Preparation of natural α-tocopherol from non-α-tocopherols

Non-α-tocopherols are hydroxymethylated and hydrogenated to produce α-tocopherol in one pot process bysimultaneously reacting with paraformaldehyde and hydrogen in the presence of catalysts of benzenesulfonic acid and 5%Pd/C in an autoclave. Effects of various operation conditions have been studied. The preferable reaction conditions are: temperature 180 ℃ to 200 ℃, pressure 5.0 MPa, acid concentration 0.5 g/100 ml ethanol, mass ratio of Pd/C to tocopherols 7.1 g/100 g, and reaction time 5.0 h. A product with α-tocopherol content of 80% was obtained by using a raw material with a total tocopherols content of 80.54%. The conversion of non-α-tocopherols is almost 100%, and the mole yield ofα-tocopherol is more than 90%.     

Catalytic dechlorination and detoxification of 1-（2-chlorophenyl） ethanol by Pd/Fe

1-（2-chlorophenyl） ethanol （CPE） is of health and environmental concern due to its toxicity and its use as an intermediate in pharmaceutical manufacturing. The current work deals with the catalytic reductive dechlorination and detoxification of CPE by Pd/Fe bimetal. CPE was effectively dechlorinated to l-phenyl ethanol （PE） accompanied by the equivalent release of chloride. The extent of CPE dechlorination increased with temperature, Fe dosage and Pd loading. A decrease in solution pH increased CPE dechlorination, resulting presumably from an increase in hydrogen production. Under the specific conditions of 20 g/L Pd/Fe, 0.10% Pd （w/w） and initial pH 5-6, the CPE dechlorination was completed within 145 rain. The dechlorination followed a pseudo-first-order kinetics with an activation energy of 56.7 kJ/mol. The results of toxicity testing showed that CPE was very toxic to Chlorella, whereas PE showed little toxicity. The toxicity of the reaction solution declined gradually and the promoting effects on Chlorella intensified consequently with the dechlorination process. Thus, the reductive dechlorination of CPE to PE by Pd/Fe was a detoxification process. It may be used to effectively reduce the toxicological effects of CPE-contaminated wastewater, thereby enhancing the performance of subsequent biological processes in wastewater treatment.     

Recovery of Dilute Acetic Acid by Catalytic Distillation Using NKC-9 as Catalyst

The reaction kinetics of dilute acetic acid with methanol using NKC-9 as catalyst was studied at temperatures of 308 K, 318 K, 323 K, 328 K. The kinetic model based on Langmuir-Hinshel-wood rate model was derived and the activation energy was 6.13×104 kJ/kmol. The experiment of recovery of dilute acetic acid was conducted in a packed bed catalytic distillation column. The optimal process parameters and operational conditions determined to make up to 85.9% conversion of acetic acid are as follows:the height of catalyst bed is 1 100 mm, reflux ratio is 4:1, and the ratio of methanol to acetic acid is 2:1. The method can be used as a guide in industrial scale recovery of 15%-30% dilute acetic acid.     

Effect of cultivating conditions on α-galactosidase production by a novel Aspergillusfoetidus ZU-G1 strain in solid-state fermentation

The work is intended to achieve optimum culture conditions of α-galactosidase production by a mutant strain ,Aspergillusfoetidus ZU-GI in solid-state fermentation （SSF）. Certain fermentation parameters involving moisture content, incubation temperature, cultivation period of seed, inoculum volume, initial pH value, layers of pledget, load size of medium and period of cultivation were investigated separately. The optimal cultivating conditions of α-galactosidase production in SSF were 60% initial moisture of medium, 28 ℃ incubation temperature, 18^h cultivation period of seed, 10% inoculum volume, 5.0-6.0 initial pH of medium, 6 layers of pledget and 10 g dry matter loadage. Under the optimized cultivation conditions, the maximum α-galactosidase production was 2037.51 U/g dry matter near the 144th hour of fermentation.     

