Hydrotalcite-like anionic clays in catalytic organic reactions

Hydrotalcite-like anionic clays (HTs; or layered double hydroxides, LDHs) can be used as precursors to mixed oxides, but their catalytic potential reaches much further. This review demonstrates that HTs can be successfully applied in a broad spectrum of organic reactions, with advantages such as improved activity, selectivity, metal dispersion, less waste production, and an improved recuperation of immobilized catalysts. HTs can be used in the as-synthesized form or after different pretreatments. The HT as such is a solid base or, depending on the elemental composition of its octahedral layers, may have redox properties. Specific metals can be incorporated either as a cation in the octahedral layer or as an anion via exchange. The anion-exchange strategy is especially successful in the context of heterogenizing homogeneous catalysts. A particular advantage for base catalysis is that the number and strength of the basic sites can be tuned precisely to a specific reaction. HTs are excellent materials to design bifunctional redox-base catalysts or to control the acid–base properties around a heterogenized metal complex. Potential applications of HTs range from the production of large-scale basic chemicals to the synthesis of small-scale specialty chemicals.     

Hydrotalcite-like anionic clays in catalytic organic reactions

Hydrotalcite-like anionic clays (HTs; or layered double hydroxides, LDHs) can be used as precursors to mixed oxides, but their catalytic potential reaches much further. This review demonstrates that HTs can be successfully applied in a broad spectrum of organic reactions, with advantages such as improved activity, selectivity, metal dispersion, less waste production, and an improved recuperation of immobilized catalysts. HTs can be used in the as-synthesized form or after different pretreatments. The HT as such is a solid base or, depending on the elemental composition of its octahedral layers, may have redox properties. Specific metals can be incorporated either as a cation in the octahedral layer or as an anion via exchange. The anion-exchange strategy is especially successful in the context of heterogenizing homogeneous catalysts. A particular advantage for base catalysis is that the number and strength of the basic sites can be tuned precisely to a specific reaction. HTs are excellent materials to design bifunctional redox-base catalysts or to control the acid-base properties around a heterogenized metal complex. Potential applications of HTs range from the production of large-scale basic chemicals to the synthesis of small-scale specialty chemicals.     

Organic geochemistry of the British Kimmeridge clay: 2. Acyclic isoprenoid alkanes in Kimmeridge shale oils

The C15---C20 isoprenoid alkane composition of Kimmeridge Clay shale oils produced by Fischer assay has been examined, and compared with the isoprenoid composition of corresponding bitumens. C16 and C18 isoprenoid alkanes are generally dominant in shale oils, while pristane (C19) and phytane (C20) dominate in bitumens. A significant proportion of the phytane in many shale oils is derived from simple evaporation of free (bitumen) phytane, while free pristane contributes less to shale oil composition. Some shale oil phytane and a large proportion of pristane is kerogen-derived. Certain shale oils contain lower concentrations of isoprenoid alkanes than corresponding bitumens, suggesting that some free alkane is thermally degraded during pyrolysis. Results thus indicate three sources for shale oil isoprenoid alkanes: thermal evaporation of free alkanes (particularly for phytane), kerogen decomposition, and possibly the cracking of higher homologues for C15---C19 alkanes. Kerogen-derived isoprenoids are suggested to arise by thermal desorption of adsorbed free alkane (particularly for phytane) and from C---O and C---C bonded species (excluding phytane) via postulated clay catalysed hydrogenation of initially formed alkenes. Comparison of shale oil and bitumen pristane/phytane ratios allows groups of oil shales to be defined, dependent on source composition, organic carbon content and maturity. Shale oil pristane/phytane ratios can also help to determine depositional environments and source composition, although maturity, shale mineralogy and competing alkene-forming pyrolytic reactions may also affect the ratios.     

Swell-shrink and strength behaviors of lime and cement stabilized expansive organic clays

Organic soils are mostly composed of decayed plant matter and weathered rock material. Often, these soils are known for their inferior engineering behavior including very high compressibility and low shear strength. In order to improve these properties, organic soils are, by and large, modified with calcium based stabilizers such as lime, cement and fly ash. However, transportation agencies in the United States have mentioned that the anticipated improvements were never achieved or the improvement obtained disappeared quickly with time. Therefore, a research study was initiated to understand the behavioral mechanisms of lime and cement stabilized organic soils. Eight natural expansive soils bearing different organic contents (varying between 2 and 6%) were selected for the present investigation. First, optimum dosages of lime and cement were determined for the selected soils. Then treated and untreated (control) specimens were prepared to study their physical and engineering behaviors of the soil specimens at varied curing periods. There is a drastic increase in unconfined compressive strength (UCS) of lime and cement treated specimens until 28 days of curing. Beyond which, a negligible improvement in UCS property was recorded for lime treated specimens and a slight decrease in UCS for cement treated soils was noticed. This reduction in strength for cement treated specimens could be attributed to the reduction in pH concentration with curing as well as the formation of inorganic calcium humic acid at this stage.     

