不同的配比对LiCoO_2和NaHSO_4·H_2O混合物在酸性焙烧产物中元素赋存状态的研究

了解废旧锂离子电池回收利用的现状和存在的问题对回收金属元素具有非常重要的意义。将LiCoO_2与NaHSO_4·H_2O按照摩尔比1∶1、1∶2、1∶3、1∶4进行混合,混合均匀后进行酸性焙烧,采用TG-DSC-MS、XRD和SEM研究了焙烧产物中元素的存在形式和赋存状态,研究结果表明:Na元素是以LiNa(SO_4)和Na_2Co(SO_4)_2的形式存在,Li元素的赋存形式是LiNa(SO_4),Co元素的赋存形式是Co_3O_4和Na_2Co(SO_4)_2,焙烧产物致密,形状不规则。     

自然循环条件下窄通道内气泡速度特性

气泡运动速度是气泡行为重要参数,对建立完善的气泡换热机理模型具有意义。以水为工质开展自然循环流动条件下窄通道内气泡速度特性实验研究。分析了单气泡和气泡群速度变化规律、影响因素以及引入摇摆运动后的速度特性。气泡速度主要取决于气泡尺寸和主流速度两个因素,摇摆条件下气泡速度会发生周期性波动,竖直稳态或摇摆动态条件下气泡形心液相速度与气泡速度近似相等。     

Theoretical kinetic study of the reaction between dimethyl disulfide and OH radicals

The potential energy profile of the reaction between dimethyl disulfide and OH^? radicals is explored by utilizing ab initio and hybrid meta density functional theory methods. Having the energies and structural data of the stationary points, statistical rate theories, such as transition state theory and variable reaction coordinate-transition state theory, are employed to compute the overall rate constants, and discuss the mechanism and product channels. On the basis of the calculations, the overall rate coefficient is predicted to be 2.49?×?10^?10?cm³?molecule^?1?s^?1 at 298?K. It is found that in the most favorable pathway, the reaction proceeds via formation of the relatively unstable intermediate CH₃S^?(OH)SCH₃ decomposing rapidly to yield CH₃S^?+CH₃SOH.     

CO2混合物热物性在CCS研究中的作用:实验数据、理论模型和典型应用

二氧化碳捕集与封存（CCS）各工艺过程的设计、运行都依赖于对CO₂及其混合物热物理性质的深入理解。同时，CCS的规模化发展和商业化进程，对CO₂混合物及其热物性的准确性提出了更高的要求。本文从实验数据、理论模型和典型应用3个方面综述了CO₂及其混合物热物性的发展现状，并尝试对发展趋势进行归纳。在实验研究方面，CO₂混合体系的研究进展视组分不同，差异较大，其中CO₂-N₂、CO₂-CH₄、CO₂-H₂O和CO₂-H₂二元体系已形成较完善的物性数据库，而CO₂-NH₃、CO₂-NO _x 和CO₂-CO体系的物性数据还比较欠缺；在物性估算方面，面向CCS的物性估算模型研究自2008年开始活跃，基于不同理论构架，目前已逐步形成面向CCS的多元化的物性估算体系。物性研究在CCS中的应用主要体现在物性是支撑CCS过程研究的基础，其不准确性在过程模拟或计算中会被“放大”，从而影响过程评估的准确性，本文从物性在循环构建和能效分析中的作用以及CO₂水合物的形成3个方面入手做了说明。文章最后对面向CCS的物性研究趋势进行了梳理，对分子模拟技术、通用性强的物性估算模型和物性在过程设计和循环分析中的角色进行了展望。     

新型热源塔溶液再生系统非稳态特性分析与实验研究

针对热源塔冬季运行时存在的吸湿问题,构建了一种新型热源塔溶液再生系统并对其进行实验测试。考虑到系统在初始运行时需要建立平衡的温度场且系统运行时存在溶液不断变浓的现象,对该溶液再生系统启动时的非稳态特性进行了研究,获取了各运行参数随初始运行次数的变化规律,同时对不同浓度下各运行参数变化规律进行了实验分析。实验结果表明：初始开机运行后,随着运行次数的增多,在总运行水量保持不变的情况下,单次运行所需电量呈下降趋势,冷凝水量呈上升趋势,最终系统趋于稳定。随着溶液浓度的变化,系统再生效率存在先增加后降低的趋势,当溶液浓度达到18.5%时出现最佳值,此时再生效率为4.28 kg/(kW·h),再生速率为749 kg/d,再生百分比为14%。该装置将溶液的真空沸腾过程和冷凝过程融合在一起,系统能耗大大降低,具有较好的节能效果。     

