Micropore Structure Evolution of Organic Matters in Coal Measures due to Bioconversion Using FE-SEM, HIP and N2 Adsorption Experiments
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摘要: 微生物降解前后的煤系有机岩（煤岩和泥页岩）储层微观孔隙结构的变化对生物成气和成藏过程具有重要的意义.利用场发射扫描电子显微镜、高压压汞仪、孔比表面积孔隙度分析仪以及分形维数理论对厌氧微生物降解前后的煤系有机岩样品储层孔隙结构演化进行分析，根据孔隙结构特征并结合微生物生态学特征，将生物气化煤系有机岩的孔隙结构类型分为3类，即孔隙直径大于5 μm的微米孔，孔隙直径介于5 μm~100 nm的微纳孔，以及孔隙直径小于100 nm大于2 nm的纳米孔.微生物作用后的煤岩与泥页岩的微米孔孔容增加，微纳孔和纳米孔孔容减小，孔隙比表面积降低，平均孔隙直径增大.分形维数对比结果表明受微生物作用的煤岩与泥页岩样品的面分形维数（D1）和孔隙结构分形维数（D2）均降低，微生物作用使得有机岩孔隙表面变的光滑，孔隙结构变得简单，有利于游离气的运移和富集.Abstract: Micropore structure characterization of organic matters in the coal measures due to bioconversion is of great significance in understanding reservoir reformation by microorganism and revealing the storage and enrichment mechanism of biogenic gas in the coal measures. Pore structure evolution of organic matters in the coal measures degraded by microbe was analyzed using field emission scanning electron microscopy (FE-SEM), high-pressure mercury intrusion porosimetry (MIP), low-pressure N2 gas adsorption pycnometry and fractal dimension FHH theory in this study. Considering the measuring range of pore size distribution (PSD) and combining the characteristics of microbial ecology, the pore structure type of coal and shale in coal measures is divided into three types. They are micropore (PSD>5 μm), micro-nanopore (5 μm-100 nm), and nanopore (2-100 nm). The PSD and micropore pore volume (PV) of coal and shale samples increase, and the specific surface area (SSA) and micro-nanopore and nanopore PV decrease after bioconversion. The surface fractal diameter (D1) and pore structure fractal diameter (D2) of coal and shale samples decrease after bioconversion, showing that the inner surface of pore becomes smooth and pore structure gets simple due to microbial action. The reformation of pore structure due to bioconversion is benefitial to the migration and enrichment of free gas in the coal measures.
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图 1 煤系有机岩微生物降解前后FE-SEM照片
Fig. 1. FE-SEM micrograph of coal and mudstone effected with microbe
图 2 由高压压汞实验测得的孔隙直径与孔隙分布频率（a）和孔容（b）相互关系
Fig. 2. Relationships between PSD and pore frequency (a), as well as PV (b) determined from MIP method
图 3 根据IUPAC分类的吸附等温线类型（a）与滞留环类型（b）
Fig. 3. Sorption isotherm types (a) and hysteresis loops (b) according to IUPAC classifications
图 4 由低压氮气吸附实验测得的煤与泥页岩吸附-解吸曲线
Fig. 4. N2 adsorption-desorption isotherms of coal and shale samples
图 5 由低压氮气吸附实验测得的孔隙直径与孔容相互关系
Fig. 5. PSD calculated by N2 adsorption branch for coal and shale samples
图 6 由氮气吸附等温线重构的lnV与ln(lnP0/P)关系
Fig. 6. Plots of lnV vs. ln(lnP0/P) reconstructed from N2 adsorption isotherms
表 1 关于煤岩和泥页岩样品的基本参数和生物气化的甲烷产气率数据
Table 1. Data of coal and mudstone basic parameters and biogenic methane yields
样品编号 岩石类型 成熟度（Ro, max, %） 有机质含量（TOC, %） 甲烷产率（µmol/g） YZ-2 泥页岩 1.58 15.0 21 YZ-2-2a / 13.2 - YZM07 煤 2.50 / 150 YZM07-2a / / - 注：a为微生物降解后的样品；/为实验未测；-为无数据.在3~4个月后，甲烷生烃量达到高峰，然后甲烷生烃量迅速下降，甲烷菌开始死亡( Bao et al., 2016 ).本次试验选取123天.
