The Complex of Crosslinked Chitosan with 4′-formal Benzo-15-crown-5 and Palladium Used as Catalyst for Asymmetric Hydrogenation of α-phenylethanone

The crosslinked chitosan was grafted by 4′-formal benzo-15-crown-5 to obtaine crosslinked chitosan with 4′-formal benzo-15-crown-5(CCTS-N=CH-B-15-C-5). Then it was loaded with palldium chloride to gain the heterogeneous catalyst, which was easily isolated from the reaction system. The influences of the Pd content of the catalyst, solvent, and temperature on asymmetric hydrogenation of α-phenylethanone have been studied. The catalyst has been found to catalyze the hydrogenation of α-phenylethanone into the chiral alcohol, α-phenyl ethanol under the mild condition. The optical yield of (R)-1-phenylethanol could be obtained as 97.1% under the following conditions: temperature, 30 ℃; solvent, ethanol; Pd content, 1.43 mmol/g; substrate concentration, 0.02 g /mL due to the cooperative effect of crown ether and chitosan polymer. The stability of this catalyst was also studied at the same time. This chiral natural crosslinked chitosan-palladium complex catalyst could be reused without appreciable change in optical catalytic activity, which will be useful for designing crosslinked-chitosan-based adsorption for metal ions for asymmetric hydrogenation.     

Systematic Studies on the Aromatization of Light Hydrocarbon(

After studying the deactivation type of ZnNi/HZSM-5 catalyst of aromatization of light hydrocarbon, the conclusion was drawn that carbon deposition was the main one of modified ZSM-5 and the catalytic activity could be recovered by charking. The reactivation mode was presumed on the basis of the investigation of the influence of temperature on reactivation process by static charking in muffle furnace and dynamic charking in reactor. Reactivation process simulating industrial charking process at macroscopic calorific effect was studied in 100 mL miniature continuous fixed-bed reactor. The result shows that charking was a diffusion process forming hot spot in catalyst from outer to inner and maximum reactivation temperature was the most important factor among the influential ones including oxygen content, space velocity, time and maximum temperature. Catalytic activity could be recovered only when temperature was higher than 575℃. Meanwhile, reactivation time was determined by space velocity and oxygen content. The best scheme (low initial burning temperature and single charking) was confirmed from the comparison of the three reactivation ones. According to the third scheme, reactivation time was cut down by one half and catalyst stability was maintained after repeated reactivation with the recovery of ZnNi/HZSM-5 catalytic activity.     

Catalytic Decomposition of Methylene Chloride by Sulfated Titania Catalysts

Catalytic decomposition of methylene chloride in air below 300℃ was studied. Sulfated tiaznia was very effective in converting 959ppm methylene chloride selectively to CO, CO2 and HCl. Complete decomposi-tion of methylene chloride was achieved at low temperature( 275℃ ). It was found that the acidic property of cata-lyst was a determinaat factor for the catalytic activity. The presence of water vapor in the feed stream remarkably reduced the catalytic activity, which could be due to the blockage of acidic sites on the surface of catalyst by water molecules. A bifunctional catalyst comprising copper oxide was developed to improve the selectivity of catalytic oxi-thrtion , which indicated that copper oxide can promote the deep oxidation of methylene chloride. The crystal form of TiO2 imposes an important influence upon the catalytic oxidation.     

Liquefaction of metal-contaminated giant reed biomass in acidified ethylene glycol system： Batch experiments

Giant reed is a suitable pioneer plant for metal-contaminated soil phytoremediation,however,it is imperative to dispose the metal-contaminated biomass after harvesting.The liquefaction of metal-contaminated giant reed biomass in ethylene glycol system with sulfuric acid as catalyst for the precursors of polyurethane compounds was studied.The results show that giant reed biomass from metal-contaminated soil is potentially liquefied and significantly affected by solvent/solid ratio,liquefaction temperature and liquefaction time （P〈0.05）.The liquefaction rate of biomass in acidified ethylene glycol system can reach 85.2% with optimized conditions of 60 min,170 ℃,3% sulfuric acid and solvent/biomass ratio of 5：1.The hydroxyl value of liquefied products is of 481 mg KOH/g while reactive hydroxyl groups of them are abundant,which is promised as potential precursors for polyurethane compounds.The solvent liquefaction is a potential method to dispose the metal-contaminated biomass,however,the containing-metal liquefied products should be studied deeply in order to get the suitable precursors in future.     