R32热力学性质计算模型及其分析

提出了R32制冷剂在饱和线(?130~78℃，0.00013~5.76 MPa)范围内饱和蒸气压、液体密度等关联式的计算模型，在此基础上推导了蒸发潜热的计算模型；建立了描述饱和气体线上(?130~78℃，0.00013~5.76 MPa)及过热区(过热度为100℃)范围内描述P-v-T关系的状态方程；在上述模型的基础上推导得到了饱和气体线及过热区范围内焓、熵、比热容的计算模型。将模型计算结果与REFPROP9.0数据源、已发表的状态方程及公开实验数据对比，各关联式计算模型的平均相对偏差均小于0.16%，最大相对偏差不超过3.7%，与已有状态方程和公开数据对比偏差小于8.7%；基于状态方程和热力学关系式推导得到的焓、熵、比热容的计算模型的平均相对偏差均小于5.2%，最大相对偏差不超过9.1%。     

Photochemical Reactions in Supramolecular Assemblies of Gels: Dimerizations and Polymerizations via Pericyclic Reactions

Gel state reactions offer new direction for the reactivity of the organic molecules or metal‐organic materials upon photoirradiation with shorter reaction times and high yields compared to solid and solution states. The restricted molecular movement among the molecules in the soft solids control the stereoselectivity of the photoproducts in the gel state reactions. To date, most of the strategies based on self‐assembly have been demonstrated in the solid state, in particular for [2+2] reactions of olefins and polymerization reactions of diacetylenes via 1,4 addition. The soft materials are of emerging materials in recent days given their many applicative day‐to‐day aspects. This review gives a glimpse of recent reports on pericyclic reactions in the gel state that are designed based on the self‐assembly concept. Also it highlights how such reactions accompany the physical changes in the structure of the gels and stereo controlled products with high yields.     

Reactive flash sintering of powders of four constituents into a single phase of a complex oxide in a few seconds below 700°C

Recent work on reactive flash sintering of powders of two oxides, bismuth and of iron oxide, into pure single phase bismuth ferrite, which was accomplished in a few seconds at low furnace temperatures, is expanded to four constituents, alumina, lithia, zirconia, and lanthana, to produce reasonably dense polycrystals of a predominantly single phase, cubic LLZO(Al). Transformation and sintering occur concurrently at a furnace temperature near 700°C, in ambient atmosphere, in just a few seconds. The process may simplify the preparation of complex ceramics with new chemistries and dopants, which are predicted from ab intio calculations to have special attributes, not only because the powders sinter quickly at low temperatures, but also because the need for stoichiometric powders as starting materials is obviated.     

Solid state reactions between SiC and Ir

Reactivity between SiC and Ir as a function of SiC-crystallinity was investigated by diffusion bonding technique under a vacuum and over the temperature range of 1200–1450 °C. As reaction products, various Ir-silicides and free unreacted-C were detected. Reactivity is strongly affected by the temperature and SiC-crystallinity involving a series of interactions, from “no reaction” to “massive exothermic reactions”. In particular, interfacial phenomena are more pronounced by the presence of defects and grain boundaries.Solid state reactions result in formation of fine C-precipitates rearranged in a quasi-periodic microstructure. On the contrary, clustering of highly ordered C-precipitates (C-graphitized) occurs after “massive reactions” take place.A relationship between the degree of graphitization (from 1 to multi-layers of graphene), temperature and SiC crystallinity was found by Raman spectroscopy. 2D-layering phenomenon is enhanced in polycrystalline SiC at high temperature.     

高温悬浮态下硫铁矿的氧化特性研究

硫铁矿的高温氧化是引起水泥生产过程中产生SO2的主要原因。采用一维炉开展了高温悬浮态下硫铁矿氧化的实验研究,并对氧化产物做了X射线衍射（XRD）分析和烧失量检测。XRD分析表明,FeS2在300 ℃时尚未发生氧化反应,从400 ℃开始出现Fe2O3的衍射峰,且随着温度升高,FeS2的衍射峰强度逐步减弱,Fe2O3衍射峰强度逐步增强。在400~800 ℃时,FeS2的氧化产物仅为Fe2O3。基于烧失量的计算表明,在10 s反应时间内,FeS2在300 ℃几乎没有发生氧化,这和XRD检测结果一致。在400 ℃和600 ℃时FeS2氧化率分别达到了50%和85%,800 ℃时达到了92%。将上述结果应用于水泥生产过程,表明在C1~C4预热器中,约64%的FeS2发生了氧化。