Application of density-functional theory to studying methylation with dimethyl carbonate and dimethyl sulfate

The activities of dimethyl carbonate and dimethyl sulfate as a methylation reagent were studied by density-functional theory (DFT). B3LYP/6-31G(d, p) methods were used to optimize the structures of dimethyl carbonate and dimethyl sulfate and calculate theirs charge densities. Dimethyl sulfate is easier than dimethyl carbonate to react with a nucleophilic reagent. In dimethyl sulfate, the alkoxy carbons are the only reactive atomic nucleus because of steric hindrance. A nucleophilic reagent is more likely to react with carbonyl carbons than alkoxy carbons of dimethyl carbonate;in the presence of a Lewis acid, the phenyl nucleophilic reagent reacts with the Lewis acid first. Lewis acid increases the negative charge density of a nucleophilic reagent in polar solvent, and also incurs an accretion of steric hindrance. Polar solvent avails to ionize dimethyl carbonate and thus enables the reaction of methylation. The frequencies of transition state calculated by Gaussion 03 confirm the inferred reaction mechanism. The harvest rates of 4-methoxyphenol in the experiments of methylation reactions of hydroquinone with respectively dimethyl carbonate and dimethyl sulfate support the foregoing theortical conclusions.     

Science Letters： Structure relationship of nitrochlorobenzene catalytic degradation process in water over palladium-iron bimetallic catalyst

Two isomers ofnitrochlorobenzene （o- andp-NCB） were treated by a Pd/Fe catalyst in aqueous solutions through catalytic amination and dechlorination. Nitrochlorobenzenes are rapidly converted to form chloroanilines （CAN） first through an amination process, and then rapidly dechlorinated to become aniline （AN） and CI^-, without the involvement of any other intermediate reaction products. The amination and dechlorination reaction are believed to take place predominantly on the surface site of the Pd/Fe catalysts. The dechlorination rate of the reductive degradation of the two isomers of nitrochlorobenzene （o-, and p-NCB） in the presence of Pd/Fe as a catalyst was measured experimentally. In all cases, the reaction rate constants were found to increase with the decrease in the Gibbs free energy （correlation with the activation energy） of NCBs formation; the activation energy of each dechlorination reaction was measured to be 95.83 and 77.05 kJ/mol, respectively for o- and p-NCB. The results demonstrated that p-NCBs were reduced more easily than o-NCBs.     

HNCO hydrolysis performance in urea-water solution thermohydrolysis process with and without catalysts

The thermolysis of urea-water solution and its product, HNCO hydrolysis is investigated in a dual-reactor system. For the thermal decomposition below about 1073 K, the main products are ammonia (NH3) and isocyanic acid (HNCO) whereas at higher temperatures the oxidation processes take effect and the products include a low concentration of nitric oxide (NO) and nitrous oxide (N2O). The gas HNCO is quite stable and a high yield of HNCO is observed. The ratio of NH3 to HNCO increases from approximately 1.2 to 1.7 with the temperature. The chemical analysis shows that H radical is in favor of HNCO hydrolysis by instigating the reaction HNCO+H·→·NH2+CO and high temperature has positive effect on H radical. The hydrolysis of HNCO over an alumina catalyst made using a sol-gel process (designated as γ-Al2O3) is investigated. The conversion of HNCO is high even at the high space velocities (6×105 h-1) and low temperatures (393–673 K) in the tests with catalysts, which enhances HNCO hydrolysis and raises the ratio of NH3 to HNCO to approximately 100. The pure γ-Al2O3 shows a better catalytic performance than CuO/γ-Al2O3. The addition of CuO not only reduces the surface area but also decreases the Lewis acid sites which are recognized to have a positive effect on the catalytic activity. The apparent activation energy of the hydrolysis reaction amounts to about 25 kJ/mol in 393–473 K while 13 kJ/mol over 473 K. The overall hydrolysis reaction rate on catalysts is mainly determined by external and internal mass-transfer limitations.     

Hydrogenation of commercial polystyrene over Pd/BaSO4 catalysts: Effect of carrier structure

A variety of barium sulfate （BaSO4） carriers with or without mesopore structure were synthesized via precipitation reaction in aqueous solution of barium hydroxide and sulfuric acid with ethylene glycol as a modifying agent, and then calcined at various temperatures. The obtained BaSO4 was used as catalyst carriers for polystyrene （PS） hydrogenation, and BaSO4 supported palladium （Pd） catalysts with Pd content of 5wt% were prepared by using impregnation method. N2 physisorption, transmission electron microscopy, X-ray diffraction and kinetics studies were used to investigate the effect of carrier structure on the dispersion and geometric location of active metal and their catalytic activities in PS hydrogenation. It was found that the pore structure of carrier played an important role in the dispersion and location of Pd grains. The activation energy values for all the Pd/BaSO4 catalysts were around 49.1 kJ/mol, while the pre-exponential factor for Pd/BSC-6H was much higher than others. The Pd/BSC-6H without mesopores had Pd grains deposited on the external surface of the carrier, and exhibited better activity than the mesoporous catalysts. It is indicated that the utilization of Pd/BSC-6H can reduce the pore diffusion of PS coils and enabled more active sites to participate in the PS hydrogenation.     

