Dec 2011, Volume 5 Issue 4

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    Rumin YANG, Fanhui MENG, Xiao WANG, Yaquan WANG

    Silicalite-1 was hydrothermally synthesized in the presence of different concentrations of Na+ using tetrapropylammonium hydroxide (TPAOH) as a template. The synthesis was followed by a base treatment. The silicalite-1samples were characterized using X-ray diffraction, scanning electron microscopy, N2 adsorption, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and NH3 temperature-programmed desorption. The samples were used as catalysts for the vapor phase Beckmann rearrangement of cyclohexanone oxime. During the synthesis, the sodium ions were incorporated onto the silicalite-1 crystals, but were then removed by the base treatment. All the catalysts exhibited nearly complete conversion of cyclohexanone oxime to ?-caprolactam with selectivities grater than 95%. Addition of less than 2.5 mol-% Na+ (relative to TPAOH) did not influence the catalytic properties. However, for Na+ concentrations≥5 mol-%, the particle sizes of silicalite-1 increased and the catalytic activities decreased, which can be attributed to carbon deposition. The results in this work are of great importance for the polymer industry.

    Hongfei CAO, Yakai FENG, Heyun WANG, Li ZHANG, Musammir KHAN, Jintang GUO

    By using the corresponding L-amino acid sodium as initiator, ?-caprolactone-depsipeptides CL-Ala and CL-Leu were prepared by the reactions of ?-caprolactone (CL) with L-alanine and L-leucine, respectively, and p-dioxanone-depsipeptide (PDO-Leu) was prepared by the reaction of p-dioxanone (PDO) with L-leucine. Two poly(?-caprolactone) oligomers (PCL-Ala and PCL-Leu) of different molecular weights with depsipeptide unit were synthesized by controlling the feed ratio of L-amino acid sodium and CL. The presence of the depsipeptide structure in these obtained products was confirmed by 1H NMR spectra and the molecular weight of the poly(?-caprolactone) oligomers was measured by gel permeation chromatography (GPC). These products contain a hydroxyl group and a carboxyl group in one molecule, which means they could act as bifunctional monomers for further polymerization to prepare high molecular weight polymers. By this way, the depsipeptide unit could be introduced into the polymers and the biodegradation rates of the novel polymers could be well controlled in vivo by the tailored molecular structures.

    Xingfu SONG, Shuying SUN, Dengke ZHANG, Jin WANG, Jianguo YU

    Magnesium hydroxide with high purity and uniform particle size distribution was synthesized by the direct precipitation method using MgCl2 and NaOH as reactive materials and NaCl as additive to improve the crystallization behavior of the product. The particle size distribution, crystal phase, morphology, and surface area of magnesium hydroxide were characterized by Malvern laser particle size analyzer, X-ray diffraction (XRD), scanning electron microscope (SEM) and Branauer-Emmett-Teller (BET) method, respectively. The purity of products was analyzed by the chemical method. The effects of synthesis conditions on the particle size distribution and water content (filtration cake) of magnesium hydroxide were investigated. The results indicated that feeding mode and rate, and reaction temperature had important effects on water content and the particle size distribution of the product, and sodium chloride improved the crystallization behavior of magnesium hydroxide. The ball-like magnesium hydroxides with the particle size distribution of 6.0–30.0 μm and purity higher than 99.0% were obtained. This simple and mild synthesis method was promising to be scaled up for the industrial production of magnesium hydroxide.

    Meijiang LI, Rui HUANG, Changzhi WU, Hujin ZUO, Guoqiao LAI, Yongjia SHEN

    Two donor-σ-acceptor molecular systems incorporating tetrathiafulvalene (TTF) and tetraphenylporphyrin (TPP) units, TTF-TPP (dyad 1) and TTF-TPP-TTF (triad 2), were synthesized. Both dyad 1 and triad 2 and their synthetic intermediates have been characterized by 1H nuclear magnetic resonance (1H NMR) and mass spectrography (MS). Their ultraviolet and visible spectroscopy (UV-Vis) and cyclic voltammetry (CV) showed negligible intramolecular charge transfer interaction in their ground states. Their fluorescence intensity was strongly quenched compared with TPP, which implied the photoinduced electron transfer occurred from the TTF unit to the TPP unit in the excited state. On the other hand, their fluorescence intensity could be modulated by sequential oxidation of the TTF unit using chemical methods, which exhibited their potential application in fluorescence molecular switch.

