Application of molecular interaction volume model in separation of Pb-Sn-Sb ternary alloy by vacuum distillation

Based on the molecular interaction volume model （MIVM）, the activities of components of Pb Sn Sb ternary alloy were predicted. The vapo^liquid phase equilibrium of Pb-Sn-Sb alloy system was calculated using the activity coefficients of Pb Sn-Sb alloy system in the process of vacuum distillation. The calculated results show that the content of Sn in vapor phase increases with the increasing distillation temperature and content of Sn in liquid phase. However, the content of Sn in vapor phase is only 0.45% （mass fraction） while 97% in liquid phase at 1100 ℃, which shows that the separating effect is very well. Experimental investigations on the separation of Pb-Sn-Sb ternary alloy were carried out in the distillation temperature range of 1100-1300 ℃ under vacuum condition. It is found that the Sn content in vapor phase is 0.54% while 97% in liquid phase at 1100 ℃. Finally, the predicted data were compared with the experimental results showing good agreement with each other.

Application of Molecular Distillation Process to Extend the True Boiling Point Curve of Petroleum Residues 400 ℃ ＋

True Boiling Point （TBP） distillation is one of the most common experimental techniques for determination of petroleum properties. The methods for performing TBP distillation experiments are described by ASTM D2892 and by ASTM D5236. However, these methods are established for petroleum fractions that reach temperatures up to 565 ~C. In this work, two petroleum residues were distilled in a falling film molecular distillation prototype and the data were used to obtain the extension of the TBP curve above a temperature of 565 ~C. It was possible to extend the TBP curve of both petroleum up to temperatures close to 700 ~C with consistency and continuity in comparison to the standard curve. In addition, an amount of raw material that was been treated as residue could be reused.

A novel purification process for dodecanedioic acid by molecular distillation

A novel purification process is involved to obtain the high purity[>99%(by mass)]dodecanedioic acid(DC_(12)).It involves a re-crystallization followed by molecular distillation from the crude product.The objective of this study is to investigate general conditions,feed rate,distilling temperature and vacuum,necessary for centrifugal distillation of DC_(12).Under the optimum conditions,distilling temperature 180℃,pressure 30 Pa and feed flow rate700 ml·h^(-1),the purity of DC_(12) in the residence reached 97.55%with a yield of 53.18%by the analysis of gas chromatography.Multiple-pass distillation made a considerable contribution by improving the purity to99.22%.Additionally,the effect of pretreatment(re-crystallization) on distillation process was revealed through a series of comparative experiments.

Determination of Thermal Properties of Cuts and Residue Streams Obtained in the Molecular Distillation Process

A real-time sensing of the molecular distillation process temperature by a FLUKE brand thermograph Ti50 IR FlexCam and thermography technique was realized. After completion of the molecular distillation, three properties of heat transport chain cuts and residues obtained in the process were estimated by Differential Scanning Calorimetry （DSC） （specific heat, enthalpy, thermal conductivity）. These properties are of great importance for improving oil characterization and for future modeling and simulation of the molecular distillation process. The results show that through the method of Differential Scanning Calorimetry, profiles have been obtained from the variation of specific heat, enthalpy and thermal condutivity as a function of temperature for samples of cuts from the distillation （ASTM D-2892） and fractions of distillate and residue from the process of molecular distillation.

Application of molecular interaction volume model in separation of Sn-Zn alloy by vacuum distillation

The activity of components of Sn-Zn binary alloy system was predicted based on the molecular interaction volume model （MIVM）. The calculated values are in good agreement with available experimental data of activities, which indicates that this model is of stability and reliability because the MIVM has a good physical basis. The vapor-liquid phase equilibrium of Sn-Zn alloy system in vacuum distillation was calculated as a function of the activity coefficient. The results show that the content of Sn in vapor phase is 4.2x 10-7 （mass fraction） while in liquid phase it is 90% （mass fraction） at 1 073 K, and the content of Sn in vapor phase increases with increasing the melt temperature and content of Sn in liquid phase. Vacuum distillation experiments were carried out on Sn-Zn alloy for the proper interpretation of the results of the MIVM in the temperature range of 973-1 273 K under pressures of 15-200 Pa. The experimental results show that the content of Sn in vapor phase is 5x 10 6 （mass fraction） while in liquid phase it is 90% （mass fraction） under the operational condition of 1 073 K, 100 rain and 15 Pa. The experimental results are in good agreement with the predicted values of the MIVM for Zn-Sn binary alloy system.

