Hydrothermal dewatering of lower rank coals. 3. High-concentration slurries from hydrothermally treated lower rank coals

A novel method of producing a product of low intra-particle porosity (<1 μm pore radius) from highly porous Latrobe Valley raw brown coals uses a combination of hydrothermal and evaporative drying. Low porosity coal was made in three different batch autoclave systems at 320 °C for residence times as low as 10 min. Higher temperatures (up to 350 °C) increased porosity slightly but the water vapour pressure and the loss of organic material were significantly increased. Although the low and high porosity products differed dramatically in appearance and hardness, other chemical and spectroscopic properties were similar with the exception of pyrolysis-gas chromatography-mass spectrometry patterns.The relationship between intra-particle porosity and the maximum wt% dry solids concentration of aqueous slurries (for a viscosity of less than 1000 mPa s), ?_max, established by earlier workers for hydrothermally treated brown coals was found to hold for the new products and was extended to a wider range of porosities and a range of mean particle sizes (mps) (20-100 μm). A range of surfactants (anionic, cationic and neutral), which led to an increase of up to 7% in ?_max for a bituminous, Blair Athol coal, increased ?_max for products of hydrothermal or the new treatment by only 2-4%. This small increase resulted, however, in the formation of slurries of the low porosity products with ?_max's of up to 64%, similar to those obtained with high rank coals, and considered to be of commercial interest.     

Effect of processing conditions on organics in wastewater from hydrothermal dewatering of low-rank coal

A study was carried out into the effects of processing conditions on the nature and amounts of organics released into wastewater from hydrothermal dewatering (HTD) of low-rank coal. Processing conditions examined included temperature, residence time, water to coal ratio in the slurry, slurry loading, and coal lithotype. High temperature and pressure treatments of low-rank coal slurries were used to simulate the HTD process. It was found that the extent of extraction of organics during HTD processing depended on the coal lithotype and increased with increasing temperature, residence time, and the proportions of steam and water present during processing. For a constant residence time, the concentration of organics in the wastewater increased exponentially with temperature over the temperature range 250-350 °C. A maximum level of approximately 7 g/l (expressed as TOC) of organics was observed following processing at 350 °C. Hot filtration of the coal slurry produced a higher organics loading compared to that found in wastewater obtained at low temperature.     

The effect of the particulate phase on coal biosolubilisation mediated by Trichoderma atroviride in a slurry bioreactor

Low rank coal is currently under-utilised because of its low calorific value and high moisture and sulphur content. Its solubilisation by both bacterial and fungal cultures has been reported, the latter more commonly. Coal biosolubilisation processes have potential to convert low rank coal to either a clean, cost-effective energy source or complex aromatic compounds for biocatalytic conversion to value-added products. This can lead to an increased utilisation of low rank coal. In this study, the key variables of the slurry that affect biosolubilisation of low rank coal by Trichoderma atroviride in submerged culture were investigated. Results showed that the key operating variables that influence coal biosolubilisation in the slurry bioreactor are coal loading and particle size affecting available surface area. These factors affect the surface area available for coal biosolubilisation. The optimum coal loading occurred between 5 and 10% (w/v); an increase above this optimum led to inhibition of the fungal culture of T. atroviride (ES11) by fragmentation of the fungal mycelium. A decrease in particle size fraction led to an increase in the degree of coal solubilisation. Coal biosolubilisation was shown to increase 4-fold when particle size was decreased from 600–850 μm to 150–300 μm. A 28% biosolubilisation of coal of 150–300 μm, characterised by a surface specific area of 2.17 cm² g^− 1, was measured as coal weight loss over 14 days at solids loading at 5%. This can be compared with a 7.8% coal weight loss at 600–850 μm diameters (0.54 cm² g^− 1). Soluble phenolic compounds are not a significant product of the coal biosolubilisation process. The change in pH observed in the presence of both coal and fungi was independent of coal loading and was not directly related to the extent of coal solubilisation. While soluble intermediates were observed as total organic, further metabolism resulted in complete oxidation of a significant fraction of the coal to CO₂.     

RHEOLOGICAL BEHAVIOR OF LOW-RANK COAL-WATER SLURRIES

The rheological behavior of low-rank coal-water slurries was studied using a Brookfleld Rheolog viscometer. A Sarpy Creek subbituminous coal from Montana, with particle sizes ranging from 0.044 mm to 0.223 mm, was used. The solids concentration in the slurry varied from 15 to 65 weight % and the temperature was maintained constant at 82°F. The rheological behavior of the slurry made from as received coal was compared with that of the slurry made from hot water dried coal

Coal-water slurries, made from both as received and hot water dried coal exhibited pseudoplastic behavior. The shear stress was found to be related to the shear rate by the power law model. As expected, the apparent viscosity was found to increase sharply with solids loading. It was also observed that the apparent viscosities of the slurries made from hot water dried coal were lower than those made from as received coal.     

