Preparation of Reference Materials for Rock Evaluation of Mudstone
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摘要:
岩石热解作为一项油气地球化学检测分析技术，广泛应用于油气勘探，在评价烃源岩生烃潜力和储集岩含油性识别等方面具有快速、经济和有效的特点。岩石热解标准物质用于岩石热解仪的校准和质量监控，以及定量计算烃源岩和储集岩岩石热解分析参数的关键物质基础。目前，岩石热解标准物质相对匮乏，现场录井岩石热解测试中大部分采用量值传递样品进行仪器校准和质量控制，给数据质量带来的一定的不确定性。同时，中国岩石热解标准物质缺少烃源岩评价的重要参数S4，国外岩石热解标准物质只有一个量值不能进行梯度标定，因此无法满足油气勘探中岩石热解分析技术应用和发展需求。鉴于此，本文按照国家标准物质研究标准和规范，研制了5个岩石热解标准物质GBW(E)070323、GBW(E)070324、GBW(E)070325、GBW(E)070326、GBW(E)070327。候选物样品采自鄂尔多斯盆地三叠系延长组、二叠系山西组、太原组和石炭系本溪组的暗色泥岩、油页岩、炭质泥岩。候选物样品经过挑选、杂质处理、颚式破碎、球磨机细磨、粉末过筛200目、混匀机混匀、60Co照射消毒灭菌、均匀性初检合格后封瓶编号。每个候选物随机抽取5×30瓶样品进行均匀性检验，F实测值均小于F0.05(29，60)，样品各组内和组间无显著系统差异，均匀性良好。采用直线拟合法进行短期稳定性和长期稳定性检验，拟合直线斜率|b1|＜t0.05×S(b1)，稳定性良好。由8家实验室采用岩石热解分析方法进行协作定值，全部定值分析数据符合正态分布，得到定值结果和相应的不确定度，定值参数为S2、Tmax、S4和参考值S1，其中S2量值范围为2.01~11.90mg/g，Tmax量值范围为437~442℃，S4量值范围为9.5~29.9mg/g，各参数量值呈一定梯度，基本覆盖了常规热解分析含量范围。该系列标准物质能满足石油勘探常规油气测试的质量控制的需求。
Abstract:BACKGROUND As an oil and gas geochemical detection and analysis technology, rock pyrolysis is widely used in oil and gas exploration. Moreover, this technology is fast, economical, and effective in evaluating the hydrocarbon-generating potential of source rocks and identifying the oiliness of reservoir rocks. Rock pyrolysis standard materials are used for the calibration and quality monitoring of rock pyrolysis instruments, as well as being the key material basis for quantitative calculation of rock pyrolysis analysis parameters for source and reservoir rocks. At present, rock pyrolysis standard materials are relatively scarce, and most of the on-site mud logging rock pyrolysis tests use value transfer samples for instrument calibration and quality control, which brings uncertainties to data quality. At the same time, the rock pyrolysis standard material in China lacks the important parameter S4 for source rock evaluation, while the rock pyrolysis standard material in foreign countries has only one value and cannot be used for gradient calibration. Therefore, it cannot meet the application and development requirements of rock pyrolysis analysis technology in oil and gas exploration.
OBJECTIVES To develop five kinds of reference materials for rock pyrolysis, with a certain gradient value of each parameter, which can satisfy the needs of conventional oil and gas testing in petroleum exploration.
METHODS Candidate samples were collected from dark mudstone, oil shale and carbonaceous mudstone in the Triassic Yanchang Formation, Permian Shanxi Formation, Taiyuan Formation and Carboniferous Benxi Formation in the Ordos Basin. After impurity treatment, jaw crushing, ball mill fine grinding, powder sieving 200 mesh, mixer mixing, 60Co irradiation disinfection and sterilization, and passing the preliminary homogeneity test, the samples were packed and numbered.
RESULTS For each candidate, 5×30 bottles of samples were randomly selected for uniformity testing, and the measured values of F were all less than F0.05(29, 60). There was no significant systematic difference within and between groups of samples, and the uniformity was good. Short-term stability and long-term stability were tested by the straight line fitting method, and the slope of the fitting line |b1| < t0.05·S(b1), had good stability. Eight laboratories adopted the rock pyrolysis analysis method for collaborative determination. All of the determination analysis data conformed to the normal distribution, and the determination results and corresponding uncertainties were obtained. The fixed value parameters are S2, Tmax, S4 and reference value S1, wherein the value range of S2 is 2.01-11.90mg/g, the value range of Tmax is 437-442℃, the value range of S4 is 9.5-29.9mg/g.
