meet the aforementioned standard. Natural and synthetic antioxidants were used in the present study to investigate their effect on the oxidative stability of distilled palm oil methyl esters. It was found that both types of antioxidant showed beneficial effects in inhibiting the oxidation of distilled palm oil methyl esters. Comparatively, the synthetic antioxidants were found to be more effective than the natural antioxidants as lower dosage (17 times less) was needed to achieve the minimum rancimat induction period of 6 h.     

Combination of a non-thermal plasma and a catalyst for toluene removal from air: Manganese based oxide catalysts

A series of manganese based catalysts have been tested in a combined plasma-catalyst reactor in the reaction of toluene removal from air. In the standard conditions (toluene = 240 ppm, energy density = 172 J/L, 1 g of catalyst, 315 mL/min), the best catalyst (manganese oxide supported on active carbon) is able to transform 55% of the toluene into carbon oxides. According to the study of the reaction mechanism, it appears that the toluene is oxidized both in-plasma by short-lived species generated by plasma and in post-plasma on the catalyst surface by the ozone formed in the plasma, the reaction on the catalyst being more selective in carbon dioxide formation than the reaction in plasma. We have shown that the toluene conversion increases when the toluene concentration in air decreases. A model able to describe the behavior of the plasma reactor and the plasma-catalyst reactor is proposed.     

Thermodynamic calculation for the activity and mechanism of Mn/TiO2 catalyst doped transition metals for SCR at low temperature

The introduction of transition metals in Mn/TiO₂ catalysts played significant roles in oxidative abstraction of hydrogen from adsorbed ammonia during the selective catalytic reduction (SCR). Thermodynamic calculation studies showed that the SCR performance was in accordance with the ammonia oxidation with transition metals, and the reaction tendency for the ammonia oxidation was decreased in the following order: CuO > Co₃O₄ > NiO > Fe₂O₃ > Cr₂O₃ > ZnO > La₂O₃ > CeO₂ > ZrO₂. In addition, Mn/TiO₂ catalyst doped metal (Fe and Cu) oxides enhanced performance for NO_x conversion, being approximately 100% at 453 K.