Effects of pore fractal structures of ultrafine coal water slurries on rheological behaviors and combustion dynamics

The ultrafine coal water slurry (CWS) with the particle size of 1-10 μm, ash content of 1-2%, solid concentration of 50% is a promising substitute fuel for diesel oil. The effects of pore fractal structures of three ultrafine CWSs on their rheological behaviors and combustion dynamics were studied in this paper. When the pore fractal dimensions of Yanzhou, Huainan and Shenhua ultrafine CWSs increase, their apparent viscosities all increase and the increase extents gradually enlarge with decreasing shear rates, while their ignition temperatures and apparent activation energies all decrease. For example, when the pore fractal dimension of Yanzhou coal increases from 2.31 to 2.43, the CWS apparent viscosity at a low shear rate of 12 s⁻¹ increases from 75 mPa s to 2400 mPa s, and that at a high shear rate of 100 s⁻¹ increases from 80 mPa s to 820 mPa s. Meanwhile, the ignition temperature of Yanzhou CWS decreases from 445 °C to 417 °C at a heating rate of 12.5 °C/min, and the apparent activation energy decreases from 104 kJ/mol to 32 kJ/mol.     

The effect of scale and interfacial tension on liquid–liquid dispersion in in-line Silverson rotor–stator mixers

The effect of scale, processing conditions, interfacial tension and viscosity of the dispersed phase on power draw and drop size distributions in three in-line Silverson rotor–stator mixers was investigated with the aim to determine the most appropriate scaling up parameter. The largest mixer was a factory scale device, whilst the smallest was a laboratory scale mixer. All the mixers were geometrically similar and were fitted with double rotors and standard double emulsor stators. 1 wt.% silicone oils with viscosities of 9.4 mPa s and 339 mPa s in aqueous solutions of surfactant or ethanol were emulsified in single and multiple pass modes. The effect of rotor speed, flow rate, dispersed phase viscosity, interfacial tension and scale on drop size distributions was investigated.     

The importance of surface hydration and particle shape on the rheological property of silica-based suspensions

Two types of ball milling methods, wet planetary ball milling and dry tumbling ball milling, were used to grind fused silica powders for the preparation of silica-based suspensions in this experiment. The effect of surface hydration and particle shape caused by the two milling methods on the slurry rheology was investigated. The results showed that, with similar particle size distribution, the viscosity of the suspensions prepared from the powders milled by wet ball milling ranged from 275 mPa s to 311 mPa s within 20 min and the suspension exhibited a continuous shear thickening behaviour whereas the viscosity of the suspensions prepared from the powders milled by dry ball milling ranged from 69 mPa s to 74 mPa s and the suspension exhibited a shear thinning behaviour first, and then exhibited a slightly shear thickening behaviour. The reasons were attributed to the differences in surface hydration and particle shape. It was postulated that the two factors affected the slurry rheology through the modification of particle interactions during the flow of high concentration suspensions.     

A generalized model for predicting non-Newtonian viscosity of waxy crudes as a function of temperature and precipitated wax

Precipitated wax, shear and thermal history have pronounced effects on viscosity and rheological behavior of waxy crudes. On the basis of mechanism of waxy crude rheology, a shear-rate-dependent viscosity model has been developed by applying theory of suspension rheology. This model is characterized by its capability to predict viscosities of crude oils with various thermal and shear history and beneficiated with pour-point-depressants (PPD). Once viscosities at only two temperatures above the wax appearance temperature and apparent viscosities at one temperature in the non-Newtonian regime are known, viscosities or apparent viscosities at any temperatures above the gel point can be predicted by using the model together with the concentration of precipitated wax at that specified temperature. Verification by using 3458 viscosity data points ranging from 5 to 2900 mPa s from 33 virgin crudes and 14 PPD-beneficiated crudes with various thermal and shear history shows that the model predicts viscosities with an absolute average deviation of 7.43%. Furthermore parameters of rheological models such as the consistency coefficient K and the flow behavior index n of the power law model may be obtained by regressing predicted viscosity data and corresponding shear-rates.     

