Study on NO heterogeneous reduction with coal in an entrained flow reactor

The effects of coal types with a wide range of volatile matter content including lignite, bituminous coal, and lean coal, as well as the effects of reaction temperature, coal particle size, the primary-zone stoichiometry (SR1) and reburning-zone stoichiometry (SR2), etc. on NO reduction efficiency were carried out systematically in an entrained flow reactor. The heterogeneous NO reduction mechanism was analyzed. The results indicate that the NO reduction efficiencies increase with decreasing SR2 and coal particle size, and with increasing reaction temperature. The char contributions to the total NO reduction efficiency increase with increasing proximate volatile matter, coal particle size, and with decreasing reaction temperature. The char contribution can be reached more than 40% when SR2 is larger than 1.06 or less than 0.92 for XLT lignite. The char contribution at the conditions of SR1 = 1.0 and SR1 = 1.2 is significantly larger than that at SR1 = 1.1 for coals with high-volatile matter at a fixed reburning fraction.     

Rheology and chemorheology of aqueous γ-LiAlO2 slurries for gel-casting

The rheological and chemorheological properties of aqueous γ-LiAlO₂ slurries for gel-casting as well as their precursor solutions of methacrylamide and N,N′-methylenebisacrylamide (MAM/MBAM) were studied in the present work. The influences of mean particle size of γ-LiAlO₂ powder, the dispersant content and solid loading, mechanical stirring time on the rheology of γ-LiAlO₂ slurries were investigated systematically. It was demonstrated that the slurries exhibited shear-thinning behaviors with relatively low viscosity which could satisfy the gel-casting process. A rotary rheometer was used to study the chemorheology of the copolymerization of MAM/MBAM solution and the gelation process of γ-LiAlO₂ slurries. The activation energy calculated from the idle time for MAM/MBAM solutions and γ-LiAlO₂ slurries were 27.5 ± 0.4 kJ/mol and 25.3 ± 0.4 kJ/mol, respectively, which revealed the catalytic effect of the γ-LiAlO₂ particles on the copolymerization process.     

Modeling the temperature in coal char particle during fluidized bed combustion

The temperatures of a coal char particle in hot bubbling fluidized bed (FB) were analyzed by a model of combustion. The unsteady model includes phenomena of heat and mass transfer through a porous char particle, as well as heterogeneous reaction at the interior char surface and homogeneous reaction in the pores. The parametric analysis of the model has shown that above 550 °C combustion occurs under the regime limited by diffusion. The experimental results of temperature measurements by thermocouple in the particle center during FB combustion at temperatures in the range 590-710 °C were compared with the model predictions. Two coals of different rank were used: lignite and brown coal, with particle size in the range 5-10 mm. The comparisons have shown that the model can adequately predict the histories of temperatures in char particles during combustion in FB. In the first order, the model predicts the influence of the particle size, coal rank (via porosity), and oxygen concentration in its surroundings.     

Hydrothermal reforming of bio-diesel plant waste: Products distribution and characterization

A viscous waste derived from a bio-diesel production plant, in the form of crude glycerol, was reacted under subcritical and supercritical water conditions and the product composition determined in relation to process conditions. Preliminary analysis of the original sample showed that the main constituent organic compounds were methanol (20.8 wt.%), glycerol (42.3 wt.%) and fatty acid methyl esters (33.1 wt.%). Uncatalyzed reforming experiments were carried out in a 75 ml Hastelloy-C batch reactor at temperatures between 300 °C and 450 °C and pressures between 8.5 MPa and 31 MPa. Oil/wax constituted more than 62 wt.% of the reactions products. At 300 °C, the main product was a waxy material containing mainly glycerol and fatty acid methyl esters. As the temperature increased to supercritical water conditions, low viscosity oils were produced and all of the glycerol was reacted. The oils contained mainly saturated and unsaturated fatty acid esters as well as their decomposition products. The gaseous products were carbon dioxide, hydrogen and methane and lower concentrations of carbon monoxide and C₂-C₄ hydrocarbons. No char formation was observed. However, during alkaline gasification with sodium hydroxide at 380 °C, the reaction products included a gaseous effluent containing up to 90% by volume of hydrogen, in addition to oil and significant amount of whitish solid residue (soap). Sodium hydroxide influenced the production of hydrogen via water-gas shift by the removal of carbon dioxide as sodium carbonate, but also decreased oil product possibly through saponification.     

