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.     

Study of heat-treated Spanish lignites: Characteristics and behaviour in co2 and o2 gasification reactions

Six Spanish lignites (raw and demineralized) have been charred to 1113 K in a N₂ atmosphere. The surface area, porosity and mineral matter content of the char coals so obtained have been studied, as well as their reactivity in CO₂ flow in the range 1073–1113 K, and in dry air in the temperature range 733–773 K. The reactivities of the raw chars in CO₂ may be explained according to the different inorganic matter content that may act as catalyst. The demineralization process brings about a lowering in reactivity and an increase, in general, in the apparent activation energy that may be interpreted as being due to a fall in mineral matter content and/or an increase in the amount of feeder pores. With regard to reactivity and apparent activation energy, in the case of dry air three groups of raw chars have been established. The differences between these three groups may be due to the different inorganic impurities present in the raw chars that catalyse the reaction of carbon with O₂ more than the porous texture parameters. Demineralization brings about a lowering in the reactivity values and a levelling off of apparent activation energies. The catalytic effect of iron has also been studied by adding different amounts of this metal to a demineralized char. The burn-off versus time curves of the different char coals have been adjusted by using the τ_0.5 parameter.     

ZnFe anomalous electrodeposition:: stationaries and local pH measurements

The kinetics of ZnFe codeposition was investigated in acid solutions. The effects of solution composition and pH were analyzed. Inhibition of H⁺ reduction and Fe deposition occurs with increasing Zn⁺⁺ concentration in sulfate solution. An activation of Zn deposition is also observed. Increasing pH causes Zn deposition activation during ZnFe codeposition. The anomalous codeposition is also favored in chloride medium. When alloy deposition becomes the main process, the interfacial pH is governed by the individual metal deposition that controls the kinetic behavior. The interfacial pH increases during separate Fe deposition, meaning that it occurs with simultaneous consumption of H⁺. Individual Zn deposition brings about an H⁺ inhibition. A correlation between the codeposition behavior of ZnFe and ZnNi in sulfate and chloride solutions suggests that the prevailing cathodic reaction governs the interfacial pH. Anomalous codeposition process does not seem to be associated with a saturation of any thermodynamic species at the electrode surface. It can only be described by kinetic arguments.     

Chemistry of hydrogen sulphide under coal liquefaction conditions: 1. Modelling hydrogen transfer catalysis

The work reported here represents initial attempts to develop a complete kinetic and mechanistic understanding of the reaction chemistry of H₂S under coal liquefaction conditions, using both model systems and coal. Hydrogen sulphide was found to promote/catalyse the transfer of hydrogen from tetralin to 2-hydroxyquinoline (2-HOQ). The presence of H₂S can increase the rate of hydrogen transfer from tetralin to 2-HOQ by a factor of 10 compared with the same reaction run in the absence of H₂S. The energy of activation for hydrogen transfer was found to decrease by ≈5 kcal mol⁻¹ in the presence of H₂S. The presence of H₂S was also found to promote loss of oxygen from 2-HOQ to form small amounts of quinoline. No evidence of CC or CN bond cleavage in 2-HOQ was noted under any of the reaction conditions studied. These results suggest that the presence of H₂S reduces the temperatures necessary to promote effective hydrogen transfer from tetralin by 50–75 °C. Moreover, they imply that similar effects occur in H₂S-promoted coal liquefaction.     

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.     

The leaching of chlorine from hard coal: Part I. Relationship between the process parameters and its effectivity

In the study the research potential offered by the Scanning Electron Microscope to investigate into the surface of hard coal for mineral substances, especially of chlorine, was utilized. The identification of such substances - basing upon the resulting X-ray spectra and photographs - allowed one to corroborate the usefulness of further investigation step - viz. leaching. Variable parameters in those investigations were: grain size, leaching temperature, time and leaching cycles. Of great importance for the efficiency of the leaching process is granulation. The smaller the grain of coal, the more chlorine was removed because the opening of pores closed in the process of fragmentation increases the carbon surface available for water molecules.     

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.     

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.     

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.     

Contribution of acoustic emission technique for monitoring damage of rubber coating on metallic surfaces: Comparison with electrochemical measurements

Chlorobutyl coatings are industrially applied on metallic inner walls of HCl storage tanks, in order to protect steel against corrosion. Rubber coating constitutes an efficient barrier against HCl penetration up to metallic surface; yet, traces of monochlorobenzene (MCB) into HCl solutions can locally damage the coating and induce both acid infiltration and rapid corrosion of steel under the coating. Acoustic emission (AE) technique, due to its non-intrusive feature and its sensitivity, is a potential technique for the detection of polymer coating damage as well as metallic corrosion under the coating. In that context, this technique was coupled and compared to electrochemical measurements at least for metal damage evaluation. AE signals produced by corrosion of bare metal in HCl solution were first characterized, and then AE and electrochemical results obtained during metal and/or coating damage were compared, in the case of physical or chemical deteriorations of the coating, in an HCl solution containing traces of monochlorobenzene. In case of physical coating damaging, AE and polarisation resistance measurements are in good correlation as soon as metallic corrosion starts. When polymer coating suffers a solvent impregnation, previously to HCl solution contact, acoustic activity increases as soon as corrosion under the coating occurs, whereas polarisation resistance measurements do not allow detecting corrosion of steel.     

