Mixed oxide supported hydrodesulfurization catalysts—a review

Support effects form important aspect of hydrodesulfurization (HDS) studies and mixed oxide supports received maximum attention in the last two decades. This review will focus attention on studies on mixed oxide supported Mo and W catalysts. For convenience of discussion, these are divided into Al₂O₃ containing mixed oxide supports, TiO₂ containing mixed oxide supports, ZrO₂ containing mixed oxide supports and other mixed oxide supports containing all the rest. TiO₂ containing mixed oxides received maximum attention, especially TiO₂–Al₂O₃ supported catalysts. A brief discussion about their prospects for application to ultradeep desulfurization is also included. An overview of the available literature with emphasis on research carried out in our laboratory form the contents of this publication.     

Mean residence time of gas in mechanically agitated gas–liquid contactors

In the present study of gas–liquid contactors, mean residence/contact time was calculated from knowledge of superficial velocity and the gas phase hold-up, for various gas rates and impeller geometry and speeds, and compared with values obtained from RTD measurements. A new correlation, involving Flow Number, Froude Number, system geometry and the physical properties, is proposed. This uses the authors data and those available in literature.     

Multi-site phase transfer catalyst assisted radical polymerisation of glycidyl methacrylate using potassium peroxydisulphate as initiator – a kinetic study

In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate (PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has been proposed to account for the experimental observations and its significance discussed.     

Solar/UV-induced photocatalytic degradation of three commercial textile dyes.

The photocatalytic degradation of three commercial textile dyes with different structure has been investigated using TiO(2) (Degussa P25) photocatalyst in aqueous solution under solar irradiation. Experiments were conducted to optimise various parameters viz. amount of catalyst, concentration of dye, pH and solar light intensity. Degradation of all the dyes were examined by using chemical oxygen demand (COD) method. The degradation efficiency of the three dyes is as follows: Reactive Yellow 17(RY17) > Reactive Red 2(RR2) > Reactive Blue 4 (RB4), respectively. The experimental results indicate that TiO(2) (Degussa P25) is the best catalyst in comparison with other commercial photocatalysts such as, TiO(2) (Merck), ZnO, ZrO(2), WO(3) and CdS. Though the UV irradiation can efficiently degrade the dyes, naturally abundant solar irradiation is also very effective in the mineralisation of dyes. The comparison between thin-film coating and aqueous slurry method reveals that slurry method is more efficient than coating but the problems of leaching and the requirement of separation can be avoided by using coating technique. These observations indicate that all the three dyes could be degraded completely at different time intervals. Hence, it may be a viable technique for the safe disposal of textile wastewater into the water streams.     

Effect of organic dopants on electrodeposition and characteristics of polyaniline under the varying influence of H2SO4 and HClO4 electrolyte media

Electrodeposition of conducting polyaniline (Pani) was made under potentiostatic condition at pH 1.0 in different electrolyte media (H₂SO₄ and HClO₄) in the absence and presence of two organic dopants, disodium salts of naphthalene-1,5-disulphonic acid (NSA) and of catechol-3,5-disulphonic acid (CSA). The rate and yield of Pani deposition were dependent on the acid medium and the dopant employed. NSA in H₂SO₄ caused an increase in rate and yield but CSA decrease when compared to the rate and yield of H₂SO₄ alone. In HClO₄ medium, both the dopants showed a decrease. With regard to DC electrical conductivity, both the dopants exhibited an enhancement in H₂SO₄ medium but NSA a decline in HClO₄. Characterisation of the electrosynthesised polymer samples by various instrumental techniques (cyclic voltammetric: CV, FTIR, UV-Visible: UV-Vis, EPR, XRD, TGA and DTG methods) revealed that between the two acid media, H₂SO₄ was the better one. Further, it enlightened the role of two organic dopants in relation to the acid media. The advantageous role of NSA in H₂SO₄ had origin on its molecular characteristics such as non-polarity, larger π-electron cloud etc., while CSA could not perform such a role because of its easily oxidisable hydroxyl groups. In HClO₄, however, both the dopants could play only an unfavourable role owing to its greater polarity and oxidizing power than H₂SO₄.     