The spontaneous combustion behavior of some low rank coals and a range of dried products

This paper compares the spontaneous combustion of two Victorian brown coals and a Pakistan lignite with that of products of the same coals which have been dried, mainly by the mechanical thermal expression technique (MTE) in which aqueous slurries of the materials are heated (125 or 200 °C) and pressed (5-15 MPa). Samples of briquettes obtained by steam heating and pressing from a similar Victorian coal have also been studied. The amount of residual moisture in the dried samples had the largest effect on T_crit values. The inorganic content of the samples varied and may also have contributed to the changes. T_crit increased with increasing particle size for the dried coals and MTE samples. There was no obvious correlation between T_crit and pore volume.     

Characterization of Chinese, American and Estonian oil shale semicokes and their sorptive potential

The primary byproduct of current oil shale oil extraction processes is semicoke. Its landfill deposition presents a potential threat to the environment and represents a waste of a potentially useable byproduct. Here we examine the sorptive characteristics of oil shale semicoke. Oil shale samples from Estonia, China and the United States were pyrolyzed at 500 and 1000 °C and their products analyzed for organic char content, surface area and porosity. Pyrolysis of the oil shales at temperatures of 500-1000 °C yields semicokes with organic char contents from 1.7% to 17.5% and BET surface areas of 4.4-57 m² g⁻¹, corresponding to 100-550 m² g⁻¹ of organic char. For comparison, the BET surface areas of class F coal fly ashes (combustion byproducts of bituminous coals) typically range from 2 to 5 m² g⁻¹, corresponding to 30-60 m² g⁻¹ of carbon while class C fly ash (from low rank coals) have carbon BET surface areas comparable to oil shale semicoke organic char surface areas.     

Effect of particle size distribution of petroleum coke on the properties of petroleum coke-oil slurry

The effect of particle size distribution of petroleum coke on the properties of petroleum coke-oil slurry (PCOS) from four Chinese petroleum coke samples, such as apparent viscosity, rheological behavior, static stability, were systematically investigated. The size and morphology of petroleum coke particle with different grinding time and the corresponding stabilizing mechanisms were analyzed by SEM and zeta potential measurements. Experiments proved the petroleum coke grinding time of 60 min is suitable for the particle distribution and stability of PCOS. Besides, the effect of the sample type and loading of petroleum coke on the properties of PCOS was studied. The factors governing the apparent viscosity and stability of slurries have been discussed. The experimental results showed that the properties of PCOS could be effectively improved, and a suitable PCOS with low viscosity and good stability could be prepared through controlling the particle size distribution and petroleum coke loading.     

A new direct coagulation casting process for alumina slurries prepared using poly(acrylate) dispersant

Direct coagulation casting (DCC) of concentrated aqueous alumina slurries prepared using ammonium poly(acrylate) dispersant has been studied using MgO as coagulating agent. Addition of small amounts of MgO increased the viscosity of the concentrated alumina slurries with time and finally transformed it in to a stiff gel. Sufficient working time for degassing and casting could be achieved by cooling the slurries to a temperature of ∼5 °C after proper homogenization after the addition of MgO. The DCC slip with alumina loading in the range of 50–55 vol% showed relatively low viscosity (0.12–0.36 Pa s at shear rate of 93 s⁻¹) and yield stress (1.96–10.56 Pa) values. The wet coagulated bodies prepared from slurries of alumina loading in the range of 50–55 vol% had enough compressive strength (45–211 kPa) for handling during mould removal and further drying. The coagulated bodies prepared from slurries of alumina loading in the range of 50–55 vol% showed linear shrinkage in the range of 4.8–2.3 during drying and 17.1–16.2 during sintering respectively. Near-net-shape alumina components with density >98% TD could be prepared by the DCC process.     

The kinetics of coal chars hydrogasification

Hydrogasification reaction of chars produced from two rank coals was investigated in temperature up to 1173 K and pressure up to 8 MPa. The reactivity of the lignite Szczerców char has been found to be slightly higher than of the subbituminous coal Janina char produced at the same conditions. A high value of the char reactivity was observed to certain carbon conversion, above which a sharp drop takes place. It has been shown that to achieve proper carbon conversion the hydrogasification reaction must proceed at temperature above 1200 K. Based on the active centres theory the kinetic equations of the hydrogasification process were developed and the kinetic constants at the maximum reaction rate evaluated for the analyzed chars.     

