Highly selective extraction of aromatics from aliphatics by using metal chloride-based ionic liquids

The separation of aromatics from aliphatics is essential for achieving maximum exploitation of oil resources in the petrochemical industry.In this study,a series of metal chloride-based ionic liquids were prepared and their performances in the separation of 1,2,3,4-tetrahydronaphthalene(tetralin)/dodecane and tetralin/decalin systems were studied.Among these ionic liquids,1-ethyl-3-methylimidazolium tetrachloroferrate([EMIM][FeCl_(4)])with the highest selectivity was used as the extractant.Density functional theory calculations showed that[EMIM][FeCl_(4)]interacted more strongly with tetralin than with dodecane and decalin.Energy decomposition analysis of[EMIM][FeCl_(4)]-tetralin indicated that electrostatics and dispersion played essential roles,and induction cannot be neglected.The van der Waals forces was a main effect in[EMIM][FeCl_(4)]-tetralin by independent gradient model analysis.The tetralin distribution coefficient and selectivity were 0.8 and 110,respectively,with 10%(mol)tetralin in the initial tetralin/dodecane system,and 0.67 and 19.5,respectively,with 10%(mol)tetralin in the initial tetralin/decalin system.The selectivity increased with decreasing alkyl chain length of the extractant.The influence of the extraction temperature,extractant dosage,and initial concentrations of the system components on the separation performance were studied.Recycling experiments showed that the regenerated[EMIM][FeCl_(4)]could be used repeatedly.

Solvent effects on Diels-Alder reaction in ionic liquids:A reaction density functional study

Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.

Ionic liquids as the effective technology for enhancing transdermal drug delivery: Design principles, roles, mechanisms, and future challenges

Ionic liquids (ILs) have been proven to be an effective technology for enhancing drug transdermal absorption. However, due to the unique structural components of ILs, the design of efficient ILs and elucidation of action mechanisms remain to be explored. In this review, basic design principles of ideal ILs for transdermal drug delivery system (TDDS) are discussed considering melting point, skin permeability, and toxicity, which depend on the molar ratios, types, functional groups of ions and inter-ionic interactions. Secondly, the contributions of ILs to the development of TDDS through different roles are described: as novel skin penetration enhancers for enhancing transdermal absorption of drugs;as novel solvents for improving the solubility of drugs in carriers;as novel active pharmaceutical ingredients (API-ILs) for regulating skin permeability, solubility, release, and pharmacokinetic behaviors of drugs;and as novel polymers for the development of smart medical materials. Moreover, diverse action mechanisms, mainly including the interactions among ILs, drugs, polymers, and skin components, are summarized. Finally, future challenges related to ILs are discussed, including underlying quantitative structure-activity relationships, complex interaction forces between anions, drugs, polymers and skin microenvironment, long-term stability, and in vivo safety issues. In summary, this article will promote the development of TDDS based on ILs.

Universal basis underlying temperature, pressure and size induced dynamical evolution in metallic glass-forming liquids

The dramatic temperature-dependence of liquids dynamics has attracted considerable scientific interests and efforts in the past decades, but the physics of which remains elusive. In addition to temperature, some other parameters, such as pressure, loading and size, can also tune the liquid dynamics and induce glass transition, which makes the situation more complicated. Here, we performed molecular dynamics simulations for Ni_(50)Zr_(50) bulk liquid and nanodroplet to study the dynamics evolution in the complex multivariate phase space, especially along the isotherm with the change of pressure or droplet size. It is found that the short-time Debye–Waller factor universally determines the long-time relaxation dynamics no matter how the temperature, pressure or size changes. The basic correlation even holds at the local atomic scale. This finding provides general understanding of the microscopic mechanism of dynamic arrest and dynamic heterogeneity.