基于MVVM的ReaxFF MD模拟的化学反应数据系统的建立

基于反应力场(reactive force field,ReaxFF)的反应分子动力学模拟的结果分析具有挑战性。国际首个ReaxFF MD化学反应分析及可视化工具VARxMD(visulization and analysis of ReaxFF molecular dynamics)可自动生成不同时刻之间完整的化学反应列表,通过物种检索进一步对反应路径进行分类。但VARxMD目前的反应分析针对的是某一确定条件下单一的ReaxFF MD模拟轨迹,利用VARxMD分析获得一次模拟的完整反应列表需要消耗大量计算资源和时间。本文提出基于数据库来储存VARxMD反应分析结果数据,基于数据库检索进一步分析反应的思路,并采用MVVM(model-view-view model)的系统设计模式、结合渐进式框架Vue.js建立了ReaxFF MD模拟的化学反应数据系统ReaxMDDB(reaction database of ReaxFF MD simulation)。系统应用于多个RP-3模型热解和氧化模拟反应数据的结果表明:该系统不仅实现了多个ReaxFF MD模拟的详细反应的统一分析和化学反应的2D分子结构显示,而且可永久保存模拟获得的反应数据集以备后续进一步分析反应机理。ReaxMDDB具有很好的通用性,为认识不同反应模拟所揭示的共性化学反应机理提供了方便的平台。

Wiped-Film Molecular Distillation Process

Based on the Bhatnagar-Gross-Krook distillation for two components in the presence equation, a new scheme of wiped-film molecular of inert gas is developed. The equations in the scheme are solved numerically by the method of finite difference and iteration. The new scheme is used to simulate the molecular distillation of dibutyl phthalate and dibutyl sebacate （ DBP-DBS ） mixture. The effects of the inert gas pressure, the distance between the evaporation surface and condensation surface, the rotation rate of blade, and the number of blades on the distillation rate and separation factor are discussed.

Enrichment of nervonic acid in Acer truncatum Bunge oil by combination of two-stage molecular distillation,one-stage urea complexation and five-stage solvent crystallization

Nervonic acid is the world’s first and only potent substance that can repair damaged nerve fibers and promote nerve cell regeneration with high nutritional value.The wide variety of fatty acids in plant oils and fats with similar structures makes the large-scale separation and purification of high-purity nervonic acid very difficult.A new combined process of molecular distillation,urea inclusion and solvent crystallization was established to prepare high-purity nervonic acid with the mixed fatty acids obtained after saponification and acidification of Acer truncatum Bunge oil as raw materials.First,according to the difference in the mean free path of fatty acids,molecular distillation was used to separate and remove C16 saturated fatty acid of palmitic acid and four C18-C20 fatty acids of stearic,oleic,linoleic,and linolenic acids.The content of C16-C20 fatty acids decreased from 72.92% to 19.22% after two-stage molecular distillation processes,in which the contents of saturated fatty acid of palmitic acid decreased to about 0.5%.Then,according to the difference in carbon chain length and saturation of fatty acid,the contents of C22-C24 saturated fatty acids of tetracosanoic and docosanoic acids decreased to 0.21% and 0.07% by urea inclusion with urea/free fatty acid preparation by saponification(SPOMFs)ratio as 0.6.In addition,all saturated fatty acids were basically separated.Finally,according to the difference in the solubility of fatty acids in solvents,the C18-C20 unsaturated fatty acids of oleic,linoleic,and linolenic acids and C22 unsaturated fatty acid of erucic acid were removed by solvent crystallization.The content of C18-C20 unsaturated fatty acids decreased to less than 5% with pentanol as the solvent after the first stage solvent crystallization.The content of erucic acid decreased to 3.47% with anhydrous ethanol as the solvent after the second to fifth stage solvent crystallization.The combined process of molecular distillation,urea inclusion and low temperature crystallization innovatively adopted an efficient,simple and easy-toindustrial solvent crystallization method to separate erucic and nervonic acids,obtaining nervonic acid with purity of 96.53% and final yield of 47.99%.