Alkali-silica reaction: A method to quantify the reaction degree

We propose a new chemical method for quantitative measurement of the reaction degrees of the alkali-silica reaction (ASR). We apply this method to a crushed natural reactive aggregate kept in contact with an alkaline solution, lime saturated by an appropriate amount of portlandite. This chemical system is designed to model the concrete capillary pores alkaline solution, in contact with reactive aggregates. Two reaction steps are taken into account in the mechanism: formation of Q₃ sites made by breaking up siloxane bonds of the reactive silica and dissolution of these Q₃ sites. The dissolution degree is measured by a selective acid treatment, and the nature of silica into solution is characterised by liquid NMR spectroscopy. The remaining silica is composed of Q₄ tetrahedrons and Q₃ protonated sites identified by solid NMR spectroscopy. These Q₃ protonated sites are measured by thermogravimetry analysis. We show that the formation Q₃ sites prevails on dissolution as the reaction progresses and contributes to an internal silica gel generation. The limiting step is the siloxane breaking up. Petrographic observations show that the reaction front penetrates in the aggregate through its porosity.     

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.     

Compatibility and incompatibility in anticorrosive painting: The particular case of maintenance painting

Despite being one of the most widely used anticorrosive protection techniques, painting often leads to incompatibility problems. Maintenance painting is also a common technique in the anticorrosive protection of metallic structures and equipment in general. When the maintenance work to be performed foresees using an old (aged) coating as an integral part of the new paint system to be applied, it is of vital importance to ensure the compatibility of the different components. Otherwise, premature failure, (bleeding, lifting blistering, cracking, etc.) may occur in a short time period. Using a previously defined methodology, this paper studies the behaviour of a number of new paint systems applied on aged paint coatings containing different types of finishing paints. Through the performance of accelerated and non-accelerated ageing tests it has been possible to select the new paint systems that are most suitable for application on old (aged) paint systems, thus allowing a reduction in the risk of incompatibility between the two.     

Infrared spectroscopic studies of adsorption and catalysis: IV. Aliphatic ketones on silica-supported nickel

The adsorption and decarbonylation of acetone, acetone-d₆, and diethylketone on silica-supported nickel have been studied between 25 and 200 °C using infrared spectroscopy. After a short period of adsorption, two surface species were observed spectroscopically at 25 °. The main one is considered to be the associatively adsorbed ketone R₂CM-OM (M = surface metal atom). The minor one is a carbonyl-containing species possibly involving a complete acetone molecule held to a metal site through a relatively weak σ-bonded interaction with the carbon atom of the carbonyl group, or a π-bonded interaction with the carbonyl group as a whole. Over longer periods of time, bands were observed which are attributable to R₂CH · OSi groups (Si = surface silicon atom of the support). These probably result from the reduction of the ketone to R₂CHOH molecules which then react with OH groups of the silica surface. The hydrogen needed for the reduction process may arise from disproportionation of some of the dissociatively adsorbed species.     

Film formation from monodisperse acrylic lattices: Part 3: Drying and ageing of acrylic latex films

The influence of drying/ageing on the structure and properties of acrylic latex films was investigated using turbidity measurements in combination with gravimetry, scanning electron microscopy (SEM), atomic force microscopy (AFM) and water vapour permeability. Ageing above the minimum film formation temperature (MFFT) leads to marked changes in a dried latex film, whereas, after ageing below the MFFT, changes are hardly found. Above the MFFT there is a continuous change in the film properties with time. This becomes obvious from the decreases in the regenerated interference minimum, water vapour permeability and corrugation height. The influence of ageing on the water absorption of the films is less straight forward. It was expected that films with a more compact structure would absorb less water. This is correct for short drying times only, from 0.5 to 3 h. Ageing of better-dried films, however, yields the opposite result: by increase of the ageing time from 3 to 150 h the water uptake increases. There are various reasons for this increase; they are discussed briefly.     

Upgrading of flash pyrolysis tars to synthetic crude oil: 1. First stage hydrotreatment using a disposable catalyst

The hydrotreatment of tars produced by flash pyrolysis of Millmerran (subbituminous), Loy Yang and Yallourn (both brown) Australian coals was investigated in a continuous reactor containing a packed bed of sulphided steelwool. Reactor performance and product yields are reported for each tar. Overall mass balances of 96.7–100.3% and carbon balances of 96.0–100.2% were achieved. Recovered yields of product oil were 82.7–86.8%, 62.1% and 75.5% wt/wt dry, char-free tar for Millmerran, Loy Yang and Yallourn tars respectively. The steelwool reactor was found to decrease the coking propensity, specific gravity, viscosity and heteroatom levels and to increase the hydrogen content of the tars. It also acted as a filter to remove the char fines present in the tar. The operating life of the reactor was limited by the build up of carbonaceous deposits within the steelwool.     

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.     

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.