Organic geochemistry of the British Kimmeridge Clay: 1. Composition of shale oils produced from Kimmeridge sediments

A series of shale oils produced by Fischer assay of Upper Jurassic Kimmeridgian oil shales, claystones and cementstones from on-shore Britain has been analysed. Oil yields are related to lithology via the quantity of sedimentary organic matter present in each lithologic unit, and also to stratigraphic horizon for certain rich, laterally uniform and persistent units. Shale oils are dark and sulphurous, containing < 50% hydrocarbons. NSO compounds are relatively important in the chromatographically separable fractions, while aliphatic hydrocarbons are usually subordinate. Unimodal normal alkane distributions maximize around nC16, while bimodal distributions have a secondary maximum around nC29. Many alkane gas chromatograms are characterized by a prominent peak due to the nC23 alkane. Certain compositional features are of pyrolytic origin (aromatics, heterocompounds, alkenes), while others are determined by the organic sedimentary input (alkane distributions, prominent nC23 alkane). Broad similarity in geochemical parameters suggests a consistency in the composition of sedimented organic matter. Smaller-scale compositional variations are thought to result from minor fluctuations in the composition of the organic sedimentary input, for example changes in the amount of terrestrial organic detritus reaching the depocentre. Results suggest a dominantly algal or bacterial organic matter source continuously operative throughout much of the Upper Jurassic over the entire region, with a smaller, more variable magnitude contribution from terrestrial sources, probably deposited in a near-shore marine shelf-sea environment under anoxic conditions.     

Analysis of clays from new deposits

It is shown that the mineral composition of clays used in the industry should be taken into account in addition to their chemical composition. Computer software was developed for this purpose.Translated from Steklo i Keramika, No. 3, pp. 21–22, March, 1996.Nllstroikeramika Joint Stock Company     

Generation and characterization of catalytic nanocomposite materials of highly isolated iron nanoparticles dispersed in clays

Nanostructured metallic iron particles in montmorillonite matrix have been prepared at ambient temperature through iron intercalation followed by reduction of resulting iron pillared montmorillonite with potassium borohydride. The resulting nanocomposites have been characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), UV–VIS-diffuse reflectance spectrometer (UV–VIS). The catalytic performances of resulting nanocomposites have been evaluated by probe phenol oxidation reaction with hydrogen peroxide. The results reveal that the nanosized iron polyoxocations intercalated clays can be successfully obtained by conventional synthesis of pillared clays, and after reduction of pillars, the highly dispersed zero-valent iron nanoparticles in clay matrix with diameter in the range of 3–10 nm can be successfully yielded. Over the nanocomposites catalyst prepared at a molar ratio of [CO ₃ ²⁻ ]/[Fe³⁺] = 0.5, the catalytic conversion of phenol oxidation is 49.5% with a 67.4% of selectivity to carbon dioxide and tar. The iron species dispersed in clay matrix may provide the catalytic active sites and the size of iron species has an effect on selectivity. More highly isolated iron nanoparticles dispersed in clays could lead to higher catalytic deep oxidation.     

Organic geochemistry of the British Kimmeridge Clay: 3. The occurrence and distribution of acyclic isoprenoid C19 alkenes in Kimmeridge Clay shale oils

The occurrence and distribution of acyclic isoprenoid C19 alkenes (pristenes) in Kimmeridge Clay shale oils has been examined. Pristenes comprise ≈ 9 to 15% of isolated alkene fractions, and ≈ 8% of total shale oil non-aromatic hydrocarbons. They are generally much more abundant than pristane, possibly because only limited hydrogenation of isoprenoid alkenes occurs during pyrolysis. Two pristene isomers are identified (mass spectrometry, retention indices, g.c. co-injection), with prist-2-ene the more abundant in several Kimmeridge shale oils. Prist-2-ene/prist-1-ene ratios show some correlation with sediment oil yield and clay mineral content. Clay-rich low oil yield sediments often give prist-2-ene dominated shale oils, whereas high oil yield sediments show prist-1-ene dominance. Results suggest the conversion of prist-1-ene to prist-2-ene during pyrolysis by a time dependent, thermodynamically favourable double bond rearrangement. Two mechanisms are suggested for the generation of prist-1-ene, the primary pyrolysis product, from C20 units CC bonded to Kimmeridge oil shale kerogen: lt]o li](i) a thermolytic, radical induced tertiary hydrogen abstraction followed by homolytic β CC bond cleavage, or li](ii) in the presence of clay minerals, a clay catalysed carbonium ion route involving Lewis acid tertiary hydrogen abstraction and heterolytic β CC bond fission. Prist-1-ene double bond rearrangement is suggested to occur by a clay-catalysed ionic pathway involving proton-donor site double bond protonation followed by collapse of the resultant tertiary carbonium ion by Lewis base deprotonation. While rearrangement is likely to be retarded in analytical flash pyrolysis, Fischer pyrolysis conditions (and laboratory thermal maturation) allow more time for secondary rearrangement. Where the rate of rearrangement is enhanced by increased clay catalyst concentration, e.g. clay rich Kimmeridge shales, prist-2-ene becomes increasingly prominent in the resultant pyrolysates.     