An extremely rapid, convenient and mild coal desulfurization new process: Sodium borohydride reduction

The present work describes the desulfurization of coal using mildly reductive method. Both a Yanzhou and a Yanshan coal (referred to as YZ and YS coal, respectively), were treated in an aqueous media employing sodium borohydride (NaBH₄) as reducing agent, which is a well known hydrogen storage. Reaction variables investigated include concentration of reductant, time, pH of initial media, temperature, stirring rate and particle size. The calorific values and ignition temperatures of the coal samples before and after treatment were determined. Results show that the total sulfur removal improved with the increase in the concentration of NaBH₄, shaking rate and temperature and with the decrease in the particle size. Meanwhile, decreasing the particle size from − 250 to − 109 μm increased the organic sulfur removal by more than six times for either of the coal samples. Considering economic rationality and operational convenience, the desulfurization conditions determined were 1.6 mM of NaBH₄ concentration, − 109 μm of particle size, neutral pH of initial media, 1 min of treated time, 100 rpm of shaking rate, 30 °C of temperature. This led to 23.8% and 59.0% reduction in the pyritic, 70.4% and 100% reduction in the sulfate, and 11.0% and 15.0% reduction in the organic sulfur, giving 31.3% and 40.8% reduction in the total sulfur for the YZ coal and the YS coal, respectively. Moreover, this resulted in the increase in the calorific values by 3.4-6.9% and the decrease in the ignition temperatures by 2-21 °C for the coal samples. The desulfurization method described here is extremely rapid, convenient, inexpensive and mild, and therefore, has considerable technological interest.     

RHEOLOGICAL BEHAVIOR OF LOW-RANK COAL-WATER SLURRIES

The rheological behavior of low-rank coal-water slurries was studied using a Brookfleld Rheolog viscometer. A Sarpy Creek subbituminous coal from Montana, with particle sizes ranging from 0.044 mm to 0.223 mm, was used. The solids concentration in the slurry varied from 15 to 65 weight % and the temperature was maintained constant at 82°F. The rheological behavior of the slurry made from as received coal was compared with that of the slurry made from hot water dried coal

Coal-water slurries, made from both as received and hot water dried coal exhibited pseudoplastic behavior. The shear stress was found to be related to the shear rate by the power law model. As expected, the apparent viscosity was found to increase sharply with solids loading. It was also observed that the apparent viscosities of the slurries made from hot water dried coal were lower than those made from as received coal.     

Fabrication of CaSiO3 bioceramics with open and unidirectional macro-channels using an ice/fiber-templated method

Porous CaSiO₃ bioceramics with open and unidirectional macro-channels of pore size more than 200 μm are of particular interest for biomedical applications. An ice/fiber-templated method was employed for the fabrication of CaSiO₃ bioceramics with interconnected lamellar pores and macro-channels of pore size more than 200 μm. The pores formed by ice crystals transformed from cellular to lamellar, while the pores formed by fibers were aligned macro-channels, which were also in alignment with the lamellar pores. Keeping the initial slurry concentration constant and increasing the packing density of fibers, the volume fraction of macro-channels and open porosity increased, and the compressive strength decreased. Maintaining the packing density of fibers and increasing the initial slurry concentration, the pore sizes of lamellar pores and open porosity decreased, and the compressive strength increased. The results indicated that it was possible to manufacture porous CaSiO₃ bioceramics with the macro-channels of 250–350 μm, lamellae spacing of 50–100 μm, open porosity of 71.12–83.94% and compressive strength of 0.87–3.59 MPa, indicating the suitability for tissue engineering.     

Multi-element determinations of N,N-dimethylformamide (DMF) coal slurries using ICP-OES