Science Letters：Evaluation of a kinetic uricase method for serum uric acid assay by predicting background absorbance of uricase reaction solution with an integrated method

A patented kinetic uricase method was evaluated for serum uric acid assay. Initial absorbance of the reaction mixture before uricase action （A0） was obtained by correcting the absorbance at 293 nm measured before the addition of uricase solution, and background absorbance （Ab） was predicted by an integrated method. Uric acid concentration in reaction solution was calculated from AA, the difference between A0 and Ab, using the absorptivity preset for uric acid. This kinetic uricase method exhibited CV〈4.3% and recovery of 100%. Lipids, bilirubin, hemoglobin, ascorbic acid, reduced glutathione and xanthine 〈0.32 mmol/L in serum had no significant effects. △A linearly responded to 1.2 to 37.5 μmol/L uric acid in reaction solution containing 15 μl serum. The slope of linear response was consistent with the absorptivity preset for uric acid while the intercept was consistent with that for serum alone. Uric acid concentrations in clinic sera by different uricase methods positively correlated to each other. By Bland-Altman analysis, this kinetic uricase method accorded with that by quantifying the total change of UV absorbance on the completion of uricase reaction. These results demonstrated that this kinetic uricase method is reliable for serum uric acid assay with enhanced resistance to both xanthine and other common errors, wider range of linear response and much lower cost.     

Modeling the kinetics of methane conversion in steam reforming process of coke-oven gas based on experimental data

Steam-reforming is an effective approach for upgrading methane and hydrocarbon of coke-oven gas into CO and H2, but the kinetic behavior needs more study. We investigated the conversion of methane in coke-oven gas by steam reforming process in an electric tubular flow at 14 kPa with temperature varying from 500 °C to 950 °C, and developed a kenetic model for , ignoring the effects of adsorption and diffusion. The optimal dynamic conditions for methane conversion 14 kPa are as follows:the ratio of the amount of water to the amount of methane is from 1.1 to 1.3;the reaction temperature is from 1 223 K to 1 273 K. The methane conversion rate is larger than 95% when the ratio of the amount of water to the amount of methane is 1.2 at a temperature above 1 223 K with the residence time up to 0.75 s.     

Technology and kinetics of free fatty acids esterification in tung oil

We studied the esterification of free fatty acids （FFA） in tung oil with methanol by using activated carbon treated with sulfuric acid as a catalyst, and investigated the effect of different temperatures, methanol/oil mole ratio and catalyst amount on the conversion of FFA. Results show that the optimal reaction condition is when the reaction time is 2 h, the mass fraction of the catalyst to total material is 5%, the molar ratio of menthol to FFA is 15 ： 1, and the reaction temperature is 368.15 K. We also investigated the kinetics of estefification at various temperatures. Results indicate that the rate-control step could be attributed to the surface reaction, and within the range of the experimental conditions, the as-calculated kinetics formula can depict the esterification processes well.     

Preparation of SO4^2-/TiO2-La2O3 solid superacid and its catalytic activities in acetalation and ketalation

SO4^2- / TiO2-La2O3, a novel solid superacid, was prepared and its catalytic activities at different synthetic conditions are discussed with esterification of n-butanoic acid and n-butyl alcohol as probing reaction. The optimum conditions have also been found, mole ratio of n（La^3＋）：n（Ti^4＋） is 1：34, the soaked consistency of H2SO4 is 0.8 tool/L, the soaked time of HESO4 is 24 h, the calcining temperature is 480 ℃, the calcining time is 3 h. Then it was applied in the catalytic synthesis often important ketals and acetals as catalyst and revealed high catalytic activity. Under these conditions on which the molar ratio of aldehyde/ketone to glycol is l： 1.5, the mass ratio of the catalyst used in the reactants is 0.5%, and the reaction time is 1.0 h, the yields of ketals and acetals can reach 41.4%-95.8%.     

