Sonochemically prepared hierarchical MFI-type zeolites as active catalysts for catalytic ethanol dehydration

In this paper, the ultrasonic-assisted desilication technique was reported as an attractive and efficient way for the preparation of hierarchical zeolites with MFI structure type. The prepared materials were used as active catalysts for the dehydration of ethanol into diethyl ether and ethylene. For all catalysts, the selectivity to diethyl ether was ca 95% or higher up to 210 °C, with catalytic activity in the range of 40–68%. In case of desilicated zeolites, at 270–290 °C, the conversion of ethanol was full with selectivity to ethylene ca 80%. MFI-type commercial zeolite was treated with a sodium and/or tetrabutylammonium hydroxide aqueous solutions (NaOH or NaOH/TBAOH) for 30 min. In the case of the application of ultrasounds, a QSonica Q700 sonicator (60 W and 20 kHz) equipped with a “1” diameter horn was used. In all cases, desilication was performed in an ice bath in order to keep the procedure conditions at low temperature.It was indicated that the use of ultrasounds during desilication procedure caused higher extraction of silicon and aluminum, which was connected with an elevated mesoporosity in relation to the samples modified in the absence of ultrasounds. Ultrasonic-assisted treatment of MFI-type zeolite caused also an apparent formation of numerous holes inside zeolite grains, resembling the look of “swiss cheese”. Furthermore, it was indicated that the samples prepared using ultrasonic irradiation exhibited enhanced catalytic properties in the dehydration of ethanol. For instance, MFI-type zeolite treated with NaOH/TBAOH alkaline mixture containing 10 mol% of TBAOH in the presence of ultrasounds (M−10 s) demonstrated higher both conversion of ethanol (59% vs. 47%) and selectivity to diethyl ether (95% vs. 93%) in comparison with zeolite modified conventionally (M−10c).The best catalyst was zeolite ultrasonically desilicated with NaOH/TBAOH solution of 70 mol% of TBAOH (M-70s). Generally, this catalyst indicated the highest conversion of ethanol, very high selectivity to diethyl ether (94-100%) at 150-210  °C and the highest selectivity to ethylene among investigated catalysts (21%, 66% and 84%) at 230  °C, 250 ^oC and 270  °C.     

Non-isothermal Dehydration Kinetics of Some Cationites

The kinetic parameters of dehydration were determined under non-isothermal conditions for different polystyrenedivinylbenzene sulfonic acid type cationites (DVB) and their dependence on the degree of cross-linking granulation, porosity, specific surface, content of SO₃M groups (M=Li, Na, K, Rb), nature of the alkali metal in partially neutralized -SO₃H groups and heating rate was investigated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study on the Synthesis of Metabolite CM2 of Clausenamide

Synthesis of the optically active metabolite of clausenamide cm2(3,5-dihydroxy-5-(α-hydroxylbenzyl)-1-methyl-4-benzylpyrrolidin-2-one)from 3-O-acetyl-clausenamide was described.     

吡啶高三蝶烯的合成

2-溴-4-甲基吡啶（1）经氯代和碘代反应合成了2-溴-4-碘甲基吡啶（3）,3和蒽酮（4）反应生成10,10-二（2-溴-4-吡啶甲基）-9（10H）蒽酮（5）,5在3 MPa下与NaOCH3反应得到10,10-二（2-甲氧基-4-吡啶甲基）-9（10H）蒽酮（6）,6经硼氢化钠还原得到蒽醇（7）,7在对甲苯磺酸催化...     

Vapor–liquid equilibrium in the system ethane + ethylene glycol

The solubility of ethane in ethylene glycol (EG) has been determined at temperatures in the range 298–398 K at pressures up to 20 MPa. The experimental results were correlated by the Peng–Robinson equation of state, and interaction parameters have been obtained for this system. The parameters in the Krichevsky–Ilinskaya equation were calculated from these interaction parameters.     

An appreciation of the chemical approach of V. V. Boldyrev to the study of the decomposition of solids

Professor Vladimir V. Boldyrev has made numerous important contributions to a wide range of chemical topics, not only limited to studies of the decompositions of solids. Of particular value has been his emphasis on exploring, in detail, the chemical steps participating in the thermal reactions of solids by carefully designed experiments that rely on more observational evidence than the run-of-the-mill collection of overall kinetic data. Some of these major contributions to both the theory and the uses of solid-state reactions are identified here and discussed in relation to his illuminating and fundamental mechanistic studies of the thermal decompositions of silver oxalate, ammonium perchlorate, potassium permanganate and the dehydration of copper sulfate pentahydrate.     

Kinetics and Mechanism of Dehydration of Heteropolyacids

The kinetics and mechanism of the dehydration and decomposition of heteropolyacids of molybdenum, tungsten and vanadium (H3+xYx+M12O40·mH2O; Y=Si, P; M=Mo, W) were studied. The data obtained on the dehydration kinetic parameters correlate with the expected structures, of these crystal hydrates, the IR data and X-ray phase analysis. This revised version was published online in July 2006 with corrections to the Cover Date.     

Use of thermo‐Raman spectroscopy and chemometric analysis to identify dehydration steps of hydrated inorganic samples—application to copper sulfate pentahydrate

In situ thermo‐Raman spectroscopy (TRS) measurements were performed in order to investigate solid‐phase transformation of the copper sulfate pentahydrate from room temperature up to 300 °C. Band‐target entropy minimization (BTEM), a blind‐source separation algorithm, was employed in order to identify and reconstruct the pure component spectra of the species involved in the dehydration process. In spite of low signal‐to‐noise ratio and elevated baseline spectral data, BTEM was successfully utilized to identify and reconstruct four pure component spectra of copper sulfate pentahydrate, trihydrate, monohydrate, and anhydrate, which were formed during this thermally induced process. Subsequent mapping of these four pure component spectral estimates back onto the preprocessed spectra yielded the relative concentrations of each individual species. Finally, the transition temperatures of each dehydration step could be unambiguously deduced from the obtained concentration profile. The current study shows that combined thermo‐Raman spectroscopy and chemometric analysis provides an effective tool to determine the dehydration temperatures as well as to identify the structures of each individual species involved in a solid‐phase dehydration process. Copyright © 2009 John Wiley & Sons, Ltd.     

Molecular dynamics simulation of thermomechanical coupling in cholesteric liquid crystals

The lack of a centre of inversion in a cholesteric liquid crystal allows linear cross-couplings between thermodynamic forces and fluxes that are polar vectors and pseudo vectors respectively. This makes it possible for a temperature gradient parallel to the cholesteric axis to induce a torque which rotates the director. This phenomenon is known as the Lehmann effect. The converse is also possible: one can drive a heat current by rotating the director. In this work a recently developed non-equilibrium molecular dynamics simulation algorithm is applied to calculate the cross-coupling coefficient between the temperature gradient and the torque for a molecular model system based on the Gay-Berne fluid. According to the Onsager reciprocity relations this cross-coupling coefficient is equal to the coupling between the director angular velocity and the heat current. The cross-coupling coefficients are found to be very small but non-zero and the Onsager reciprocity relations are satisfied within the statistical uncertainty.     

无水三氯化铝催化乙醇脱水反应制乙烯的实验研究

针对浓硫酸或五氧化二磷作催化剂的不足,该研究采用无水三氯化铝催化乙醇制乙烯,可使反应体系在120~130℃左右产生大量乙烯气体。同时从理论上探究了无水三氯化铝催化乙醇脱水的机理,并从教学演示实验的角度改进了反应装置,取得了较好的实验效果。