Polymeric ionic liquids(PILs)with high acid density:Tunable catalytic performance for biodiesel production

A series of polymeric ionic liquids(PILs)used as effective heterogeneous catalysts for biodiesel production via esterification of free fatty acids(FFAs)were effectively prepared by the reaction of poly(ethylene imine)(PEI)polymers with different molecular weight and 1,3-propanesultone,followed by the further acidification with differential effective acids,i.e.H2SO4,CF3SO3H,CH3SO3H or p-toluenesulfonic acid(p-TSA).Ultrahigh acidity and catalytic performance were achieved and could be fine-tuned by simply adjusting the molecular weight of PEI and by further treatment of acids.Specifically,under the optimal conditions(i.e.reaction temperature was 70℃,reaction time was 2.0 h,catalyst dosage was 3.15%(mass),and alcohol/acid molar ratio was 14:1)acquired through the Box-BEHNKEN response surface methodology,a high oleic acid conversion of 98.42%could be obtained over the optimal PIL,PEI(70000)-PS-p-TSA.Additionally,our PILs also showed high generality for esterification of other FFAs,with general high conversion over 90%noted in each case even under much milder reaction conditions compared to other conventional catalysts.

The opportunities and challenges of ionic liquids in perovskite solar cells

Metal halide perovskite solar cells(PSCs)have shown great potential to become the next generation of photovoltaic devices due to their simple fabrication techniques,low cost,and soaring power conversion efficiency(PCE).However,mismatched with the quickly updated PCEs,the improvement of device stability is challenging and still remains a critical hurdle in the path to commercialization.Recently,ionic liquids(ILs)have been found to play multiple roles in obtaining efficient and stable PSCs.These ILs usually consist of large organic cations and organic or inorganic anions,which have weak electrostatic attraction and are generally liquid at around 100℃.ILs are almost non-volatile,non-flammable,with high ionic conductivity and excellent thermal and electrochemical stability.The roles of ILs in PSCs vary with their composition,that is,the types of anions and cations.In this review,we summarize the roles of anions and cations in terms of precursor solutions,additives,perovskite/charge transport layer interface engineering,and charge transport layers.This article aims to set up a structure–property-stability-performance correlations conferred by the IL in PSC and provide assistance for the anion and cation selection for improving the quality of perovskite film,optimizing interface contact,reducing defect states,and improving charge extraction and transport characteristics.Finally,the application of IL in PSCs is discussed and prospected.

Ionic liquids-SBA-15 hybrid catalysts for highly efficient and solvent-free synthesis of diphenyl carbonate

Diphenyl carbonate(DPC)is one of the versatile carbonates,and is often used for the production of polycarbonates.In recent years,the catalytic synthesis of DPC has become an important topic but the development of a highly active metal-free catalyst is a great challenge.Herein,a series of ionic liquids-SBA-15 hybrid catalysts with different functional groups have been developed for the synthesis of DPC under solventfree condition,which are effective and clean instead of the metal-containing catalysts.It is found that in the presence of[SBA-15-IL-OH]Br catalyst,methyl phenyl carbonate(MPC)conversion of 80.5%along with 99.6%DPC selectivity is achieved,the TOF value is thrice higher than the best value reported by using transition metal-based catalysts.Moreover,the catalyst displays remarkable stability and recyclability.This work provides a new idea to design and prepare eco-friendly catalysts in a broad range of applications for the green synthesis of carbonates.

Separation of lithium and nickel using ionic liquids and tributyl phosphate

With the vigorous development of the electronics industry,the consumption of lithium continues to increase,and more lithium needs to be mined to meet the development of the industry.The content of lithium in the solution is much higher than that of minerals,but the interference of impurity ions increases the difficulty of extracting lithium ions.Therefore,we prepared an imidazole-based ionic liquid(1-butyl-3-methylImidazolium bis(trifluoromethyl sulfonyl)imide)(IL)for efficient lithium extraction from aqueous solutions by solvent extraction.Using an extraction consisting of 10%IL,85% tributyl phosphate(TBP),and 5% dichloroethane and an organic to aqueous phase ratio(O/A)of 2/1,over 64.23% of Li were extracted,and the extraction rate after five-stage extraction could reach more than 96%.The addition of ammonium ions to the solution inhibited the extraction of Ni,and the separation coefficient between lithium and nickel approached infinity,showing a very perfect separation effect.Fouriertransform infrared spectroscopy and slope methods were used to analyze the changes that occurred during extraction,revealing possible extraction mechanisms.In addition,the LiCl solution generated during the preparation of ionic liquids was mixed with the stripping solution,and the battery-grade lithium carbonate was prepared by Na_(2)CO_(3) precipitation,with a purity of 99.74%.This study provides an efficient and sustainable strategy for recovering lithium from the solution.

