【摘要】：近年來，我國在陸域和海域都已獲得天然氣水合物實物樣品，研究分析指出我國的水合物資源儲量非常豐富，有著巨大的應用潛力。若天然氣水合物資源轉入商業(yè)性開發(fā)，必將緩解我國能源緊張局勢和油氣供需矛盾。此外，水合物技術在工業(yè)應用領域也有廣闊的發(fā)展前景。氣體水合物具有強大的儲氣能力，以水合物為核心的新型儲運技術以及由此研發(fā)的相關能源供給技術有著巨大的應用前景。水合物與其它常規(guī)能源的不同之處在于它的穩(wěn)定賦存需要特殊的高壓低溫熱力學條件，其動態(tài)聚散過程也伴隨強烈的熱交換現象。因此，本研究以天然氣水合物為研究對象，選取其中的熱物理參數為重點關注的科學問題，將水合物的動態(tài)聚散過程作為重要背景條件開展一系列實驗研究�；谘芯恐薪⒌募夹g方法和分析手段進一步開展與水合物熱特性相關的科學研究。 研究中通過改變氣相-液相-固相反應材料的成分，開展一系列水合物合成與分解的模擬實驗。利用高壓差示掃描量熱儀結合激光拉曼等光譜分析手段測定水合物摩爾分解熱；通過自主研制的水合物熱物性模擬實驗裝置探索含水合物沉積物熱導率與飽和度相關關系；通過自主研制的水合物熱擴散效應實驗裝置，利用電加熱等水合物分解手段討論分解過程中含水合物多孔介質溫度梯度受熱源距離、加熱時間的影響，闡明水合物熱擴散特征。 通過研究建立高壓差示掃描量熱儀在水合物動態(tài)聚散過程的熱流曲線分析技術、水合物熱導率測定技術和水合物熱激發(fā)分解模擬實驗方法并結合相應的理論模型指導，進一步開展水合物熱力學、動力學相關問題應用研究。其中包括不同條件下水合物相平衡分析技術、水合物亞穩(wěn)態(tài)規(guī)律研究、水合物生成過程的質量傳遞研究以及水合物熱激發(fā)分解過程與試開采效率研究等。 研究主要成果包括：（1）通過模擬實驗方法闡明了水合物分解熱、熱導率、熱擴散能力及相平衡條件等一系列熱物性參數在不同條件下的變化特征；（2）證實了水合物亞穩(wěn)定現象并指出冰的存在不是水合物亞穩(wěn)定存在的必要條件；（3）實驗研究了水合物合成過程物質傳遞特征，，指出氣體向水合物膜移動是反應過程中的主要物質傳遞方式；（4）通過對不同條件下水合物動態(tài)聚散實驗過程分析，推斷溫度和壓力這兩個控制水合物反應的主要驅動力對水合反應的作用方式不同：溫度偏重影響水合反應的誘導時間，而壓力則更能決定水合物的飽和度。
[Abstract]:In recent years, the physical samples of natural gas hydrate have been obtained in the land and sea area in China. The research and analysis show that the reserves of hydrate resources in China are very rich and have great application potential. If natural gas hydrate resources turn to commercial exploitation, energy tension and contradiction between supply and demand of oil and gas will be alleviated in China. In addition, hydrate technology has a broad prospect in industrial applications. Gas hydrate has a strong gas storage capacity. The new storage and transportation technology with hydrate as the core and the related energy supply technology developed therefrom have great application prospects. The difference between hydrates and other conventional energy sources is that their stable existence requires special thermodynamic conditions at high pressure and low temperature, and the dynamic accumulation and dispersion process is accompanied by a strong heat exchange phenomenon. Therefore, in this study, natural gas hydrate as the research object, select the thermal physical parameters as the focus of the scientific issues, the hydrates dynamic accumulation process as an important background conditions to carry out a series of experimental studies. Based on the technical methods and analytical methods established in the research, further scientific research related to the thermal characteristics of hydrates is carried out. A series of simulation experiments of hydrate synthesis and decomposition were carried out by changing the composition of gas-liquid phase solid phase reaction materials. The molar decomposition heat of hydrate was determined by means of high pressure differential scanning calorimeter and laser Raman spectroscopy. By using the self-developed experimental apparatus of hydrate thermal diffusion effect, the influence of heat source distance and heating time on the temperature gradient of hydrated porous media during the decomposition process is discussed by means of electric heating and other means of hydrate decomposition, and the characteristics of hydrate thermal diffusion are expounded. The heat flow curve analysis technique of high pressure differential scanning calorimeter in the process of hydrate dynamic accumulation and dispersion, the determination of hydrate thermal conductivity and the simulation experiment method of hydrate thermal excitation decomposition were established. Further research on the application of hydrate thermodynamics and kinetics. It includes the analysis technology of hydrate phase equilibrium under different conditions, the study of the metastable law of hydrate, the mass transfer of hydrate formation process, the process of thermal excited decomposition of hydrate and the study of trial mining efficiency, etc. The main results are as follows: (1) the characteristics of thermal properties of hydrate decomposition, thermal conductivity, thermal diffusivity and phase equilibrium conditions are illustrated by simulation experiments; (2) it is proved that the existence of ice is not a necessary condition for the existence of hydrate metastable. (3) the material transfer characteristics of hydrate synthesis process are studied experimentally. It is pointed out that the migration of gas to hydrate membrane is the main way of mass transfer in the reaction process. (4) the dynamic accumulation and dispersion process of hydrate under different conditions is analyzed. It is inferred that temperature and pressure, the two main driving forces controlling hydrate reaction, play different roles in hydration reaction: temperature bias affects the induction time of hydration reaction, and pressure can determine the hydrate saturation more.
【學位授予單位】：中國海洋大學
【學位級別】：博士
【學位授予年份】：2014
【分類號】：P744.4

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