Zhang Xiaotao, Shen Bin, Tian Tao, Li Shizhen, Xu Xuemin, Yang Jiajia, Sun Weilin, Qin Jing
National Research Center for Geoanalysis, Chinese Academy of Geological Science, Beijing 100037, China.
Shaanxi Coal Geology Group Co., Ltd. Key Laboratory of Coal Resources Exploration and Comprehensive Utilization, Ministry of Natural Resources, Xi'an 710021, China.
ACS Omega. 2024 Mar 12;9(12):13764-13781. doi: 10.1021/acsomega.3c08330. eCollection 2024 Mar 26.
Shale gas was recently found in the Lower Cambrian Niutitang Formation (LCNF) of the Micangshan tectonic zone of south Shaanxi (MTZSS), but not in commercial quantities. To determine the laws governing the generation, enrichment, and desorption of shale gases in overmatured shale strata in the LCNF of MTZSS, we carried out in situ desorption experiments on nine shale core samples and got 168 desorbed gas samples at different phases of desorption. Also measured were the chemical and carbon isotopic compositions of these desorbed gas samples and the geochemical parameters of the shale core samples. CH was the predominant hydrocarbon shale gas identified in the 82.06-98.48% range, suggesting that the gases were mainly dry. The nonhydrocarbon gases found were CO and H. The CH content of the desorbed gas samples dropped continuously during desorption, lowering the dryness index to 98.48 and 92.26% of the first and last desorbed shale gas, respectively. The change in the gas ratio during shale gas desorption proved that the adsorbability of the LCNF to the various gases follows the trend H > CO > CH > CH > He. Further, δCH and δCH become heavier during desorption, showing isotopic fractionation arising from the desorption-diffusion coeffect. As the desorption temperature increases, the value of δCH increases because CH is more sensitive to temperature than CH, so it is with the ethane. Similar to the LCNF shale gas in other areas of China, the desorbed shale gases are characteristic of carbon isotope reversal (CIR) (δCH > δCH). The cracking of the residual soluble organic matter at the high overmaturity stage mixed with the cracking of kerogen at the early stage of maturation, causing CIR. Furthermore, the desorbed gas content was proportionally and inversely related to the CIR degree and final dryness index of the desorbed gas, respectively. Moreover, the carbon isotope fractionation degree of CH and δC of the last desorbed gas correlated positively with the desorbed gas content and the desorbed time of the gas. In conclusion, the four parameters are effective parameters for identifying shale gas sweet spots.
最近在陕南米仓山构造带(MTZSS)的下寒武统牛蹄塘组(LCNF)发现了页岩气,但尚未达到商业开采量。为了确定MTZSS的LCNF中超成熟页岩地层中页岩气的生成、富集和解吸规律,我们对9个页岩岩芯样品进行了原位解吸实验,并在不同解吸阶段获得了168个解吸气样品。还测量了这些解吸气样品的化学和碳同位素组成以及页岩岩芯样品的地球化学参数。CH是在82.06 - 98.48%范围内识别出的主要烃类页岩气,表明这些气体主要是干气。发现的非烃类气体是CO和H。解吸气样品中的CH含量在解吸过程中持续下降,干燥指数分别降至第一次和解吸最后阶段页岩气的98.48%和92.26%。页岩气解吸过程中气体比例的变化证明,LCNF对各种气体的吸附能力遵循H > CO > CH > CH > He的趋势。此外,δCH和δCH在解吸过程中变重,表明解吸 - 扩散协同效应导致同位素分馏。随着解吸温度升高,δCH值增加,因为CH比CH对温度更敏感,乙烷也是如此。与中国其他地区的LCNF页岩气类似,解吸的页岩气具有碳同位素反转(CIR)(δCH > δCH)的特征。高过成熟阶段残余可溶有机质的裂解与成熟早期干酪根的裂解混合,导致了CIR。此外,解吸气含量分别与解吸气的CIR程度和最终干燥指数成反比。而且,最后解吸气的CH碳同位素分馏程度和δC与解吸气含量和解吸气时间呈正相关。总之,这四个参数是识别页岩气甜点的有效参数。