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QUANTITATIVE ANALYSIS FOR NANOPORE STRUCTURE CHARACTERISTICS OF SHALES USING NMR AND NMR CRYOPOROMETRY
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摘要: 选取威远海相页岩（1#）、焦石坝海相页岩（2#）、瑶曲凝灰岩（4#）及瑶曲陆相页岩（5#和6#），采用场发射扫描电镜（FE-SEM）与低场核磁共振（NMR），研究中国海相页岩和陆相页岩之间的孔隙结构特征的差异化特征。核磁共振冻融法（NMRC）可以精细探测页岩的纳米范围的孔隙结构。该方法可以拓展到结合核磁共振弛豫分析进行微观测量，详细探测不同孔径尺度下页岩的孔隙结构。测试温度梯度变化越小，孔隙分布测量的结果越精细。测试结果表明，从样品5#，2#，6#，1#至样品4#的孔隙率逐个减小。NMRC，LFNMR，压汞法（MIP），气体吸附法（GA）在它们各自的有效测量范围内，孔径分布表现出良好的一致性。因此，将NMRC，LFNMR与GA和MIP等方法组合，可以更准确地评估储层页岩的孔隙结构。研究结果表明，陆相页岩（5#瑶曲页岩）的纳米孔隙更发育，与海相页岩相比也许具有更高的商业开发价值。Abstract: Based on the differences in pore structure characteristics between marine and continental shale in China, Weiyuan marine shale(1#), Jiao Shiba marine shale(2#), Yaoqu tuff(4#) and Yaoqu continental shale(5# and 6#)were selected to study the pore structure characteristics using cold field emission scanning microscopy(FE-SEM) and nuclear magnetic resonance(NMR). Nuclear magnetic resonance cryoporometry(NMRC)was employed to represent nano-scale pore structure. This method can be extended to microns measurement combining nuclear magnetic resonance relaxation analysis to detect in detail the pore structure of shales under the different aperture scales. The smaller the test temperature gradient is, the finer the result of pore distribution is. Test results show decreasing porosity from sample 5#, 2#, 6#, and 1# to sample 4#. NMRC, low field nuclear magnetic resonance(LFNMR), mercury intrusion porosimetry(MIP) and gas adsorption(GA)methods show good agreement of pore size distribution in their respective scope of application. Hence, the pore structure of the reservoir shale can be evaluated more accurately by combining NMRC, LFNMR with GA and MIP. Thus the nano-pores of continental shale(5# Yaoqu shale) are clearly better developed and will more likely have a higher commercial exploitation value than those of marine shale.
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图 2 样品T2谱分布
a. 1#样品；b. 2#样品；c. 4#样品；d. 5#样品；e. 6#样品
Figure 2. T2 spectral distribution of samples
图 10 含水量和信号强度的校准曲线
Figure 10. The calibration curve between water content and signal intensity of sample 2#
图 11 不同样品孔径分布的比较
Figure 11. Comparison of the pore volume distributions among different samples with pore diameter increasing
表 1 页岩矿物成分分析结果(%)
Table 1. Analysis results of shale mineral content(%)
编号 取样地点 岩性 石英含量 钾长石含量 钠长石含量 方解石含量 白云石含量 黄铁矿含量 菱铁矿含量 BI脆性系数 1# 威远 页岩 38.5 3.1 19.7 6.8 13.8 3.6 / 52.3 2# 焦石坝 页岩 36.3 0.9 8.6 6.4 5.5 5.5 / 42.7 4# 瑶曲 凝灰岩 31.5 5.0 22.3 1.3 10.2 / 6.2 39.3 5# 瑶曲 页岩 28.6 0.8 15.4 / / / / 34.1 6# 瑶曲 页岩 21.4 0.5 5.5 / / 20.8 / 29.2 BI=石英含量/(石英含量+碳酸盐岩含量+黏土含量) 
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表 2 页岩孔隙测试方法比较
Table 2. Pore test methods comparison
方法 样品质量 样品尺寸 测试范围 孔隙有效测试范围 测试时间 MIP 1~2g 小于$φ$10.0mm×H15mm 3nm~400μm 100nm~100μm 1 h GA 3~8g 小于$φ$6mm×H6mm 0.5~400nm 2~50nm 11 h LFNMR 1~2g 小于$φ$25mm×H30mm 2nm~100μm 2nm~10μm 10min NMRC 1~2g 小于$φ$10mm×H25mm 2nm~1μm 2~100nm 3 h
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