Preparation of CeO_2-Modified Mg(Al)O-Supported Pt–Cu Alloy Catalysts Derived from Hydrotalcite-Like Precursors and Their Catalytic Behavior for Direct Dehydrogenation of Propane

A series of PtCuCeMgAl quintuple hydrotalcite-like compounds with different Ce contents were synthesized by one-pot method. After calcining and reduction, CeO_2-modified Mg(Al)O-supported Pt–Cu alloy catalysts were obtained. To understand the effect of Cu and Ce, the structure and physico-chemistry properties of the catalysts were characterized and analyzed, and the catalytic behaviors were investigated in a direct dehydrogenation of propane to propene. The results show that the Pt~(4+), Cu~(2+), and Ce~(3+) ions can be incorporated into the brucite-like layers and the Ce content significantly affects the interaction strength between Pt and Cu and the dehydrogenation performance of propane. Under the reaction conditions, the highest propane conversion(45%) with 89% selectivity to propene and a 40% propene yield were achieved with a 0.3 wt% Ce-modified PtCu/Mg(Al)O catalyst. The improved catalytic performance is related to the easy formation of Pt–Cu alloy phase, excellent resistance to sintering, and coke deposits of active components modified by CeO_2.     

Optimization of biotransformation from phytosterol to androstenedione by a mutant Mycobacterium neoaurum ZJUVN-08

Biotransformation of phytosterol(PS) by a newly isolated mutant Mycobacterium neoaurum ZJUVN-08 to produce androstenedione has been investigated in this paper.The parameters of the biotransformation process were optimized using fractional factorial design and response surface methodology.Androstenedione was the sole product in the fermentation broth catalyzed by the mutant M.neoaurum ZJUVN-08 strain.Results showed that molar ratio of hydroxypropyl-β-cyclodextrin(HP-β-CD) to PS and substrate concentrations were the two most significant factors affecting androstenedione production.By analyzing the statistical model of three-dimensional surface plot,the optimal process conditions were observed at 0.1 g/L inducer,pH 7.0,molar ratio of HP-β-CD to PS 1.92:1,8.98 g/L PS,and at 120 h of incubation time.Under these conditions,the maximum androstenedione yield was 5.96 g/L and nearly the same with the non-optimized(5.99 g/L),while the maximum PS conversion rate was 94.69% which increased by 10.66% compared with the non-optimized(84.03%).The predicted optimum conditions from the mathematical model were in agreement with the verification experimental results.It is considered that response surface methodology was a powerful and efficient method to optimize the parameters of PS biotransformation process.     

An in-plane low-noise accelerometer fabricated with an improved process flow

We present a bulk micromachined in-plane capacitive accelerometer fabricated with an improved process flow, by etching only one-fifth of the wafer thickness at the back of the silicon while forming the bar-structure electrode for the sensing capacitor. The improved flow greatly lowers the footing effect during deep reactive ion etching （DRIE）, and increases the proof mass by 54% compared to the traditional way, resulting in both improved device quality and a higher yield rate. Acceleration in the X direction is sensed capacitively by varying the overlapped area of a differential capacitor pair, which eliminates the nonlinear behavior by fixing the parallel-plate gap. The damping coefficient of the sensing motion is low due to the slide-film damping. A large proof mass is made using DRIE, which also ensures that dimensions of the spring beams in the Y and Z directions can be made large to lower cross axis coupling and increase the pull-in voltage. The theoretical Brownian noise floor is 0.47 μg/Hz^1/2 at room temperature and atmospheric pressure. The tested frequency response of a prototype complies with the low damping design scheme. Output data for input acceleration from -1 g to 1 g are recorded by a digital multimeter and show very good linearity. The tested random bias of the prototype is 130 μg at an averaging time of around 6 s.     