Ionic liquids based on guanidinium cations and TFSI anion as potential electrolytes

Sixteen new guanidinium salts based on small cations and TFSI⁻ anion were prepared and characterized. Physical and electrochemical properties of these products, including melting point, thermal stability, viscosity, conductivity and electrochemical window were investigated. Reducing symmetry of cations can reduce the melting points, and 12 products are liquids at room temperature. The viscosities of cg22TFSI, cg12TFSI and cg13TFSI were 45, 46 and 52 mPa s at 25 °C, respectively. Electrochemical and thermal stabilities of these ILs permitted them to become promising electrolytes used in electrochemical devices.     

Development of an improved falling ball viscometer for high-pressure measurements with supercritical CO2

This study presents the development of an improved technique for viscosity measurements under high pressure. The apparatus is based on the principle of the falling ball viscometer, implemented in a high-pressure autoclave fitted with visualisation windows. The originality here is that the balls fall through a tube open at both ends with a diameter slightly greater than that of the balls, allowing a simplified modelling and numerical simulation. A numerical approach has been used for viscosity determination. Calculations have been made with COMSOL Multiphysics^® with the laminar Navier-Stokes model for Newtonian mixtures. It includes the specific hydrodynamic effects without the need for a calibration fluid. However, validation experiments were carried out at atmospheric pressure with dimethylsulfoxide (DMSO) at 298, 308 and 318 K and with cocoa butter at 313 and 353 K, with values of viscosity in the range from 1.4 to 45.4 mPa s. Comparative measurements with literature data have been conducted with cocoa butter saturated with carbon dioxide at 313 and 353 K and for pressures ranging from 0.1 to 25 MPa. At 313 K, viscosity varies from 45.4 mPa s to 3.1 mPa s while at 353 K it varies from 12.4 to 1.9 mPa s. For both isotherms tested, within the range 0-15 MPa, the higher the CO₂ dissolution in the cocoa butter, the lower the viscosity. However, this decrease in viscosity is more pronounced at the lowest temperature. Above 15 MPa the CO₂ dissolution effect on viscosity becomes insignificant, i.e. within the experimental error, due to a counter effect linked with the high hydrostatic pressure. Furthermore, the limits of use of this method have been determined. This technique is revealed as reliable and can therefore be used with other binary systems.     

Two regime transitions to pseudo-homogeneous and heterogeneous bubble flow for various liquid viscosities

The gas hold-up variation and regime transition were investigated with different liquid viscosities ranging from 1.0 mPa s to 31.5 mPa s using a 0.15-m-in-diameter bubble column. In contrast to common observations, the gas hold-up graph with the superficial gas velocity could be categorized into three flow regimes: homogeneous, pseudo-homogeneous and heterogeneous flow regimes. The formation of large bubbles caused a transition from the homogeneous to the pseudo-homogenous flow regime, in which large bubbles rose vertically without oscillatory turbulence. According to the results from the dynamic gas disengagement (DGD) technique, large bubbles began to form at the transition superficial gas velocity to the pseudo-homogeneous flow regime. The transition to a heterogeneous flow regime was initiated by the turbulent movement of large bubbles. The transition superficial velocities to pseudo-homogeneous and heterogeneous flow regimes, u_t1 and u_t2, decreased with increasing liquid viscosity below a critical viscosity and converged to a certain value above that viscosity. However, the correlations from the literatures could not make a reasonable estimation of the transition superficial velocities because they did not consider the possible transition to a pseudo-homogeneous flow regime. Therefore, the two transition points should be predicted separately.     

