【作者】 杨阳；

【导师】 孙友宏；

【作者基本信息】 吉林大学 ， 地质工程， 2014， 博士

【摘要】 能源问题是目前世界亟待解决的问题，天然石油不可再生，我国原油对外依存度逐年增加，资源严重匮乏，对于油页岩资源的开发利用重新回到了人们的视野。吉林省属于资源短缺大省，但是其油页岩资源丰富，在我国油页岩储量居首位。目前对油页岩资源的开发利用还处于地下开挖，地表干馏的状态，可供地表开挖干馏的部分油页岩越来越少，且地表干馏环境污染严重等缺陷制约着其发展。原位裂解油页岩技术可以克服地表干馏法的多数缺陷，但是技术并不成熟，还处于试验阶段。吉林省油页岩资源含油率低，储层薄，埋深较深，目前的原位开采技术并不适用于吉林省的油页岩资源的开采，因此针对吉林省油页岩资源创新提出了高压-工频电加热原位裂解油页岩技术，为油页岩原位开采技术提供了新的思路。通过阅读大量文献，进行初步的基础试验，在理论与试验的基础上，中俄学者提出高压击穿-工频加热的裂解方法。本文利用所设计的高压-工频发生器、室内试验反应釜进行了不同距离、不同电压、不同电流等因素影响下的试验。由于试验过程中温度的不易测量且很难控制，利用基础试验得出的规律对高压-工频电加热原位裂解试验的结果进行反推来判断试验过程中的平均温度，进一步验证该技术的机理。首先对100-700℃7个温度节点下保温两个小时的块状油页岩样品进行热重分析，工业分析，对其产物进行气相色谱分析。试验所得的热失重峰值相对于原样的热重分析其失重峰值有滞后现象，是因为在块状样品随着环境温度的升高，热量从样品表面传递到样品的内部的过程，因此失重峰值温度向后偏移。在室内试验与原位开采的过程中都应该考虑到内部传热的过程，将温度控制在500℃左右。通过加热试验后其产物与残渣分别进行了大量的检测，得出油页岩样品的平均温度随温度的升高产物与残渣成分的变化规律，当平均温度在500℃-600℃时，产气量达到最大值，气体量的峰值随着温度的升高逐渐前移，是因为高温使得大分子的烃类物质断裂生成小分子的烃类，更有利于气体产物提纯。以固体击穿理论、等离子体理论、传热学理论为基础，对高压-工频电加热原位裂解技术的可行性进行论证，并同时与ICP原位转化工艺对比，针对吉林省油页岩资源的特点，高压-工频电加热原位裂解技术的加热通道垂直于层理，相同厚度的油页岩层具有更大的有效加热面积。对油页岩原位裂解过程中的热量传递规律建立物理模型，并进行仿真模拟。由于随着温度的升高油页岩材料的大部分物理性质都会随之变化，因此在模拟的过程中将导热系数、介电常数、比热等参数随温度的变化考虑其中，建立了非稳态模型。对室内油页岩裂解试验进行了模拟，根据模拟结果判断油页岩矿层达到裂解温度的区域与时间，通过后期的室内试验进行验证，为原位开采提供数据基础。建立了油页岩高压-工频电加热原位裂解实验平台，高压-工频发生器可通过电流或者电压对油页岩进行击穿；室内反应釜为试验提供了安全可靠的空间，并满足温度和压力的校核。试验平台可以更直观和方便的观察油页岩的裂解过程，并可进行重复试验，为原位开采提供试验基础和借鉴意义。并进行了高压-工频电加热原位裂解技术的室内试验，经过对油页岩样品的击穿与加热，成功产生页岩油和可燃气体，验证高压-工频电加热原位裂解油页岩技术的可行性，并且该技术方法使能量积聚在油页岩内部，即能量损失小；进行高压-工频电加热原位裂解油页岩的室内试验，根据试验数据拟合出在相同试验条件下，相同性质的油页岩击穿时间与电流/电压及距离的函数关系，为原位试验提供参考；通过对是产物进行热重分析、X衍射分析、元素分析，可得高压-工频电加热原位裂解油页岩的试验表明以电极作为加热体，其附近的油页岩发生了剧烈的裂解反应，根据油页岩裂解规律可反推其平均温度达到600℃以上，内圈的温度达到了860℃以上。高压-工频电加热原位裂解油页岩技术可以成功产生油气，理论与试验上都验证了这种技术原理的可行性，其产油气速度快，能量损失小，无地表环境污染，是一种很有前景的油页岩原位裂解技术。更多还原

