注入二氧化碳及氮气驱替煤层气机理的实验研究

论述了我国开采煤层气目前存在的问题,并且通过煤对二氧化碳（CO2）、甲烷（CH4）、氮气（N2）吸附机理的分析,提出注入二氧化碳（CO2）或氮气（N2）提高煤层气采收率技术的可行性。并从其注气驱替煤层气的作用机理的不同,从理论上和实验中得出注入二氧化碳（CO2）的效果要优于氮气（N2）。     

H2、N2、CO和CO2在液体石蜡中的溶解度和传质系数的研究

在机械搅拌高压釜中测定了290．15～513．15K、0．5～4．0MPa范围内H2、N2、CO和CO2在液体石蜡中的溶解度和体积传质系数。结果表明,H2、N2、CO和CO2的平衡溶解度均随着压力的升高而增大,N2、CO和CO2的平衡溶解度随温度的升高而减小,但氢气的平衡溶解度随温度的升高而增加。回归了各种气体的溶解度系数H1与温度丁的关联式。H2、N2、CO和CO2的体积传质系数均随着压力和温度的升高而增大,温度和压力对不同气体的体积传质系数的影响各不相同,氢气的体积传质系数受温度和压力变化的影响较大,二氧化碳的次之,一氧化碳和氮气的变化较小。     

不可采煤层CO2封存的数值模拟

将CO2注入不可采煤层进行封存(CO2-ECBM)能在封存CO2的同时回收甲烷,因而是一项具有良好前景的CO2处置技术。CO2或者CO2/N2混合气注入煤层后在煤层中运移涉及到多组分气体在煤中的吸附、多组分气体以及气、水两相在煤层中的扩散渗流等过程。基于上述过程,建立了考虑煤基质吸附气体后的膨胀效应、能够描述多组分气体在煤层中吸附/解吸扩散渗流过程的数学模型,并采用数值解法对模型进行了求解,与已有的模拟结果比较表明建立的模型是可靠的;利用该模型研究了煤层渗透率、不同气体差异性吸附膨胀系数、煤对CO2/CH4的吸附比、以及注入气体组成对于CO2封存以及煤层气生产的影响,研究结果可以为CO2-ECBM项目的场地条件选择以及工艺参数的优化提供依据。     

煤表面吸附H_2S气体特性量子化学分析

为探究煤层中硫化氢的吸附性质,建立山西铁新含硫化氢煤表面分子模型,利用软件Gaussian09,通过密度泛函理论(DFT)在B3LYP/6-311G上计算煤表面分子与H2S、CO2、CH4、N2气体分子的吸附能.进一步模拟了硫化氢和甲烷混合气体共存条件下,二者的依存关系.结果表明:煤吸附硫化氢的吸附能为2.230 k J/mol,键长、键角均无变化,表明煤对硫化氢存在吸附,且为物理吸附;煤对四种气体吸附能力依次为CO2CH4N2H2S,硫化氢为弱吸附气体;硫化氢的存在促进煤对甲烷的吸附;煤对硫化氢和甲烷混合气体的吸附能大于煤对单个气体的吸附能.     

注入增产法提高煤层气采收率的理论探讨

美国Amoco公司开发的注入增产法是一项很有前途的提高煤层气采收率的方法,为此笔者在研究煤对二元气体吸附特征的基础上,探讨了注入增产法的基本原理。结果表明,煤对常见气体的吸附能力由强到弱为：二氧化碳、甲烷、氮气、氢气;煤对二元混合气体总的吸附及对甲烷的吸附均符合Langmiur方程,但在ＣＨ４＋Ｈ２或ＣＨ４＋Ｎ２的吸附系统中,对Ｈ２或Ｎ２吸附时吸附量与压力之间不遵从此关系式,而在ＣＨ４＋ＣＯ２吸附系统中,煤对ＣＯ２的吸附量和压力之间的关系仍可用Langmuir方程定量描述;注入增产法提高煤层瓦斯抽放率是通过注入其它气体使煤对甲烷的吸附量减小来实现的,且注入Ｎ２优于ＣＯ２。     

急倾斜煤与CO_2突出厚煤层透气性系数、瓦斯（CO2）涌出衰减系数的测定

通过对急倾斜煤与CO2突出厚煤层透气性系数、瓦斯（CO2）涌出衰减系数的测定,分析总结出煤二层为透气性较好的煤层,属容易抽放煤层。为合理布置瓦斯（CO2）抽放钻孔提供了科学依据。     

CO2煤层注入埋藏意义及原理分析

二氧化碳的煤层处置即CO2-ECBM（Enhanced Coallbed Methane Recovery）技术。主要是通过将收集到的二氧化碳注入煤层。借助于煤基质块的吸附作用将二氧化碳“固定”埋藏于地下。实现减少大气中温室气体的作用。     

大气压DBD甲烷二氧化碳转化方法研究

在不使用催化剂,吸收剂的环境友好条件下,利用大气压介质阻挡强电离放电加速电子及激励气体分子方法,将CH4和CO2气体激发、电离和离解成CH3,CH2,CH,H,CO,O,OH等活性粒子,并在非平衡等离子体反应器内重新组合,生成合成气、气态烃及含氧有机物醇、酸等有价值产物,甲烷的转化率高达60%以上,二氧化碳或氮气的加入使甲烷的转化率有明显提高,甲烷与二氧化碳反应气的最佳体积比为3/1.当甲烷体积分数为75%时,可得到H2/CO摩尔比为3的高质量的合成气,收集到的液体产物主要有醇、酸和水等.     

