蒙脱土催化的有机化学反应

本文从合成有机化学角度, 按反应类型综述了蒙脱土类催化剂近年来在有机化学反应中的应用。这些结果表明这类催化剂比传统的催化剂在产率、选择性等多方面有更高的效率。     

Leaching of rubidium from biotite ore by chlorination roasting and ultrasonic enhancement

Aiming at the problems of the low grade of rubidium (Rb) in biotite, and long leaching time and low leaching efficiency of Rb in mica ore, the chlorination roasting-assisted ultrasonic enhanced water leaching method was employed to extract Rb from biotite ore in this study. During the chlorination roasting process, the optimal conditions were obtained, namely roasting temperature 900 °C, roasting time 40 min, and the mass ratio of ore to calcium chloride 1:1, the optimum leaching rate was 96.75 %. Compared with conventional leaching, the ultrasonic field could greatly shorten the leaching time and realize fast and efficient leaching of Rb. The optimal conditions for ultrasonic enhanced leaching were: ultrasonic power 100 W, leaching temperature 60 °C, leaching time 20 min, liquid–solid ratio 4:1, the Rb leaching rate was 98.73 %, which was 40 min shorter than conventional leaching. The particle size and SEM results indicated that the samples by ultrasonic leaching were smaller, no agglomeration phenomenon in a large area, and the surface of the samples was relatively smooth.     

Per-O-acetylation of sugars catalysed by montmorillonite K-10

The inexpensive solid acid, montmorillonite K-10, is shown to be an efficient catalyst for the per-O-acetylation of several mono -, di - and trisaccharides. The pyranose forms accounted for 75–100% of the acetylated products.     

Nitration of phenolic compounds by metal-modified montmorillonite KSF

The nitration of phenolic compounds with 60% nitric acid (1.2 equiv) has been carried out in the presence of metal-modified montmorillonite KSF, prepared from different metals (V, Mo, W; Sc, La, Yb, Eu, In, Bi, Ti, Zr, Hf) and KSF or nitric acid treated HKSF, as catalysts. These catalysts showed good stabilities and high catalytic activities in nitration process. In addition, these catalysts can be recovered easily and reused for many times in nitration. This process is an eco-safer and environment-benign way for clean synthesis of nitrated phenolic compounds.     

Electron spectra of Hammett dye-indicators sorbed by montmorillonite

Theoretical and Experimental Chemistry -     

Sorption of copper by suspended particulate matter

The sorption of copper by suspended particulate matter from river water was investigated as a function of pH and solids concentration. Water was collected from the Delaware River and particulate matter was concentrated using Tangential-Flow Filtration (TFF). The adsorption of copper increased with increasing pH until pH 9.0. A decrease in copper adsorption was found for higher pH values. The adsorption of copper was greater for the samples with added copper than for the suspension for which no metal was added. An increase of copper adsorption proportional to particulate matter concentration was also observed. At both pH 6.0 and 7.0, there was a decrease in the adsorption of copper with increasing copper concentration.     

Alteration of yeast activity by gamma radiation

Yeast is an important component in microbe based industrial technologies. Due to the techno-economic reasons, the fermentation technique has acquired renewed interest. The effect of -radiation on the fermentation reaction has been investigated. The studies show that exposure of the fermentation mixture to -radiation at 5 kGy enhance alcohol production, whereas irradiation at higher doses, viz., 10 kGy and 25 kGy caused a considerable reduction in the alcohol yield. Therefore, low dose irradiation of fermentation mixtures can be applied for increasing the alcohol production by about 25%.     

Alteration of Bacterial Cellulose Properties by Diacetylglycerol

Bacterial cellulose (BC) was altered by means of 0.5-2.5% w/v diacetylglycerol in acetone-water through impregnation process provided DGBC composites. Results from the scanning electron microscope images, revealed that diacetylglycerol filled the pores of BC, leads to the significant enhanced in hydrophilicity and caused a smoother BC morphology. The addition of diacetylglycerol into BC caused a slightly changed in crystallinity indexes and bring about the reduction in tensile strength and Young's modulus but increased in elongation at break and toughness. The significant reduction of tensile strength and Young's modulus was achieved for DGBC 2.5% as well as for elongation at break and hydrophylicity improvement. Through the impregnation method, diacetylglycerol serves as biodegrada–ble and safe plasticizer, resulted in less rigid and higher ductility DGBC composites.     