Structural and electrical properties of brush plated ZnTe films

Zinc telluride thin films were deposited by the brush plating technique at a potential of −0.90 V (SCE) on conducting glass and titanium substrates at different temperatures in the range 30–90 °C. The films were polycrystalline in nature with peaks corresponding to the cubic phase. Direct band gap of 2.30 eV was observed. XPS studiers indicated the formation of ZnTe. Depth profiling studies indicated a uniform distribution of Zn and Te throughout the entire thickness. EDAX measurements were made on the films and it was found that there was a slight excess of Te. The carrier concentration was found to vary from 10¹⁴–10¹⁵ cm⁻³ with increase of substrate temperature. The mobility was found to vary from 5 to 60 cm² V⁻¹ s⁻¹.     

Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si/Al ratios

Al-SBA-15 of varying Si/Al ratios in the range 11.4–78.4 was synthesized using tri-block copolymer P123. The calcined materials were examined by XRD, pore size distribution, surface area, ²⁷Al NMR spectroscopy. The acidity and acid strength distribution were studied using microcalorimetric adsorption of NH₃. The acidic properties were also examined by cumene cracking reaction as a function of Si/Al ratios. Systematic variation of acidity and activity was observed as a function of Si/Al ratio. The initial heats of NH₃ adsorption correlated well with activity indicate that acid sites with ΔH > 100 kJ/mole is responsible for cumene cracking activity. Linear correlations were obtained with total acidity and cumene cracking activities. The tetrahedral aluminum was found to be responsible for the observed acidities and catalytic activities.     

Radiation-Induced Senescence Reprograms Secretory and Metabolic Pathways in Colon Cancer HCT-116 Cells

Understanding the global metabolic changes during the senescence of tumor cells can have implications for developing effective anti-cancer treatment strategies. Ionizing radiation (IR) was used to induce senescence in a human colon cancer cell line HCT-116 to examine secretome and metabolome profiles. Control proliferating and senescent cancer cells (SCC) exhibited distinct morphological differences and expression of senescent markers. Enhanced secretion of pro-inflammatory chemokines and IL-1, anti-inflammatory IL-27, and TGF-β1 was observed in SCC. Significantly reduced levels of VEGF-A indicated anti-angiogenic activities of SCC. Elevated levels of tissue inhibitors of matrix metalloproteinases from SCC support the maintenance of the extracellular matrix. Adenylate and guanylate energy charge levels and redox components NAD and NADP and glutathione were maintained at near optimal levels indicating the viability of SCC. Significant accumulation of pyruvate, lactate, and suppression of the TCA cycle in SCC indicated aerobic glycolysis as the predominant energy source for SCC. Levels of several key amino acids decreased significantly, suggesting augmented utilization for protein synthesis and for use as intermediates for energy metabolism in SCC. These observations may provide a better understanding of cellular senescence basic mechanisms in tumor tissues and provide opportunities to improve cancer treatment.     

Effect of sintering on the catalytic functionalities of MOS2/Al2O3 catalysts

Effect of sintering on physico-chemical and catalytic properties of Mo, Co-Mo, Ni-Mosupported on -Al₂O₃ is reported. Such effects on hydrodesulfurization (HDS), hydrogenation (HYD) and hydrodeoxygenation (HDO) are investigated as a function of sintering temperature. The results indicated that HDS and HYD have different optimum calcination temperatures and these functionalities originate from different sites. The results are discussed in the light of molybdenum sulfide dispersion, promotional effects and phase transformations of active component, promoters and support.     

Halogen-free acylation of toluene over FeSBA-1 molecular sieves

Three-dimensional cage type iron substituted mesoporous silica with different iron contents (FeSBA-1) was synthesized in a highly acidic media using cetyltriethylammonium bromide and tetraethylorthosilicate as a template and a silica source, respectively. Acylation of toluene with acetic anhydride (AA) was carried out over FeSBA-1 mesoporous catalysts with different n_Si/n_Fe ratios in the temperature range 80–180 °C for a time-on-stream of 1–6 h under liquid phase conditions. The important factors affecting the conversion and the selectivity of the reaction, such as the reaction temperature, feed ratio, catalyst weight and time-on-stream were studied and the results are discussed in detail. The reaction conditions were optimized and the n_AA/n_Toluene ratio of 2 and catalyst weight of 0.1 g (3.3 wt% of total reaction mixture) were maintained for all catalytic runs. It was found that the catalytic activity is strongly influenced by the amount of tetrahedral iron in the catalysts. Among the catalysts used in the present study, FeSBA-1(36) showed a high toluene conversion and selectivity to p-methylacetophenone (p-MAP) under the optimized reaction conditions. It was also found that the selectivity for p-MAP was always higher than m-MAP and o-MAP for all the catalysts and the activity of the catalysts changes in the following order: FeSBA-1(36) > FeSBA-1(90) > FeSBA-1(120).