Towards the improvement of thermal efficiency in lignite‐fired power generation: Concerning the utilization of Polish lignite deposits in state‐of‐the‐art IGCC technology

Integrated coal Gasification Combined Cycle (IGCC) is the most advanced technology for coal‐fired power generation. The two‐stage entrained flow gasification process allows for the use of a wide range of coal, as long as the gasification temperature is above the ash melting point of a used fuel. In this gasification technology, lignite, which often has a low ash melting point, can be preferably utilized. However, ash fluidity is also another importance, because the behaviour of molten slag can diminish a stable ash discharge from a gasifier. As the eligibility of coal ash properties is a considerable factor, water physically and chemically kept in lignite (30 – 60% in mass) attributes to deteriorating gasification efficiency, because it causes significant heat loss and increasing oxygen consumption. Developing a thermal evaporative lignite drying method will be a necessary attempt to apply lignite to the coal gasification process. For those preceded objectives, coal and ash properties and drying characteristics of several grades of Polish lignite, extracted from Belchatow and Turow deposits, have been experimentally investigated in a preliminary study evaluating the applicability and consideration for its utilization in state‐of‐the‐art clean coal technology, IGCC. This paper particularly discusses the eligibility of Polish lignite from the perspective of the fusibility and fluidity of ash melts and the fundamental drying kinetics of lignite in superheated steam in the light of water removal. The viscosity of ash melts is measured at high temperature up to 1700 °C. In the drying tests, the significant influence of structural issues, because of the provenance and origin of lignite on the drying characteristics, was found by applying the method of sensitivity analysis of physical propensity. This paper concludes that the investigated Polish lignite has characteristics favourable for utilization in IGCC technology, once the precautions related to its high moisture have been carefully addressed. Copyright © 2016 John Wiley & Sons, Ltd.     

Metabolic Activation of Heterocyclic Amines and Expression of Xenobiotic‐Metabolizing Enzymes in the Gastrointestinal Tract of Rats

Heterocyclic amines get entry into human body mainly through ingestion of pan‐fried meats cooked at high temperatures. Exposure of the gastrointestinal tract (GIT) to ingested xenobiotics prior to delivery to the liver may lead to metabolic activation, which may explain the high incidence of GIT carcinogenesis. Therefore, this study investigated the mutagenic activation of 2 heterocyclic amines, 2‐aminoanthracene (2‐AA) and 3‐amino‐1‐methyl‐5H‐prydo[4,3‐b]indole (Trp‐P‐2), in the GIT of rats. In addition, the constitutive mRNA expression profiles of xenobiotic‐metabolizing enzymes (XMEs) in the GIT of rats were examined. Metabolic activation of 2‐AA was detected in all GIT tissues except the duodenum and rectum, and it was detected at high levels in the ileum and cecum. Furthermore, we revealed high metabolic activation of 2‐AA and Trp‐P‐2 in the jejunum. The mRNA expression of phase I and II enzymes in rat GIT corresponded with their mutagenic activation ability. In conclusion, our results suggest that different expression levels of XME among GIT tissues may contribute to the tissue‐specific differences in metabolic activation of xenobiotics such as heterocyclic amines in rats.     

Novel fatty acid esters of (7E, 12E, 18R, 20Z)-variabilin from the marine sponge Ircinia felix

The methanolic extract of the marine sponge Ircinia felix has yielded nine novel fatty acid esters, (7E, 12E, 18R, 20Z)-variabilin (5Z, 9Z)-22-methyltricosadienoate, (7E, 12E, 18R, 20Z)-variabilin (5Z, 9Z)-tetracosadienoate, (7E, 12E, 18R, 20Z)-variabilin hexadecanoate, (7E, 12E, 18R, 20Z)-variabilin 10-methylhexadecanoate, (7E, 12E, 18R, 20Z)-variabilin 15-methylhexadecanoate, (7E, 12E, 18R, 20Z)-variabilin 14-methylhexadecanoate, (7E, 12E, 18R, 20Z)-variabilin 9-octadecenoate, (7E, 12E, 18R, 20Z)-variabilin octadecanoate, and (7E, 12E, 18R, 20Z)-variabilin 2,11-dimethyloctadecanoate, along with the recently described (7E, 12E, 18R, 20Z)-variabilin 11-methyloctadecanoate. The characterization of the new fatty acids (5Z, 9Z)-22-methyltricosadienoic and 2,11-dimethyloctadecanoic acids is also described. The chemical structures were determined by extensive spectroscopic, chromatographic, and chemical analyses.     

Optical Spectra of Synthetic Spinels in the System MgAl2O4–MgCr2O4

Unpolarized optical spectra were measured in the wavelength range 322–1666 nm by the diffuse reflection technique from spinel powders synthesized in the system MgAl₂O₄–MgCr₂O₄. The spectra were interpreted by the crystal-field theory on the basis of trigonally distorted spinel octahedra with D_3d symmetry. For chromium-rich solid solutions, including the MgCr₂O₄ end-member, results after peak fittings showed octahedral D_3d local symmetry around Cr³⁺ ions, identical to the crystallographic site symmetry. For chromium-poor solid solutions, however, octahedral C_3v local symmetry was suggested around Cr³⁺ ions, different from the D_3d crystallographically expected.     

