Combination of nuclear magnetic resonance spectroscopy and nonlinear methods to analyze the copolymerization of phosphonic acid derivatives

We demonstrate in this study that the combination of modern inline monitoring methods [here: inline nuclear magnetic resonance (NMR)] with simulations gains more exact and profound kinetic results than previously used methods like linearization without that combination. The ¹H-NMR spectroscopic data (more than 100 data points) are used to construct the copolymerization diagram. The reactivity ratios are obtained applying the van Herks nonlinear least square method. The examination of the radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) with (2-{[2-(ethoxycarbonyl)prop-2-en-1-yl]oxy}ethyl) phosphonic acid (ECPPA) as important adhesive monomer used in dentistry yields reactivity ratios of r_HEMA = 1.83; r_ECPPA = 0.42. The copolymerization diagram reflects nonideal, non-azeotropic copolymerization. The sequence distribution of the obtained by Monte Carlo simulation indicates the generation of statistical copolymers. As an important finding, it is demonstrated that the repeating units responsible for etching and adhesion are arranged over the whole polymer chain, which is necessary to achieve proper functionality. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48256.     

Modelling of black carbon statistical distribution and return periods of extreme concentrations

Eight datasets of 1-h black carbon (BC) concentrations measured in Warsaw agglomeration (Poland), at urban background and sub-urban sites, and in Racibórz, a small town in Upper Silesia district (regional background site) were analyzed to evaluate BC levels, daily profiles and statistical distributions of concentrations in Central-Eastern European region. The observed mean levels ranged from 1483 ng m⁻³ in suburban site during summer to 3358 ng m⁻³ in regional background site in winter. Observed diurnal patterns were bimodal in the locations dominated by traffic emissions, but unimodal, with elevated evening peak in individually heated residential area. Three theoretical frequency distributions were applied to fit analyzed datasets separately. The lognormal distribution was the most appropriate to represent the middle-range values, while the high concentrations were satisfactorily predicted by the type I two-parameter exponential distribution which was used to estimate the return periods of extreme concentrations for winter months.     

一种实用的多数据库量子信息检索协议

针对目前量子私有信息检索不能适用与云存储的多数据库问题,基于现在成熟的量子密钥分发方法,提出了一种适合在多数据库环境下,实用的量子私有信息检索协议。对于不同大小的数据库,协议可通过调节参数θ和k,在保证数据库安全及用户隐私的情况下,完成信息的检索。性能分析结果表明,协议的通信复杂度低,检索成功率高、易于实施。     

Potential for rice straw ethanol production in the Mekong Delta,Vietnam

This study is to evaluate the potential for development of a cellulosic ethanol facility in Vietnam. Rice straw is abundant in Vietnam and highly concentrated in the Mekong Delta, where about 26 Mt year⁻¹ of rice straw has been yearly produced. To minimize the overall production cost (PC) of ethanol from rice straw, it is crucial to choose the optimal facility size. The delivered cost of rice straw varied from 20.5 to 65.4 $ dry t⁻¹ depending on transportation distance. The Mekong Delta has much lower rice straw prices compared with other regions in Vietnam because of high density and quantity of rice straw supply. Thus, this region has been considered as the most suitable location for deploying ethanol production in Vietnam. The optimal plant size of ethanol production in the region was estimated up to 200 ML year⁻¹. The improvement in solid concentration of material in the hydrothermal pre-treatment step and using residues for power generation could substantially reduce the PC in Vietnam, where energy costs account for the second largest contribution to the PC, following only enzyme costs. The potential for building larger ethanol plants with low rice straw costs can reduce ethanol production costs in Vietnam. The current estimated production cost for an optimal plant size of 200 ML year⁻¹ was 1.19 $ L⁻¹. For the future scenario, considering improvements in pre-treatment, enzyme hydrolysis steps, specific enzyme activity, and applying residues for energy generation, the ethanol production cost could reduce to 0.45 $ L⁻¹ for a plant size of 200 ML year⁻¹ in Vietnam. These data indicated that the cost-competitiveness of ethanol production could be realized in Vietnam with future improvements in production technologies.     

