Coal liquefaction by hydrogen produced from methanol: 3. Examination of reaction conditions

Coals were liquefied in a 50 ml autoclave using hydrogen produced from methanol with decomposition and hydrogenation catalysts under various conditions. The conversion increased with increasing reaction temperature and time. This reaction is more suitable for the liquefaction of lower-rank coals. The hydrogen pressure had little effect on the conversion in the range of the ratio of methanol to coal of 2 g/g. The use of a solvent is very effective in increasing the liquefaction, especially at short times.     

Microstructure refinement of alumina: Optimisation by gas pressure sintering process

This paper investigates densification and grain growth evolutions during gas pressure sintering of alumina. Isothermal sintering runs are performed under different nitrogen pressures: atmospheric pressure and 2 MPa. Experimental data are fitted thanks to constitutive laws in order to understand nitrogen pressure effect on densification and grain growth mechanisms of a fine-grained alumina. An optimal run of densification is proposed as an application of these results.     

Chemistry of hydrogen sulphide under coal liquefaction conditions: 2. Synergistic effects of H2S and the mixed solvent system tetralin and tetrahydroquinoline on liquefaction of a moderately reactive coal

A preliminary study was undertaken to evaluate the effects of mixed solvents and added H₂S on the overall conversions of a moderately reactive coal (Wyodak-2) as defined by tetrahydrofuran solubility. Conversion efficiencies were measured as a function of time and of H₂S concentration in the H₂S-tetrahydroquinoline (THQ) solvent system. The specific solvent systems studied included tetralin and mixtures of tetralin and THQ, with and without H₂S. In all cases, coal conversion was enhanced by the presence of H₂S, THQ or both, relative to the use of tetralin alone. Conversion as a function of THQ concentration was also determined. The relative abilities of the various combinations to effect conversion were found to be as follows: tetralin < 5 wt% THQ-tetralin < 3 wt% H₂S-tetralin < 10 wt% THQ-tetralin = 20 wt% THQ-tetralin < 3 wt% H₂S-20 wt% THQ-tetralin. From these results, it is concluded that both H₂S and THQ operate synergistically to provide enhanced yields of high-quality coal liquids. The relations between conversion, H₂S concentration and nitrogen incorporation are discussed.     

Non-destructive characterisation of alumina/aluminium titanate composites using a micromechanical model and ultrasonic determinations: Part II. Evaluation of microcracking

A method for non-destructive detection of microcracks in ceramic composites is described. The method involves the combination of ultrasound characterisation with the application of a three-phase micromechanical model, which considers cracks and pores as void constituents. Four alumina-aluminium titanate materials with different levels of microcracking, from no cracks (monophase alumina) to severely cracked (alumina + 40 vol.% of aluminium titanate) including an alumina + 10 vol.% aluminium titanate material with incipient microcracking have been developed to test the validity of the method. Specimens have been fabricated by colloidal processing and the longitudinal and transverse ultrasound velocities have been determined by the ultrasonic pulse-echo and transmission ultrasound-immersion techniques, employing a digital signal processing. It has been demonstrated that it is possible to differentiate between pores and microcracks, both modelled as void constituents, in terms of the aspect ratio.     

Cement composition and sulfate attack: Part I

Four cements were used to address the effect of tricalcium silicate content of cement on external sulfate attack in sodium sulfate solution. The selected cements had similar fineness and Bogue-calculated tricalcium aluminate content but variable tricalcium silicates. Durability was assessed using linear expansion and compressive strength. Phases associated with deterioration were examined using scanning electron microscopy and X-ray diffraction. Mineralogical phase content of the as-received cements was studied by X-ray diffraction using two methods: internal standard and Rietveld analysis.The results indicate that phase content of cements determined by X-ray mineralogical analysis correlates better with the mortar performance in sulfate environment than Bogue content. Additionally, it was found that in cements containing triclacium aluminate only in the cubic form, the observed deterioration is affected by tricalcium silicate content. Morphological similarities between hydration products of high tricalcium aluminate and high tricalcium silicate cements exposed to sodium sulfate environment were also observed.     