Complete degradation of high-loaded phenol using tungstate-based ionic liquids with long chain substituent at mild conditions

Phenol in waste water threatens human health and is difficultly to be decomposed by nature.Efficient degradation of high-loaded phenol in water under mild condition is still a great challenge.Herein,ionic liquids with tungstate anion were designed and prepared.It was found that dodecyltrimethylammonium tungstate could catalyzed degradation of phenol into gases and water thoroughly at 323 k in 8 h.Tungstate anion revealed good catalytic oxidative activity and long carbon chain group connecting with cation of ionic liquids enriched phenol around catalysts,which induced the complete degradation of phenol at mild conditions.Increasing the amounts of hydrogen peroxide benefited to the total degradation of phenol.In addition,the ionic liquid could be reused for its excellent thermal stability.Our work provided a different strategy to treat waste water containing phenol efficiently.

Modeling of liquid film thickness around Taylor bubbles rising in vertical stagnant and co-current slug flowing liquids

The hydrodynamic study of the liquid film around Taylor bubbles in slug flow has great significance for understanding parallel flow and interaction between Taylor bubbles.The prediction models for liquid film thickness mainly focus on stagnant flow,and some of them remain inaccurate performance.However,in the industrial process,the slug flow essentially is co-current flow.Therefore,in this paper,the liquid film thickness is studied by theoretical analysis and experimental methods under two conditions of stagnant and co-current flow.Firstly,under the condition of stagnant flow,the present work is based on Batchelor's theory,and modifies Batchelor's liquid film thickness model,which effectively improves its prediction accuracy.Under the condition of co-current flow,the prediction model of average liquid film thickness in slug flow is established by force and motion analysis.Taylor bubble length is introduced into the model as an important parameter.Dynamic experiments were carried out in the pipe with an inner diameter of 20 mm.The liquid film thickness,Taylor bubble velocity and length were measured by distributed ultrasonic sensor and intrusive cross-correlation conductivity sensor.Comparing the predicted value of the model with the measured results,the relative error is controlled within 10%.

A simple hydroxypyridine ionic liquids for conversion of CO_(2)into quinazoline-2,4(1H,3H)-diones under atmospheric conditions

The transformation of CO_(2)into high value-added product is a promising pathway for utilizing CO_(2).However,the process tends to require harsh reaction conditions owing to CO_(2)chemical inertness.Designing a high efficiency catalytic system with environmentally benign characteristic are important determinants.In this work,protic ionic liquids[TMG][2-OPy]were prepared via one-step neutralization between 1,1,3,3-tetramethylguanidine and 2-hydroxypyridine,applying to the domain of synthesizing quinzoline-2,4(1 H,3H)-diones from CO_(2)and 2-aminobenzontiles without any solvent or metal,achieving the yield of 97%at 90℃for 8 h under atmospheric.A series of substrates with good to acceptable yield were detected,revealing the generality and universality of the catalyst.Furthermore,the system could be facilely reused for at least six runs,retaining the yield of 94%.A preliminary kinetic equation is calculated with the activation energy of 68 kJ·mol^(-1),and a plausible reaction mechanism was put forward.This study highlights that the[TMG][2-OPy]enables to activate CO_(2)carboxylation efficiently.

Preparation of Ionic Liquids Immobilized on FMIL-101 Catalysts for Conversion of CO_(2)to Propylene Carbonate

Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.

