苯胺盐酸盐在氯化物体系中溶解度及自一致热力学模型
文献类型：学位论文
| 作者 | 孙顺平 |
| 学位类别 | 硕士 |
| 答辩日期 | 2012-04-13 |
| 授予单位 | 中国科学院研究生院 |
| 导师 | 李志宝 |
| 关键词 | 溶解度 无水氯化镁 苯胺盐酸盐 电解质NRTL模型 |
| 其他题名 | Solubility of Aniline Hydrochloride in Chloride Systems and Self-Consistent Thermodynamic Model |
| 学位专业 | 化学工程 |
| 中文摘要 | 金属镁及其合金具有重量轻、密度小、强度高等特性，被广泛用于飞船、导弹、汽车、消费类电子产品等的制造。目前金属镁的生产工艺主要有两种：热还原法（皮江法）和电解法。皮江法在制备金属镁的过程中存在能耗高、污染环境等缺点，我国已明确指出不鼓励发展皮江法。电解法资源利用率高、污染小可以大规模生产，发达国家80%以上的金属镁都是采用电解法生产的。电解法炼镁的关键是高纯无水氯化镁的制备。我国青海盐湖蕴藏着丰富的氯化镁资源，为了充分利用盐湖镁资源，用苯胺盐酸盐([HAE]Cl)与氯化镁在适当条件下形成复盐[HAE]Cl?MgCl2?6H2O，该复盐经加热脱水制得电解用无水氯化镁。围绕该工艺，本文就苯胺盐酸盐在混合电解质和混合溶剂体系中的溶解度展开研究，主要研究内容包括： (1) [HAE]Cl在电解质体系中溶解度的测定。实验测定了278～370K苯胺盐酸盐在水中及氯化镁溶液中的溶解度，结果表明苯胺盐酸盐的溶解度随温度的升高而增大随氯化镁浓度的增大而减小。通常盐湖氯化镁资源中含有NaCl、CaCl2等杂质，为确定杂质对复盐合成的影响，实验分别测定了288～348K苯胺盐酸盐在NaCl (0.5?3.8mol?kg-1)、CaCl2 (0.5?4.5mol?kg-1)、AlCl3 (0.5?2.8mol?kg-1)、HCl (1.19?6.98 mol?kg-1)溶液及混合电解质NaCl?AlCl3?H2O、NaCl?CaCl2?H2O体系中的溶解度。苯胺盐酸盐的溶解度随电解质氯化物浓度的增大而减小。 (2) [HAE]Cl在混合醇体系中溶解度的测定。为制备晶形良好的复盐晶体，提出采用反溶剂结晶法，在此工艺中苯胺盐酸盐在混合溶剂中的相平衡关系是关键。因此，实验分别测定温度288～328K条件下苯胺盐酸盐在CH3OH、C2H5OH、C3H7OH溶液中，三个三元混合溶剂体系CH3OH–C2H5OH–H2O、C2H5OH–C3H7OH–H2O、CH3OH–C3H7OH–H2O中，及一个四元混合溶剂体系CH3OH–C2H5OH–C3H7OH–H2O中的溶解度。 (3) 以电解质NRTL模型为基础建立自一致热力学模型。由活度系数和所测得的溶解度计算得到苯胺盐酸盐的平衡常数，结合文献数据依托电解质NRTL模型，拟合实验数据得到了[HAE]Cl?H2O、[HAE]Cl?MgCl2、MgCl2?H2O、[HAE]Cl?NaCl、[HAE]Cl?CaCl2和[HAE]Cl?AlCl3间的二元交互作用参数，从而建立起[HAE]?H?Mg ?Na?Ca?Al?Cl?H2O体系自一致热力学模型。对于混合溶剂体系，拟合实验数据得到[HAE]Cl–CH3OH、[HAE]Cl–C2H5OH、[HAE]Cl–C3H7OH间的交互作用参数，建立起[HAE]Cl–CH3OH–C2H5OH–C3H7OH–H2O体系的自一致热力学模型。所建立的化学模型可准确的预测苯胺盐酸盐在混合电解质及混合溶剂体系中的溶解度，并作出[HAE]Cl–MgCl2–H2O体系和[HAE]Cl–C2H5OH–H2O体系相图，从而为合成复盐制备电解用无水氯化镁打下基础。 |
| 英文摘要 | Metal magnesium and its alloys with lightweight, low density and high intensity properties, are widely used for shuttle, missiles, automobile and consumer electronic products. The technologies of magnesium production can be divided into two main types: the Pidgeon process and electrochemical methods. Pidgeon process is resource and energy-intensive and leads to relatively severe environmental pollution. Compared to the Pidgeon process, electrochemical method is an advanced technology with low energy consumption. The key problem of electrochemical method is to prepare high purity anhydrous magnesium chloride. China is rich in brine resources containing considerable amount of magnesium chloride. In order to make full use of salt lake magnesium resources, preparation of anhydrous magnesium chloride by using thermal decomposition of complex [HAE]Cl?MgCl2?6H2O is a potential process for commercial application. The complex is synthesized by crystallization of aniline hydrochloride and bischofite. In