A slurry nebulisation technique was applied for elemental analysis of bituminous coals SARM 18, SARM 19 and four coals from three different seams in Witbank, South Africa, by inductively coupled plasma optical emission spectroscopy (ICP-OES). Major elements (Al, Ca, Fe, Mg, S, Si and Ti) and trace elements (Ba, Cr, Mn, Ni, Sr, V, Zn and Zr) in coal were determined. Various slurry preparations were evaluated using two dispersants (glycerol and Triton X-100) and by varying the concentration of dispersants, between 0.1% and 1.0% (v/v). The effect of initially solubilising the ground coal in N,N-dimethylformamide (DMF) was investigated by varying the volume of DMF added. The effect of wet grinding with DMF was investigated. Wet grinding with DMF was shown to drastically reduce particle sizes (50.0% < 0.28 μm and 90.0% < 6.17 μm) as compared to dry grinding (50.0% < 5.25 μm and 90.0% < 11.1 μm). The reduced particle sizes and increased transport efficiency of the coal slurries led to improved analytical recoveries of elements in the reference coal, SARM 18. The best analytical recoveries for all elements were achieved using 0.1% Triton X-100 with 10.0% DMF. Results obtained by ICP-OES after wet grinding of the coal with DMF, using 0.1% Triton X-100, also gave excellent recoveries (Al, 100%; Ca, 103%; Cr, 106%; Fe, 102%; Mg, 100%; Mn, 104%; Ni, 109%; Si, 102%; Ti, 95.0%; and V, 108%). The results obtained with 10.0% DMF and 0.1% Triton X-100 were in agreement with certified values for all selected elements according to paired t-test at the 95.0% confidence level. Selected elements (Al, Ca, Fe, Mg, Mn, Si, Ti and V) were also analysed with X-ray fluorescence for comparison with results obtained from ICP-OES. Analysis by ICP-OES of microwave digested coal was also carried out. It is suggested that the DMF slurry technique could be used for routine analysis of bituminous coals.     

Pressurised flash drying of Yallourn lignite

A previously developed 1D model of lignite drying for pulverised lignite feeding into a conventional pulverised fuel boiler during the coal milling process is applied to lignite in an entrained flow configuration at elevated pressure. A combustor fired with diesel and air was used to produce a flue gas at 800 °C and 10 atm to flash dry Yallourn lignite at a nominal feed rate of 725 kg/h along a 50 m duct. A coal feeder arrangement was also developed which provides a simple positive feeding device for feeding against a back pressure. The feeder takes as an input coal which is nominally <50 mm and discharges it as a finely divided product with a mean particle size of approximately 1.0-1.5 mm. The comparison between model predictions and measured temperature profiles for the flue gas and final moisture content of the dried coal product showed excellent agreement. Coal moisture was reduced from 67 wt% to between 30 and 40 wt%, depending upon on the coal feed rate and particle size. The small variation in the final outlet temperature observed between the model and experimental results is due to heat losses from the exposed duct work to the environment.     

高浓度料浆制备磨矿特性研究

为优化高浓度料浆制备技术,在实验室高浓度料浆制备的基础上,采用两级磨矿工艺,进行了料浆粒度分布和磨矿单位能耗的研究。实验结果表明:第一级磨矿时间19 min时,粒径<45μm的煤粒质量分数约为95%,能耗16.0 kWh/t;第二级磨矿时间35 min时,粒径<20μm的煤粒质量分数约为95%,能耗36.0 kWh/t。两级磨矿均可得到符合要求的粒度分布,研磨过程中得到的相关参数可为工业化应用提供基础设计依据参考。     

Coenzyme Q10 nanoparticles prepared by a supercritical fluid-based method

A supercritical fluid-based method is proposed to produce coenzyme Q₁₀ (CoQ₁₀) nanoparticles. First, CoQ₁₀/polyethylene glycol 6000 composite particles are prepared by a modified PGSS (particles from gas-saturated solutions) process with controlling the flow rate of the gas-saturated solution. Then, CoQ₁₀ nanoparticles are obtained by dissolving the composite particles into water. The effect of experimental variables of the modified PGSS process, including pressure, temperature, flow rate of the gas-saturated solution, and mass fraction of CoQ₁₀, on the CoQ₁₀ particle size and particle size distribution was investigated. Results show that CoQ₁₀ slurry product with a median diameter of 190 nm and yield of 89.8% can be prepared at an optimum condition (operating pressure of 25 MPa, operating temperature of 80 °C, gas-saturated solution flow rate of 1.02 mL/min, CoQ₁₀ mass fraction of 40% and nozzle diameter of 100 μm) via the supercritical fluid-based method.     