Non-destructive characterisation of alumina/aluminium titanate composites using a micromechanical model and ultrasonic determinations: Part I. Evaluation of the effective elastic constants of aluminium titanate

A method to evaluate the elastic constants of aluminium titanate in alumina/aluminium titanate composites is described. Results are derived from a three-phase micromechanical model proposed to relate the velocity of propagation of ultrasounds in the materials with their microstructural characteristics and the elastic behaviour of the constituents. Dense and un-cracked alumina and alumina + 10 vol.% aluminium titanate specimens have been fabricated by colloidal processing and the longitudinal and transverse ultrasound velocities have been determined by the ultrasonic jointly pulse-echo and transmission ultrasound-immersion techniques, employing a digital signal processing. In order to assure the adequacy of the proposed method, results for monophase alumina have been compared to those obtained from the resonance frequencies of high density alumina plates tested in flexure and shear. The values of elastic moduli obtained using the two methods were coincident, which assured the validity of the non-destructive proposed method.     

Simultaneous removal of asphaltenes and water from water-in-bitumen emulsion: II. Application feasibility

Application feasibility of the accelerated deasphaltening process for simultaneous removal of asphaltenes and water from a water-in-bitumen emulsion has been examined with a pilot plant having capacity of 1.590 m3/day. The solvent (n-pentane) was injected into the emulsion from three locations with progressively increasing temperature from 423 K. The first solvent injection precipitated the asphaltenes in bitumen, the second broke the emulsion and facilitated the phase separation, and the third extracted the oil that remained in heavy asphaltenes/water phase. The effects of operation parameters such as temperature, solvent/bitumen ratio, feed rate and feedstock composition on the quality of DAO (Deasphaltening oil) were investigated. The DAO with the yield of ~ 80 wt.% and asphaltene content of < 0.5 wt.% was produced under optimal operating conditions, and the residual product was a porous solids containing 38% sulfur, 47% nitrogen, 64% MCR, and 85% metals (nickel and vanadium) of the bitumen. For a real application in oil industry, other important aspects including energy efficiency, solvent recovery and water purification have been discussed.     

Entrained flow gasification of coal: 1. Evaluation of mixing and reaction processes from local measurements

Local mixing and reaction processes were studied within a laboratory-scale, entrained coal gasifier at atmospheric pressure, using a Utah high-volatile, low-sulphur bituminous coal at a design flow rate of 24.5 kg h⁻¹. The coal-oxygen-steam feed mass ratio was 1.00:0.91:0.27. A water-quenched sample probe was used to collect radial gas and char samples at seven different axial positions in the 124 cm long reactor for the measurement of gasification products and residual char composition. The observed carbon conversion was 79 ± 3%. Coal hydrogen and oxygen were converted more rapidly and more completely than carbon. Devolatilization, which occurred very rapidly near the inlet, led to most of this carbon conversion; heterogeneous char reactions with CO₂ and steam apparently accounted for the balance. Oxygen was consumed through reaction with volatiles very quickly in the upper gasifier region. These data were used to evaluate mixing and reaction characteristics within the reactor. Agreement of measurements with predictions from a generalized two-dimensional entrained coal gasification model was good.     

Conversion of bituminous coal in COH2O systems: 3. Soluble metal catalysis

The oxyanions of the highest oxidation states of several transition metals, including W, Mo, Cr and Mn, were found to catalyse the liquefaction of Illinois No. 6 coal in $\text{CO}\text{H}{}_2\text{O}$ systems at 400°C. Unlike the high pH (s> 12) required in the base-catalysed system, the effective range for these metal-mediated conversions extend down to pH < 5.0. The benzene-soluble product was found to have a higher $\text{H}\text{C}$ ratio than the starting coal, and the metals were reduced to water-insoluble, lower oxidation states during conversion. A chain scheme is suggested as an explanation for the data.     

Ash chemistry and mineralogy of an Indonesian coal during combustion: Part 1 Drop-tube observations

The paper reports a systematic and comprehensive laboratory investigation into the ash chemistry and mineralogical changes undergone by a low-rank Indonesian coal during combustion. Combustion experiments conducted in a drop-tube furnace included ash formation experiments (using cyclone and filter arrangement) under closely controlled conditions in the range of 1200–1400 °C and deposition experiments at a probe temperature of 750 °C. Tests conducted with raw coal, coal/additive mixtures and washed coal indicated significant changes in ash characteristics. Of the ash formation and deposit samples examined, the raw coal + bauxite showed the lowest glass content and high contents of corundum indicating low ash deposition propensities. When compared to the ash formation samples, the deposit samples showed even significantly lower glass contents and were enriched in quartz. With the exception of the raw coal + bauxite sample, all are characterized by high silica and iron and moderate aluminium contents. In contrast, the raw coal + bauxite sample have low silica and much higher alumina contents which is in agreement with XRD observations. QEMSCAN™ results showed that the ash particles are sparsely distributed suggesting lack of a deposit initiation layer. Experimental observations suggest that the use of raw coal with bauxite would appear to offer the best performance with respect to handling ash-related issues. Present findings are of practical significance to power utilities employing Indonesian coal as there is no comprehensive work reported in the literature on ash chemistry and mineralogy of such coals.     