Ionic liquids based on functionalized guanidinium cations and TFSI anion as potential electrolytes

Eight new functionalized guanidinium ILs based on small cations containing ether group (methoxyethyl group) or ester group (methyl acetate group) and TFSI⁻ anion were synthesized and characterized. Physical and electrochemical properties of these products, including melting point, thermal stability, viscosity, conductivity and electrochemical window, were investigated. All the products were liquids at room temperature, and they had low-melting points. The viscosities of cg1(2o1)TFSI and cg2(2o1)TFSI were 46 and 48 mPa s at 25 °C, respectively. Electrochemical and thermal stabilities of these functionalized guanidinum ILs permitted them to become potential electrolytes used in electrochemical devices.     

Investigations on the mechanical properties of hybrid nanocomposite hard coatings on polycarbonate

Hybrid nanocomposite coatings derived from titanium tetraisopropoxide and epoxy or acrylic modified silanes were deposited on polycarbonate (PC) by dip coating employing various withdrawal speeds followed by ultraviolet and thermal curing. The effect of different organic functional groups in the precursors and ageing effect of these sols were systematically studied with respect to thickness, abrasion resistance, pencil scratch test, nanoindentation hardness and transmittance. The gels derived from the freshly prepared and aged sols were structurally characterized by FT-IR and TEM analysis. The viscosities of the sols were monitored with time. The change in viscosity is rapid for sol from epoxy modified silane. The thickness of the coatings increases with increase in viscosity in case of both the silane precursors. The scratch as well as abrasion resistance increases as a function of coating thickness. The pencil scratch hardness improves from 2B for the bare PC to a maximum of 3H for the coating obtained from an aged sol derived from epoxy modified silane. Also, the abrasion resistance of the coatings from same sol was maximum as evidenced by a <6% change in haze after 500 cycles, vis-a-vis 40% for the bare PC. The coatings from a freshly prepared sol of acrylic modified silane and titania showed the maximum nanoindentation hardness of 0.52 GPa, when compared to 0.23 GPa for the bare PC.     

A simple device to test biodiesel process intensification

In this paper, we have studied the KOH catalyzed transesterification reaction of vegetable oil with methanol in a tubular reactor filled with small spheres of stainless steel of different sizes. Three different packed bed configurations have been tested corresponding to different fluid dynamic situations. The first configuration corresponds to the tubular reactor filled with spheres of 2.5 mm of diameters; in the second configuration an opportune amount of spheres of 1 mm has been added to the mentioned spheres of 2.5 mm for filling the void volume of the octahedral cavities between the bigger spheres; in the third configuration an opportune amount of spheres of 0.39 mm has been added to spheres of 2.5 mm for filling the void volume of the tetrahedral cavities between the bigger spheres. The three mentioned configurations give place to the formation of micro-channels with an approximated size of respectively 1000 μm, 500 μm and 300 μm. These systems, subjected to fluid dynamic characterization, have shown a very high local turbulence (static mixer), in particular, when a packed bed reactor with dual size packing is used. Then, kinetic transesterification runs have been made by using the three mentioned packed bed reactors and a very high productivity has been obtained as a consequence of the induced local micro-mixing. A simplified kinetic model has been developed, which is able to describe many runs in batch conditions reported by the literature. This model resulted unsuitable to simulate the continuous runs performed in the described packed bed reactors. Our conclusion is that monophasic models, often proposed in the literature, are not able to describe the kinetic behavior of KOH catalysed transesterification in microchannels devices. At last, the described microchannels device represents, as it will be discussed, an ideal connection between a traditional tubular packed bed reactor and the recently appeared microreactors that are very efficient in mass and energy transfer operations for process intensification.     

Physico-chemical properties of heavy crude oil-in-water emulsions stabilized by mixtures of ionic and non-ionic ethoxylated nonylphenol surfactants and medium chain alcohols

This work describes the formulation and evaluation of concentrated, heavy oil-in-water emulsions stabilized by mixtures of ethoxylated surfactants and normal alcohols. The rheology, stability and droplet size of these emulsions were investigated as functions of the emulsification process parameters. The parameters investigated for this study include emulsifier agent composition, presence of additives, pH and salinity of the continuous aqueous phase, emulsification temperature, oil content and emulsion aging. The produced emulsions had viscosities ranging from 30 to 150 mPa s and represent a 30-fold reduction of the crude oil viscosity. Sauter mean diameters of the droplets ranged from 10 to 50 μm. The emulsions were produced by mixing the oil with an aqueous solution containing medium normal-chain alcohols and small quantities of a mixture of ethoxylated nonylphenol and ethoxylated amine surfactants. The presence of these alcohols led to a sharp decrease in the droplet size of the emulsion. This size decrease had a direct impact on the emulsions’ stability and apparent viscosity. The rheological parameters of the aged emulsions were also essentially constant over a 42-day period.     