阿莫西林胶囊在中国健康人体内的生物等效性研究

目的:研究阿莫西林胶囊在中国健康人体内的生物等效性。方法:以单中心、开放式、随机、双制剂、两周期、两序列交叉试验设计,共48例受试者(空腹试验和餐后试验各24例),口服0.25 g阿莫西林胶囊受试制剂或参比制剂。高效液相色谱—串联质谱(LC-MS/MS)分析方法测定给药后不同时间阿莫西林的血药浓度,并计算主要药代动力学参数,判定两制剂是否等效。结果:空腹试验显示,受试制剂和参比制剂阿莫西林的药物峰浓度(C_(max))分别为(5483.296±1321.102)ng/mL、(5611.291±1659.407)ng/mL,从时间0到t之间血药浓度—时间曲线下面积(AUC_(0-t))分别为(13255.3±1715.7)h·ng/mL、(13115.5±2091.7)h·ng/mL,从0时到无限时间(∞)的血药浓度—时间曲线下面积(AUC_(0-∞))分别为(13329.4±1718.8)h·ng/mL、(13192.7±2107.1)h·ng/mL,达峰时间(T_(max))均为1.38 h。餐后试验显示,受试制剂和参比制剂阿莫西林的C_(max)分别为(4218.072±780.598)ng/mL、(4156.713±877.752)ng/mL,AUC_(0-t)分别为(13073.9±1584.3)h·ng/mL、(12817.8±1575.5)h·ng/mL,AUC_(0-∞)分别为(13166.8±1606.0)h·ng/mL、(12914.8±1587.2)h·ng/mL,T_(max)均为3.00 h。两种试验制剂C_(max)、AUC_(0-t)、AUC_(0-∞)几何均值比值的90%置信区间(CI)均在可接受的生物等效性范围内(80%~125%)。结论:两种阿莫西林胶囊在中国健康志愿者体内吸收速度和吸收程度生物等效。

一种测量液膜厚度的超声相控阵实验装置

气液两相流存在于核反应堆蒸发、飞行器冷却、化工生产降膜蒸发等过程,界面波的动态测量对工业过程监控和生产优化具有重要意义。界面波的准确识别与特性参数测量是开展科学研究与工程实践的重要前提。基于超声相控阵测量系统,设计了扇扫的测量方式,可以用于气液界面清晰的流型中液膜厚度和界面波形态三维测量。通过静态标定和圆管验证,确定了像素点和液膜厚度之间的关系,在气相表观流速为0.0719~0.4316 m/s,液相表观流速为0.0567~1.4161 m/s的工况下进行实时动态实验,获得了实时流动过程中较高精度的截面气液相界面信息,并构建了管道内部界面波三维分布形态,为界面波特性研究提供了一种实验参考方法。

液氮冻结和冻融条件下煤体力学特性及裂隙演化教学实验设计

该文设计了液氮冻结煤岩实验装置,并进行了液氮冻结和冻融条件下煤体力学特性实验,研究了液氮冻结时间和冻融次数对煤体力学强度及裂隙演化的影响规律,定量分析了液氮冷浸对煤体力学特征的影响。通过基于机理分析的实验教学拓展延伸,能够使学生从原理层面分析实验结果,学习宏微观结合的分析方法,加深对实验课程的理解,提高创新能力,开拓学术视野。

锌冶炼过程中提取镓的技术研究及其进展

针对镓从锌冶炼过程中回收占比低的问题,总结分析了锌冶炼过程中镓回收技术研究进展.在鼓风炉炼锌(ISP)工艺中,镓主要富集在鼓风炉炉渣里,其质量分数通常在0.025%~0.031%,从鼓风炉炉渣中回收镓主要有还原蒸发法、高温氯化挥发法、硫酸浸出法、碱熔–浸出法、还原熔炼–电解法和还原熔炼–熔融造渣法等方法,但这些工艺普遍流程长,回收率低,加工成本偏高,部分工艺环境污染大,难以工业化应用.传统的湿法炼锌工艺中,大于93.5%的镓富集在浸出渣中,浸出渣处理以火法还原挥发工艺为主,在回转窑挥发浸出渣工艺中90%的镓保留在窑渣中,导致镓的回收流程长且回收率低,湿法处理浸出渣存在镓和铁分离的难题,至今未得到有效解决.氧压浸出炼锌工艺中,镓主要富集在锌粉置换渣里,锌粉置换渣采用酸性浸出和萃取工艺分离富集镓,最终制备金属镓,镓的综合回收率达到71%.通过对火法和湿法炼锌中镓回收工艺进行分析,对镓回收工艺中存在的关键问题和分离技术进行了总结,提出萃取分离、乳状液膜和树脂吸附有望成为锌冶炼过程中回收镓的绿色高效短流程关键技术.

