Solvent extraction study of protactinium(V) with methyl-iso-butyl carbinol and methyl-iso-butyl ketone

In order to study the extraction pattern of protactinium in different types of extracting agents and compare the similarity of patterns of extraction with dubnium and thereby unraveling its chemistry, solvent extraction of protactinium(V) with methyl-iso-butyl carbinol (MIBC) and methyl-iso-butyl ketone (MIBK) was studied using Pa-233 as a radiotracer. The extraction efficiencies of Pa were determined as a function of shaking time, concentrations of mineral acids, and extractant concentrations using the two extractants. The results show that MIBK is more suitable for the extraction of protactinium than MIBC in benzene. Furthermore, the effect of the F anion is also discussed.

Liquid-liquid extraction of protactinium(V) using tri-iso-octylamine

Solvent extraction of protactinium with tri-iso-octyl-amine (TIOA) in xylene, benzene, carbon tetrachloride and chloroform from HCl, HF, HNO3, HClO4 and H2SO4 media was studied using Pa-233 as a radiotracer. The extraction efficiencies of protactinium were determined as a function of shaking time, concentrations of mineral acids in aqueous phase, extractant concentrations and diluents in organic phase. The extraction mechanism was discussed. The results show that the extracted species in the organic phase is [(R3N-H)(n)Pa(OH)(x)Cl-y(5-x-y)].

BTEX的环境行为与生态毒理

BTEX是苯(benzene)、甲苯(toluene)、乙苯(ethylbenzen)和二甲苯(xylene)的统称,存在于原油和石油产品中,同时作为化工原料应用于农药、塑料及合成纤维等制造业。BTEX广泛存在于大气、水体和土壤等环境介质,对相应的生态系统和人类健康产生严重危害。本文分析了各环境介质中BTEX的来源及分布特征,探讨了其在各种环境系统间的迁移和转化规律,重点从生殖发育毒性方面讨论了BTEX产生的人体健康效应,最后对今后研究重点进行了探讨。

On-line concentration of neutral and charged species in capillary electrochromatography with a methacrylate-based monolithic stationary phase

A method involving self-concentration, on-column enrichment and field-amplified sample stacking for on-line concentration in capillary electrochromatography with a polymer monolithic column is presented. Since monolithic columns eliminate the frit fabrication and the problems associated with frits, the experimental conditions could be more flexibly adjusted to obtain higher concentration factor in comparison with conventional particulate packed columns. With self-concentration effect, the detection sensitivity of benzene and hexylbenzene is improved by a factor of 4 and 8, respectively. With on-column enrichment and ultralong injection, improvement as high as 22 000 times in detection sensitivity of benzoin is achieved. Furthermore, a combination of the three above-mentioned methods yields up to a 24000-fold improvement in detection sensitivity for caffeine, a charged compound. Parameters affecting the efficiency of on-line concentration are investigated systematically. In addition, equations describing on-line concentration process are deduced.

Structure and acidity of Mo/H-MCM-22 catalysts studied by NMR spectroscopy

A comprehensive study on physical and chemical properties of Mo/MCM-22 bifunctional catalysts has been made by using combined analytic and spectroscopic techniques, such as adsorption, elemental analysis, and Xe-129 and P-31 NMR of adsorbed trialkylphosphine oxide probe molecules. Samples prepared by the impregnation method with Mo loadings ranging from 2-10 wt.% have been examined and the results are compared with that obtained from samples prepared by mechanical mixing using MoO3 or Mo2C as agents. Sample calcination treatment is essential in achieving a well-dispersed metal species in Mo/MCM-22. It was found that, upon initial incorporation, the Mo species tend to inactivate both Bronsted and Lewis sites locate predominantly in the supercages rather than the 10-membered ring channels of MCM-22. However, as the Mo loading exceeds 6 wt.%, the excessive Mo species tend to migrate toward extracrystalline surfaces of the catalyst. A consistent decrease in concentrations of acid sites with increasing Mo loading < 6 wt.% was found, especially for those with higher acid strengths. Upon loading of Mo > 6 wt.%, further decreases in both Bronsted and Lewis acidities were observed. These results provide crucial supports for interpreting the peculiar behaviors previously observed during the conversion of methane to benzene over Mo/MCM-22 catalyst under non-oxidative conditions, in which an optimal performance was achieved with a Mo loading of 6 wt.%. The effects of Mo incorporation on porosity and acidity features of the catalyst are discussed. (C) 2004 Published by Elsevier B.V.