Slip casting using wet-jet milled slurry

Green bodies fabricated by slip casting using wet-jet milled slurries at different solid contents (10, 30, and 50 vol.%), which had low viscosity, had very high relative density and showed very small shrinkage during sintering, as comparing to the ball-milled slurries. The square of the thickness of green bodies was proportional to casting time indicating slip casting was implemented well. The relative density of the green body prepared by the wet-jet milled slurries was 67%, indicating much higher than that of the ball-milled slurries. After sintering, the linear shrinkage of the sintered bodies prepared by wet-jet slurries at different solid contents was constant at 11%. On the other hand, the linear shrinkage of the sintered bodies prepared by the ball-milled slurries was dependent on the solid contents in slurries. Thus, it was possible to produce not only green bodies with high density but also sintered bodies with low shrinkage by using the wet-jet milled slurries.     

Combustion characteristics of coals using a drop-tube furnace

Fourteen coals were selected for char refiring tests using a drop-tube furnace (DTF) in order to compare with previous tests on a 1 MW combustion facility. Each coal was sieved into two size fractions (53-75 and 106-125 μm) and characterised using proximate analysis and conventional petrographic tests as well as a test for % unreactives using image-analysis. The coal fractions were then pyrolysed at 1300 °C for 200 ms in 1 vol% oxygen in nitrogen. The reactivity, morphology and surface area of the chars were evaluated using thermal, optical and adsorption techniques. Each char fraction was then passed through the DTF at 1300 °C using a residence time of 600 ms and a furnace atmosphere of 5 vol% oxygen in nitrogen to evaluate burnout propensity. The characteristics of the coals, the chars and the residues after refiring were compared to determine whether any links exist between burnout, intermediate char products and coal composition. The link between % unreactives and burnout was confirmed for high volatile bituminous coals. Results obtained from two low volatile coals confirmed that their burnout was better than predicted from their properties. For the S. American (Guasare) coal poorer than expected burnout was obtained, as in previous work, but only for the larger size fraction.     

Liquefaction and/or solubilization of Spanish coals by newly isolated microorganisms

A screening procedure has been set up for isolating microorganisms capable of liquefying coal. Spanish coals were used in the tests, namely a brown lignite from Galicia, sub-bituminous coal from Teruel and hard coal from Minas Figaredo S.A. (Asturias). Among the isolated strains several microorganisms proved capable of liquefying untreated lignite. When lignites were pretreated a more intense and rapid liquefaction was achieved, chelating agents being among the best pretreatments. None of the isolated microorganisms could satisfactorily liquefy sub-bituminous and hard coals in solid media. On the other hand, some fungi grew specifically on the untreated coals, engulfing them and in many cases a soft slurry was obtained. Several of the isolated microorganisms were able to solubilize all three untreated Spanish coals in liquid media. Coal solubilization was measured spectrophotometrically at 300, 400 and 450 nm.     

Coal lump devolatilization and the resulting char structure and properties

Lumps of six bituminous coals, from 20 to 40 mm in size, were devolatilized in a laboratory oven in nitrogen atmosphere at different final temperatures ranging from 300 to 800 °C. The structure and morphology of the resulting chars with different degree of devolatilization have been examined under an optical microscope in order to better understand the formation mechanism of different types of char. The swelling of the caking coals and the fissuring of the non-caking coals were characterised by image analysis and some correspondences between the distribution of lithotypes within the initial coal lumps and the char structure obtained were revealed. The relation between chars structure and properties was also investigated. The char lumps obtained from caking coal exhibit better resistance to breakage than their parent coal lumps while non-caking coals show the opposite behaviour. For both caking and non-caking coals, a significant decrease of resistance is observed in the intensive devolatilization temperature range from 400 to 600 °C.     

Preparation of high solid loading and low viscosity ceramic slurries for photopolymerization-based 3D printing

In this study, high solid loading and low viscosity cordierite slurries are successfully developed for the first time for photopolymerization-based additive manufacturing. The processability of the slurries is mainly determined by their rheological properties and photocuring parameters. The slurry preparation involves the orthogonal optimization of compositions in order to achieve suitable viscosity, stability and homogeneity. The photocuring parameters of the as-prepared slurries, including penetration depth D_p and critical exposure E_c, are also determined experimentally. Results show that viscosity increases with reduction in particle size. A higher solid-volume fraction also results in an exponential growth in viscosity. As for the dispersant amount, a concentration of 5?wt% leads to the lowest viscosity. Particle size also play an important role in the solid loading capacity of the slurries, as results suggest that smaller particles improve performance. In terms of the photocuring behaviors, the addition of 2?wt% photoinitiator generates an optimal curing process. 40?vol% solid loading leads to the thickest curing depth for all slurries with different types of particle sizes. Finally, a cordierite part with a complex hollow structure and a fine resolution is successfully fabricated. The present study offers a material basis for the polymerization-based 3D printing of porous cordierite structures.     

