Ultrasound‐activated Knoevenagel condensation of malononitrile with carbonylic compounds catalysed by alkaline‐doped saponites

α,β‐Unsaturated nitriles have been synthesized by Knoevenagel condensation of a carbonylic compound with malononitrile, assisted by sonochemical irradiation. Two alkaline‐promoted clays (Li⁺‐ and Cs⁺‐exchanged saponites) have been employed as catalysts. The influence of the carbonylic compound (benzaldehyde or cyclohexanone) and the use of a solvent on the catalytic activity have been studied. Remarkable increase in the conversion values has been found when the reaction is activated by ultrasound, as compared with the thermal activation. In this green, solvent‐free procedure, α,β‐unsaturated nitriles have been produced in very high yields (97%) when the Cs⁺‐saponite is used as catalyst. Copyright © 2004 Society of Chemical Industry     

Acidogenic fermentation of blended food‐waste in combination with primary sludge for the production of volatile fatty acids

The performance of a laboratory‐scale anaerobic acidogenic fermenter fed with a mixture of blended kitchen food‐waste and primary sludge from a sewage treatment plant was investigated for the production of volatile fatty acids (VFA). The operating variables for acidogenic fermentation were kitchen food‐waste content (10 and 25 wt %), hydraulic retention time (HRT: 1, 3 and 5 days), temperature (ambient: 18 ± 2 °C, and mesophilic: 35 ± 2 °C) and pH (varied from 5.2 to 6.7). The experimental results indicated that effluent VFA concentrations and VFA production rates were higher at ambient temperature than at mesophilic conditions. The net amount of VFA with 10 wt % food‐waste increased up to 920 mg dm^?3 with an increase of HRT, but contrasting results (a decrease of 2610 mg dm^?3) were found due to the conversion of VFA into biogas in the case of 25 wt % food‐waste, which increased significantly at HRT of 3–5 days. In terms of biogas composition (CO₂ and CH₄), the organic matter was converted into CO₂ through the oxidative pathway by facultative species at low temperature while mesophilic temperature and optimum pH (6.3–7.8) played a pivotal role in increasing rate of conversion of VFA into biogas by methanogenesis. Rates of VFA production and their conversion are dependent on the food‐waste content in the mixture. Yet, the higher concentration of food‐waste (25% compared with 10%) did not produce VFA proportionally due to the increased rate of conversion of VFA into gaseous products. The maximum VFA production rate (0.318 g VFA_produced g^?1 VS_fed day^?1) was achieved in the 10 wt % food‐waste at ambient temperature and at a 5‐day HRT. Copyright © 2005 Society of Chemical Industry     

Nutrient removal performance of an anaerobic–anoxic–aerobic process as a function of influent C/P ratio

The laboratory scale anaerobic–anoxic–aerobic (A²O) process fed with synthetic brewage wastewater was designed to investigate the effects of changing feed C/P ratio on the performance of biological nutrient removal (BNR) processes. In the experiment, the influent chemical oxygen demand (COD) concentration was kept at approximately 300 mg L^?1 while the total phosphorus concentration was varied to obtain the desired C/P ratio. Results showed that when the C/P ratio was lower than 32, phosphorus removal efficiency increased as C/P ratio increased linearly, while when the C/P ratio was higher than 32, the P removal efficiency was maintained at 90–98%, and effluent P concentration was lower than 0.5 mg L^?1. However, regardless of the C/P ratio, excellent COD removal (90% or higher) and good total nitrogen removal (75–84%) were maintained throughout the experiments. It was also found that very good linear correlation was obtained between COD uptake per unit P released in the anaerobic zone and C/P ratio. In addition, the P content in the wasted activated sludge increased with the decrease in the C/P ratio. Based on the results, it was recommended that the wastewater C/P ratio and its effects be incorporated into BNR design and operational procedures, appropriate C/P ratios were used to achieve the effluent treatment goals. Copyright © 2005 Society of Chemical Industry     

Analysis of supersaturation and nucleation in a moving solution droplet with flowing supercritical carbon dioxide