Liquid-phase hydrodechlorination of chlorinated benzenes over active carbon supported nickel catalysts under mild conditions

Liquid phase hydrodechlorination of chlorinated benzenes was studied over Ni/active carbon (Ni/AC), Ni/gamma-Al2O3, Ni/SiO2 and Raney Ni. The complete dechlorination of chlorobenzene (ClBz) was realized at 333-343 K on Ni/AC under hydrogen atmosphere of 1.0 MPa in the presence of alkaline hydroxide. Dichloro- and trichlorobenzenes were also hydrodechlorinated with 50-95% yields of benzene under the similar conditions, as above. The reaction follows zero-order to ClBz concentration and 1.9 order to hydrogen pressure. The reaction does not proceed in the absence of alkaline hydroxide, suggesting the complete coverage of active nickel surface with produced chlorine and the removal of the chlorine ion with hydroxide ion as a rate-limiting step. The active catalysts were characterized by H-2 chemisorption and transmission electron microscopy techniques. The apparent activity strongly depends on the active area of nickel on catalyst surface. (C) 2004 Published by Elsevier B.V.

A comparative study of non-oxidative pyrolysis and oxidative cracking of cyclohexane to light alkenes

Naphthene is generally considered difficult to convert in traditional pyrolysis, but the ring rupture becomes fairly easy with the presence of oxygen in the gas phase oxidative cracking of the model compound, cyclohexane. About 86.8% conversion of cyclohexane, 43.7% yield of light alkenes, 6.6% yield of benzene and 14.3% yield of CO could be obtained at 750 degreesC, at which temperature the pyrolysis of cyclohexane was negligible, while at 850 degreesC, the total yield of alkenes, benzene and CO was as high as 80% (50%, 12% and 18%, respectively) with 98% conversion of cyclohexane. The gas phase oxidative cracking process could be run in an autothermal way (cyclohexane/O-2 mole ratio of 0.69-0.8 in theory), which would minimize energy consumption and capital costs of the whole process. CO prevailed in the produced CO, and the yield Of CO2 was always below 1%, which means about 90% Of CO2 emission by fuel burning in pyrolysis would be saved. The gas phase oxidative cracking process appears to be an environmentally benign and efficient route for light alkene production with naphthene rich feedstocks. (C) 2004 Published by Elsevier B.V.

The role of coke in the deactivation of Mo/MCM-22 catalyst for methane dehydroaromatization with CO2

The effect of space velocity on reaction performance and coke deposition over 6Mo/MCM-22 catalyst in methane dehydro-aromatization (MDA) with CO2 were studied. The characterization of catalysts reacted at different space velocity after the same amount of methane feed by TG, TPO and Benzene/NH3-TPD techniques suggested that the inert coke maybe responsible for the deactivation of catalyst because of its blockage effect for pore system.

Shape selectivity in methane dehydroaromatization over Mo/MCM-22 catalysts during a lifetime experiment

Dehydroaromatization of CH4 with 2% CO2 on 6Mo/MCM-22 in a 100-h lifetime test was carried out at 993 K, atmospheric pressure and 1500 mL/gh. The duration of the lifetime test can be divided into an induction stage, stable stage and deactivation stage on the basis of the selectivities of hydrocarbons and coke. The characteristics of deposited coke with different time onstream were studied using TPO and TG techniques. There were two peaks corresponding to two kinds of coke recorded in TPO profiles, and the oxidation temperature of coke shifted to higher values with less hydrogen content with the increase of coke deposits. BET and Benzene-TPD techniques were employed to study the variation of specific surface area of the external and micropore surface versus time onstream. With the accumulation of coke deposits, although the pores became partially blocked and the internal surface decreased, methane could still enter the channel and was converted to benzene with shape selectivity until a critical value of coke deposition was reached.

Combination of CH4 oxidative coupling reaction with C2H6 oxidative dehydrogenation by CO2 to C2H4

A new process has been suggested for converting natural gas to ethylene by combining oxidative coupling of methane with ethane dehydrogenation to provide an efficient method for the utilization of thermicity and CO2. From their thermodynamics, it is clear that the exothermicity from CH4 oxidative coupling reaction (DeltaH(800degreesC) = -174.3 kJ mol(-1)) can support C2H6 dehydrogenation by CO2 (DeltaH(800degreesC) = + 180.2 kJ mol(-1)). Meanwhile, the two reactions can be conducted under the same reaction conditions, such as the reaction temperature and reaction pressure as well as space velocity. In addition, the CO2 yielded from CH4 oxidative coupling reaction can be directly used for C2H6 dehydrogenation. Two kinds of catalyst are developed for this combined process with an achievement, from which C2H4 content in tail gas can reach attractively 16.4%, which can be used directly to produce ethylbenzene by the alkylation of benzene. (C) 2002 Elsevier Science Ltd. All rights reserved.