High-resolution electron microscopy of montmorillonite and montmorillonite/epoxy nanocomposites

With the use of high-resolution transmission electron microscopy the structure and morphology of montmorillonite (MMT), a material of current interest for use in polymer nanocomposites, was characterized. Using both imaging theory and experiment, the procedures needed to generate lattice images from MMT were established. These procedures involve careful control of the microscope's objective lens defocus to maximize contrast from features of a certain size, as well as limiting the total dose of electrons received by the sample. Direct images of the MMT lattice were obtained from neat Na+ MMT, organically modified MMT, and organically modified MMT/epoxy nanocomposites. The degree of crystallinity and turbostratic disorder were characterized using electron diffraction and high-resolution electron microscopy (HREM). Also, the extent of the MMT sheets to bend when processed into an epoxy matrix was directly visualized. A minimum radius of curvature tolerable for a single MMT sheet during bending deformation was estimated to be 15 nm, and from this value a critical failure strain of 0.033 was calculated. HREM can be used to improve the understanding of the structure of polymer nanocomposites at the nanometer-length scale.     

Sorption and desorption of thorium from aqueous solutions by montmorillonite

The sorption and desorption of thorium on a West Anatolian montmorillonite has been studied by application of a batch technique. Experimental procedures are outlined and results for thorium contacted with montmorillonite are reported and discussed. The thorium concentration range was between 200–4000 ppm (8.5×10^–4–1.7×10^–2M). The sorption and desorption coefficients varied between 1.586–0.216 ml g^–1 and 0.829–0.168 ml g^–1, respectively, and sorption was not fully reversible. The data could be fitted to Freundlich and Langmuir isotherms. The quantity of the sorbed thorium was much lower than its theoretical CEC. This was attributed to a blocking of montmorillonite's CEC by thorium islands in the interlayer.     

Interaction of granitic biotite with selected lanthanides and actinides

The interaction of granitic biotite with aqueous solutions of La, Nd, Th and U (concentration 10 to 1000 mg·l^-1) was studied using instrumental neutron activation analysis (INAA) and ¹²C-Rutherford backscattering spectroscopy (¹²C-RBS). For comparison, the sorption of La and Nd by granitic feldspar and natural zeolite heulandite was also investigated. The experimental results showed that biotite exhibits higher sorption ability towards La and Nd, (maximum uptake 2.09 and 7.98 mg/g, respectively) than the feldspar and the heulandite. The interaction of biotite with Th is also intense, the metal being preferably concentrated at the near-surface layers of the crystals. This indicates that other sorption mechanisms (adsorption and surface precipitation) than ion-exchange take place at the solid/solution interface. The same phenomenon was also observed in the case of U, although the corresponding metal uptake was found to be considerably lower.     

Cation removal and lattice alteration of a biotite by a resin charged with different cations

Summary A suspension of a biotite was shaken with a synthetic cation exchanger. Alteration of the mineral lattice and amounts of cations taken up by the resin as a function of time and species of the cations with which the resin was originally saturated, was studied.A H⁺–charged resin first caused an expansion, then a contraction, but later the lattice seemed to have been completely broken down.When the resin was originally saturated with NH₄ ⁺ or Ca⁺⁺ no evident change of the basal spacing was observed.Both Na⁺– and Mg⁺⁺–charged resin caused expansions of the lattice with the consequent formation of a vermiculite-like mineral.

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Zusammenfassung Eine Biotitsuspension wurde mit einem synthetischen Kationenaustauscher behandelt. Der Einfluß auf das Gitter und die vom Austauscher gebundenen Kationen wurde in Abhängigkeit von der Zeit und von der Art der ursprünglich am Austauscher gebundenen Kationen untersucht. Ein mit einem H+beladener Austauscher verursacht zunächst eine Schichtaufweitung, dann eine Kontraktion, bevor das Gitter vollständig zerstört wird. Wenn der Austauscher mit NH⁺ ₄ oder Ca⁺⁺ beladen war, wurde keine merkliche Anderung des Schichtabstandes beobachtet. Mit Na+ und Mg⁺⁺-Austauschern trat eine Gitteraufweitung auf unter Bildung vermikulitähnlicher Minerale.

     

Functionalization of montmorillonite by acrylamide polymers containing side-chain ammonium cations

Stable polyacrylamide (polyAA)–montmorillonite adducts were prepared by two distinct processes: (1) free radical copolymerization of AA with alkaline clay previously treated with 2-(N-methyl-N,N-diethyl ammonium iodide)ethylacrylate (QD1) and (2) direct interactions of alkaline montmorillonite with various preformed copolymers of AA with QD1. The structure of the adducts as determined by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X-ray diffraction was shown to consist of AA macromolecules inserted between lamellar layers whose spacing was larger than in the polymer-free clay. The polymer was strongly attached to the inorganic surfaces, probably due to cooperative formation of electrostatic bonding. The thermal stability of the organic polymers in the resulting complexes was substantially enhanced while the mobility of macromolecules decreased.     