Simulation of Molecular Distillation Process for Lactic Acid

In this work, a procedure to simulate the MD （molecular distillation） process for lactic acid purification was developed. The simulation was carried out with the aid of the Aspen Plus Process Simulator. Flash vessel was used to represent the MD process since the software does not present this unit operation. The simulation results with efficiency factors were in agreement with previously reported experimental data.

Optimization of Molecular Distillation for Removal of Limonene from Ponkan Essential Oil Using Response Surface Methodology

Ponkan (Citrus reticulate Blanco) is one of the most popular citrus fruits for daily consumption and processing in China. In this study, limonene was removed from ponkan essential oil (PEO) by using an effective methodology to estimate the optimum levels of three independent variables of molecular distillation (MD) in order to minimize the limonene content and (b) maximize the removal rate. A three-factor Box-Behnken design (BBD) was employed to evaluate the effect of distilling temperature (45.00~55.00 ℃), wiper rolling speed (150.00~250.00 r/ min) and distilling pressure (25.00~35.00 Pa). The optimum parameters within the experimental range of the variables were extrapolated to be: distilling temperature 47.00℃, wiper rolling speed 203.00 r/min and distilling pressure 30.00 Pa. Optimal values extrapolated by response surface methodology (RSM) for the limonene content and removal rate of the desirable PEO were 47.82% and 84.67%, respectively.

Modeling of Molecular Distillation Parameters： Case Study of Green Coffee Oil （Coffea arabica）

In principle, the free fatty acids, diterpene fatty acid esters and triglycerides from green coffee oil can be separated effectively, by a suitable separation process, due to the differences between molar mass and vapor pressures. In addition, in the case of component separation by molecular distillation, boiling point is replaced by evaporation rate at a given temperature. Several experiments and theoretical analyses have been carried out to identify the impact of important parameters （mean free path, evaporation rate, relative volatility and Knudsen number）, which determine the performance of these processes and degree of separation. In this work, a process development based on molecular distillation, for the enrichment of coffee diterpenes from green coffee oil is presented. The distillates were enriched in diterpene fatty acid esters and free fatty acids, while the residues were enriched in high molar mass triglycerides.

Volatile Components and Antitumor Activity of Ganoderma lucidum Spore Oil and Its Molecular Distillation Components

[Objectives]To compare the effects of molecular distillation on the flavor and antitumor activity of Ganoderma lucidum spore oil.[Methods]G.lucidum spore oil was separated and purified by molecular distillation technology,and the volatile components of different components of molecular distillation were analyzed by gas chromatography-ion mobility spectrometry(GC-IMS)technology.Human liver carcinoma cells(HepG2),human breast cancer cells(MCF-7),and human cervical cancer cells(Hela)were selected as the tumor cell lines to be tested,and the cell viability was detected by the MTT assay.[Results]Molecular distillation effectively reduced small molecular substances produced by oil oxidation in G.lucidum spore oil,such as heptanal,octanal,linalool,hexanal,E-2-octanal,3-ethylpyridine,etc.Among the heavy components,the content of esters was relatively high,mainly including ethyl levulinate,ethyl crotonate,and amyl butyrate.The MTT cytotoxicity test indicated that G.lucidum spore oil and its molecular distillation components had certain inhibitory effects on the growth of three tumor cells,and G.lucidum spore oil crude oil had the most significant antitumor activity.G.lucidum spore oil crude oil,heavy component,and light component had the most significant antitumor activity on HepG2 cells,followed by MCF-7 cells,and the weakest antitumor activity on Hela cells.The quality of G.lucidum spore oil became higher after molecular distillation,and the rancid smell was reduced,and molecular distillation had little effect on the antitumor activity of G.lucidum spores.[Conclusions]Molecular distillation technology can be applied to the refining of G.lucidum spore oil to improve product quality.