Silicone-containing polymer matrices as protective coatings: Properties and applications

The paper addresses the technologically important problem of porous building materials protection, e.g. sandstone, limestone, marble against soiling. Protective coatings applied to the surface of porous building material should be characterized by very efficient water vapour permeability and self-cleaning properties.     

Chromate leaching from inhibited primers: Part I. Characterisation of leaching

Leaching and characterisation studies have been undertaken on two chromate-inhibited epoxy polyamide primers. Leaching was carried out in 5% (w/v) NaCl solutions at different pH values (1, 3, 5 and 7) and the amount of Cr released into solution was monitored over time. Cr release was initially high, but as the immersion time increased the leaching from the primers slowed. Prior to and after immersion, the primers were characterised by a number of techniques including electron microprobe analysis, X-ray microdiffraction, Raman spectroscopy, and positron annihilation lifetime spectroscopy. The unexposed primers were found to contain the inorganic phases SrCrO₄, BaSO₄ and TiO₂ (anatase or rutile). Upon immersion, water uptake by the primers was observed, together with a decrease in the amount of SrCrO₄ in the primers. These studies provide insights into the mechanism of chromate leaching from inhibited primers.     

Autogenous deformations of cement pastes: Part II. W/C effects, micro-macro correlations, and threshold values

A broad experimental study has been performed, from the end of mixing up to 2 years, on a set of plain cement pastes prepared with the same type I ordinary portland cement (OPC) and various water-to-cement ratios (W/C), and cured at various constant temperatures. Several parameters have been measured on the hydrating materials, such as chemical shrinkage, volumetric and one-dimensional autogenous deformations, degree of hydration of the cement, Ca(OH)₂ content and Vicat setting times. Drying shrinkage has also been measured on the mature materials. In this part II of the paper, the effects of W/C within the range 0.25-0.60 have in particular been analysed in relation to the microstructural characteristics of the materials. This micro-macro analysis has highlighted a W/C threshold value (located around 0.40) both at the macro-level (on autogenous, but also on drying deformations and durability-related properties) and at the micro-level (characteristics of the hydration products, MIP porosity and pore size distribution, etc.).In addition, volumetric and one-dimensional autogenous shrinkage deformations have been compared in the case of W/C=0.25 and T=20 °C. Finally, a critical twofold (chemical and structural) effect of calcium hydroxide has been found. When significant structural effects, generated by the formation and the growth of large-size Ca(OH)₂ crystals, take place, swelling can become prominent, as observed for one-dimensional autogenous deformations in the case of medium and high W/C, and deviations are recorded on linear relationships.     

Polymorphism of tricalcium silicate, the major compound of Portland cement clinker: 2. Modelling alite for Rietveld analysis, an industrial challenge

A comprehensive quantification of the various phases of clinkers by X-ray diffraction with a Rietveld-like analysis is an important industrial challenge. Various available structural models are used for the most frequent M1 and M3 polymorphs of alite usually found in industrial clinkers, referred to as M1- or M3-based clinkers. In this paper, the effect of C₃S structural model is investigated. Four models are tested and compared using either synthetic M1 and M3 alites or M1- and M3-based clinkers. The comparison validates the available models for M1 and M3 alites and an average model, given here, derived from our recently proposed M1 structure as a catch-all model when the nature of the clinker is unknown. The latter model is meant to be used for industrial on-line quantification.     

Polymorphism of tricalcium silicate, the major compound of Portland cement clinker: 1. Structural data: review and unified analysis

This paper reviews the literature devoted to structural investigations, with a special concern to the various notations used by different authors. A unified analysis of the known T1, M1, M3 and R polymorphs is proposed. The superstructure relations between the various unit cells are discussed, together with the evidence of common 1D and 2D structural elements in all these polymorphs. These structural elements are related to the observed properties.     