基于计算机视觉的常用玻璃量器自动检定装置

玻璃量器作为常规配套设备,其需求量日益增长,常用玻璃量器的检定任务越来越重,传统的人工检定已不能满足日益增长的业务需求。该文提出了一种图像法和反馈控制技术相结合的容量示值检定自动化技术,即一种基于图像处理的常用玻璃量器检定自动化装置,主要解决加液自动化功能、容量示值读数自动化功能。开发集数据采集、处理、原始记录生成、报告打印等多功能于一体的软件系统。

基于GA的RBF神经网络气液两相流持液率预测模型优化

为了提高气液两相流持液率预测精度,针对传统径向基函数(RBF)神经网络预测气液两相流持液率网络拓扑结构困难和收敛速度慢等问题,提出一种基于遗传算法(GA)优化径向基函数神经网络的气液两相流持液率预测模型。通过系统聚类算法和灰色关联度分析(GRA)对收集的实验数据进行处理,优选出最优模型特征,同时结合遗传算法确定了RBF神经网络结构参数。基于室内实验数据进行训练,并与常用于持液率预测的反向传播(BP)神经网络、GA-BP神经网络及RBF神经网络进行对比,评估了模型的准确性及可行性。结果表明:GA-RBF神经网络模型均方误差为0.0017,均方根误差为0.0416,平均绝对误差为0.0281,拟合度为0.9483。相较于其他神经网络模型,该预测模型表现出更高的计算精度和更强的泛化能力。

青藏高原东侧九龙夏季非降水云的观测特征

青藏高原东侧九龙地区是西南涡多发区,利用该地区新型探测设备开展云探测,有助于增强对西南涡多发区云特征的认识。利用2018—2019年6—8月九龙站地基微波辐射计资料,分析了该地区夏季非降水云的出现率、液态水路径及过冷水路径的观测特征。结果表明:九龙夏季非降水云出现率月均值在67%~82%之间,以低云和中云为主,高云较少;低云出现率表现为白天低、夜间高,而中云和高云则相反;云出现率的垂直分布表现为单峰形态,在约2km高度存在云出现率峰值8.1%;受大气热力层结日变化影响,云出现率的单峰垂直分布呈现日夜差异。另外,九龙夏季非降水云的液态水路径均值为0.433kg·m^(-2),其中低云、中云、高云的液态水路径均值分别为0.665、0.240、0.102kg·m^(-2);低云的液态水路径日变化特征与其出现率相似,而中云和高云的液态水路径日变化特征不明显。此外,九龙夏季非降水云中冷云的过冷水路径均值为0.154kg·m^(-2),其中低云、中云、高云的过冷水路径均值分别为0.065、0.166、0.102kg·m^(-2);总体上过冷水路径在液态水路径中的占比约为34.3%~38.8%,过冷水路径占比随云的高度而增大,这使得中云和高云的过冷水路径日变化与其液态水路径相似。与同纬度华中地区相比,九龙夏季非降水云具有明显不同的特征,这与两地之间的大气水汽特征差异密切相关。

纤维素生物质与废塑料共催化热解制取富烃液体燃料的研究进展

生物质能是国际公认的零碳可再生能源,其高效利用成为缓解能源与环境危机的关键,并对中国实现“碳达峰”和“碳中和”的目标具有重要意义。纤维素生物质与废塑料的共催化热解技术,不仅能制备高附加值的富烃液体燃料,还可达到“以废治废”的目的,进而实现生物质与废塑料的高效资源化利用。本工作从生物质与废塑料高值化利用的角度出发,对生物质和废塑料共催化热解制备富烃液体燃料的研究现状进行了综述,介绍了纤维素生物质和废塑料的基础化学特性差异,论述了废塑料种类、催化剂种类、物料和催化剂比例、催化热解温度等因素对生物质和废塑料共催化热解生物油产率和品质的影响,阐述了生物质和废塑料单独催化热解过程中的化学反应机理,并揭示了共催化热解过程中的协同反应机理,展望了该领域未来的发展方向,为生物质与废塑料的高附加值利用提供参考与思路。