Preparation and characterization of oxide films containing crystalline TiO2 on magnesium alloy by plasma electrolytic oxidation

Oxide films have been produced on AM60B magnesium alloy using plasma electrolytic oxidation process in an alkaline phosphate electrolyte with and without addition of titania sol. The microstructure and composition of the oxide films were analyzed by Scanning Electron Microscope (SEM), X-ray Photoelectron Spectroscope (XPS) and X-ray Diffraction (XRD). The corrosion resistances of the oxide films were evaluated using potentiodynamic polarization measurements in 3.5 wt% NaCl solution. It is found that the oxide film containing crystalline rutile and anatase TiO₂ compounds are produced in an alkaline phosphate electrolyte with addition of titania sol. The oxide film formed in electrolyte with addition of titania sol has more uniform morphology with less structural imperfections than that formed in electrolyte without addition of titania sol. The results of potentiodynamic polarization analysis show that the oxide film formed in the present modified electrolyte is successful in providing superior corrosion resistance for magnesium alloy.     

Enhanced heavy oil recovery through interfacial instability: A study of chemical flooding for Brintnell heavy oil

This study is aimed at developing an alkaline/surfactant-enhanced oil recovery process for heavy oil reservoirs with oil viscosities ranging from 1000 to 10,000 mPa s, through the mechanism of interfacial instability. Instead of the oil viscosity being reduced, as in thermal and solvent/gas injection processes, oil is dispersed into and transported through the water phase to production wells.Extensive emulsification tests and oil/water interfacial tension measurements were conducted to screen alkali and surfactant for the oil and the brine samples collected from Brintnell reservoir. The heavy oil/water interfacial tension could be reduced to about 7 × 10⁻² dyn/cm with the addition of a mixture of Na₂CO₃ and NaOH in the formation brine without evident dynamic effect. The oil/water interfacial tension could be further reduced to 1 × 10⁻² dyn/cm when a very low surfactant concentration (0.005-0.03 wt%) was applied to the above alkaline solution. Emulsification tests showed that in situ self-dispersion of the heavy oil into the water phase occurred when a carefully designed chemical solution was applied.A series of 21 flood tests were conducted in sandpacks to evaluate the chemical formulas obtained from screening tests for the oil. Tertiary oil recoveries of about 22-23% IOIP (32-35% ROIP) were obtained for the tests using 0.6 wt% alkaline (weight ratio of Na₂CO₃ to NaOH = 2:1) and 0.045 wt% surfactant solution in the formation brine. The sandpack flood results obtained in this project showed that a synergistic enhancement among the chemicals did occur in the tertiary recovery process through the interfacial instability mechanism.     

Heat transfer and flow behaviour of aqueous suspensions of titanate nanotubes (nanofluids)