A comparison of the results obtained from grinding in a stirred media mill lignite coal samples treated with microwave and untreated samples

Various studies have been carried out on the effect of microwave-treatment on grinding different types of coal. However, the effect of microwave treatment on grinding coal samples −3.35 mm in size which can be considered to be fine is still under investigation. The purpose of this paper is to make contributions to these studies conducted. In the study, lignite coal samples with pyritic sulphur and 25% structural moisture were crushed below −3.35 mm particle size using jaw and cone crushers and then classified into three different mono size groups by Russel sieve. For a complete removal of the structural moisture from the lignite coal, a microwave application with 600 W needs approximately 35% more energy consumption than that with 850 W. The untreated coal samples and the ones treated with microwave at 850 W were ground for 5, 15, 30, 60, 120 s in a stirred media mill. The breakage rates of microwave-treated coal increased and accordingly the ground products of microwave-treated coal yielded finer particles than −106 μm as compared to untreated coals. The untreated and microwave-treated feed coals of −3350 μm and −1180 μm particle sizes were ground for 2 min in the stirred media mill. It was found that the increases in the rate of weight percentages for −106 μm particle size fraction after 2 min of grinding of untreated and microwave-treated feed coals of −3350 μm and −1180 μm were found to be 15.81% and 2.69%, respectively. Moreover, Hardgrove Index (HGI) test results of lignite coal showed that the HGI index value increased by approximately 23% after microwave treatment with 850 W.     

Fast pyrolysis of empty fruit bunches

This short communication describes the evaluation of the fast pyrolysis behaviour of empty fruit bunches (EFB), one of the solid wastes of the rapidly expanding palm oil industry. A 150 g/h fluidised bed bench scale fast pyrolysis unit is used to study the impact of the following key variables; the reactor temperature in the range of 400-600 °C, the residence time in the range of 0.79-1.32 s, and a range of particle sizes (with percentage of ash content) obtained by sieving of <150 μm (8.49%), 150-250 μm (7.46%), 250-300 μm (6.70%) and 355-500 μm (4.83%). The results confirmed the shape of the yield curve for EFB and indicated the significant difference when comparing the literature values for yields with the results obtained in this study along with the systems being used.     

Pyrolysis of wood at high temperature: The influence of experimental parameters on gaseous products

The pyrolysis of wood was carried out in an Entrained Flow Reactor at high temperature (650 to 950 °C) and under rapid heating conditions (> 10³ K s^− 1). The influence of the diameter and initial moisture of the particle, reactor temperature, residence time and the nature of the gaseous atmosphere on the composition of the gaseous products has been characterised. Particle size, between 80-125 and 160-200 μm, did not show any impact. Pyrolysis and tar cracking essentially happen in very short time period: less than 0.6 s; the products yields are only slightly modified after 0.6 s in the short residence times (several seconds) of our experiments. Higher temperatures improve hydrogen yield in the gaseous product while CO yield decreases. Under nitrogen atmosphere, after 2 s at 950 °C, 76% (daf) of the mass of wood is recovered as gases: CO, CO₂, H₂, CH₄, C₂H₂, C₂H₄ and H₂O. Tests performed under steam partial pressure showed that hydrogen production is slightly enhanced.     

Numerical studies of pulverized coal combustion in a tubular coal combustor with slanted oxygen jet

A pure two-fluid model for turbulent reacting gas-particle flow of coal particles is developed using a unified Eulerian treatment of both the gas and particle phases. The particles' history caused by mass transfer due to moisture evaporation, devolatilization and char reaction is described. Both velocity and temperature of the coal particles and the gas phase are predicted by solving the momentum and energy equations of the gas and particle phases, respectively. A k-ε-k_k two-phase turbulence model, EBU-Arrhenius turbulent combustion model and four-flux radiation heat transfer model are incorporated into a comprehensive model. The above comprehensive mathematical model is used to simulate two-dimensional gas-particle flows and pulverized coal combustion in a newly designed tubular oxygen-coal combustor of blast furnace. Predicted results of isothermal gas-particle flows are in good agreement with those obtained by measurements. The results also show that the proposed tubular oxygen-coal combustor prolongs the coal particle residence time and enhances the mixing of coal and oxygen. Results indicate that smaller coal particles of 10 μm diameter are heated and devolatilized rapidly and have volatile combustion in the combustor, while larger coal particles of 40 and 70 μm in diameter are heated but not devolatilized, and combustion of such particles does not occur in the tubular combustor.     

Microbial desulphurization of coal containing pyritic sulphur in a continuously operated bench scale coal slurry reactor

Pre-combustion microbial desulphurization of coal containing total sulphur (3.90%) and pyritic sulphur (2.80%) has been evaluated in a coal slurry reactor. The coal slurry reactor operated at hydraulic retention time (HRT) of 96 h with a coal pulp density of 15 percent and remove 79 percent of pyritic sulphur and 76 percent of ash with an increase in the calorific value of coal from 4400 to 6800 kcal kg⁻¹ at a pyritic load of 1.9 kg pyritic sulphur kg⁻¹ MLSS d⁻¹. The treated coal yield is 72 percent. The biochemical kinetic coefficients, viz. yield coefficient (Y) and decay coefficient (K_d) in the coal slurry reactor system are 0.178 and 0.007 d⁻¹, respectively, while maximum growth rate (μ_max) and half saturation rate constant (K_s) are 0.025 h⁻¹ and 0.220 g l⁻¹ as pyrite, respectively.     