On the induction period of methane aromatization over Mo-based catalysts

The behavior of different species during the temperature-programmed surface reaction (TPSR) of methane over various catalysts is traced by an online mass spectrometer, It is demonstrated that the transformation of MoO3 to molybdenum carbide hinders the activation of methane as well as the succeeding aromatization in the TPSR, If this transformation process is done before the reaction, the temperature needed for methane activation and benzene formation will be greatly lowered (760 and 847 K, respectively). On the basis of comparison of the catalytic behavior of molybdenum supported on different zeolites, it is suggested that the initial activation of methane is the rate-determining step of this reaction. For the cobalt catalysts supported on HMCM-22 or Mo catalysts supported on TiO2, no benzene formation could be observed during the TPSR, However, the prohibition of benzene formation is different in nature over these two catalysts: the former lacks the special properties exhibited by molybdenum carbide, which can continuously activate methane even when multiple layers of carbonaceous species are formed on its surface, while the latter cannot accomplish the aromatization reaction since there are no Bronsted acid sites to which the activated intermediates can migrate, although the activation of methane can be achieved on it. Only for the catalysts that possess both of these properties, together with the special channel structure of zeolite, can efficient methane aromatization be accomplished. (C) 2000 Academic Press.

Gas-aerosol partitioning of semi volatile carbonyls in polluted atmosphere in Hachioji, Tokyo

Gaseous and particulate semi volatile carbonyls have been measured in urban air using an annular denuder sampling system. Three dicarbonyls, five aliphatic aldehydes and two hydroxy carbonyls were observed. Concentrations of other biogenic and anthropogenic volatile organic compounds (VOCs), SO2, CO, NO2 and particle concentration were also measured. Estimated gas-aerosol equilibrium constants for the carbonyls showed an inverse correlation with the concentrations of anthropogenic pollutants such as benzene, isopentane and SO2. This suggests that the increase in the fraction of non-polar anthropogenic particles in the atmosphere could change the average property of the ambient aerosols and drive the gas particle equilibrium of the carbonyls to the gas phase. This trend is uncommon in remote forest air. In this study, we examined the factors controlling the equilibrium in the polluted atmosphere and show that there is a difference in gas-aerosol partition between polluted and clean air.

Synthesis of isomeric bis(amine anhydride)s for novel poly(amine imide)s by Pd-catalyzed amination of 4-chlorophthalic anhydride

Two novel bis(amine anhydride) monomers, N,N'-bis(3,4-dicarboxyphenyl)-1,4-phenylenediamine dianhydride I and N,/N'-bis(3,4-dicarboxyphenyl)-1,3-phenylenediamine dianhydride 11, were prepared via palladium-catalyzed amination reaction of 4-chloro-N-methylphthaliniide with 1,4-phenylenediamine or 1,3-phenylenediamine, followed by alkaline hydrolysis of the intermediate bis(amine imide)s and subsequent dehydration of the resulting tetraacids. A series of new poly(amine imide)s were prepared from the synthesized dianhydride monomers with various diamines in NMP via conventional two-step method.

Crystallization behavior of a thermoplastic polyimide derived from 3,3 ',4,4 '-oxydiphthalic dianhydride and 4,4 '-oxydianiline

Nonisothermal and isothermal crystallization kinetics of an aromatic thermoplastic polyimide derived from 3,3',4,4'-oxydiphthalic dianhydride and 4,4'-oxydianiline have been investigated by means of differential scanning calorimetry (DSC) and wide-angle X-ray diffraction. The results for nonisothermal crystallization study showed that a weak melting peak appeared during the first heating process, whereas no crystallization peak appeared in the DSC curve during the subsequent cooling process. On the other hand, the study for the isothermal crystallization in the temperature range of 260-330 degrees C showed that a new exothermic peak appeared at lower temperature for the samples crystallized for 100 min at 300 degrees C.

Effect of the nature of annealing solvent on the morphology of diblock copolymer blend thin films

The morphologies and structures for the thin film of blend systems consisting of two asymmetric polystyrene-block-polybutadiene (SB) diblock copolymers induced by annealing in the vapor of different solvents, namely, cyclohexane, benzene, and heptane, which have different selectivity or preferential affinity for a certain block, were investigated by tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM). The results revealed that even a slight preferential affinity of good solvent for one block would strongly alter the morphology of the blend thin film.