Study of direct type ethanol fuel cells: Analysis of anode products and effect of acetaldehyde

The anode products are observed when ethanol fuel is circulated in the direct ethanol fuel cell system using Nafion^® as an electrolyte. The main products are CO₂ and acetaldehyde. I-V characteristics of a direct type fuel cell using ethanol and acetaldehyde as fuels are investigated. Anode and cathode overpotentials are also measured to analyze the characters of the polarization curves obtained for both fuels. The MEA consisted of PtRu anode catalyst. The voltage drops as the concentration of acetaldehyde solution increases. In the case of ethanol solution, the voltage increases as the concentration increases. The anode overpotential increases as the concentration of acetaldehyde increases although the increase of cathode overpotential is smaller than that of anode overpotential. The opposite result is observed for ethanol solutions, i.e., the anode overpotential increases as the concentration of ethanol decreases. This result shows that the voltage drop observed for acetaldehyde solution results from the anode overpotential. Rotating disc electrode (RDE) measurements and polarization curve measurements were also performed to confirm the relation between acetaldehyde concentration and overpotentials. It is supposed that the electrocatalytic oxidation mechanism of acetaldehyde on PtRu catalyst is different from that of ethanol.     

Water electrolysis under microgravity: Part 1. Experimental technique

Water electrolysis was conducted in both alkaline (25 wt.% KOH, 2 wt.% KOH) and acid (0.1N H₂SO₄) solutions for 8 s under microgravity environment realized in a drop shaft. The gas bubble formation of hydrogen and oxygen on platinum electrodes was observed by CCD camera. In alkaline solutions, a bubble froth layer grew on the electrode surface. Hydrogen bubble size was smaller than that of oxygen. The current density at constant potential decreased continually with time. In spite of the growth of a bubble froth layer on the electrode, the electrolysis never stopped, apparently because fresh electrolyte is supplied to the electrode surface by microconvection induced by the gas bubble evolution. In acid solution, hydrogen gas bubbles frequently coalesced on the cathode surface, yielding a larger average bubble than that of oxygen. The current density did not vary at constant potentials from -0.4 to −0.8 V versus reversible hydrogen electrode (RHE), because the effective electrode surface area was significantly reduced by the larger bubble size compared to alkaline electrolyte. The present experiments indicate that, especially in a microgravity environment, the bubble evolution behavior and the resultant current-potential curves are significantly influenced by the wettability of the electrode in contact with the electrolyte.     

Simultaneous removal of asphaltenes and water from water-in-bitumen emulsion: I. Fundamental development

Simultaneous removal of asphaltenes and water from a water-in-bitumen emulsion by adding light paraffinic solvents was investigated with a bench-scale unit. Asphaltene precipitation in bitumen, emulsion breaking, and phase separation were found to be largely dependent on solvency and temperature. Increasing temperature facilitated the precipitation of asphaltenes in bitumen, and accelerated the separation of the light deasphalting oil (DAO)/solvent phase and the heavy asphaltenes/water phase. The removal of 98 +% asphaltenes and 99.9 +% water from the emulsion was achieved with the n-pentane/bitumen volumetric ratio of 3.0 in temperature range of 423–453 K. The interaction between asphaltene particles and water droplets is actually beneficial to the removal process. For process design and optimization, the operation pathway including two-step solvent injections at different temperature, the supercritical recovery of solvent from DAO stream and the solidification of asphaltenes by depressurization, as well as other important issues have been addressed.     

An identification study of vermiculites and micas: Adsorption of metal ions in aqueous solution

This study deals with the identification of vermiculite in the presence of mica. Three natural silicates were first subjected to expansion by rapid heat treated at 400 °C. Then, the starting silicates and their derived heat-treated products were analyzed by X-ray diffraction, FT-IR spectroscopy, N₂ adsorption at − 196 °C, and helium density measurement. The adsorption of cadmium, chromium, and lead was also carried out. Two of the silicates are composed of mainly biotite and the other of biotite and vermiculite. In general, the results of X-ray diffraction, FT-IR spectroscopy, and helium density measurements are well in agreement. The heat treatment at 400 °C has little effect on the chemical composition, structure, and texture of the silicates. The development of microporosity is small in the silicates. Surprisingly, the adsorption capacity toward chromium and lead is larger for the biotite silicate than for the vermiculite containing silicate.