Semi—solid Processing of Steel—Al—7 Graphite BInding Plate

The bonding of steel plate to Al-7 graphite slurry was studied for the first time.The relationship model about preheat temperature of steel plate,solid fiaction of Al-7 graphite slurry,rolling speed and nterfacial shear strength of bonding plate could be established by artificial neural networks perfectly.This model could be optimized with a genetic algorthm.The optimum bonding parameters are :516℃ for preheat temperature of steel plate,32.5% for solid fraction of Al-7 graphite slurry and 12mm/s for rolling speed,and the largest interfacial shear strength of bonding plate is 70.6MPa.     

Optimization of RPC technique for refining the intermediate transformation microstructure

The influence of processing parameters of relaxation-precipitation-controlling phase transformation(RPC) technique,finish rolling temperature,reduction ration and relaxing time on the microstructure was studied by thermo-simulation for a low carbon Nb and Ti containing micro-alloyed steel.The microstructure was investigated by optical microscope,transmission electron microscope and electron back scatter diffraction(EBSD).The statistical results of the packet size were calculated.It shows that,after PRC procesas,the steel is a composite microstructure of bainite and matensite.The best thermo-simulation process for refinement in this experiment is deformation for 30% at 850℃,and then relaxing at this temperature for 60s to 200s,Increasing the reduction ratio from 30%to 60% or decreasing the deformation temperature to 800℃ would cause the best relaxation time to become shorter,increasing the deformation temperature to 900℃ would cause the refinement effect to be weak.     

Crystallization process of 2-chloro-4,6-diaminoresorcinol

In order to get 2-chloro-4,6-dinitroresocinol(CDNR) with high purity,which influences the synthesis of 4,6-diaminoresorcinol dihydrochloride,the solubility of CDNR in various solvents was measured by laser method and ethanol was chosen as the solvent.The recrystallization process of CDNR was investigated and crystallizing parameters such as cooling rate,temperature and time were discussed.Experimental results show that the time and temperature of crystallization greatly affect the yield and a higher yield can be received at-8 ℃ for 5 h.Slow cooling rate is helpful to the crystallization of CDNR,and the mechanical stirring or ultrasonic treatment can increase the yield and the purity of CDNR.     

Equilibrium and kinetics of adsorption of Ca(Ⅱ) ions onto KCTS and HKCTS

The adsorption of Ca(Ⅱ) ions from aqueous solution by chitosan α-ketoglutaric acid(KCTS) and hydroxamated chitosan α-ketoglutaric acid(HKCTS) was studied in a batch adsorption system.The Langmuir and Freundlich adsorption models were applied to describing the equilibrium isotherms,and isotherm constants were determined.The kinetics of the adsorption with respect to the initial Ca(Ⅱ) ions concentration,temperature and pH was investigated.The pseudo-first-order and second-order kinetic models were used to describe the kinetic data and the rate constants were evaluated.The results show that the experimental data fit well to the Langmuir isotherms with a high correlation coefficient(R2).The pseudo-second-order rate expression provides the best fitting kinetic model.The pseudo second-order kinetic model is indicated with the activation energy of 26.22 kJ/mol and 6.16 kJ/mol for KCTS and HKCTS,respectively.It is suggested that the overall rate of adsorption of Ca(Ⅱ) ions is likely to be controlled by the chemical process.     

