化学计量学在过程分析中的应用及进展

评述了化学计量学方法在生产过程分析中各个方面 ,如过程优化、过程模拟、仪器及仪器校正、过程监测等方面的应用 ,并展望了化学计量学在过程分析中的应用前景     

改进层次分析法在污水处理工艺选择中的应用

采用传统的层次分析方法(Analytic Hierarchy Process,AHP)进行污水生化处理工艺的选择时,其科学性和可操作性均较低,而改进的AHP法采取三标度法,判定矩阵较易构造,且无需进行一致性检验。本研究采用改进的AHP法,建立了4层10指标4方案的污水处理工艺综合评价体系,分别对MBR、A~2/O、A/O和氧化沟工艺的经济效益、环境影响及技术性能进行分析。结果表明,MBR、A~2/O、A/O和氧化沟工艺的评价体系公式计算结果分别为0.3137、0.3379、0.2085和0.1552。因此,在我国东北地区,综合考虑经济效益、环境影响及技术性能,A~2/O工艺为最适宜的生化处理工艺,其次是MBR工艺和A/O工艺,而氧化沟工艺为最不推荐的工艺。改进的AHP法可对现有污水处理工艺的经济效益、环境影响及技术性能进行直观的评价,从而为现有工艺的运行管理以及新工艺的设计提供理论及实践依据。     

氟碳铈矿提取稀土的绿色化学进展

氟碳铈矿是稀土工业的重要原材料，目前从氟碳铈矿提取稀土主要采用酸法工艺，该工艺虽然稀土回收高，但流程长，试剂消耗长，成本较高，同时酸法产生ＨＦ及废酸碱污染环境。因此寻找低成本，低污染的绿色化学处理工艺是近几十年中人们一直努力的方向。本文系统介绍了氟碳铈矿分解工艺的发展，并着重介绍邓氯化铵法提取氟碳铈矿稀土的的新工艺。该工艺采用盐类分解并氯化氟碳铈矿，直接用水浸取回收稀土，不引入酸和碱，提高了反应选择性，减轻了稀土在稀土杂质分负荷，降低了化工材料消耗，简化了工艺，提高了回收率，是符合绿色化学要求的工艺。     

An aspen simulation of fuel production by hydrolysis of woody biomass

An integrated process, in which woody biomass was converted to fuel, was simulated using the ASPEN simulator. For purposes of simulation, the process was divided into four sections, biomass refining, hydrolysis, bioreaction, and fuel separation. Detailed attention was paid to the hydrolysis process and the bioreactor, while a general simulation of the front-end biomass refining process and fuel separation step at the end of the process is included. A simulation of the biomass and active microbial system required the definition of nonconventional streams. The emphasis in this study was upon the effect of varying acid recycle in the two-step hydrolysis process. As the recycle ratio increases the operating cost of the overall process passes through a minimum. Suggestions for the refinement and extension of this approach are discussed. Its advantages in establishing the cost of proposed technologies, assessing areas where research and development are required and evaluating schemes for enhancing energy efficiency were all evaluated.     

Analysis of Volatile Components of Jasmine and Jasmine Tea during Scenting Process

Jasmine tea is widely loved by the public because of its unique and pleasant aroma and taste. The new scenting process is different from the traditional scenting process, because the new scenting process has a thin pile height to reduce the high temperature and prolong the scenting time. We qualified and quantified volatiles in jasmine and jasmine tea during the scenting process by gas chromatography-mass spectrometry (GC-MS) with a headspace solid-phase microextraction (HS-SPME). There were 71 and 78 effective volatiles in jasmine and jasmine tea, respectively, including 24 terpenes, 9 alcohols, 24 esters, 6 hydrocarbons, 1 ketone, 3 aldehydes, 2 nitrogen compounds, and 2 oxygen-containing compounds in jasmine; 29 terpenes, 6 alcohols, 28 esters, 8 nitrogen compounds, 1 aldehyde, and 6 other compounds in jasmine tea. The amounts of terpenes, esters, alcohols, nitrogen compounds, and hydrocarbons in jasmine and tea rose and then fell. The amount of oxygenated compounds of tea in the new scenting process first rose and then fell, while it showed a continuous upward trend during the traditional process. The amount of volatiles in jasmine and tea produced by the new scenting process were higher than that of the traditional scenting process at the same time. This study indicated that jasmine tea produced by the new scenting process had better volatile quality, which can provide proof for the new scenting process.     

