Effect of water on HDS of DBT over a dispersed Mo catalyst using in situ generated hydrogen

A novel process was developed for the bitumen emulsion upgrading, wherein emulsion breaking and upgrading occurred in the same reactor using H₂ generated in situ from the water in the emulsion via the water gas shift reaction (WGSR). In this study, dibenzothiophene (DBT) was chosen as a model compound to investigate the effect of water and in situ H₂ on hydrodesulfurization (HDS). All the experiments were performed in a 1-L autoclave reactor at temperatures between 300 and 380 °C using in situ H₂ and ex situ H₂ (externally supplied H₂) over a dispersed Mo catalyst formed from phosphomolybdic acid (PMA). At very low water content, water was found to promote the HDS reaction in the ex situ H₂ run probably because it facilitates the formation of more active dispersed MoS_x species. At higher water content, however, water inhibits every individual reaction in the reaction network in the HDS of DBT, blocking the hydrogenation pathway more than the hydrogenolysis pathway. The relative reactivity of the in situ and ex situ H₂ depends on the water content present in the reaction system. At an optimized mole ratio of H₂O:CO (1.35), higher HDS activity was observed in the in situ H₂ run compared to ex situ H₂ run, and particularly, the hydrogenation pathway was promoted in the in situ H₂ run.     

Processing and Properties of TiB2 with MoSi2 Sinter-additive: A First Report

The densification of non-oxide ceramics like titanium boride (TiB₂) has always been a major challenge. The use of metallic binders to obtain a high density in liquid phase-sintered borides is investigated and reported. However, a non-metallic sintering additive needs to be used to obtain dense borides for high-temperature applications. This contribution, for the first time, reports the sintering, microstructure, and properties of TiB₂ materials densified using a MoSi₂ sinter-additive. The densification experiments were carried out using a hot-pressing and pressureless sintering route. The binderless densification of monolithic TiB₂ to 98% theoretical density with 2–5 μm grain size was achieved by hot pressing at 1800°C for 1 h in vacuum. The addition of 10–20 wt% MoSi₂ enables us to achieve 97%–99%ρ_th in the composites at 1700°C under similar hot-pressing conditions. The densification mechanism is dominated by liquid-phase sintering in the presence of TiSi₂. In the pressureless sintering route, a maximum of 90%ρ_th is achieved after sintering at 1900°C for 2 h in an (Ar+H₂) atmosphere. The hot-pressed TiB₂–10 wt% MoSi₂ composites exhibit high Vickers hardness (∼26–27 GPa) and modest indentation toughness (∼4–5 MPa·m^1/2).     

Microstructure and Properties of Spark Plasma-Sintered ZrO2–ZrB2 Nanoceramic Composites

In a recent work, ¹ we have reported the optimization of the spark plasma sintering (SPS) parameters to obtain dense nanostructured 3Y-TZP ceramics. Following this, the present work attempts to answer some specific issues: (a) whether ZrO₂-based composites with ZrB₂ reinforcements can be densified under the optimal SPS conditions for TZP matrix densification (b) whether improved hardness can be obtained in the composites, when 30 vol% ZrB₂ is incorporated and (c) whether the toughness can be tailored by varying the ZrO₂–matrix stabilization as well as retaining finer ZrO₂ grains. In the present contribution, the SPS experiments are carried out at 1200°C for 5 min under vacuum at a heating rate of 600 K/min. The SPS processing route enables retaining of the finer t -ZrO₂ grains (100–300 nm) and the ZrO₂–ZrB₂ composite developed exhibits optimum hardness up to 14 GPa. Careful analysis of the indentation data provides a range of toughness values in the composites (up to 11 MPa·m^1/2), based on Y₂O₃ stabilization in the ZrO₂ matrix. The influence of varying yttria content, t -ZrO₂ transformability, and microstructure on the properties obtained is discussed. In addition to active contribution from the transformation-toughening mechanism, crack deflection by hard second phase brings about appreciable increment in the toughness of the nanocomposites.     

Organoclays for soil remediation: Adsorption of 2,4-dichlorophenol on organoclay/aquifer material mixtures studied under static and flow conditions

A column material containing organophilic clay particles was developed for soil remediation. 2,4-dichlorophenol adsorption on aquifer material with an effective particle diameter d < 1 mm and various partially modified dioctadecyldimethylammonium–montmorillonite/aquifer material mixtures were studied under static and flow conditions. The 2,4-dichlorophenol adsorption on the aquifer material was negligible. On organoclay/aquifer material mixtures the adsorption capacity increased with increasing organoclay content and the adsorption isotherms could be fitted by the Freundlich equation. In columns filled with organoclay/aquifer material mixtures, the 2,4-dichlorophenol retardation increased with increasing organoclay content up to 1% (w / w). Above 1.5–2.0% (w / w) the permeability of the column material decreased. The HYDRUS_1D model, which solves the convection–dispersion equation for solute transport, was used in a forward and inverse mode to simulate 2,4-dichlorophenol breakthrough in the columns. The simulations revealed that 2,4-dichlorophenol transport exhibited an additional kinetic effect not observed in the batch experiments.     