this work, the solubility of aniline hydrochloride in mixed electrolyte systems and mixed solvent systems have been investigated in detail. The main research contents in this thesis are summarized as follows: (1) Determine the solubilities of [HAE]Cl in various electrolyte systems. The solubility of [HAE]Cl in pure water and MgCl2 solution was determined over the temperature range from 278 to 370 K, and the results show that the solubility of [HAE]Cl increases with increasing temperature but decreases with the increasing concentration of MgCl2. Furthermore, the solubility of [HAE]Cl in different concentrations of NaCl (0.5?3.8 mol?kg-1), CaCl2 (0.5?4.5 mol?kg-1), AlCl3 (0.5?2.8 mol?kg-1) , HCl (1.19?6.98 mol?kg-1) and their mixed solutions was determined using dynamic method at the temperature range from 288 to 348 K. (2) Determine the solubilities of [HAE]Cl in mixed alcohols systems. In order to synthesize the complex [HAE]Cl?MgCl2?6H2O with good crystalline form, the anti-solvent crystallization method may be used so that the solubility of aniline hydrochloride is required. The solubility of [HAE]Cl was measured in the following systems: ○1 binary solvent systems [HAE]Cl–CH3OH–H2O, [HAE]Cl–C2H5OH–H2O, [HAE]Cl–C3H7OH–H2O; ○2 ternary solvent systems [HAE]Cl–CH3OH–C2H5OH–H2O, [HAE]Cl–C2H5OH–C3H7OH–H2O, [HAE]Cl–CH3OH–C3H7OH–H2O; ○3 quaternary solvent system [HAE]Cl–CH3OH–C2H5OH –C3H7OH–H2O. (3) Establish a self-consistent model for the mixed electrolyte system and mixed solvent systems with electrolyte NRTL model. The equilibrium constant of [HAE]Cl was obtained using the mean ionic activity coefficients of [HAE]Cl and solubility in pure water at different temperatures. This new equilibrium constant was used to determine the new binary ENRTL interaction energy parameters such as [HAE]Cl?H2O, [HAE]Cl?MgCl2, MgCl2?H2O, [HAE]Cl?NaCl, [HAE]Cl?CaCl2 and [HAE]Cl?AlCl3. Therefore, a self-consistent model for [HAE]?H?Mg?Na?Ca?Al?Cl?H2O was established. Similarly，the experimental data was regressed and binary interaction energy parameters for [HAE]Cl–CH3OH, [HAE]Cl–C2H5OH, [HAE]Cl–C3H7OH were obtained. The self-consistent models established could predict the solubility of [HAE]Cl in the mixed electrolyte and mixed solvent systems very well, providing thermodynamic basis for preparing anhydrous magnesium chloride. |
| 语种 | 中文 |
| 公开日期 | 2013-09-25 |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/1873]  |
| 专题 | 过程工程研究所_研究所（批量导入） |
| 推荐引用方式 GB/T 7714 | 孙顺平. 苯胺盐酸盐在氯化物体系中溶解度及自一致热力学模型[D]. 中国科学院研究生院. 2012. |
入库方式： OAI收割
来源：过程工程研究所
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