Product compositions in rapid hydropyrolysis of coal

The rapid hydropyrolysis of a Montana lignite and a Pittsburgh Seam bituminous coal has been examined at a high heating rate (1000 °C s^?1). The results are interpreted in the light of those presented previously for pyrolysis of the two coals. A complex situation involving simultaneous chemical and mass transfer rate control is revealed, and it is apparent that the pyrolysis phase cannot be treated separately from the hydropyrolysis phase. Three key process variables, hydrogen pressure, temperature, and particle diameter, are seen to have major effects on the total yields of products. There appears to be an important tradeoff between high hydrogen pressures and high temperatures. Under the present conditions of almost zero vapour residence time at elevated temperatures, methane is the principal product of reaction between hydrogen and coal, and the yields of light aromatic liquids are small.     

Free radicals in coal and coal conversions. 6. Effects of liquefaction process variables on the in-situ observation of free radicals

To determine the effects and relative importance of process variables in coal liquefaction, a uniquely designed and fabricated high-pressure/high-temperature electron spin resonance (e.s.r.) apparatus is used to monitor the in-situ formation and behaviour of free radicals, which are generally assumed to be the key factor. It is concluded that the temperature is the most significant single process variable that affects free radical formation; for Powhatan No. 5 coal there is a 9-fold increase in going from 400 to 460 °C. At 460 °C the other process variables tested can affect significantly the free radicals significantly, but at 400 °C these variables have essentially no effect on free radicals formation. The next most significant effect is due to the combination of solvent nature and residence time. Tetralin and the SRC-II heavy distillate quench the free radicals from Powhatan No. 5 to the same extent with one significant difference. In tetralin the maximum concentration is observed shortly after the slurry achieves its highest temperature, whereas in the SRC-II heavy distillate experiments the concentration is still increasing, at 460 °C, even after 1 h of reaction. The heating time, pressures and types of gas used affect the free radical concentration to a much smaller extent. The conversions obtained in the in-situ e.s.r. experiments using SRC-II heavy distillate as the solvent are somewhat lower than those obtained with tetralin as the solvent. The corresponding oil yields with tetralin are considerably higher than with SRC-II heavy distillate.     

Growth of carbon nanofilaments on coal foams

Nanofilamentous carbon was grown on a carbon foam by catalytic chemical vapour deposition (CVD) using the decomposition of ethylene/hydrogen mixtures over Ni. The carbon foam was obtained from a coal by a two-stage thermal process, with the first stage taking place at a temperature within the plastic region of the precursor coal. The extent of porosity and the pore size of the foam were mainly influenced by the pressure reached in the reactor during the first stage. In the CVD process, 700 °C was the optimum temperature for obtaining good yields of nanofilaments. A low ethylene/hydrogen ratio (1/4) in the reactive gas gave rise to almost only short and thin carbon nanostructures. A higher proportion of C₂H₄ (4/1, C₂H₄/H₂) gave better yields of nanofilaments, with good proportions of higher-length and higher-diameter (up to around 0.5 μm) structures. Among the carbon forms produced, transmission electron microscopy revealed the predominance of fishbone-type nanofibres, with some bamboo-like nanotubes being also observed.     

NaOH-activated ground fly ash geopolymer cured at ambient temperature

NaOH-activated ground fly ash geopolymers, cured at room temperature, were studied in this paper. Ground fly ash (GFA), with a median particle size of 10.5 μm, was used as source material. NaOH concentrations of 4.5-16.5 M (M) were used as an alkali activator. Compressive strength tests and microstructure observations using SEM, EDX, XRD and FTIR were performed. Results indicated that GFA gave higher strength geopolymer paste compared to original fly ash. Ground fly ash could be used as a source material for making geopolymers cured at room temperature. An increase in NaOH concentration from 4.5 to 14.0 M increased the strength of GFA geopolymer pastes. Microstructure studies indicated that NaOH concentrations of 12.0-14.0 M created new crystalline products of sodium aluminosilicate. The compressive strengths at 28 days of 20.0-23.0 MPa were obtained with the NaOH concentrations of 9.5-14.0 M. Increasing the NaOH concentration beyond this point resulted in a decrease in the strength of the paste due to early precipitation of aluminosilicate products.