Direct reduction of SO2 to elemental sulfur by the coupling of cold plasma and catalyst (I)

The direct reduction of SO2 to elemental sulfur in flue gas by the coupling of cold plasma and catalyst, being a new approach for SO2 reduction, was studied. In this process, CO2 can be disassembled to form CO, which acts as the reductant under the cold plasma. With the coupling of the cold plasma and the catalyst, sulfur dioxide was selectively reduced by CO to elemental sulfur with a byproduct of metal sulfate, e.g., FeSO4. In the present work, Fe2O3/gamma-Al2O3 was employed as the catalyst. The extent of desulfurization was more than 80%, and the selectivity of elemental sulfur is about 55%. The effects of water vapor, temperature, and the components of simulated flue gas were investigated. At the same time, the coupling of thermogravimetry and infrared method and a chemical analysis method were employed to evaluate the used catalyst. In this paper, we will focus on the discussion of the catalyst. The discussions of the detail of plasma will be introduced in another paper.

Thioreduction of cyclopentanone and hydrodesulfurization of dibenzothiophene over sulfided nickel or cobalt-promoted molybdenum on alumina catalysts

Two series of sulfided Ni or Co promoted Mo/alumina catalysts, having different Ni or Co loadings, were characterized by their activities for the transformation of cyclopentanone into cyclopentanethiol (flow reactor, 220 degrees C, atmospheric pressure) and for the hydrodesulfurization of dibenzothiophene (flow reactor, 340 degrees C, 3 MPa hydrogen pressure). The addition of the promoter increased significantly the activity of the Mo/alumina catalyst for both reactions, up to a maximum obtained with the catalysts having a (promoter)/(promoter+Mo) molar ratio equal to 0.3-0.4. This increase in activity was due in part to an increase in the hydrogenating properties of the Mo/alumina catalyst. However, an additional modification of the catalyst (basic and nucleophilic properties) must be considered to account for the spectacular effect of the promoter on the rate of the dibenzothiophene direct desulfurization reaction. (C) 1999 Elsevier Science B.V. All rights reserved.

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

The peroxometalate-based polymer immobilized ionic liquid phase catalyst [PO4{WO(O-2)(2)}(4)]@PIILP has been prepared by anion exchange of ring opening metathesis-derived pyrrolidinium-decorated norbornene/ cyclooctene copolymer and shown to be a remarkably efficient system for the selective oxidation of sulfides under mild conditions. A cartridge packed with a mixture of [PO4{WO(O-2)(2)}(4)]@PIILP and silica operated as a segmented or continuous flow process and gave good conversions and high selectivity for either sulfoxide (92% in methanol at 96% conversion for a residence time of 4 min) or sulfone (96% in acetonitrile at 96% conversion for a residence time of 15 min). The immobilized catalyst remained active for 8 h under continuous flow operation with a stable activity/selectivity profile that allowed 6.5 g of reactant to be processed (TON = 46 428) while a single catalyst cartridge could be used for the consecutive oxidation of multiple substrates giving activity-selectivity profiles that matched those obtained with fresh catalyst.

Mercaptans extraction from jet-fuel streams using ionic liquids

Desulfurization is one of the most important processes in the refining industry. Due to a growing concern about the risks to human health and environment, associated with the emissions of sulfur compounds, legislation has become more stringent, requiring a drastic reduction in the sulfur content of fuel to levels close to zero (< 10 ppm S). However, conventional desulfurization processes are inefficient and have high operating costs. This scenario stimulates the improvement of existing processes and the development of new and more efficient technologies. Aiming at overcoming these shortcomings, this work investigates an alternative desulfurization process using ionic liquids for the removal of mercaptans from "jet fuel" streams. The screening and selection of the most suitable ionic liquid were performed based on experimental and COSMO-RS predicted liquid-liquid equilibrium data. A model feed of 1-hexanethiol and n-dodecane was selected to represent a jet-fuel stream. High selectivities were determined, as a result of the low mutual solubility between the ionic liquid and the hydrocarbon matrix, proving the potential use of the ionic liquid, which prevents the loss of fuel for the solvent. The distribution ratios of mercaptans towards the ionic liquids were not as favorable, making the traditional liquid-liquid extraction processes not suitable for the removal of aliphatic S-compounds due to the high volume of extractant required. This work explores alternative methods and proposes the use of ionic liquids in a separation process assisted by membranes. In the process proposed the ionic liquid is used as extracting solvent of the sulfur species, in a hollow fiber membrane contactor, without co-extracting the other jet-fuel compound. In a second contactor, the ionic liquid is regenerated applying a sweep gas stripping, which allows for its reuse in a closed loop between the two membrane contactors. This integrated extraction/regeneration process of desulfurization produced a jet-fuel model with sulfur content lower than 2 ppm of S, as envisaged by legislation for the use of ultra-low sulfur jet-fuel. This result confirms the high potential for development of ultra-deep desulfurization application.

Assessment of hydrogen sulfide removal from biogas using a field scale anoxic biotrickling filter.

Hydrogen sulphide is one of the most toxic and corrosive compound present in swine-derived biogas streams.In this study, afield scale biotrickling filter for the removal of hydrogen sulfide was investigated.A Biofilter packed with supporting biofilm materials was fed continuously with a proprietary nutrient solution and operatedfor over 73days. The system has been operating with a H2S inlet concentrations ranging from 1,000to 3,000 ppm.Significant removal efficiencies >95% was demonstrated. pH of the stock feeding solution decreased from 6.2 to as low as 3.5within couple days.The resulting drop in pH provided circumstantial evidence to support biological H2 Soxidation to sulphuric acid by sulfide-oxidizers. Sulfur precipitation was also observed to occur. The results suggested that H2S removal from biogas stream can be efficiently achieved using portable, low cost and maintenance free biotrickling filters.