Techno-economic analysis of biocatalytic processes for production of alkene epoxides

A techno-economic analysis of two different bioprocesses was conducted, one for the conversion of propylene to propylene oxide (PO) and other for conversion of styrene to styrene epoxide (SO). The first process was a lipase-mediated chemo-enzymatic reaction, whereas the second one was a one-step enzymatic process using chloroperoxidase. The PO produced through the chemo-enzymatic process is a racemic product, whereas the latter process (based on chloroperoxidase) produces an enantio-pure product. The former process thus falls under the category of high-volume commodity chemical (PO); whereas the latter is a low-volume, high-value product (SO).A simulation of the process was conducted using the bioprocess engineering software SuperPro Designer v6.0 (Intelligen, Inc., Scotch Plains, NJ) to determine the economic feasibility of the process. The purpose of the exercise was to compare biocatalytic processes with existing chemical processes for production of alkene expoxides. The results show that further improvements are needed in improving biocatalyst stability to make these bioprocesses competitive with chemical processes.     

疏水缔合水溶性聚合物的合成研究进展

综述了疏水缔合水溶性聚合物的合成的最新研究进展。主要合成方法有非均相共聚、均相共聚、胶束共聚、反相微乳液聚合、无皂乳液聚合、活性阴离子聚合以及超临界二氧化碳介质等。     

稀土萃取分离过程自动控制研究现状及发展趋势

在简要描述稀土萃取分离生产过程的基础上,综述了目前国内外稀土萃取分离过程中稀土元素成分在线检测的方法、装置及其应用现状;稀土串级萃取分离生产过程的计算机流程模拟以及稀土萃取生产过程的自动控制方法、技术及其应用现状.指出了稀土元素组分含量的软测量方法,以综合生产指标为目标的稀土萃取分离生产过程优化控制方法以及由生产过程管理系统和过程控制系统两层结构组成的稀土萃取分离生产过程综合自动化系统已成为稀土萃取分离生产过程自动化未来发展的方向.     

恒温过程的热量传递

目前,基于物化教材上对"恒温过程"和"热"的定义,初学者在理解恒温过程的热量传递时往往会产生很大困惑。对概念的孤立和片面理解是造成该结果的根本原因。本文借助数学上的极限思想,以理想气体的恒温可逆膨胀过程为例,对该过程的能量传递做出详细剖析,以消除物理化学初学者在入门期的学习障碍。     

Micronization of tolbutamide using rapid expansion of supercritical solution with solid co-solvent (RESS-SC) process

Micronization of a sulfonylurea antidiabetic agent, tolbutamide, using rapid expansion of supercritical solution with solid co-solvent (RESS-SC) process was investigated in this study. Menthol was selected as the solid co-solvent in the RESS-SC process owing to its high vapor pressure and ease of removal by sublimation. The tolbutamide particles were micronized successfully from its original mean size of 89.4 ??m to the smallest mean size of 2.1 ??m through the RESS-SC process. The use of solid co-solvent in this process enhanced the saturated solubility of tolbutamide in supercritical carbon dioxide and inhibited the particle growth during pressure expansion after the nozzle. In addition, polymorph conversion from form I to form II after the RESS-SC process was confirmed by XRD and DSC analyses. Measurements of the dissolution rate profiles before and after the RESS-SC process were also investigated. It is shown that the micronized tolbutamide by the RESS-SC process had novelty in dissolution behavior compared to that of the original compound. Its dissolution rate was enhanced by 8.8 times after the RESS-SC process.     

Miniemulsion copolymerization of vinyl acetate and butyl acrylate. IV. Kinetics of the copolymerization

The copolymerization kinetics of conventional emulsions and miniemulsions of 50:50 and 25:75 molar ratios vinyl acetate–butyl acrylate monomer mixtures were studied using sodium hexadecyl sulfate as surfactant. Hexadecane was the cosurfactant used in the preparation of the miniemulsions, and ammonium persulfate was the initiator used in the polymerizations. The rate of polymerization showed four regions which extended to different conversions depending on the type of emulsion used (conventional or miniemulsion). The rate of polymerization for the miniemulsion process was always slower than for the conventional process. The dependence of the rate on the initiator concentration was higher for the miniemulsion process. The number of particles nucleated in the miniemulsion copolymerization process was lower than in the conventional emulsion copolymerization process. The initiator and surfactant concentration dependence of the number of particles were 0.8 and 0.25 for the miniemulsion copolymerization process and 0.0 and 0.68 for the conventional emulsion copolymerization process respectively. These effects were attributed to the different particle nucleation mechanism operating in each process.     

固体核磁共振弛豫在高分子研究中的应用

本文综述了近年来固体核磁弛豫方法在高分子研究中的应用，共分５个部分加以介绍：（１）自旋－晶格弛豫过程；（２）在旋转坐标系中的＾１３Ｃ自旋－晶格弛豫过程；（３）交叉极化速率和旋转坐标系中的＾１Ｈ自旋－晶格弛豫过程；（４）自旋－自旋弛豫过程；（５）动态结构导致的线形变化。本文主要讨论磁性核的各种弛豫过程以及它们与分子结构和分子运动的关系。     

Deacidification of citric acid solutions by electrodialysis

Electrodialysis is a useful process to deacidify citrus juices. Besides the known allanion exchange membrane process, two alternative electrodialysis processes were investigated: a three-stream process using cation and anion exchange membranes and a twostream process with alternately arranged bipolar and anion exchange membranes. The results taken from a laboratory electrodialysis cell show, that according to current efficiency, consumption of sodium hydroxide and by-production of sodium citrate or citric acid the alternative processes are favourable, especially the process using bipolar membranes.     