Titanate nanotubes of an aspect ratio of ~ 10 are synthesized, characterised and dispersed in water to form stable nanofluids containing 0.5, 1.0 and 2.5 wt.% of the nanotubes. Experiments are then carried out to investigate the effective thermal conductivity, rheological behaviour and forced convective heat transfer of the nanofluids. The results show a small thermal conductivity enhancement of ~ 3% at 25 °C and ~ 5% at 40 °C for the 2.5 wt.% nanofluid. The nanofluids are found to be non-Newtonian with obvious shear thinning behaviour with the shear viscosity decreasing with increasing shear rate at low shear rates. The shear viscosity approaches constant at a shear rate higher than ~ 100-1000 s^− 1 depending nanoparticle concentration. The high shear viscosity is found to be much higher than that predicted by the conventional viscosity models for dilute suspensions. Despite the small thermal conduction enhancement, an excellent enhancement is observed on the convective heat transfer coefficient, which is much higher than that of the thermal conductivity enhancement. In comparison with nanofluids containing spherical titania nanoparticles under similar conditions, the enhancement of both thermal conductivity and convective heat transfer coefficient of the titanate nanotube nanofluids is considerably higher indicating the important role of particle shape in the heat transfer enhancement. Possible mechanisms are also proposed for the observed enhancement of the convective heat transfer coefficient.     

The measurement and characterisation of residence time distributions for laminar liquid flow in plastic microcapillary arrays

Residence time distributions (RTDs) for a thermoplastic microreactor system were experimentally measured using fibre optic probes and step change concentration inputs. The distributions were then compared to models assuming plug flow superimposed by axial dispersion. The disc-shaped plastic microreactors contained microcapillary arrays of up to 19 parallel channels with diameters around 230 μm and lengths of 10 m. Two different systems were investigated, with either 1 or 19 active capillaries. The magnitude of axial dispersion in those two systems was characterised using Peclet numbers, which were in the range of 15-221 depending on flow rate, demonstrating that molecular dispersion along a single 10 m capillary can provide near plug flow characteristics. The multiple-capillary array showed small perturbations of this plug flow like RTD behaviour as the 19 microcapillaries displayed slight variations in diameter. These results confirm that the flow inside the presented plastic multiple capillary device provides a near plug flow behaviour for the use in continuous microreactors.     

Heavy crude oil viscosity reduction and rheology for pipeline transportation

Different methods of reducing the viscosity of heavy crude oil to enhance the flow properties were investigated. Experimental measurements were conducted using RheoStress RS100 from Haake. Several factors such as shear rate, temperature and light oil concentration on the viscosity behavior have been studied. This study shows that the blending of the heavy crude oil with a limited amount of lighter crude oil provided better performance than the other alternatives. Experimental measurements in terms of shear stress τ-shear rate and yield stress τ₀ were conducted on the mixture of heavy crude oil-light crude oil (O-light). The results showed a significant viscosity reduction of 375 mPa s at a room temperature of 25 °C. This study shows that the heavy crude oil required a yield stress of 0.7 Pa, whereas no yield stress was reported for the heavy crude oil-light crude oil mixture.     

Instrument for ceramic particle dispersion II: Computational fluid dynamics analysis

A planetary-type mixer using a container equipped with stainless steel mesh has been developed. For various slurries (Al₂O₃ in water), each modeled as Newtonian fluid, the shear stress was calculated using computational fluid dynamics (CFD) under various mixing conditions and with different equipment properties. The meshed-geometry included more than 100,000 nodes with hexahedral cells in one zone, with quadrilateral cells in the remaining zones. The fluid viscosity, rotation rate, and mesh opening affected the maximum shear stress. The shear stress increased concomitantly with increasing fluid viscosity. The container rotation rate and the maximum shear stress share a proportional relation. For a fluid with 9.2 mPa s, the shear stress was 134 Pa or more for a 0.81 mm and larger mesh opening, as observed at the bottom of the container. Mesh having an opening smaller than 0.81 mm generated high shear stress on the mesh surface. The maximum shear stress increased with decreasing mesh opening size. The particle size distributions of the Al₂O₃ particles in the slurries after treatment by the mixer were estimated under conditions similar to those of the calculations. Results show peaks in the particle size distributions of the Al₂O₃ particles in the slurries before treatment at 0.2 and 2-70 μm because of the primary particle size and agglomerates. The amounts of the agglomerate decreased concomitantly with the decreased mesh opening size. When slurries pass through the small mesh openings, high shear stress is generated. That achieves the good dispersion of the sub-micron sized Al₂O₃ particles in the slurry.     