A design method and numerical study for a new type parabolic trough solar collector with uniform solar flux distribution

The non-uniform concentrated solar flux distribution on the outer surface of the absorber tube can lead to large circumferential temperature difference and high local temperature of the absorber tube wall,which is one of the primary causes of parabolic trough solar receiver(PTR)failures.In this paper,a secondary reflector used as a homogenizing reflector(HR)in a conventional parabolic trough solar collector(PTSC)was recommended to homogenize the solar flux distribution and thus increase the reliability of the PTR.The design method of this new type PTSC with a HR was also proposed.Meanwhile,the concentrated solar flux distribution was calculated by adopting the Monte Carlo ray-trace(MCRT)method.Then,the coupled heat transfer process within the PTR was simulated by treating the solar flux calculated by the MCRT method as the heat flux boundary condition for the finite volume method model.The solar flux distribution on the outer surface of the absorber tube,the temperature field of the absorber tube wall,and the collector efficiency were analyzed in detail.It was revealed that the absorber tube could almost be heated uniformly in the PTSC with a HR.As a result,the circumferential temperature difference and the maximum temperature could be reduced significantly,while the efficiency tended to decrease slightly due to the inevitably increased optical loss.Under the conditions studied in this paper,although the collector efficiency decreased by about 4%,the circumferential temperature difference was reduced from about 25 to 3 K and the maximum temperature was reduced from667 to 661 K.     

Equilibrium and kinetics of adsorption of Ca（ II ） ions onto KCTS and HKCTS

The adsorption of Ca(Ⅱ) ions from aqueous solution by chitosan α-ketoglutaric acid(KCTS) and hydroxamated chitosan α-ketoglutaric acid(HKCTS) was studied in a batch adsorption system.The Langmuir and Freundlich adsorption models were applied to describing the equilibrium isotherms,and isotherm constants were determined.The kinetics of the adsorption with respect to the initial Ca(Ⅱ) ions concentration,temperature and pH was investigated.The pseudo-first-order and second-order kinetic models were used to des...     

Four-function Principle for Optimization Design of Green High Performance Massive Concrete

A four-function principle was proposed for the optimization design of green high performance massive concrete（GHPMC）based on the theory of value engineering and the adiabatic temperature change control.A set of concrete formulas were designed according to the orthogonal experiment.The experimental results were analyzed by applying the variance analysis method to find out the effects of influential factors and determine the optimum mixture formula.In addition,the four-function principle was successfully applied to optimize the mixture formula in field massive concrete engineering.The practical results show the adiabatic temperature change of massive concrete could be efficiently controlled,and the excellent durability,good workability and high compressive strength could be achieved.     

Fabrication and Properties of Multilayer Chitosan Membrane Loaded with Tinidazole

With the aim of providing effective periodontal disease therapeutic method, multilayer membranes which were loaded with drug for guided tissue regeneration were prepared using an immerseprecipitation phase inversion technique. Single layer, bi-layer and tri-layer membranes were fabricated with chitosan used as cartier and tinidazole as medicine model which was loaded on the membrane. The influence of layer on structure and properties of membrane were studied by SEM, UV spectrophotometer and mechanical test. Drug release properties of three types of layer membranes were also investigated. The results showed that release rate could be slown down in both bi-layer and tri-layer membranes （to 11 days and 14 days respectively） and tri-layer membrane lasted the longest. After a process of rapid release, the concentration of tinidazole which was released by the membrane was maintained at an efficient dosage level. Compared with single layer and bi- layer membranes, we found tri-layer membrane could play a role in controlling low-rate drug release especially at the early stage of release, and keep an efficient dosage at affected part for a long period of time. The loss of drug which loaded on membrane decreased from 84.6% for single layer to 13.04% for tri-layer. The mechanical strength of three types of membrane were detected and showed that it could meet the requiremens of clinical practice. The membranes especially with tri-layer could be more valuable in application.     