Optimization of Saccharification and Fermentation Process in Bioethanol Production from Oil Palm Fronds

Oil Palm Frond (OPF) is one of lignocellulosic biomass, which can be utilized as raw material for bioethanol production. Bioethanol is produced as alternative energy to substitute gasoline. There are four steps in bioethanol production from OPF, i.e pretreatement, saccharification, fermentation and purification process. In this study, optimization of saccharification and fermentation process for OPF was investigated. Two methods and the variations of enzyme concentration were carried out in the saccharification and fermentation process. Separate hydrolysis and fermentation process (SHF) and simultaneous saccharification and fermentation process (SSF) were conducted to produce ethanol optimally. Variations of enzyme concentration used in this process were 10, 20, 30 and 40 FPU/g substrate. The result shows that the highest ethanol concentration can be obtained in SSF process with 30 FPU/g substrate of enzyme concentration. The process produced 59.20 g/L ethanol (95.95% yield ethanol) at 96 h of SSF process.     

Study of the effect of technological parameters of extractive wastewater purification in production of bisphenols

Effect of various technological parameters of the process in which wastewater formed in production of bisphenols is purified to remove phenol. The optimal parameters of the process were determined, with which a processed wastewater is obtained with phenol concentration that enables recycling of wastewater into the technological process and its partial delivery to treatment facilities.     

Ways of controlling the selectivity of cyclohexane oxidation

Operation of an industrial installation for cyclohexane oxidation was analyzed, and causes of the low process selectivity (45–52%) were elucidated. The relationships of cyclohexane oxidation under laboratory conditions maximum similar to those of the industrial process were studied. Measures were suggested for optimizing the process so as to increase the yield of the target products by a factor of 1.2–1.6, decrease the amount of cyclohexane spent for the formation of by-products by a factor of 1.2–1.8, and increase the process selectivity to 68%.     

微量元素对固态锡在持续升温时氧化过程的影响

用DTA、TG研究了不同粒度纯Sn和含微量Ga、S、Cu时的Sn在20℃·min-1的持续升温过程中的氧化过程,测定了升温过程中间产物的XRD图.结果表明,随着粒度增大,Sn开始氧化的温度提高.添加0.1%的Ga提高了锡的氧化稳定性,表面生成一层SnO;添加微量Cu对Sn的氧化影响很小;添加0.1%的S时,氧化稳定性降低.氧化过程中,除添加Ga者外,其它无中间产物SnO生成.     

CARBEX process,a new technology of reprocessing of spent nuclear fuel

Advances in the CARBEX process, a new aqueous chemical method for reprocessing of spent nuclear fuel (SNF) in carbonate media, are considered. A review of carbonate methods for SNF reprocessing is given. The CARBEX process concept is presented and experimental data for every stage of the CARBEX process: high-temperature oxidation of spent fuel composition, its oxidative dissolution in carbonate aqueous solutions, extraction refining of U(VI) and Pu(VI), solid-phase re-extraction of carbonate complexes of U(VI) and Pu(VI), and obtaining of uranium and plutonium dioxide powders for fabrication of ceramic nuclear fuel, are discussed. It was shown that the CARBEX process can be more effective and safe than the well-known industrial PUREX process.     

Experimental investigation and multiphysics simulation on the influence of micro tools with various end profiles on diametrical overcut of holes machined using electrochemical micromachining for a predetermined optimum combination of process parameters

Electrochemical micromachining (EMM) process is generally applied to shaping of electrically conductive materials which has been gaining popularity in the production of biomedical, MEMS, aerospace and nuclear components. The dimensional accuracy is affected by various process parameters of EMM and by the end profile of the cathode (tool) used to machine the feature. In this study, it is proposed to investigate the EMM process to know the influence of various process parameters on the diametrical overcut of the machined hole and the optimum combination of process parameters to produce holes with minimum diametrical over cut. A bare electrode with flat end is used for this purpose. Later, insulated electrode with flat end and bare electrodes with various end profiles are used to drill holes at the optimum combination of process parameters on Titanium grade II sheet to identify the most suitable micro tool to produce holes with minimum diametrical overcut and minimum stray machined zone. The EMM process of drilling holes using insulated electrode with flat end and bare electrodes with various end profiles are simulated at the optimum combination of process parameters using COMSOL Multiphysics V4.2a software. Results justified the use of multiphysics simulation to understand the process before conducting experiments so that costly trial and error experiments can be reduced to a minimum.