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表 2 基于高压压汞和低压氮气吸附数据的孔隙分类的孔容、比表面积和孔径分布
Table 2. Pore volume (PV), specific surface area (SSA) and pore size distribution (PSD) based on pore structure classification by MIP, N2 physisorption for coal and shale samples
样品编号 岩石类型 基于MIP数据的微米孔与微纳孔 基于N2吸附的纳米孔 PV (cm3/100 g) SSA (m2/g) PSDa (µm) BJH PV (cm3/100 g) BET SSA (m2/g) DFT PV (cm3/100 g) PSDb (nm) > 5 µm 100 nm~5 µm > 100 nm 2~100 nm YZ-2 泥页岩 30.51 8.74 4.62 0.34 2.63 17.43 0.28 6.87 YZ-2-2 34.49 7.47 2.45 0.68 2.16 9.12 0.07 7.84 YZM07 煤 48.67 8.37 1.23 1.85 0.37 0.96 0.01 14.78 YZM07-2 67.40 3.79 0.74 3.85 0.36 0.80 0.006 16.20 注：aPSD为通过压汞法测得的平均孔径，bPSD为根据BJH解吸分支等温线计算得到平均孔径.
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表 3 煤岩与泥页岩高压压汞进汞率和孔容分布数据
Table 3. Data of pore frequency and pore volume based on MIP for coal and shale samples
YZ-2 YZ-2-2 YZM07 YZM07-2 孔隙直径
（nm）进汞率
（%）dV/d
(lgd)孔隙直径
（nm）进汞率
（%）dV/d
(lgd)孔隙直径
（nm）进汞率
（%）dV/d
(lgd)孔隙直径
（nm）进汞率
（%）dV/d
(lgd)206 900 0.14 0.04 206 900 0.40 0.05 223 100 0.72 0.05 204 400 0.00 0.06 126 900 3.08 0.09 126 900 4.05 0.11 130 800 3.24 0.10 133 100 3.47 0.21 92 570 5.22 0.35 92 570 4.45 0.19 83 490 4.46 0.14 95 470 6.72 0.50 78 980 9.34 0.55 78 980 3.65 0.23 71 450 1.71 0.16 72 280 11.63 0.79 66 510 9.74 0.45 66 510 4.17 0.25 54 690 3.57 0.19 57 080 12.56 0.89 53 050 9.30 0.36 53 050 6.78 0.32 46 760 2.55 0.24 47 100 10.37 0.89 44 520 6.82 0.30 44 520 6.45 0.39 41 030 2.70 0.31 39 370 9.40 0.81 38 350 4.31 0.26 38 350 6.29 0.42 36 120 3.34 0.36 34 870 5.66 0.74 33 790 3.44 0.23 33 790 5.70 0.45 32 050 3.35 0.42 30 920 5.27 0.72 30 080 2.90 0.22 30 080 5.62 0.47 28 410 4.63 0.56 27 660 4.90 0.69 27 180 2.32 0.20 27 180 4.82 0.45 25 440 5.09 0.65 24 870 4.09 0.57 24 060 2.66 0.19 24 060 5.56 0.41 23 050 5.20 0.73 22 360 3.35 0.46 21 510 2.20 0.17 21 510 4.39 0.35 21 030 5.07 0.70 20 250 2.42 0.38 19 540 1.72 0.15 19 540 3.10 0.28 19 020 4.99 0.63 18 430 2.11 0.36 17 670 1.50 0.14 17 670 2.51 0.24 17 230 4.48 0.57 16 830 1.92 0.33 16 040 1.52 0.15 16 040 2.36 0.22 15 730 3.74 0.54 15 440 1.54 0.27 14 650 1.39 0.13 14 650 1.89 0.19 14 460 3.38 0.50 14 180 1.32 0.24 13 530 