Needle penetrometry with variable force loading for measuring viscosity of pelletized coal upon heating

A needle penetrometry was performed loading steady force in a range from 1×10⁻³ to 2 N to pelletized coal upon heating via a cylindrical needle. From the observed effects of shear rate on apparent viscosity of softening coal pellet, defined as the shear-rate to shear-stress ratio, it was found that the pellet behaved as a Newtonian fluid for shear rates lower than a critical one while as a pseudo-plastic fluid for higher shear rates. The penetrometry was also carried out varying the force with time. The variable force loading enabled to maintain the shear rate well below the critical one, and thereby to measure the apparent viscosity of coal pellets as Newtonian fluids over a temperature range from 600 to 800 K. Upon heating at 10 K min⁻¹, the apparent viscosity of Goonyella coal pellet decreased from about 10¹⁰ Pa s at 640 K down to a minimum of about 10⁴ Pa s at 755 K, and increased up to 10⁹ Pa s at 800 K. In a course of heating as above, the viscosity of Blind Canyon coal pellet decreased above 600 K, underwent a minimum of about 10⁶ Pa s at 715 K, and increased up to 10¹⁰ Pa s at 770 K. Decreasing the heating rate from 10 to 3 K min⁻¹ caused the minimum viscosities of the pellets to increase by 1-2 orders of magnitude.     

Dissolution and rheological behaviour of hematite and quartz particles in aqueous media at pH 1

In this study we investigate isothermal, atmospheric acid dissolution behaviour of quartz and hematite minerals which constitute two of the predominant host gangue phases of typical low grade limonitic laterite ores. Batch dissolution tests were carried out on 57 wt.% solid dispersions for 4 h at pH 1 and 25 and 70 °C to establish the influential role of oxide mineralogy/chemistry on rheology and leaching behaviour. The results show that the two minerals displayed a weakly temperature and time-independent, non-Newtonian rheological behaviour with low shear yield stresses (<4 Pa) and viscosities (9–17 mPa s). Hematite dissolution rate was significantly higher compared with that of quartz under similar conditions. Quartz dissolution mechanism was substantially volume diffusion controlled at lower agitation rate (600 rpm) whilst for hematite it was both volume diffusion and chemical reaction controlled. These mechanisms reflected activation energies of 17.7 ± 0.9 and 28.5 ± 1.4 kJ/mol, respectively, for quartz and hematite. At 800 and 1000 rpm, dissolution of both minerals was chemical reaction-controlled with similar activation energies (32.6 ± 1.7 and 32.2 ± 1.6 kJ/mol). The findings underscore the need for higher agitation rates and elevated temperatures, to overcome both volume diffusion and chemical reaction limitations for enhanced acid leaching of these two fairly refractory oxides studied herein.     

Porous titania microspheres with uniform wall thickness and high photoactivity

Highly porous titania particles were prepared by depositing thin films of titania, using alternating reactions of TiCl₄ and hydrogen peroxide, on poly(styrene-divinylbenzene) (PS-DVB) template particles via atomic layer deposition (ALD) at 77 °C. The composition of the titania films was verified by XPS analysis and the titania films were directly observed by TEM. TGA/DSC was used to study the thermal decomposition of the polymer template. Porous titania particles with uniform wall thicknesses were successfully obtained after the template PS-DVB was removed by oxidation in air at 400 °C for 24 h. Verification of the resulting porous structure of the titania particles was done by cross-sectional SEM and nitrogen adsorption–desorption analysis. Porous titania particles were treated at different temperatures. XRD analysis was used to determine the microstructure and phase transformation of titania at elevated temperatures. The photocatalytic activity of these porous titania particles was studied by methylene blue decomposition under UV light at room temperature and was found to be comparable to that of commercial anatase titania nanoparticles (~20 nm). Depositing Na₂SO₄ on TiO₂ retarded the TiO₂ phase transformation from anatase to rutile during calcination and, thus, greatly increased the photoactivity of the porous titania particles.