Acidity of montmorillonite pillared by alumina, zirconia and chromia

Acidic properties of Al-, Zr- and Cr- pillared montmorillonites prepared from Jelšovy Potok bentonite (Central Slovakia) have been investigated using temperature-programmed desorption of ammonia. The number of acid sites varied with different interlayer cations from 0.06 to 0.23 mmol g⁻¹. The character of acid sites was similar in the case of Al- and Zr- forms. It is obvious that the chromium analogue contains fewer acid sites, nevertheless, they seem to be stronger compared to Al- and Zr- pillared montmorillonites.     

Alteration of the endocytotic pathway by photosensitization with fluoroquinolones

The endocytotic pathway is profoundly altered by the UVA-induced photosensitization of HS 68 fibroblasts by the fluoroquinolone (FQ) antibiotics lomefloxacin, BAYy 3118, norfloxacin and ciprofloxacin, which preferentially localize in lysosomes. The endocytosis of low-density lipoproteins (LDL) loaded with two carbocyanine dyes compatible for effective Forster-type resonance energy transfer (FRET), namely 3,3'-dioctadecyloxacarbocyanine perchlorate (DiO) as the donor and 1'-dioctadecyl-3,3,3',3'-tetramethylindocarbocyanine perchlorate (DiI) as the acceptor, has been used as a model system. Binding of LDL to their cell surface receptors is impaired by irradiation with 10 J cm(-2) of UVA and/or treatment with 250 microM BAYy 3118 during 2 h. Perturbation of the plasma membrane by the FQ is revealed by the change in the rate of exchange of DiO from the LDL to the cell membrane as compared to untreated cells. The lysosomal degradation of LDL, demonstrated by the disappearance of FRET between DiO and DiI, is partly inhibited by the FQ. The actin filament network, involved in the fusion of mature endosomes with lysosomes, is readily destroyed upon photosensitization with the four FQ. However, actin depolymerization can be avoided by incubation of the cells with trans-epoxysuccinyl-1-leucylamido-(4-guanidino)butane, an inhibitor of lysosomal cathepsins prior to FQ photosensitization. All these data suggest that several components of the endocytotic pathway are impaired by photosensitization with these FQ.     

Mechanisms of Enhanced Oil Recovery by Surfactant-Induced Wettability Alteration

Different measurements were conducted to study the mechanisms of enhanced oil recovery (EOR) by surfactant-induced wettability alteration. The adhesion work could be reduced by the surfactant-induced wettability alteration from oil-wet conditions to water-wet conditions. Surfactant-induced wettability alteration has a great effect on the relative permeabilities of oil and water. The relative permeability of the oil phase increases with the increase of the water-wetness of the solid surface. Seepage laws of oil and water are greatly affected by surfactant-induced wettability alteration. Water flows forward along the pore wall in the water-wet rocks and moves forward along the center of the pores in the oil-wet rocks during the surfactant flooding. For the intermediate-wet system, water uniformly moves forward and the contact angle between the oil–water interface and the pore surface is close to 90°. The direction of capillary force is consistent with the direction of water flooding for the water-wet surface. While for the oil-wet surface, the capillary force direction is opposite to the water-flooding direction. The highest oil recovery by water flooding is obtained at close to neutral wetting conditions and the minimal oil recovery occurs under oil-wet conditions.     

Effect of cetyltrimethylammonium bromide addition on the emulsions stabilized by montmorillonite

The wettability of montmorillonite could be in situ modified by cationic surfactant cetyltrimethylammonium bromide (CTAB). The type and stability of emulsions prepared from montmorillonite with different concentrations of cationic surfactant were investigated, and a double phase inversion of emulsions was observed. The adsorption of CTAB on montmorillonite particles was studied by surface tension and zeta potential measurements, and the variation of the wettability of particles with the concentration of CTAB was characterized by the contact angle measurements. The adsorption of particles at the surface of emulsion droplets was observed by laser-induced confocal scanning microscopy. At low surfactant concentrations, the adsorption of CTAB on montmorillonite increased the hydrophobicity of the particles, and the stability of oil-in-water emulsions was enhanced. With the increase of the CTAB concentration, montmorillonite particles changed from hydrophilic to hydrophobic, and water-in-oil emulsions were obtained. However, at higher surfactant concentrations, the emulsions inverts to O/W again because montmorillonite particles were reconverted into hydrophilic due to the formation of CTAB bilayer on the surface of montmorillonite.