Reinforcing effect of silica on the properties of styrene butadiene rubber–reclaim rubber blend system

Incorporation of silica into styrene butadiene rubber (SBR)–reclaim rubber (RR) blend system was carried out by sol–gel technique and conventional method. A well known silica coupling agent bis(3‐triethoxysilyl propyl) tetrasulfide was found to affect the curing characteristics and mechanical properties of SBR/RR vulcanizate. Here, the effect of RR on silica reinforcement was studied for different SBR/RR blend system. Silica incorporation by conventional mechanical mixing in absence of TESPT showed a much higher tensile properties than that of silica incorporated by the in situ sol–gel reaction of tetraethoxy silane both in presence and absence of TESPT. Studies of equilibrium swelling in a hydrocarbon solvent were also carried out. ATR study indicates that RR forms bond with silica particles due to the presence of active functional site on RR. The amount of silica incorporated by sol–gel reaction was determined through thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) studies further indicate the coherency and homogeneity in the silica filled SBR/RR vulcanizate. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 957–968, 2006     

Kinetics of alkylation of phenol with methanol over Ce-exchanged NaX zeolite

The alkylation of phenol with methanol was investigated in vapor phase over a series of cerium-exchanged NaX zeolite with Ce loadings ranging from 0 to 10.43 wt%. The catalyst MX-4 with 8.86 wt% cerium was found to be the best one with total cresols selectivity of 72% at a temperature of 573 K and MeOH to phenol mole ratio of 4:1. The catalyst was also found to be quite stable in the operating range investigated. It was established that the stronger acid sties are required for C-alkylation compared to O-alkylation. From the study of the effects of various parameters, the optimum operating condition for highest cresols selectivity were determined as: MeOH to phenol mole ratio, 4:1; temperature, 623 K; space-time, 10.2 kg h/kgmole under atmospheric pressure. From the kinetic analysis of the experimental data, the apparent activation energy for the reaction was determined as 57.2 kJ/mole.     

Transient testing of soy methyl ester fuels in an indirect injection,compression ignition engine

An evaluation of the exhaust emissions from a compression ignition engine for fuels composed of 100 and 30% methyl esters of soy oil (SME) is described. These fuels were compared with a low-sulfur, petroleum #2 diesel fuel in a Caterpillar 3304, prechamber, 75 kW diesel engine, operated over heavy- and light-duty transient test cycles developed by the United States Bureau of Mines. More than 60 h of testing was performed on each fuel. The objective was to determine the influence of the fuels upon diesel particulate matter (DPM) and gaseous emissions. The effect of a modern diesel oxidation catalyst (DOC) also was determined in an effort to minimize emissions. Neat SME produced a higher volatile fraction of the DPM, but much less carbon soot fraction, leading to overall DPM reductions of 23 to 30% for the light- and heavy-duty transients. The DOC further reduced the volatile fraction and the total DPM. The SME fuel reduced gaseous emissions of CO by 23% and hydrocarbons by over 30% without increasing NO_x. The DOC further reduced CO and hydrocarbon levels. Mutagenicity of the SME exhaust was low. Results indicate that SME fuel, used with a proper DOC, may be a feasible emission reduction technology for underground mines. References to specific products do not imply endorsement by the U.S. Bureau of Mines, a now defunct agency.     

Microwave-Hydrothermal Processing of BiFeO3 and CsAl2PO6

Microwave-hydrothermal (M-H) processing was compared with conventional-hydrothermal (C-H) processing in the crystallization of BiFeO₃ and CsAl₂PO₆ phases. The presence of the microwave field led to accelerated kinetics of the crystallization of both these phases as detected by powder X-ray diffraction. The acceleration of reaction rates under microwave field is expected to lead to energy savings during ceramic processing.     

Study of wettability test of pure aluminum against uncoated and coated carbide inserts

The wide application of aluminum in different industries has increased the need for finding the suitable cutting tool. In contrast to ferrous materials, the dry machining of aluminum is a great challenge. Wetting test is widely used to find out the chemical affinity of aluminum with different tool materials before proceeding for actual machining. Wettability tests were carried out in a high vacuum brazing chamber to find out the spreadability of aluminum on cutting tools. Mono or multilayer coated carbide tools with a top coating of TiC, TiN, Al₂O₃, TiB₂, MoS₂ and diamond on cemented carbide (WC-Co) cutting tool inserts were used in the experiment. The results revealed that diamond/graphite is the most inert for aluminum.     

Poly(ethyleneterephthalate) glycolysates as effective toughening agents for epoxy resin

The potential of poly(ethyleneterephthalate) glycolysates toward improving the energy absorption characteristics of cycloaliphatic epoxy resins has been explored. Microwave‐assisted glycolytic depolymerization of PET was performed in the presence of polyether diols of different molecular weights. The obtained glycolysates were blended with epoxy, and their mechanical properties were studied under both quasi‐static and dynamic conditions. Significant improvements were observed, which were found to depend both on the amount as well as nature of glycolysate. Amine functionalities were introduced at the terminal positions of glycolysates to improve the compatibility between the two phases. The amine derivatives exhibited superior performance and the Mode I fracture toughness (K_IC) of epoxy increased by ～18% in optimized compositions, which is indicative of its improved notch sensitivity. Neat epoxy specimens fractured in a brittle fashion, but all the blends exhibited ductile failure, as evidenced by surface morphological investigations. The mechanical properties of epoxy blends prepared with analogous aliphatic polyols, both before and after amine functionalization, were also studied which clearly reveal the beneficial role of aromatic groups toward improving the toughness of the base cycloaliphatic epoxy resin without compromising on the material stiffness. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39941.