    Fushan WEN, Lingling SUN, Jinhyeok KIM

    Sb3+-doped YBO3 crystals were prepared through a low-temperature hydrothermal method and a high-temperature solid-state technique, respectively. The effects of preparation methods on the morphologies and luminescent properties of YBO3 phosphors were investigated. The YBO3 crystals from the hydrothermal system look like flowers, whereas those from the solid-state process look like some agglomerates of little spheres. The Sb3+-doped YBO3 powders prepared via both methods showed the blue emission with the peak at around 452 nm, which corresponds to the 3P11S0 transition of Sb3+ ions. However, the emission intensity of the Sb3+-doped YBO3 from the hydrothermal system is about 3.5 times as much as that from the solid-state process. The (Sb3+,Eu3+) co-doped YBO3 crystals were also prepared through the two methods. The results showed that the emission intensity of Sb3+ ions in (Sb3+, Eu3+) co-doped YBO3 synthesized by the hydrothermal method is stronger than that by the solid-state process.

    Xiaobin JIANG, Baohong HOU, Yongli WANG, Jingkang WANG

    In this paper a porous media seepage model was applied to analyze the permeability and study the seepage process of crystal pillar formed in the preparation of electronic grade phosphoric acid (EGPA). By inspecting the seeping process, the structure parameter of crystal pillar could be obtained. Two basic ideal models (perfectly separated model and perfectly connected model) were presented and a characterized factor φ was introduced to modify the model. A good simulation result was obtained which met the experiment result well. The relationship between φ and permeability were also discussed. The characterized factor φ showed potential application on optimizing process.

    Dingding JING, Yongli WANG, Zhijian CHEN, Lina ZHOU, Jingkang WANG

    Penicillin sulfoxide is the intermediate for the synthesis of 7-amino-3-desacetoxycephalosporanic acid which is one of the most important nucleuses of cephalosporin antibiotic. In this contribution, two crystal structures of penicillin sulfoxide (forms I and II) were determined by X-ray diffraction, and their thermotropic properties were investigated by differential scanning calorimetry (DSC). Furthermore, the transformation of form II to form I was studied quantitatively by Raman spectroscopy, and its rates at different temperatures were determined. The results indicate that penicillin sulfoxide is more stable as form I, and the temperature plays an important role in the crystal transformation.

    Shuyong CHEN, Xigang YUAN, Bo FU, Kuotsung YU

    Interfacial Marangoni convection has significant effect on gas-liquid and/or liquid-liquid mass transfer processes. In this paper, an approach based on lattice Boltzmann method is established and two perturbation models, fixed perturbation model and self-renewable interface model, are proposed for the simulation of interfacial Marangoni convection in gas-liquid mass transfer process. The simulation results show that the concentration contours are well consistent with the typical roll cell convection patterns obtained experimentally in previous studies.


    Computational fluid dynamics (CFD) was used to investigate the hydrodynamic parameters of two internal airlift bioreactors with different configurations. Both had a riser diameter of 0.1 m. The model was used to predict the effect of the reactor geometry on the reactor hydrodynamics. Water was utilized as the continuous phase and air in the form of bubbles was applied as the dispersed phase. A two-phase flow model provided by the bubbly flow application mode was employed in this project. In the liquid phase, the turbulence can be described using the k-? model. Simulated gas holdup and liquid circulation velocity results were compared with experimental data. The predictions of the simulation are in good agreement with the experimental data.


    A Plackett-Burman design was employed for screening 18 nutrient components for the production of inulinase using streptomyces sp. and pressmud as the substrate via solid-state fermentation (SSF). From the experiments, three nutrients viz. yeast extract, FeSO4·7H2O, and NH4NO3 were found to be the most significant components. Hence these three components were selected and optimized using Response Surface Methodology (RSM). The optimum conditions are: yeast extract 0.00274 g/gds, FeSO4·7H2O 0.00011 g/gds and NH4NO3 0.00772 g/gds. The effect of the substrate concentration and initial moisture content were also studied. A substrate concentration of 12 g and an initial moisture content of 65% are optimum for the maximum production of inulinase (89 U/gds).


    The magnetohydrodynamic (MHD) boundary layer slip flow and solute transfer over a porous plate in the presence of a chemical reaction are investigated. The governing equations were transformed into self-similar ordinary differential equations by adopting the similarity transformation technique. Then the numerical solutions are obtained by a shooting technique using the fourth order Runge-Kutta method. The study reveals that due to the increase in the boundary slip, the concentration decreases and the velocity increases. On the other hand, with an increase in the magnetic field and mass suction, both boundary layer thicknesses decreased. As the Schmidt number and the reaction rate parameter increases, the concentration decreases and the mass transfer increases.