1.08 0.12 13 530 1.36 0.15 13 270 2.97 0.44 13 140 0.92 0.19 12 510 0.97 0.11 12 510 1.09 0.13 12 220 2.70 0.42 12 140 0.87 0.18 11 590 0.88 0.10 11 590 1.04 0.13 11 300 2.29 0.36 11 310 0.74 0.16 10 830 0.78 0.10 10 830 0.86 0.11 10 540 1.75 0.33 10 550 0.70 0.16 10 180 0.70 0.10 10 180 0.65 0.10 9 852 1.72 0.37 9 786 0.77 0.15 9 624 0.56 0.09 9 624 0.56 0.10 9 267 1.76 0.36 9 176 0.47 0.12 9 122 0.52 0.08 9 122 0.48 0.08 8 715 1.52 0.32 8 680 0.44 0.13 8 541 0.57 0.08 8 541 0.55 0.08 8 192 1.51 0.31 8 220 0.4 0.12 8 061 0.55 0.09 8 061 0.42 0.07 7 753 1.20 0.26 7 788 0.39 0.12 7 670 0.53 0.10 7 670 0.37 0.07 7 366 0.92 0.25 7 418 0.33 0.12 7 299 0.52 0.09 7 299 0.34 0.08 7027 0.88 0.25 7 036 0.40 0.11 6 874 0.63 0.09 6 874 0.52 0.08 6 626 1.06 0.23 6 690 0.32 0.10 6 463 0.56 0.08 6 463 0.47 0.08 6 238 1.08 0.23 6 327 0.32 0.09 6 128 0.45 0.08 6 128 0.45 0.08 5 909 0.88 0.21 5 999 0.29 0.09 5 839 0.42 0.07 5 839 0.45 0.08 5 568 0.87 0.17 5 691 0.28 0.08 5 507 0.42 0.06 5 507 0.39 0.05 4 434 2.47 0.14 5 146 0.31 0.05 4 443 1.15 0.05 4 443 0.88 0.04 2 748 4.58 0.10 3 600 1.03 0.05 2 868 2.61 0.05 2 868 1.81 0.04 1 248 3.99 0.05 1 881 1.72 0.04 1 420 3.87 0.05 1 420 2.70 0.04 49 2.21 0.02 770 1.37 0.02 568.8 4.39 0.04 569 4.11 0.05 236 0.77 0.01 349 0.64 0.01 259.4 3.07 0.03 259 3.56 0.04 142 0.26 0.01 201 0.24 0.01 149.3 1.49 0.02 149 1.69 0.02 96 0.10 0.00 134 0.13 0.00 99.63 0.89 0.02 100 0.79 0.02 71 0.01 0.00 98 0.04 0.00 72.85 0.67 0.02 73 0.47 0.01 56 0.00 0.00 76 0.02 0.00 56.92 0.46 0.02 57 0.33 0.01 50 0.00 0.00 61 0.00 0.00 50 0.35 0.02 50 0.24 0.01 50 0.00 0.00
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表 4 基于FHH模型计算微生物降解前后煤与泥页岩的分形维数结果
Table 4. Fractal dimensions derived from fractal FHH model
样品编号 P/P0=0~0.5 P/P0=0.5~1.0 吸附/脱附曲线类型a A1 D1 相关系数(R2) A2 D2 相关系数(R2) YZ-2 －0.225 4 2.774 6 0.995 3 －0.363 9 2.636 1 0.996 0 A类 YZ-2-2 －0.309 2 2.690 8 0.992 7 －0.482 4 2.517 6 0.999 6 A类 YZM07 －0.462 5 2.537 5 0.997 6 －0.393 4 2.606 6 0.988 1 A类 YZM07-2 －0.486 6 2.513 4 0.997 8 －0.442 0 2.558 0 0.992 7 A类 注：a存在吸附滞留环的A类与可逆等温线-不存在吸附滞留环的B类分类标准均为基于N2吸附脱附曲线数据所得.
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