Photocatalysts prepared from layered clays and titanium hydrate for degradation of organic pollutants in water

Reaction between titanium hydrate sol of strong acidity and four smectite clays were utilized to create composite nanostructures of titanium dioxide (TiO₂) and silicate nanoparticles. The acidic sol solution reacts with the clay platelets and leaches out part of the magnesium or aluminum in the clay, while the sol particles hydrolyze further, yielding larger precursors of TiO₂ nanoparticles and condense on the fragmentised pieces of the leached silicate. Moreover, introducing PEO surfactants into the synthesis can significantly increase the porosity and surface area of the composite solids. The TiO₂ in the product are crystal grains of several nanometres in size. They disperse on silicate plates or are separated by silicate fragments and voids such that they are accessible to organic molecules. The mechanism of the synthesis reaction is distinguishingly different from conventional pillaring process. The composite solids provide highly effective photocatalysts for the degradation of phenol and synthetic dyes in aqueous solution.     

Optimization of drying through analytical modeling: clays as bonding agents in refractory materials

The objective of this study was to investigate the clay drying as a unit operation in the refractory materials processing. Two clays that varied in chemical and mineralogical compositions were experimentally tested in a laboratory dryer. The results obtained on the green samples prior to drying indicated that clays have adequate plasticity and refractoriness for application in shaped refractories. The operating parameters of the dryer were regulated: temperature ranged from 40 to 60 °C, humidity increased in the interval 30–70%; and the airstream rate was 1.3 m/s. The correlation analysis between operating parameters and calculated and/or measured drying outputs was conducted for better comprehension of the clay׳s role as a refractory binder. Subsequently, a mathematical optimization of the drying regime was conveyed. The effect of the variables (operation parameters) on the drying parameters (critical moisture, equilibrium moisture, dryness degree, etc.) was compared and evaluated. The response surface method, standard score analysis, cluster method, and principal component analysis were used as a means of the drying regime optimization. Assessment of the drying regime impact on the dried samples quality highlighted optimal result for both clay types: SS=0.95, temperature 50 °C, and humidity 40%. Multiple comparison analyses pointed out that optimized combination of the drying operation parameters decreases the quantity of conducted tests. Furthermore, optimal combination of drying parameters reduces negative effects of clay binder inherent properties on the resulting product which in return improves energetic and economic sustainability of refractories production.     

Thermogravimetry and decomposition kinetics of British Kimmeridge Clay oil shale

The characteristics of volatile matter evolution and the kinetics of thermal decomposition of British Kimmeridge Clay oil shale have been examined by thermogravimetry. TG has provided an alternative to the Fischer assay for shale grade estimation. The following relation has been derived relating TG % volatiles yield to the shale gravimetric oil yield: oil yield (g kg^?1) = (TG volatiles, % × 5.82) ? 28.1 ± 14.5 g kg^?1. A relationship has also been established for volumetric oil yield estimation: oil yield (cm³ kg^?1) = (TG volatiles, % × 4.97) – 5.43. TG is considered to give a satisfactory estimation of shale oil yield except in certain circumstances. It is found to be less reliable for low yield shales producing <≈40 cm³ kg^?1 of oil (≈10 gal ton^?1) where oil content of the TG volatiles is low: volumetric yield estimation accuracy is affected by variations in shale oil specific gravity. First order rate constants, k = 4.82 × 10^?5s^?1 (346.3 cm³ kg^?1shale) and k = 6.78 × 10^?5s^?1 (44.6cm³ kg^?1shale) have been obtained for the devolatilization of two Kimmeridge oil shales at 280 °C using isothermal TG. Using published pre-exponential frequency factors, an activation energy of ≈57.9 kJ mol^?1 is calculated for the decomposition. Preliminary kinetic studies using temperature programmed TG suggest at least a two stage process in the thermal decomposition, with two maxima in the volatiles evolution rate at ≈450 and 325 °C being obtained for some samples. Use of published pre-exponential frequency factors gives activation energies of ≈212 and 43 kJ mol^?1 for these two stages in the decomposition.     

含氮杂环类有机发光材料研究进展

含氮杂环类有机材料作为一类性能比较优良的发光材料,越来越受到人们的关注。本文主要介绍了近年来有机含氮杂环类发光材料的最新发展,重点综述了噁二唑环系、吡唑啉衍生物类和咔唑及其衍生物类发光材料的合成和性能。