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含四氢呋喃或叔丁胺体系水合物生成实验研究
其他题名Hydrate Formation in a System with Tetrahydrofuran or Tert-butylamine
王东雷
导师樊栓狮
2008-06-04
学位授予单位中国科学院广州能源研究所
学位授予地点广州能源研究所
学位名称硕士
关键词混合水合物 添加剂 四氢呋喃 叔丁胺 储气
摘要天然气水合物是由一定大小的客体分子与水在一定的温度和压力条件下生成的一种非固定化学计量的笼型晶体化合物。目前,研究者不仅把天然气水合物当作一种潜在的能源,而且研究开发相关的应用技术,一个重要研究方向就是通过加入添加剂来改善原有体系水合物的热力学条件和动力学特性,从而拓宽水合物技术的应用领域。 本文在新设计加工的水合物生成热力学和动力学研究装置上对合成天然气-THF-水体系水合物的生成过程进行了研究,探讨了该体系水合物的相平衡条件和温度、压力对其生成过程的影响,另外,我们还对甲烷-叔丁胺-水体系水合物生成过程进行了研究,探讨了温度、压力、初始反应物量和溶液叔丁胺浓度对水合物生成过程的影响。 实验结果表明:(1)新设计加工的实验装置能够满足气体水合物相平衡测试要求。(2)四氢呋喃能够显著降低合成天然气-水体系水合物的相平衡压力,当溶液浓度为5.6mol%时相平衡压力降低最多。(3)合成天然气-THF-水体系中生成结构Ⅱ型混合水合物,9.3mol%的叔丁胺溶液-甲烷体系中同时生成纯叔丁胺结构VI型和甲烷/叔丁胺结构II型两种水合物。(4)合成天然气-THF-水体系中水合物形成过程分为气体溶解、晶核形成、和水合物生长三个阶段;甲烷-叔丁胺-水体系中水合物形成过程包括分子接触聚集、骨架形成和晶体增长三个阶段。(5)对合成天然气-THF-水体系来说,水合物生成过程的诱导时间随温度降低而增大,随初始压力升高而线形降低,水合物生成速率和最终储气量均随温度降低而增大,随初始压力升高而增大。对甲烷-叔丁胺-水体系来说,诱导时间随温度降低而减小,随压力升高而降低;CH4水合反应速率随温度或压力升高而增大;最终储气量随温度降低而增大,在温度恒定条件下,当溶液浓度为9.3mol%时,如果初始反应物量较少,则最终储气量随压力升高而增大不明显,如果初始反应物量较多,则最终储气量随压力升高反而降低;当浓度变为5.6mol%时,最终储气量则显著增大。 本文选用四氢呋喃和叔丁胺作为添加剂,通过对合成天然气-THF-水体系和甲烷-叔丁胺-水体系中水合物的热力学条件和生成过程进行研究,为水合物应用技术的开发提供基础数据。
其他摘要Natural gas hydrates(NGHs) are nonstoichiometic clathrate crystalline compounds that are formed by physically stable interaction between water and relatively small guest molecules at high-pressure and low-temperature conditions. Now NGHs are regarded as a potential energy source. In addition, many new applied technologies are developed. In order to widen the applications of these technologies we can change the thermodynamic conditions and kinetic characteristics of hydrates through adding additives such as tetrahydrofuran(THF), sodium dodecyl sulfate(SDS) and so on. In this thesis, a new equipment for the thermodynamic and kinetic researches of gas hydrate was designed and built. In this equipment a series of experiments about the formations of hydrate in a synthetic nature gas(methane 91.9 mol %, ethane 5.11 mol %, propane 2.99 mol %)-THF-water system were carried. The hydrate disappearance conditions in this system were measured, and the influences of the temperature and initial pressure on the formation of the hydrate were investigated by the constant volume method. In addition, the influences of the temperature, the pressure, the initial reaction quantity and the tert-butylamine(tBuNH2) concentration in reactant solution on the formation of the hydrate in a methane- tBuNH2-water system were investigated by constant temperature and precooling method. The results showed that the new equipment can be used to measure hydrate disappearance conditions of gas hydrate. The equilibrium pressures of hydrate in the synthetic nature gas-water system were reduced when THF had been added to this system, and when THF concentration in reactant solution was 5.6 mol % the reduction was largest. The hydrate in the synthetic nature gas-THF-water system was structure II mixed hydrate, and THF mainly occupied the large cages of sII hydrate.Two hydrate structures, pure tBuNH2 Structure VI and methane/tBuNH2 Structure II, may form simultaneously in the methane- tBuNH2-water system. It is considered that hydrate formation mechanism in synthetic nature gas-THF-water system may undergo three steps: gas dissolving, nucleation and growing of hydrate, and hydrate formation mechanism in methane- tBuNH2-water system may also undergo three steps: contacting and gathering of reactants molecules, forming of hydrate framework, and growing of hydrate. For synthetic nature gas-THF-water system, induction time of the hydration reaction increased when the temperature decreased, and decreased linearly when initial pressure increased, the rate of hydrate formation and the final gas storage capacity increased when the temperature decreased, and increased when initial pressure increased. For methane- tBuNH2-water system, induction time of the hydration reaction decreased when the temperature decreased, and decreased when the pressure increased, the rate of hydrate formation with CH4 increased when the temperature or the pressure increased. For this system, the final gas storage capacity increased when the temperature decreased, at the constant temperature, the final gas storage capacity increased scarcely when the pressure increased while tBuNH2 concentration in reactant solution was 9.3 mol % and 30.0 sample was loaded in the reactor, and decresed when the pressure increased while tBuNH2 concentration in reactant solution was 9.3 mol % and 100.0 sample was loaded in the reactor. For this system, the final gas storage capacity increased remarkably when tBuNH2 concentration in reactant solution reduced as 5.6 mol %. In this thesis, THF and tBuNH2 were selected as additives, the thermodynamic conditions and kinetic processes of hydrates in synthetic nature gas-THF-water system and methane- tBuNH2-water system were studied. The results can provide base datas to the developments of applied technologies about gas hydrate.
页数73
语种中文
文献类型学位论文
条目标识符http://ir.giec.ac.cn/handle/344007/5780
专题中国科学院广州能源研究所
推荐引用方式
GB/T 7714
王东雷. 含四氢呋喃或叔丁胺体系水合物生成实验研究[D]. 广州能源研究所. 中国科学院广州能源研究所,2008.
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