Pretreatment of copper-bearing refractory gold ores by bio-heap leaching

The refractory gold ores associated with rich copper and trapped in pyrite and quartz were studied. With conventional technique （all-sliming cyanidation）, the gold recovery rate is only 51.78%. To eliminate the negative effects of copper and pyrite on cyanidation and increase the gold recovery rate, the investigation on bio-heap leaching pretreatment was made, by which Cu would be dissolved and gold would be liberated from pyrite. The experiment adopted mixed bacteria, mainly ThiobaciUus ferrooxidan （named T.fl ）, as the bacterial catalyst for bio-preconditioning and was carried out in a PVC column with a diameter of 20 cm and a height of 1.3 m loaded with gold ores. The temperature was controlled between 28 and 30℃, the pH value was kept between 2.0-2.5, and the flux of sprinkling bacterial liquid was maintained 0.80 L/h. After 45-day＇s bio-oxidization, among the samples sizing from 0 to 5 mm, the oxidation rates of Cu, Fe and S were respectively 44.62%, 28.16% and 25.46%, and the gold recovery rate by cyaniding increased to 80.35%. The bio-heap leaching pretreatment can therefore effectively dissolve Cu and liberate gold from pyrite and lead to the increase of gold extraction.     

Controllable ion exchange synthesis of Ir/Carbon catalyst

In this paper,a carbon based iridium (Ir) catalyst was prepared by an ion exchange procedure using H2IrCl6 as precursor and a strong basic anion exchange resin as substrate. The Ir/Carbon sample was obtained by carbonizing the precursor. Effects of carbonization parameters such as temperature and time on size and dispersion of iridium crystallite were studied. Samples were prepared at 400 oC and 500 oC to investigate the effect of carbonization temperature. The SEM image of the Ir/Carbon composite shows a hard particle of 0. 2 - 0. 4 mm in diameter,which maintains a spherical shape. The TEM images of the catalyst show that no obvious effects of carbonization temperature or time are observed on the iridium particle size. Calcinated Ir nanoparticles prepared in ion exchange still keep their small particle-sized and narrow-sized distribution. The content of Ir supported on carbon can be well controlled simply by adjusting the relative ratio of Ir to carbon. Such a promising synthesis procedure is a versatile approach that can be extended to the fabrication of some carbon-supported metal catalysts or as a simple,rapid,and highly sensitive method.     

Preparation and Swelling Behavior of Physically Crosslinked Hydrogels Composed of Poly（vinyl alcohol） and Chitosan

The physically crosslinked poly（vinyl alcohol）/chitosan （CS） composite hydrogels were prepared by cyclic freezing/thawing techniques, and the microstructure and swelling behavior of the hydrogels in the simulated gastric （pH 1.0） and intestinal （pH 7.4） media were investigated. The experimental results of infrared spectra （IR）, scanning electron microscope （SEM） and differential scanning calorimetry （DSC） demonstrated that poly（vinyl alcohol） and chitosan had good miscibility in the composite hydrogels, and the addition of chitosan perturbed the formation of poly（vinyl alcohol） crystallites. The swelling kinetics results indicated that the composite hydrogels had good pH sensitive properties to the acidic environments, and with the increase of chitosan content in the blend, the maximum swelling degreed and the swelling rate both increased, but it led to more dissolution at pH 1.0. And the composite hydrogels also exhibited good reversible swelling behavior with pH value of the swelling medium altering between 1.0 and 7.4. In addition, the higher freezing/thawing cycle times resulted in the lower swelling rate. Therefore, the swelling behavior of the composite hydrogels could be adjusted by changing the chitosan contents and the freezing/thawing cycle times.     

Relationship Between Structures and Reactivity of Polycyclic Arenes Toward Hydrogenation

Hydrogenation reactions of polycyclic arenes (PAs) were carried out in the presence of Ni and sulfur at 300℃ to examine the structural effect of PAs on their reactivities toward hydrogenation. Hydrogen was observed to be transferred preferentially to some fixed positions in PAs and different PAs displayed some difference in hydrogenation reactivity. The results can be interpretcd on the hydrogen-accepting ability of carbon atoms from different positions in PAs and the resonance stability of aryl radicals resulting from H-atom addition as well as the adsorption strength of PAs on catalyst surface.     