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.     

Oil agglomeration of a lignite treated with microwave energy: Effect of particle size and bridging oil

Oil agglomeration of Sivas–Divriği (S–D) Uluçayır lignite fines was carried out using kerosene and kerosene–extract oil (which was obtained from lignite treated with microwave energy) mixture as a bridging oil. The effects of parameters such as the amount and type of bridging oil, microwave time and particle size on the agglomeration performance were investigated. The amount of kerosene was varied from 5 to 30 wt.% of the initial lignite loading. The values of the grade and recovery increased with an increase in the amount of kerosene added. Extract oil fraction of the lignite extract at various ratios in kerosene increased the agglomeration recovery from 95.88% to 98.55%. The effect of microwave time was investigated and it was found that the grade was also increased with increasing microwave time (4, 8 and 10 min). The grade of char (microwave time: 8 min) was increased in comparison with the original lignite while decreasing its recovery. Dense medium separations of the lignite were conducted and the results of their grade recovery performances were compared with those of agglomeration of the particles. During the inspection of particle size effect on the dense medium separation, the recovery was increased remarkably (from 12.07% to 89.50%) with increasing particle size, while decreasing the grade (from 0.732 to 0.697). In the oil agglomeration of lignite the recovery values were increased with increasing particle size.     

Oil agglomeration of a lignite treated with microwave energy: Effect of particle size and bridging oil

Oil agglomeration of Sivas–Divriği (S–D) Uluçayır lignite fines was carried out using kerosene and kerosene–extract oil (which was obtained from lignite treated with microwave energy) mixture as a bridging oil. The effects of parameters such as the amount and type of bridging oil, microwave time and particle size on the agglomeration performance were investigated. The amount of kerosene was varied from 5 to 30 wt.% of the initial lignite loading. The values of the grade and recovery increased with an increase in the amount of kerosene added. Extract oil fraction of the lignite extract at various ratios in kerosene increased the agglomeration recovery from 95.88% to 98.55%. The effect of microwave time was investigated and it was found that the grade was also increased with increasing microwave time (4, 8 and 10 min). The grade of char (microwave time: 8 min) was increased in comparison with the original lignite while decreasing its recovery. Dense medium separations of the lignite were conducted and the results of their grade recovery performances were compared with those of agglomeration of the particles. During the inspection of particle size effect on the dense medium separation, the recovery was increased remarkably (from 12.07% to 89.50%) with increasing particle size, while decreasing the grade (from 0.732 to 0.697). In the oil agglomeration of lignite the recovery values were increased with increasing particle size.     

Effect of CTAB as a foaming agent on the properties of alumina ceramic membranes

Alumina-ceramic membranes were prepared by gelcasting process using CTAB as a foaming agent. To increase the fineness, the starting alumina powder was milled for 1 h in a ball mill before the casting process. Particle size distribution and surface area measurements of the as-received and milled alumina powder were examined. The casted alumina membranes were sintered at 1500 °C. Sintering parameters in terms of bulk density (BD) and apparent porosity (AP) were determined by the Archimedes method. Pore size distribution of the sintered porous alumina membranes was measured using mercury porosimeter. Microstructure of sintered membranes was investigated by scanning electron microscope (SEM). Cold crushing strength (CCS) of the sintered specimens was also evaluated. The result revealed that the properties of porous ceramics such as porosity, average pore size, pore size distribution and cold crushing strength could be controlled by adjusting the preparation conditions e.g. solid loading, sintering temperature and foaming agent. The open porosity, cold crushing strength and average pore size of the alumina ceramics sintered at 1500 °C were around 58.35%, 18 MPa and178 nm, respectively.     

氧化锆、不锈钢复合粉体浆料流变性的研究

初步探索金属-陶瓷复合粉体浆料的粘度与浆料的pH值、分散剂含量、固体含量之间的关系,制备出高固体含量(体积分数为40%)、低粘度(0.32Pa·s)的氧化锆、不锈钢复合粉体浆料.     

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.