【Abstract】 Energy is the serious problem to be solved for the world. The crude oil is non-renewable, that makes the resource shortage even more, and the crude oil externaldependenceof our countryincreases every year. The development and utilization ofoil shale has come back to people’s vision, and has become an important bargainingchip at the High Oil Price Times. Jilin province seriously lacks of energy, but it isvery rich of oil shale resources, its reserves in the first place of China. Thedevelopment and utilization of oil shale are still in the stage of undergroundexcavation and ground retorting. And the oil shale available for excavating andretorting is dwindling. The serious environmental pollution restricts thedevelopment of retorting. While the in-situ conversion technology could overcomethe most shortcomings of retorting, it is not mature enough, still in the experimentalstage. The oil shale of Jilin province has low oil content, thin reservoir and bigburied depth, so that there is no in-situ conversion technique applicable for theexploration of the oil shale of Jilin province. Therefore, high voltage-powerfrequency electrical heating method has been innovated for Jilin oil shale resources,and which also provide a new thinking for in-situ oil shale pyrolysis process.The high voltage-power frequency electrical heating method of oil shalepyrolysis is put forward on the basis of theory and experiment. High voltage-powerfrequency generator and reactor have been designed and manufactured, and theexperiments are done at different factors such as distance, voltage and current in thispaper. The average temperature in the experiment is judged by the inversion of theexperiment results from the law summarized by basic experiment, just because thetemperature is too difficult to test.The7oil shale samples are tested by thermogravimetric analysis (TGA),industrial analysis and gas chromatographyanalysis，after keeping the samples atdifferent temperature each for two hours. The weight lost peak from theexperiment has a lag relative to the TGA peak, it is because the temperature of theoil shale block increases with the environment temperature, and the heat need timeto transfer from the surface to the inside so that the peak temperature migratesbackward. The heat transfer process should be considered in both experiment andin-situ mining, and the pyrolysis temperature should be controlled at about500℃. The variation ofingredients on product and residues is concluded through testing.When the average temperature is at500℃-600℃,gas production reaches itsmaximum, and the peak moves forward gradually as the temperature rises. That isbecause the high temperature makes the macromolecular hydrocarbon fracture intosmall molecule, which is more conducive for gaseous product purification.The feasibility of high voltage-power frequency electrical heating in-situpyrolysis method is demonstrated on solid breakdown theory, plasma theory andheattransfer theory. Compared with the In-situ Conversion Process, the heatingchannel of high voltage-power frequency electrical heating in-situ pyrolysis methodis perpendicular to oil shale bedding, and has larger effective heating area at samethickness, and more suitable for the in-situ mining of Jilin oil shale resources. Thephysical model is established to analogue simulate the heat transfer law in the in-situ pyrolysis process.Most physical property of oil shale will change as thetemperature increases, and these variation as thermal conductivity, dielectricconstant, specific heat and other parameters are considered in the simulation to builda non-steadystate model. The simulation of experiment is done to adjust the areaand time of the oil shale reaching pyrolysis temperature, and verified by the lateexperiment, providing data base for in-situ mining.The test platform is built for high voltage-power frequency electrical heatingin-situ pyrolysis method, the high voltage-power frequency generator is used tobreak down the oil shale by controlling the current or voltage; the experiment reactorhas met the temperature and pressure check that is used to provide a safe and reliabletest space. The pyrolysis process could be more intuitive and convenient observedand the experiments can be repeated over the test platform, which providing anexperimental basis and reference for in-situ mining of oil shale. The experimentsare done to produce the shale oil and fuel gas through the breaking down and heating,which proves that the method is available for in-situ mining of oil shale. And thistechnique make the energy accumulated in the oil shale, the energy loss is small.The function of the breaking down current/voltage, time and distance is matched atthe same experiment condition, same oil shale property according to the experimentdata, providing the reference for in-situ experiment. Through the thermalgravimetric analysis, X diffraction analysis, elemental analysis of the product, whatcan be concluded is the electrodes are the heating part, the oil shale near the electrodes pyrolysis violently. The average temperature reaches more than600℃,the internal temperature reaches860℃which are estimated according to the law ofoil shale pyrolysis.The high voltage-power frequency electrical heating method of oil shalepyrolysis can successfully produce the shale oil and fuel gas, whose feasibility isverified by the theory and experiment. This method is a promising in-situ pyrolysistechnique for oil shale, for its fast production of shale oil and gas, small energy lossand no environmental pollution.更多还原