A supercritical antisolvent (SAS) process is employed for production of solid nanoparticles from atomized droplets of dilute solution in a flowing supercritical carbon dioxide (SC CO₂) stream by attaining extremely high, very rapid, and uniform supersaturation. This is facilitated by a two‐way mass transfer of CO₂ and solvent, to and from the droplet respectively, rendering rapid reduction in equilibrium solubility of the solid solute in the ternary solution. The present work analyses the degree of supersaturation and nucleation kinetics in a single droplet of cholesterol solution in acetone during its flight in a flowing SC CO₂ stream. Both temperature and composition are assumed to be uniform within the droplet, and their variations with time are calculated by balancing the heat and mass transfer fluxes to and from the droplet. The equilibrium solubility of cholesterol with CO₂ dissolution has been predicted as being directly proportional to the Partial Molar Volume Fraction (PMVF) of acetone in the binary (CO₂–acetone) system. The degree of supersaturation has been simulated up to the time required to attain almost zero cholesterol solubility in the droplet for evaluating the rate of nucleation and the size of the stable critical nuclei formed. The effects of process parameters have been analysed in the pressure range of 7.1–35.0 MPa, temperature range of 313–333 K, SC CO₂ flow rate of 0.1136–1.136 mol s^?1, the ratio of the volumetric flow rates of CO₂‐to‐solution in the range of 100–1000, and the initial mole fraction of cholesterol in acetone solution in the range of 0.0025–0.010. The results confirm an extremely high and rapid increase in degree of supersaturation, very high nucleation rates and stable critical nucleus diameter of the order of a nanometre. Copyright © 2005 Society of Chemical Industry     

Rheological properties of polypropylene modified by high‐intensity ultrasonic waves

A new method using high‐intensity ultrasonic waves, instead of peroxide‐aided reactive extrusion, was applied to modify a linear polypropylene into a branched structure. The ultrasonic waves induced chain scission and created reactive macromolecules of polypropylene successfully in the melt state without any peroxide. To enhance and control the recombination reaction during sonication, a multifunctional agent and an antioxidant were used. The rheological property measurements clearly confirmed that the modified polypropylene had a nonlinear branched structure. It showed shear‐thinning behaviors in its viscosities at low frequencies, high elastic behaviors in Cole–Cole plots, and a high rheological polydispersity index in comparison with a linear polypropylene. The degradation or recombination of polypropylene was adequately controlled by an antioxidant, which stabilized the structure during sonication. Also, the use of an antioxidant was quite effective in improving the extrusion processability by delaying the instability of the extrudate to a higher shear rate. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

酸催化二甘醇脱水环化反应研究

以硫酸、磷钨酸、ZRP-5分子筛为催化剂,研究了二甘醇(DEG)脱水环化的反应规律。结果表明,DEG发生分子内脱水环化反应,生成1,4-二氧六环(DOX),DEG分子间脱水不仅可以生成四甘醇、六甘醇等,同时可生成三甘醇、五甘醇等一系列的多甘醇(PEG)。不仅DEG可以脱水环化生成DOX,在反应中生成的PEG也同样可以进行生成DOX的反应。对于二甘醇(DEG)脱水环化反应,硫酸是性能优良的催化剂,反应可以在较低的温度下进行,馏出产物中DOX选择性大于95％。     

A scheme to randomly generate surface dust points for the 3D complex variable boundary element method (CVBEM)

A scheme to randomly generate dust points on the surface of a three-dimensional (3D) object is proposed. This scheme will potentially eliminate the bias of a density of points which are approximately equally spaced on the surface, as well as eliminate possible weighting requirements for areas of higher density. This method has the potential to reduce computational effort, as fewer points might be required to define the surface area. The global trial function vector can be assigned to these dust points and then entered into the complex variable boundary element method (CVBEM) commercial code. This scheme can be applied to each piece of a system that is comprised of a connected multiple geometry. A noticeable benefit of this approach is that the same problem can be studied several times, using a new random distribution of surface points each time. The smallest error can then be determined and that run selected. The Mathematica code used to generate the scheme is attached as an appendix.     

美国食品安全管理法规与举措

以美国国会研究服务部对第107届国会就食品安全方面的一份报告为基础,主要对美国的公共健康问题现状、美国食品安全的联邦规范框架组成、美国食品安全控制最新进展和国会对食品安全提出的新议题做了综述,对我国的食品安全控制和管理体系的建设发挥一点借鉴作用。     

常减压蒸馏装置阻垢剂进料管腐蚀与防护

通过对常减压蒸馏装置阻垢剂进料管的材质、性能、工作条件及腐蚀形貌、腐蚀产物的全面分析,找出了使进料管发生大面积腐蚀的腐蚀介质为环烷酸.并提出了减缓阻垢剂进料管环烷酸腐蚀的措施,主要包括选用更耐蚀的316或316 L材质以及改进三通结构等.     

Measurement of the Metal Surface Acidity/Electronegativity of Pt(110)

In previous work, it has been found that a hydrogen-covered Pt(110) surface is acidic, but quantification of the acidity has not yet been done. In this paper a spectroscopic method is developed to measure the acidity of a metal surface for the first time. The technique involves measuring the intensity of the N–H stretch from the C₅H₄XNH⁺ that forms when hydrogen coadsorbs with pyridine, 2-fluoropyridine and 3-fluoropyridine. The Bethe approximation is then used to estimate the metal surface acidity/electronegativity (MSAEL). The proton affinity/MSAEL of Pt(110) has been determined to be 907 ± 4 kJ/mol at high coverage. This is the first time the MSAEL has been measured on a metal surface. Implications for fuel cell catalysis are discussed.