碳酸锂结晶动力学与机理研究

本文对碳酸锂自碳酸氢锂溶液中结晶的过程动力学进行了研究。研究了碳酸锂的结晶速率,包括晶核生长速率、晶粒长大速率与温度和质量浓度之间的关系。实验表明:晶核生长和晶粒长大速率可用二级反应速率方程来描述,并计算出了不同温度、质量浓度下,碳酸锂的结晶速率常数和表观活化能;诱导期与过饱和度之间的关系符合经典的相生成的热力学理论,并以此为依据推导出了晶体表面自由能和临界晶核半径等临界状态的热力学参数。晶体的生长机制表明,Li2CO3自LiHCO3溶液中的结晶主要受扩散机制控制。     

交互四元体系Li+, K+//CO32-, B4O72- -H2O 298K 相关系及平衡液相物化性质的研究

针对西藏扎布耶盐湖卤水组成,用等温溶解平衡法研究了四元体系Li^ ,K^ //CO3^2-,Ba4O7^2-H2O 298K时的溶解度,测定了该体系的物化性质（密度,粘度,pH值,电导率,折光率）,该四元体系298K时的相图由5条溶解度单变量线,4个结晶区及2个共饱点组成,4个结晶区分别对应于盐Li2CO3,K2CO3.3/2H2O,Li2B4O7.3H2O及K2B4O7．4H2O,2个共饱点中,一个为Li2CO3,K2CO3.3/2H2O及K2B4O7．4H2O三盐共饱点,另一个为Li2CO3,Li2CO3,Li2B4O7.3H2O及K2BO7．4H2O的三盐不相称共饱点,体系属四元水合物相图I型,四种原始组份间未形成复盐或固溶体,应用Pitzer电解质溶液理论拟合了Li2CO3,K2CO3,Li2B4O7和K2B4O7的单盐参数及有关的混合离子作用参数,在此基础上计算了该四元体系298K时的溶解度,计算值与实验值基本吻合。     

碳酸锂常压鼓泡碳化宏观反应动力学研究

基于Li2CO3与CO2在水溶液中的反应,在浆态鼓泡床反应器内对粗Li2CO3常压鼓泡碳化反应的动力学进行了实验研究,且对影响碳化过程的诸因素进行了深入的研究和探讨.结果表明,Li2CO3的转化率随表观气速的增大而增大,随反应温度、固体质量浓度、颗粒粒径、反应器中浆料填充度的增大而减小.动力学研究表明:在反应的前期过程受控于化学反应,随反应的进行该过程逐渐转变为内扩散控制.通过对实验数据的拟合得出了实验范围内过程的宏观动力学方程.该研究为Li2CO3碳化工艺条件的优化和反应器的放大设计等提供了基础效据.     

碳酸锂碳化三相反应动力学研究

利用5 L的气液固三相机械搅拌反应器,研究了Li2CO3碳化三相反应动力学。对影响碳化过程的诸因素进行了深入的研究和探讨。结果表明,Li2CO3的碳化率随CO2压力、气流大小、搅拌速度的增大而增大;随反应温度、固体浓度、颗粒粒径、物料填充度的增大而减小。通过对实验数据的拟合得出实验范围内该过程的动力学方程;得出该过程受控于化学反应,并计算出了该过程的表观活化能-17.37 kJ/mol。该研究为Li2CO3碳化工艺条件的优化和反应器的设计等问题提供了基本理论依据。     

四元体系Li+,K+//CO32-,B4O72- -H2O 273 K介稳相平衡研究

针对西藏扎布耶盐湖卤水组成,用等温蒸发平衡法研究了四元体系Li+,K+//CO23-,B4O27--H2O 273 K的相平衡,测定了平衡时各组分的溶解度及平衡液相的密度。四元体系Li+,K+//CO32-,B4O72--H2O273 K时的相图由5条溶解度单变量线、4个结晶区及2个共饱点组成。4个结晶区分别为对应于盐Li2CO3,K2CO3.1.5H2O,K2B4O7.4H2O及Li2B2O4.16H2O。2个共饱点中,一个为Li2CO3,K2CO3.1.5H2O及K2B4O7.4H2O三盐相称共饱点,另一个为Li2CO3,K2B4O7.4H2O和Li2B2O4.16H2O的三盐不相称共饱点。体系属四元水合物相图Ⅰ型,4种原始组分间未形成复盐或固溶体。对于该四元体系273 K和288 K下的介稳相图发现,碳酸锂盐的溶解度呈现较明显的负温度效应,它在273 K下的结晶相区比在288 K下的要小,且析出固相为偏硼酸锂;而碳酸钾、硼酸钾及硼酸锂结晶区则比288 K下的大。     