A Real-time Prediction System for Molecular-level Information of Heavy Oil Based on Machine Learning

Acquiring accurate molecular-level information about petroleum is crucial for refining and chemical enterprises to implement the“selection of the optimal processing route”strategy.With the development of data prediction systems represented by machine learning,it has become possible for real-time prediction systems of petroleum fraction molecular information to replace analyses such as gas chromatography and mass spectrometry.However,the biggest difficulty lies in acquiring the data required for training the neural network.To address these issues,this work proposes an innovative method that utilizes the Aspen HYSYS and full two-dimensional gas chromatography-time-of-flight mass spectrometry to establish a comprehensive training database.Subsequently,a deep neural network prediction model is developed for heavy distillate oil to predict its composition in terms of molecular structure.After training,the model accurately predicts the molecular composition of catalytically cracked raw oil in a refinery.The validation and test sets exhibit R2 values of 0.99769 and 0.99807,respectively,and the average relative error of molecular composition prediction for raw materials of the catalytic cracking unit is less than 7%.Finally,the SHAP(SHapley Additive ExPlanation)interpretation method is used to disclose the relationship among different variables by performing global and local weight comparisons and correlation analyses.

Subpicosecond laser ablation behavior of a magnesium target and crater evolution:Molecular dynamics study and experimental validation

The micro-ablation processes and morphological evolution of ablative craters on single-crystal magnesium under subpicosecond laser irradiation are investigated using molecular dynamics(MD) simulations and experiments.The simulation results exhibit that the main failure mode of single-crystal Mg film irradiated by a low fluence and long pulse width laser is the ejection of surface atoms,which has laser-induced high stress.However,under high fluence and short pulse width laser irradiation,the main damage mechanism is nucleation fracture caused by stress wave reflection and superposition at the bottom of the film.In addition,Mg[0001] has higher pressure sensitivity and is more prone to ablation than Mg[0001].The evolution equation of crater depth is established using multi-pulse laser ablation simulation and verified by experiments.The results show that,under multiple pulsed laser irradiation,not only does the crater depth increase linearly with the pulse number,but also the quadratic term and constant term of the fitted crater profile curve increase linearly.

Molecular dynamics simulation study of nitrogen vacancy color centers prepared by carbon ion implantation into diamond

Nitrogen vacancy(NV)color centers in diamond have useful applications in quantum sensing andfluorescent marking.They can be gen-erated experimentally by ion implantation,femtosecond lasers,and chemical vapor deposition.However,there is a lack of studies of the yield of NV color centers at the atomic scale.In the molecular dynamics simulations described in this paper,NV color centers are pre-pared by ion implantation in diamond with pre-doped nitrogen and subsequent annealing.The differences between the yields of NV color centers produced by implantation of carbon(C)and nitrogen(N)ions,respectively,are investigated.It is found that C-ion implantation gives a greater yield of NV color centers and superior location accuracy.The effects of different pre-doping concentrations(400–1500 ppm)and implantation energies(1.0–3.0 keV)on the NV color center yield are analyzed,and it is shown that a pre-doping concentra-tion of 1000 ppm with 2 keV C-ion implantation can produce a 13%yield of NV color centers after 1600 K annealing for 7.4 ns.Finally,a brief comparison of the NV color center identification methods is presented,and it is found that the error rate of an analysis utiliz-ing the identify diamond structure coordination analysis method is reduced by about 7%compared with conventional identification+methods.

基于MD模拟的低能FIB辐照金刚石靶材亚表层损伤形成机理研究

聚焦离子束(focused Ion beam,FIB)作为一种用于金刚石微铣刀的特种加工方式,其引发的损伤程度直接关联到刀具的加工性能和寿命。课题组采用LAMMPS软件进行分子动力学(Molecular Dynamics,MD)模拟,结合SRIM软件的分析结果,探究单晶金刚石亚表层损伤的形成机理和入射离子能量对损伤深度和范围的影响。模拟结果表明:随着入射离子能量的提升,离子束在材料内的渗透深度及引起的非晶层和点缺陷损伤均有所增加;进一步的研究发现损伤形成过程中材料局部温度的上升可能诱发自退火现象,且与离子入射能量成正比,该现象对于理解聚焦离子束加工引起的损伤有着至关重要的意义;而势能的变化与损伤形成之间的显著对应关系揭示了第一邻近原子的势能明显高于第二邻近原子,进而高于Other类型原子,这一发现有助于深入理解损伤形成的微观过程。因此,精确控制入射能量是实现金刚石材料高精度聚焦离子束加工的关键,且对自退火效应和势能变化的研究对损伤监控与控制同样重要。