低渗透油藏CO2驱与N2驱室内实验对比研究

为了对比研究CO2驱与N2驱在低渗透油藏的驱油效果,在室内进行了多组长岩心驱替实验。研究结果表明:渗透率相同条件下,CO2驱油效果好于N2。随着渗透率的增加,CO2驱与N2驱的驱油效率增加,但差值越来越小;定速度注入CO2和N2时,注入压力都呈现出先升高后降低,最后趋于平稳的变化趋势;且CO2驱注入压力变化幅度大于N2驱;水驱后转CO2驱或N2驱都能明显降低注入压力,且N2驱降压能力要强于CO2驱;CO2气水交替驱采出程度明显高于连续CO2驱;N2气水交替驱采出程度与连续N2驱相差不大。     

流固耦合作用下注气开采煤层气增产规律研究

提高低渗透煤层气产量是我国煤层气开采中急需解决的关键问题，加速煤层甲烷解吸过程的注气增产方法是提高低渗透煤层气产量的有效途径。由于排采降压在孔隙流体压力变化的范围内会引起储层孔隙介质的应力和应变的变化，造成有效渗透率和孔隙度的降低，同时也影响注气和产气的动态参数。研究这些规律，首先建立了注气开采煤层气多组分流体扩散渗流的流固耦合模型，利用数值方法研究了注气开采煤层气的增产机理。研究表明，注入二氧化碳气体不但减少了煤层甲烷的分压．加速了煤层甲烷的解吸；而且二氧化碳气体比甲烷气体更易吸附，竞争吸附置换煤层甲烷分子，从而提高了煤层气产量，同时必须重视耦合作用对注气增产造成的不利影响。     

Non-CO2 greenhouse gases and climate change

Earth's climate is warming as a result of anthropogenic emissions of greenhouse gases, particularly carbon dioxide (CO(2)) from fossil fuel combustion. Anthropogenic emissions of non-CO(2) greenhouse gases, such as methane, nitrous oxide and ozone-depleting substances (largely from sources other than fossil fuels), also contribute significantly to warming. Some non-CO(2) greenhouse gases have much shorter lifetimes than CO(2), so reducing their emissions offers an additional opportunity to lessen future climate change. Although it is clear that sustainably reducing the warming influence of greenhouse gases will be possible only with substantial cuts in emissions of CO(2), reducing non-CO(2) greenhouse gas emissions would be a relatively quick way of contributing to this goal.     

Thermal simulation of the formation and evolution of coalbed gas

Thermal simulation experiment of gas generation from the peat and the coals were performed using the high temperature and pressure apparatus, at temperature ranging from 336.8-600℃, a pressure of 50MPa and two heating rates of 20℃/h and 2℃/h, and the evolution and formation of coalbed gas components were studied. Results show that for the coals, the gaseous products are mainly composed of hydrocarbon gases. However, for the peat the content of hydrocarbon gases in gaseous products is lower than that of non-hydrocarbon components. In the generated hydrocarbon gases methane is predominant and heavy hydrocarbon gases (C2-5) are present in small amount. Meanwhile, carbon dioxide (CO2) predominates the generated non-hydrocarbon gases, and hydrogen (H2) and sul-furated hydrogen (H2S) are existent in trace amount. It is also observed that temperature is the main factor controlling the evolution of coalbed gas generation. With increasing vitrinite reflectance, methane rapidly increases, CO2 sightly increases, and C2-5 hydrocarbons first increase and then decrease. The peat and Shanxi formation coal have a higher generative potential of coalbed gases than coals and Taiyuan formation coal, respectively, reflecting the effect of the property of organic matter on the characteristics of coalbed gas component generation. In this study, it is found that low heating rate is favorable for the generation of methane, H2 and CO2, and the decomposition of C2-5 hydrocarbons. This shows that heating time plays an important controlling role in the generation and evolution of coalbed gases. The results obtained from the simulation experiment in the study of coalbed gases in natural system are also discussed.     