    Ganesh TILEKAR, Kiran SHINDE, Kishor KALE, Reshma RASKAR, Abaji GAIKWAD

    The capture of CO2 by transition metal (Mn, Ni, Co and Zn) aluminates, calcium aluminate, calcium zirconate, calcium silicate and lithium zirconate was carried out at pre- and post-combustion temperatures. The prepared metal adsorbents were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), surface area analysis and acidity/alkalinity measurements. The different experimental variables affecting the adsorbents ability to capture CO2, such as the mol ratio of metal ions, the pressure of CO2, the exposure time and the temperature of the adsorbent were also investigated. Calcium zirconate captured 13.85 wt-% CO2 at 650°C and 2.5 atm and calcium silicate captured 14.31 wt-% at 650°C. Molecular sieves (13X) and carbon can only capture a negligible amount of CO2 at high temperatures (300°C–650°C). However, the mixed metal oxides captured reasonable amount of CO2 at these higher temperatures. In addition, calcium aluminate, calcium zirconate, calcium silicate and lithium zirconate adsorbents captured CO2 at both pre and post-combustion temperatures. The trend for the amount of captured carbon dioxide over the adsorbents was calcium aluminate<lithium zirconate<calcium zirconate<calcium silicate.

    Li XU, Li-Shun DU, Jing HE

    The effects of the operating pressure, cross flow velocity, feed concentration, and temperature on the streaming and Zeta potential of the membranes were studied. The permeate flux and the retention rate under different nanofiltration operating conditions were also investigated. The results show that the higher pressure, feed concentration, temperature, and lower cross flow velocity lead to the higher absolute value of streaming and Zeta potential. The permeate flux of the nanofiltration decreases with the feed concentration and increases with not only the pressure but also the cross flow velocity and temperature. The higher the pressure and the cross flow velocity, the higher the retention rate. The lower feed concentration and higher temperature leads to lower retention rate. The effects of the operating conditions on the permeate flux and the retention rate were explained by the variation of the membrane charge property.


    The effects of different solvent/water coagulation mediums, different coagulation bath temperatures (CBT) and different coagulants on the performance, morphology and thermal stability of polysulfone membranes were investigated. The CO2/CH4, H2/CH4 and H2/N2 separation performance of the membranes were studied by gas permeation. Changing the N,N-dimethyl acetamide (DMAc)/water coagulation medium ratio from pure water to 90/10 vol%, resulted in a complete disappearance of the macrovoids throughout the polysulfone (PSf) polymeric matrix. The PSf membrane prepared in a CBT of 25°C showed the best gas separation performance with ideal selectivities of 46.29, 39.81 and 51.02 for H2/CH4, CO2/CH4 and H2/N2 respectively, and permeances of 25 and 21.5 GPU for H2 and CO2 at 25°C and 10 bar respectively. By increasing the amount of solvent in the gelation bath, the selectivities of H2/CH4, CO2/CH4 and H2/N2 were dramatically reduced from 46.29, 39.81 and 51.02 to 16.08, 20.2 and 18.5 respectively at 25°C and 10 bar. Reducing the CBT from 80°C to 5°C led to a complete elimination of macrovoids. Using methanol as a coagulant resulted in a less selective membrane compared with membranes from ethanol and water coagulants. The H2 and CO2 permeances were respectively about 3 and 9 times more than those for ethanol and water coagulants. Coated membranes were heated at different temperatures to investigate the suppression of undesirable CO2 plasticization. The membranes were stabilized against CO2 plasticization by a heat-treatment process.

    Jinli ZHANG, Nan LIU, Wei LI, Bin DAI

    Polyvinyl chloride (PVC) has become the third most used plastic after polyethylene and polypropylene and the worldwide demand continues to increase. Polyvinyl chloride is produced by polymerization of the vinyl chloride monomer (VCM), which is manufactured industrially via the dehydrochlorination of dichloroethane or the hydrochlorination of acetylene. Currently PVC production through the acetylene hydrochlorination method accounts for about 70% of the total PVC production capacity in China. However, the industrial production of VCM utilizes a mercuric chloride catalyst to promote the reaction of acetylene and hydrogen chloride. During the hydrochlorination, the highly toxic mercuric chloride tends to sublime, resulting in the deactivation of the catalyst and also in severe environmental pollution problems. Hence, for China, it is necessary to explore environmental friendly non-mercury catalysts for acetylene hydrochlorination as well as high efficiency novel reactors, with the aim of sustainable PVC production via the acetylene-based method. This paper presents a review of non-mercury heterogeneous and homogeneous catalysts as well as reactor designs, and recommends future work for developing cleaner processes to produce VCM over non-mercury catalysts with high activity and long stability.