RP-3高温氧化初始阶段反应机理的ReaxFF MD模拟

本文采用ReaxFFMD方法对一种较新的RP-3四组分替代燃料模型的高温氧化过程进行了研究。利用作者所在课题组研发的独特分析工具VARxMD,对燃烧过程中主要物种(燃料分子、O_2、C_2H_4、·CH_3)随时间和温度的演变规律及其化学反应进行了系统分析。ReaxFFMD模拟得到的燃料和氧气消耗量、乙烯和甲基自由基的生成量与相同温度和初始压力条件下CHEMKIN的计算结果处于同一量级,同时获得了详细的物质结构信息和反应列表。进一步对模拟得到的反应机理形式进行观察后发现,模拟获得的机理形式与文献中的描述一致。对燃料分子第一步反应数量的统计发现,其类型主要为攫氢反应和分子内断裂反应,且后者占主导;燃料分子第一步反应数量的统计也定性展现了不同燃烧条件下各类反应发生的可能性。对氧元素相关的反应分析发现,氧分子和C_1-C_3小分子发生的反应所占比例较大,能在一定程度上为机理简化提供有益线索。在对反应机理分析的基础上获得了RP-3四组分替代燃料体系高温氧化过程的化学反应网络。我们认为,ReaxFFMD反应分子动力学模拟、结合VARxMD对模拟结果深入分析的方法是有潜力系统认识燃料氧化反应机理的新方法,对构建燃料的燃烧反应机理库有一定的帮助。

利用SFE-MD技术分离提纯玫瑰精油及其成分分析

用超临界CO2流体萃取技术（SFE）萃取平阴玫瑰浸膏,用分子蒸馏技术（MD）进行精制,所得玫瑰精油呈淡黄色,质量标准达到FCC（2004）,得率由传统水蒸气蒸馏法的0.03%提高到0.1%.超临界CO2流体萃取最佳工艺条件为：萃取压力25 MPa,温度50 ℃,CO2流量25 kg/h,萃取时间2.5 h;分子蒸馏温度为80～120 ℃;所得精油GC-MS分析,检测出63种成分,主体呈香成分为酯类物质,质量分数超过50%,相对分子质量主要集中在200～250.

辽河油田兴42块兴53井组MD膜驱油研究

将辽河油田兴42油藏岩心以不同方式处理并饱和兴隆台采油厂脱气脱水原油,在65～67℃下用兴二联回注水驱替至流出液含水98%,再用MD 1膜驱剂(一种单分子双季铵盐,分析试剂)的0.01mmol/L水溶液驱替至含水98%,得到了如下驱油结果并从MD膜驱油机理作了解释:在水驱基础上MD膜驱提高采收率的幅度,在直接饱和原油的岩心上一般很高,3个岩心为13.32%～15.73%,1个岩心为8.86%;在含束缚水的油饱和岩心上略低(15.92%和9.37%);在洗油、洗盐的含束缚水的油饱和岩心上极低(1.96%);在油中长期浸泡后的洗油、洗盐、含束缚水油饱和岩心上则很高(16.19%和15.93%);在直接饱和油的非油藏岩心上很低(4.04%)。在兴42块兴53一注五采高含水井组实施了MD膜驱油先导性矿场试验(井组油井含水80.0%～98.3%,平均92.4%),1998年5～10月注入有效成分25%的工业膜驱剂40t,注入液浓度2500～3000mg/L,注入总量0.005PV。5口采油井中有4口增产油、增产气并减产水,有效期超过2年。截止2000年11月有效期尚未结束,每注入1t工业膜驱剂已增产原油172t,经济效益可观。给出并讨论了膜驱油前后全井组和2口典型井的产油、含水曲线及全井组产气曲线。膜驱油过程伴随油井增产气过程,其特点是检验膜驱是否有效及有效期长短的矿场判据。图5表4表5。