β-环糊精修饰Ni/SFCC强化C9石油树脂催化加氢性能

以废弃的流化催化裂化催化剂（简称SFCC）为载体、β-环糊精为金属络合剂、硝酸镍为镍源，采用湿法浸渍法制备β-环糊精修饰的Ni/SFCC催化剂（简称Ni/SFCC-CD催化剂），考察其对C9石油树脂的催化加氢性能。通过BET比表面积测试、H2程序升温还原、X射线光电子能谱等手段对催化剂的物相结构进行表征，研究β-环糊精的作用机理及其对催化剂加氢性能的影响。研究结果表明：在反应温度为260 ℃、反应压力为7 MPa、反应时间为2.0 h的最优条件下，采用Ni/SFCC-CD催化C9石油树脂加氢，可制得溴值为1.45 gBr/（100 g）、色号（加纳德）小于1的水白色氢化C9石油树脂，催化剂循环使用4次后仍保持良好活性；β-环糊精的作用机理是：β-环糊精与硝酸镍产生络合作用，抑制硝酸镍的分解、控制NiO的结晶过程和增强活性组分Ni与载体之间的相互作用力，从而提高了Ni/SFCC-CD的催化活性和稳定性。     

Transesterification of Palm-based Methyl Palmitate into Esteramine Catalyzed by Calcium Oxide Catalyst

The technology for transesterification reactions between methyl esters and alcohols is well established by using classical homogeneous alkaline catalysts, which provide high conversion of methyl esters to specialty or nonindigenous esters. However, in certain products where the purity of the esters is of concern, the removal of homogeneous catalysts after the completion of the reaction is a challenge in terms of production cost and water footprint. Therefore, a study to investigate the potential of heterogeneous catalysts was conducted on reactions between methyl palmitate and triethanolamine. The degree of basicity and active surface area of calcium oxide (CaO), zinc oxide (ZnO), and magnesium oxide (MgO) were first characterized by using temperature-programmed desorption (TPD-CO₂) and Brunauere–Emmett–Teller (BET), respectively. Among the metal oxides investigated, the CaO catalyst showed the best catalytic activity toward the transesterification process as it gave the highest conversion of methyl palmitate and yielded fatty esteramine compositions similar to the conventional homogeneous catalyst. The optimum transesterification condition by using the CaO catalyst utilized a lower vacuum system of approximately 200 mbar, which could minimize a considerable amount of energy consumption. Furthermore, low CaO dosage of 0.1% was able to give a conversion of 94.5% methyl ester and formed esteramine at 170 °C for 2 h. Therefore, the production of esterquats from esteramine may become more economically feasible through the methyl ester route by using the CaO catalyst, which can be recycled three times.     

A design of a robust discrete-time controller

In this paper, we proposed a robust discrete-time controller. This control system, which is derived from the idea of the normalized plant, does not include plant parameters. Thus, we obtain a control system independent of plant parameters and that has the same structure as a conventional optimal servo control system. Simulation and experimental results show that the proposed method is fairly robust to plant parameter variations and external disturbances.     

Effect of Different Cosolvents on Transesterification of Waste Cooking Oil in a Microreactor

Biodiesel was prepared from waste cooking oil combined with methanol. The process was performed via transesterification in a microreactor using kettle limescale as a heterogeneous catalyst and various cosolvents under different conditions. n‐Hexane and tetrahydrofuran were selected as cosolvents to investigate fatty acid methyl esters (FAMEs). To optimize the reaction conditions, the main parameters affecting FAME% including reaction temperature, catalyst concentration, oil‐to‐methanol volumetric ratio, and cosolvent‐to‐methanol volumetric ratio were studied via response surface methodology. Under optimal reaction conditions and in the presence of the cosolvents n‐hexane and tetrahydrofuran, high FAME purities were achieved. Considering the experimental results, the limescale catalyst is a unique material, and the cosolvent method can reduce significantly the reaction time and biodiesel production cost.