Drying of Sewage Sludge During Composting in an Updraft Dryer with the Concept of Using Self-Energy Generated Within the System

An innovative technology for sewage treatment systems is proposed. A mixture of sewage sludge and char particle is subjected to drying in the progress of composting in an updraft column. Exothermic heat generated during composting is utilized for energy of sludge drying. The char particle in the mixture contributes to enhancement of composting and drying rate. This study presents drying and composting behaviors of sludge to examine the effect of char addition. A fundamental drying experiment was carried out by hot-air heating of the sample in a small vessel. The drying characteristic curve for a mixture of sludge and char was greater than the sample of only sludge over a whole period if the drying rates were compared with the same moisture content. The drying behavior could be analyzed with a reasonable agreement by the water front receding model. The enhancement effect of drying and composting of sludge by char addition was confirmed by examination using a pilot scale of the updraft column whose volume was 50 m³. Sludge with 400% dry base (80% wet base) in moisture content could be dried successfully to lower moisture content than 67% dry base (40% wet base) only by exothermic heat during composting without supplying any auxiliary energy from the outside, and the treatment time was reduced by mixing char in sludge. The behavior was analyzed with a satisfactory agreement by a theoretical model employing moisture diffusion parameters determined from the drying characteristic curve.     

Current distribution in a two-dimensional narrow gap cell composed of a gas evolving electrode with an open part

On the basis of the observation of gas bubbles evolved by electrolysis, a two-dimensional vertical model cell composed of electrodes with open parts for releasing gas bubbles to the back side is proposed. The model cell consists of two layers. One layer forms a bubble curtain with a maximum volume fraction of gas bubbles in the vicinity of the working electrode with open parts. The other. being located out of the bubble layer, is a convection layer with a small volume fraction distributed in the vertical direction under forced convection conditions. The cell resistance and the current distribution were computed by the finite element method when resistivity in the back side varied in the vertical direction along the cell. The following three cases for overpotential were considered: no overpotential, overpotential of the linear type and overpotential of the Butler-Volmer type. It was found that the cell resistance was determined not only by the interelectrode gap but also by the percentage of open area and in some cases by the superficial surface area. The cell resistance varied only slightly with the distribution of the bubble layer in the back side.Nomenclature b linear overpotential coefficient given byb=/i - C proportionality constant given by Equation 15 - d ₁ distance between front side of working electrode and separator - d ₂ thickness of separator - F Faraday constant - I total current per half pitch - i current density at working electrode - i ₀ exchange current density - L length of a real electrolysis cell - n number of electrons transferred in electrode reaction - O _p percentage of open area given by Equation 1 - p pitch, i.e. twice the length of the unit cell, defined by 2(BC) in Fig. 4 - q thickness of bubble curtain, defined by (AM) in Fig. 4 - R gas constant - r _t total cell resistance - r unit-cell resistance defined by (V – V _eq)/I - r _rs residue ofr from sum ofr ₀ andr - r ₀ ohmic resistance of solution when0 _p=0 - r resistance due to overpotential when0 _p=0 - s electrode surface ratio or superficial surface area given by Equation 2 for the present model - T absolute temperature - t thickness of working electrode defined by EF in Fig. 4 - V cell voltage - V _eq open circuit potential difference between working and counter electrodes - solution velocity in cell - ₀ solution velocity at bottom of cell - w width of working electrode, defined by 2(DE) in Fig. 4 - x abscissa located on cell model - y ordinate located on cell model - anodic transfer coefficient - linear overpotential kinetic parameter defined byb/[_bc(p/2)] - d infinitesimally small length on the boundary - volume fraction of gas bubbles in cell - dimensionless cell voltage defined bynF(V – V _eq)/RT - overpotential at working electrode - Butler-Volmer overpotential kinetic parameter defined by [nFi _0bc(p/2)]/RT - coordinate perpendicular to boundary of model cell - ₁ resistivity of bubble-free solution - ₂ resistivity of separator - _bc resistivity of bubble curtain - potential in cell     

Syntheses of group 4 transition metal complexes bearing 2-pyridinethiolate ligands and their catalytic activities for ethylene polymerization

Titanium bis(2-pyridinethiolate) complexes, Ti(6-R-SPy)₂(NMe₂)₂ (6-R-SPy = 6-R-2-pyridinethiolate, 3a: R = H; 3b: R = Me; 3c: R = Ph; 3d: R = C₆H₄-4-Me; 3e: R = C₆H₄-4-t-Bu; 3f: R = C₆H₃-3,5-Me₂), and the titanium bis(2-pyridinolate) complexes, Ti(6-Ph-OPy)₂(NMe₂)₂ (6-Ph-OPy = 6-phenyl-2-pyridinolate, 8) were prepared by treating Ti(NMe₂)₄ with 2 equiv. of 6-R-2-pyridinethiol or 6-Ph-2-pyridinol. The cis-configuration of the diamido moieties in the pseudo octahedral geometry was elucidated by X-ray crystallography for 3a. Reaction of M(NMe₂)₄ (M = Ti, Zr) with 4 equiv. of 2-pyridinethiol cleanly gave tetrakis(pyridinethiolate) complexes, M(6-H-SPy)₄·THF (6: M = Ti; 7: M = Zr). The triangular dodecahedral geometries of 6 and 7 were also revealed by X-ray crystallography. These complexes catalyzed ethylene polymerization upon activation with MAO (methylaluminoxane) or MMAO (modified MAO). The catalytic activities of titanium bis(6-aryl-pyridinethiolate) systems were found to be remarkably higher than that of titanium bis(6-methyl-pyridinethiolate) system. Among the complexes synthesized in this study, Ti[6-(C₆H₃-3,5-Me₂)-SPy]₂(NMe₂)₂ (3f)/MMAO showed the highest activity (1200 kg/Ti-mol h atm) for ethylene polymerization at 60 °C under atmospheric pressure. In contrast, the activity of the corresponding 6-aryl-pyridinolate system 8/MMAO was rather low (9.3 kg/Ti-mol h atm). Both the N-S chelating structure and the bulky aryl substituents are essential for the high activities of the 6-aryl-pyridinethiolate complexes.