Decoioration and mineralization of yeast wastewater by using Ce-Fe/Al2O3 as heterogeneous photo-Fenton catalyst

Decoloration and mineralization of yeast wastewater were investigated by using Ce-Fe/Al2O3 as a heterogeneous photo-Fenton catalyst in fluidized bed reactor in order to solve the problem of yeast wastewater discharge. The experimental results were assessed in terms of total organic carbon（TOC） reduction. The operational and reaction conditions affecting the efficiencies of TOC removal such as initial pH value, H2O2 concentration, catalyst loading and UV power were studied. The results show that TOC is reduced from 347.6 mg/L to 10.8 mg/L, color is changed from 500 units to 0 under the conditions as follows： initial pH value 6. 0, H2O2 concentration of 1. 000 g/L, catalyst loading of 5 g/L, reaction duration of 120 rain and reaction temperature of 30 ℃. The irradiated Ce-Fe/Al2O3 catalyst was complexed with 1,10-phenanthroline and then it was subjected to Fourier transform infrared spectroscopy and diffuse reflectance spectroscopy to confirm the formation of Fe（Ⅱ） in the solid state. Heterogeneous photo-Fenton reaction proves to be effective for the treatment of yeast wastewater.     

Effect of Pd doping on the acetone-sensing properties of NdFeO_3

The acetone-sensing properties of the undoped and Pd doped perovskite-type oxides NdFeO3 were investigated from room temperature to 400°C. The perovskite-type NdFeO3 was synthesized by a sol-gel method, and the dopants Pd with the content from 1wt% to 5wt% were implanted into NdFeO3 nanoparticles by thermal diffusion. X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques show that NdFeO3 is an orthorhombic structure with the average particle size of about 40 nm. A giant acetone-sensing response of 675.7 is observed when the Pd content in NdFeO3 powders is about 3wt%. The response and recovery time of the sensor to the 5×10-4 acetone gas are 16 and 1 s, respectively. At the same time, it performs a good selectivity to acetone gas and may be a new promising material candidate for the acetone-sensor development.     

Application of experimental design in optimization of crude oil adsorption from saline waste water using raw bagasse简

Experimental design was applied in the optimization of crude oil adsorption from saline waste water using raw bagasse.The application of response surface methodology（RSM） was presented with temperature,salinity of water,pH,adsorbent dose,and initial oil content as factors.A quadratic model could be used to approximate the mathematical relationship of crude oil removal on the five significant independent variables.Predicted values and experimental values are found to be in good agreement with R2 of 97.44%.The result of optimization shows that the maximum crude oil removal is equal to 67.38% under the optimal condition of temperature of 46.53 °C,salinity of 37.2 g/L,pH of 3,adsorbent dose of 9 g/L and initial oil content of 300×10-6.     

Influence of Excessive SiO_2 or TiO_2 on the Electric Properties of Ba_(0.92)Ca_(0.08)TiO_3 PTCR Ceramics

The dependence of electrical properties of Ba0.92Ca0.08TiO3 PTC ceramics on the SYO2 or TiO2 content was studied. The dependence of room, temperature resistivity on the SiO2 content was determined by the variation of the microstructure of Ba0.92Ca0.08TiO3 PTC ceramics . It was shown that a small amount of excessive TiO2 (2mol% ) added could increase the dielectric constant of materials, and it results in a reducing of the potential height (e·) of grain boundary. Thus, samples with particularly low room temperature resistivity were obtained. The relationship of PTC effect with the TiO2 content was also discussed by using the chemistry defect theory . The inferior PTC effect caused by excessive TiO2 may be concerned with the behavior of oxygen vacancies in the grains of ceramics.