五元体系Li~+,K~+//CO_3~(2-),SO_4~(2-),B_4O_7~(2-)-H_2O 273K介稳相平衡研究

采用等温蒸发法研究了五元体系Li+、K+//CO32-、SO42-、B4O72-、H2O 273 K介稳相平衡关系,测定了它们在273 K条件下的介稳平衡的溶解度和溶液密度,根据实验数据绘制了相应的该五元体系在273 K条件下Li2CO3饱和的介稳平衡相图(干盐投影图和水含量图)。研究结果表明该五元体系介稳平衡中有复盐K2SO4-Li2SO4生成,其低温273 K时介稳相图中有4个共饱点和9条单变量曲线,6个Li2CO3饱和的结晶区分别为LiBO2-8H2O、K2B4O7-4H2O、K2CO3-3/2H2O、K2SO4、Li2SO4-H2O和复盐K2SO4-Li2SO4。对该五元体系在288 K和273 K时的介稳平衡相图进行了比较和讨论。     

高纯硼酸制备过程中的结晶动力学

采用HCl气体液相酸化硼砂的中和反应,并结合重结晶法与离子树脂交换法,制备了高纯H3BO3产品. 实验考察了H3BO3-NaCl-H2O体系中溶液过饱和度、结晶温度、结晶时间、搅拌速度及溶液中所含杂质等因素对H3BO3结晶过程的影响. 结果表明,溶液浓度为18.26%、结晶温度为10℃、结晶时间为480 min、搅拌速度为300 r/min,并选取适当的降温方式有利于H3BO3析晶,结晶率大于83%,晶体呈细小颗粒状. 体系中所含的NaCl杂质促进了H3BO3析晶. 由实验数据得到该体系中H3BO3的结晶动力学曲线,并建立了结晶动力学方程,结晶反应级数为2.     

高温下L12ZrO3吸附CO2的研究进展

Li2ZrO3能够在高温下吸附CO2,并且其吸附效率高、速度快、稳定性好且能够重复利用。作者对近年来有关Li2ZrO3材料吸附CO2的研究进行了分析,比较了Li2ZrO3的各种合成方法的优缺点,介绍了Li2ZrO3吸附CO2的反应机理,分析了影响Li2ZrO3吸附CO2的吸附量及速率的各种因素,并对高温下吸附CO2的Li2ZrO3材料的前景进行了展望。     

添加晶种的KNO_3水溶液间歇结晶动力学模型

针对添加晶种的二次成核结晶过程的特点,并基于Beer Lambert定律、ΔL定律和粒数衡算理论,建立了包含透光率变量的间歇结晶动力学模型。运用该模型对KNO3水溶液冷却结晶实验的溶液质量分数、相对过饱和度以及透光率数据进行关联,一次性获得了结晶体系的二次成核和生长动力学参数,其值与文献值吻合较好。尝试以光学法关联动力学模型的研究,将有助于结晶机理的深入认识,为动力学模型的进一步发展提供思路。     

PVC-MnO2的制备及其对锂离子的吸附行为

MnCO3和Li2CO3经高温煅烧合成Li4Mn5O12,再与聚氯乙烯(PVC)和N,N-二甲基甲酰胺溶液混合,干燥、酸洗后制得粒径3?4 mm的多孔球形PVC?MnO2锂离子筛,用其吸附Li离子. 结果表明,PVC?MnO2吸附Li离子的反应符合Langmuir方程和拟二级动力学方程,吸附焓变为0.358 kJ/mol,吸附反应为吸热反应,Li离子最高吸附量可达23.4 mg/g.     

溶胶-凝胶法制备Li_2ZrO_3纳米颗粒及其高温二氧化碳吸收性能

通过柠檬酸溶胶-凝胶法制备纳米级锆酸锂(Li_2ZrO_3)材料,利用扫描电子显微镜和X射线衍射仪对Li_2ZrO_3材料的形貌与结构进行表征,利用热重分析仪测试Li_2ZrO_3材料的高温CO_2吸收性能.结果表明,合成的Li_2ZrO_3材料具有良好的高温CO_2吸收性能.在CO_2分压为0.05 MPa、550℃、20min内吸收容量可达20%(质量分数);45 min内可达吸收平衡,平衡吸收量达27%(质量分数).经3次吸收解吸循环后其吸收性能没有明显下降,表明Li_2ZrO_3材料具有良好的稳定性.     

添加Li_2O的CaO-B_2O_3-SiO_2系微晶玻璃的性能研究

以Li_2O为烧结助剂,采用DTA、XRD、SEM等分析手段研究了添加1.0～2.5 wt%Li_2O对CaO-B_2O_3-SiO_2(CBS)系微晶玻璃性能的影响.结果表明:Li_2O降低了CBS系微晶玻璃的玻璃转变温度和析晶温度.未添加Li_2O的试样在930 ℃烧结,而添加Li_2O的试样可以在820 ℃以下烧结,Li_2O显著降低了试样的烧结温度.当Li_2O添加量为1.0wt%时,试样可以在760～820 ℃范围内烧结,800 ℃烧结试样介电常数为5.71,介电损耗为0.0024(测试频率为10 MHz).     