Mathematical model for electroosmotic dewatering of activated sludge

The mechanical dewatering of activated sludge is difficult due to its high compressibility, which can be improved by electroosmosis. In electroosmosis, direct electric field is applied to sludge cake. Based on the conductivity modes of different sludge beds, a model is presented in which sludge cake consists of two series parts in the circuit: a dewatered bed and an undewatered one. The dewatered bed called solid conductor is mainly made up of immovable water and sludge particles. The undewatered bed includes movable water and solid conductor, which are connected in parallel in the circuit. The model describes the variation of water content with time and electric power consumption as a function of water content in sludge cake, and interprets the reason for the variation of electroosmotic dewatering rate. Comparison with the experimental data for electroosmotic dewatering under constant voltage supports the validity of the model.     

Location optimization for the tuned mass damper system on a long-span floor

The L4 roof of Beijing Olympic International Conference Center is a long-span floor with a tuned mass damper system. The locations of dampers in the layout are not optimal theoretically. This paper is about the location optimization of the 74 sets of dampers on the floor. The main content includes the establishment of a 2D dot-matrix model for the structure, the optimal location combination searched by a genetic algorithm, and the optimal results for five working conditions by calculating the total weight.     

A Novel Method for Synthesizing p-Benzoquinone by Direct Catalytic Oxidation of Benzene with Hydrogen Peroxide over Copper-Doped TS-1

Existing methods for synthesizing p-benzoquinone have drawbacks with respect to environmental protection, production scale, or industrial value. Therefore, it is imperative that a simple and environmentally friendly alternative be developed. The approach that involves preparing p-benzoquinone by the catalytic oxidation of benzene with hydrogen peroxide(H_2O_2) over copper-modified titanium silicalite-1(Cu/TS-1) has a certain superiority due to its green synthesis and mild reaction conditions. In this study, Cu/TS-1 catalyst was prepared by the wet impregnation of TS-1 with an aqueous solution of Cu(NO_3)_2 and then characterized by X-ray diffraction, Fourier transform infrared spectroscopy, diffuse reflectance UV–Vis spectroscopy, scanning electron microscopy, inductively coupled plasma mass spectrometry, X-ray fluorescence, and analysis of the N_2 adsorption–desorption isotherms. The results reveal that Cu species exist mainly in the form of amorphous Cu O that is well dispersed on the surface of catalysts, with no major change in the molecular sieve framework. After optimizing the reaction conditions, a desirable p-benzoquinone selectivity(88.4%) and benzene conversion(18.3%) were obtained when the doping of Cu in Cu/TS-1 is 1.95 wt%. In addition, Cu/TS-1 can be conveniently regenerated, showing a slight decrease in catalytic capability after initial use, which then stabilizes in subsequent circulations. The satisfactory stability and low cost of synthesizing Cu/TS-1 give this method considerable potential for further industrialization.     

Changes in biochemical constituents and induction of early sprouting by triadimefon treatment in white yam （Dioscorea rotundata Poir.） tubers during storage

The ability of triadimefon(TDM),a triazolic fungicide,to alter the biochemical constituents and thereby minimizing the days required for sprouting in white yam(Dioscorea rotundata Poir.) tubers during storage under(30±2) °C in the dark,was studied.TDM at 20 mg/L was given to tubers by dipping the tubers in treatment solution containing 20 mg/L TDM on 10,25 and 40 d after storage(DAS).Starch,sugars,protein,amino acid contents as well as protease and α-amylase activities were estimated on 15,30 and 45 DAS from two physiological regions viz.,apical and basal regions of the tubers.In normal conditions(control) sprouting occurred on 70 to 80 DAS.The starch content decreased,while protein,amino acid,sugar contents and protease and α-amylase activities were increased due to TDM treatment and led to early sprouting.     

Decomposition of cellulose to produce 5-hydroxymethyl-furaldehyde in subcritical water

A method for decomposition of cellulose to produce 5-hydroxymethyl-furaldehyde （5- HMF） in subcritical water-carbon dioxide binary system was proposed. A series of experiments were performed in a batch reaction vessel. Main products of the decomposition of cellulose are 5-HMF, furfural, levulinic acid and 1, 2, 4-benzenetrioI.The optimum condition for the preparation of 5-HMF was found as 523.15 K, 5.0% carbon dioxide mole fraction, and 30 min reaction time. The addition of carbon dioxide to water conduced to the decomposition of cellulose to 5-HMF. As can be seen from the distribution of the prod-ucts, the decomposition mechanism of cellulose is similar to the hydrothermal reaction of D-glucose and D-fructose.