300-Myr-old magmatic CO2 in natural gas reservoirs of the west Texas Permian basin

Except in regions of recent crustal extension, the dominant origin of carbon dioxide in fluids in sedimentary basins has been assumed to be from crustal organic matter or mineral reactions. Here we show, by contrast, that Rayleigh fractionation caused by partial degassing of a magma body can explain the CO2/3He ratios and delta13C(CO2) values observed in CO2-rich natural gases in the west Texas Val Verde basin and also the mantle 3He/22Ne ratios observed in other basin systems. Regional changes in CO2/3He and CO2/CH4 ratios can be explained if the CO2 input pre-dates methane generation in the basin, which occurred about 280 Myr ago. Uplift to the north of the Val Verde basin between 310 and 280 Myr ago appears to be the only tectonic event with appropriate timing and location to be the source of the magmatic CO2. Our identification of magmatic CO2 in a foreland basin indicates that the origin of CO2 in other mid-continent basin systems should be re-evaluated. Also, the inferred closed-system preservation of natural gas in a trapping structure for approximately 300 Myr is far longer than the residence time predicted by diffusion models.     

高温高压条件下甲烷和二氧化碳溶解度试验

根据不同温度和压力条件下测得的甲烷和二氧化碳两种气体在碳酸氢钠型水中的溶解度数据,对两种气体的溶解度与温度、压力及地层水矿化度之间的关系进行研究。结果表明:在地层水中的溶解机制不同,导致两种气体的溶解度值随温度、压力条件的变化具有不同的演变特征;综合前人低温(小于90℃)测试的溶解度数据,可将甲烷溶解度与温度之间的演变关系划分为缓慢递减(0~80℃)、快速递增(80~150℃)和缓慢递增(大于150℃)3个阶段;二氧化碳溶解度随温度的升高而逐渐降低,随压力升高而逐渐增大,其溶解与析离能力受压力影响更为明显;实际地层中,两种气体间溶解度的差异演变影响了天然气的空间分布。     

玉米芯活性炭的制备及储气性能

天然气、氢气、二氧化碳等气体的吸附研究在洁净气体代油燃料的强化存储、温室气体减排、大气治理等方面具有重要意义,其重点内容是高效吸附材料的开发．以玉米芯为原料,采用磷酸活化法制备了含有较高中孔比例的活性炭,其比表面积达到1,610,m2/g,孔容为1.72,cm3/g,中孔体积达到1.14,cm3/g,占孔容的66％．测定了H2、N2、CH4和 CO2在该吸附剂上的吸附等温线．在0.4,MPa 时,CO2对 CH4的选择性达到2.76,对 N2的选择性达到7.63,对 H2的选择性达到42.31,具有良好的分离应用前景．测定了水存在条件下甲烷在该活性炭上的吸附等温线,由于孔尺寸有利于甲烷水合物的生成,因此甲烷吸入量较在干燥吸附剂上提高了82％．根据克劳修斯-克拉佩龙方程计算了甲烷水合物的生成焓为-64.37,kJ/mol．     

Increased soil emissions of potent greenhouse gases under increased atmospheric CO2

Increasing concentrations of atmospheric carbon dioxide (CO(2)) can affect biotic and abiotic conditions in soil, such as microbial activity and water content. In turn, these changes might be expected to alter the production and consumption of the important greenhouse gases nitrous oxide (N(2)O) and methane (CH(4)) (refs 2, 3). However, studies on fluxes of N(2)O and CH(4) from soil under increased atmospheric CO(2) have not been quantitatively synthesized. Here we show, using meta-analysis, that increased CO(2) (ranging from 463 to 780 parts per million by volume) stimulates both N(2)O emissions from upland soils and CH(4) emissions from rice paddies and natural wetlands. Because enhanced greenhouse-gas emissions add to the radiative forcing of terrestrial ecosystems, these emissions are expected to negate at least 16.6 per cent of the climate change mitigation potential previously predicted from an increase in the terrestrial carbon sink under increased atmospheric CO(2) concentrations. Our results therefore suggest that the capacity of land ecosystems to slow climate warming has been overestimated.     

氮化钼催化剂上CO加氢反应的原位红外研究

采用MoO3 或CoMoOy 与N2 /H2 的程序升温还原反应 ,合成出了BET比表面积为 16 5m2 /g和 15 8m2 /g的Mo2 N和CoMoNx。用CO的加氢反应作为探针反应 ,并结合原位傅立叶变换红外光谱 (FT IR)技术评价了合成催化剂的加氢性能。结果表明 ,氮化钼催化剂具有较高的CO加氢活性和CH4 选择性 ,催化剂的预处理条件对其反应性能有明显的影响 ,钝化态的氮化钼经在 6 73K下的加氢还原并不能提高其加氢性能     

温室气体减排与CO2资源化宏观研究与探讨

介绍了近一段时间全球温室气体减排的进展及面临的形势,并预测了未来二氧化碳的排放趋势.着重对CO2的资源化问题进行了分析和探讨,从CO2作为再生资源的角度讨论了CO2的回收、利用和处置技术;同时指出资源化问题存在的挑战和负面影响.证明CO2资源化对温室气体减排作用不明显,应大力提倡"无悔"行动.最后从热力学角度分析了CO2问题的本质.