Alumina trihydrate crystallization. Part 1. Secondary nucleation and growth rate kinetics

The kinetics of crystallization of alumina trihydroxide (hydrargillite) from caustic aluminate solutions of industrial composition (second stage BAYER process) were studied in a laboratory batch isothermal crystallizer. The yield and crystal size distribution of precipitate with time were obtained by varying the initial seed concentration. In this paper, the mass balance was used to determine nucleation and growth rate kinetics. First, from among the laws available in the literature, those which applied to alumina trihydrate crystallization were defined (model A). Kinetic constants of this model were calculated from experimental results. Then, a model based on a secondary nucleation mechanism was proposed (model B) that fits experimental data, and explains the induction periods found in the decomposition of aluminate solutions, even when seeds are present.     

Speculations on a New Mechanism of Crystal Growth from Aqueous Solutions

The activity of lead ions to form heterogeneous nuclei in supersaturated KCl solutions was shown (in previous publications) to account quantitatively for the effect of these ions on the limit of stability of the supersaturated solutions, the rate of crystallization, and the co-precipitation of the lead ions with the crystallizing salt. Hence the process of crystal growth is described as the deposition of subcolloidal sized nuclei on the crystal seed. Many otherwise perplexing phenomena recorded in the literature, and observed in studies of various aspects related to the crystallization of KCl and NaCl, prove to be a direct consequence of this mechanism of crystallization. Other examples indicate that heteronucleation and a similar growth mechanism may be prevalent in the crystallization of several salts from their aqueous solutions. Some implications and possible applications of the proposed growth mechanism are also discussed.     

Kinetics and nanostructures in cryogenic crystallization of binary eutectic salt solutions

The mechanism of structure formation is proposed in the crystallization of droplets of binary eutectic solutions in cryogenic liquids. Theoretical relationships are derived for calculating the rate of crystallite growth and the size of nanocrystals that form. Calculated values of the size of forming nanocrystals are compared with the experimental data.     

Heterogeneous cryogenic crystallization of suspensions containing carbon nanotubes

The mechanism of structure formation is proposed in heterogeneous crystallization of droplets of binary eutectic solutions containing carbon nanotube particles in cryogenic liquids. Theoretical relationships are derived for calculating the rate of crystallite growth and the size of salt nanocrystals that form. Calculated values of the size of produced nanocrystals are compared with experimental data.     

Direct comparison of surface crystal growth kinetics in chalcogenide glass measured by microscopy and DSC

Surface crystallization in fine powder Se₇₀Te₃₀ chalcogenide glass was studied by differential scanning calorimetry (DSC) and optical microscopy. A complex kinetic analysis of these experimental data reveals that the contracting sphere mechanism (R3 model) is the rate determining step of crystal growth, and the conventional Johnson–Mehl–Avrami–Kolmogorov model cannot be used in this case. Moreover, it is clearly shown that the particle size distribution should be considered in crystallization studies. Actually, when the particle size effect is taken into account, the simulated DSC curves for the R3 model agree very well with the experimental data over the entire temperature range. The crystallization kinetics determined from the nonisothermal DSC data are consistent with previously reported isothermal crystallization data for the same powder fraction. The crystal growth rate calculated from isothermal and nonisothermal DSC data agrees very well with the microscopically measured surface and bulk crystal growth rate.     

低分压CO2在有机胺水溶液中的溶解度

建立了一套用于测定低分压CO2在有机胺水溶液中溶解度的实验装置。在298、308 K下分别测定了低分压CO2在较低浓度的乙醇胺(MEA)、二乙醇胺(DEA)水溶液中的溶解度。结果表明,在较低的溶解度下,CO2在有机胺水溶液中的平衡分压接近于0;当溶解度增大到一定程度后,平衡分压随其增加而急剧增大,同时,温度的升高和有机胺浓度的增大均能增大CO2的平衡分压。通过实验数据拟合得到的理论模型参数与实验值符合较好。     

电解法再生热钾碱溶液的实验研究

为了降低二氧化碳(CO_2)捕集过程中的成本,对利用膜电解技术再生热钾碱吸收液的机理进行了研究.以K_2CO_3和KHCO_3的混合液作为模拟液,用离子膜电解装置对其进行脱碳处理,得出电解再牛的方法.可以使回收液中的KHCO_3转化率达到100%,该过程在析出CO_2的同时产生H_2,起到了对热钾碱吸收液再生利用的作用.