| 题名 | 相转移催化元素硫歧化反应及其在难选矿石处理中的应用 |
| 作者 | 邓彤 |
| 学位类别 | 博士 |
| 答辩日期 | 1985-06-30 |
| 授予单位 | 中国科学院研究生院 |
| 导师 | 陈家镛 |
| 中文摘要 | 本工作将有机合成中的相转移催过程推广到无机反应中。用四氯乙烯作元素硫的有机溶剂，四丁基铵氢氧化物作催化剂，实现了元素硫歧化反应的相转移催化。在温度45－70℃、氢氧离子浓度0.02－0.14M范围内，研究了该反应寝阶段的动力学，实验测得元素硫歧化的表观速度服从表达式Ra = K~*[Q~+]aq ··[OH]aq·[S]_(org)~(1/2)，并导得表观活化能为难9 kj/mol。采用液－－流体系伴有快速化学反应的传质模型解释本体系动力学，指出元素硫歧化反应真实的化学动力学是氢氧离子和元素硫的一级反应。比较了四氯乙烯、二甲苯和四氯乙烷三种溶剂以及四乙基铵、四丁基铵，十六烷基三甲基铵和三辛基甲基铵四种相转移催化剂的影响。推测了元素硫的歧化反应机理。讨论了本体系相转移催化的证据。为利用相转移催化技术改进以元素硫歧化反应为基础的加压水热硫化过程提供了依据。 |
| 英文摘要 | Kinetics of phase transfer catalyzed disproportionation of elemental sulfur at the initial stage was investigated at OH~- concentration from 0.02 to 0.14 M with temperature between 45 and 70 ℃。The linear dependence of the observed volumetric rate of disproportionation of elemental sulfur Ra on the rate of agitation within the range from 680 1270 rpm indicates the characteristics of a typical interfacial reaction. It has shown that Ra was direstly proportional to the concentrations of both the phase transfer catalyst and the hydroxide ions in aqueous solution and to the 0.5 power of sulfur concentration in the organic phase within the range studied in the present work. Ra can be expressed by following equation Ra = K~*(Q~+)q(OH)aq(S)_(org)~(1/2) M/s where Q~+ is the concentration of phase transfer catalyst with subcripts aq and org for aqueous and organic phase respectively. The apparent activation energy was derived as 79 kj/mol with the temperature range of 45 to 70 C. The effectiveness of catalysls of various quaternary ammonium compounds was found to inorease in the following order: (C_2H_5)_4N~+ < (C_4H_9)N~+ << C_(16)H~(33) (CH_3)_3N~+<<(C_8H~(17))_3CH_3N~+. Xylene was found to be an effective solvent for the reaction studied as well as tetrachloroethylene, but tetrach-loroethylane can't be used as the solvent for the present reaction. The mathematical model of mass transfer with fast chemical reaction in liquid-liquid system was adopted to explain the results of kinetic study. It was indicated from the model that the disproportionation of elemental sulfur is first order reaction with respect to the concentration of hydroxide ions in aqueous phase and concentration of sulfur in the organic phase respectively. |
| 语种 | 中文 |
| 公开日期 | 2013-09-27 |
| 页码 | 192 |
| 内容类型 | 学位论文 |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/2072]  |
| 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 | 邓彤. 相转移催化元素硫歧化反应及其在难选矿石处理中的应用[D]. 中国科学院研究生院. 1985. |
| 个性服务 |
| 查看访问统计 |
| 相关权益政策 |
| 暂无数据 |
| 收藏/分享 |
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。
修改评论