CONCLUSIONS In accordance with the national standard material research standards and specifications, five reference materials for rock pyrolysis, GBW(E)070323, GBW(E)070324, GBW(E)070325, GBW(E)070326 and GBW(E)070327, were successfully developed. The value of each parameter presents a certain gradient, which basically covers the content range of conventional pyrolysis analysis.
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Key words:
- mudstone /
- reference materials /
- rock pyrolysis analysis /
- standard value /
- certified value parameter
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表 1 候选物均匀性检验结果
Table 1. Homogeneity test results for the candidate materials
候选物编号 参数 平均值
(x)标准偏差
(S)相对标准偏差
RSD (%)单元间方差
(S12)单元内方差
(S22)F实测值 RJ1 S1 (mg/g) 0.16 0.0072 4.59 0.0001 0.00004 1.74 S2 (mg/g) 1.99 0.0270 1.36 0.0008 0.0007 1.04 Tmax (℃) 440 0.9934 0.23 1.0973 0.9333 1.18 S4 (mg/g) 9.25 0.1802 1.95 0.0337 0.0319 1.05 RJ2 S1 (mg/g) 0.64 0.0121 1.89 0.0002 0.0001 1.43 S2 (mg/g) 3.59 0.0701 1.95 0.0052 0.0048 1.09 Tmax (℃) 442 1.2492 0.28 1.5709 1.5556 1.01 S4 (mg/g) 17.07 0.2000 1.30 0.0614 0.0438 1.40 RJ3 S1 (mg/g) 0.17 0.0085 5.03 0.0001 0.0001 1.47 S2 (mg/g) 5.69 0.0584 1.03 0.0038 0.0032 1.19 Tmax (℃) 436 0.6800 0.16 0.5686 0.4111 1.38 S4 (mg/g) 15.01 0.4244 2.83 0.1268 0.2509 0.62 RJ4 S1 (mg/g) 0.33 0.0213 6.35 0.0005 0.0004 1.05 S2 (mg/g) 7.37 0.0841 1.14 0.0082 0.0065 1.27 Tmax (℃) 441 0.8244 0.19 0.7295 0.6556 1.11 S4 (mg/g) 12.05 0.3805 3.16 0.1107 0.1613 0.69 RJ5 S1 (mg/g) 1.84 0.0105 6.63 0.5504 0.8365 1.36 S2 (mg/g) 11.73 0.2212 1.89 0.0576 0.0447 1.29 Tmax (℃) 441 0.922 0.21 1.0456 0.7556 1.38 S4 (mg/g) 29.66 0.6478 2.18 0.4381 0.4106 1.07 
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表 2 候选物长期稳定性检验结果
Table 2. Long-term stability test results for the candidate materials
候选物编号 定值参数 平均值
(x)标准偏差
(S)相对标准偏差
RSD (%)b1 t0.05×S(b1) RJ1 S1 (mg/g) 0.17 0.009 5.37 -0.0004 0.0018 S2 (mg/g) 2.00 0.0683 3.42 -0.0035 0.0215 Tmax (℃) 441 0.854 0.19 0.0238 0.2257 S4 (mg/g) 9.26 0.2674 2.89 0.0194 0.0601 RJ2 S1 (mg/g) 0.63 0.0161 2.55 -0.0001 0.0057 S2 (mg/g) 3.45 0.1216 3.53 -0.0234 0.0508 Tmax (℃) 441 0.7696 0.17 -0.0357 0.2244 S4 (mg/g) 17.08 0.1508 0.88 0.0133 0.0403 RJ3 S1 (mg/g) 0.17 0.0125 7.60 0.0007 0.0049 S2 (mg/g) 5.69 0.0730 1.28 0.0059 0.0218 Tmax (℃) 437 0.8239 0.19 0.0357 0.1871 S4 (mg/g) 15.19 0.2319 1.53 0.0093 0.0376 RJ4 S1 (mg/g) 0.34 0.0198 5.86 -0.0013 0.0074 S2 (mg/g) 7.32 0.1523 2.08 0.001 0.0373 Tmax (℃) 440 0.9542 0.22 0.0357 0.2133 S4 (mg/g) 12.18 0.2012 1.65 -0.013 0.0268 RJ5 S1 (mg/g) 1.83 0.1181 6.45 0.0074 0.0275 S2 (mg/g) 11.98 0.23 1.92 -0.018 0.0506 Tmax (℃) 442 0.9927 0.22 -0.0536 0.2624 S4 (mg/g) 29.4 0.6 2.04 -0.0435 0.2434
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表 3 标准物质定值结果及扩展不确定度
Table 3. Certified values and expanded uncertainties of the reference materials
样品编号 液态烃S1参考值(mg/g) 热解烃S2标准值及不确定度(mg/g) 最高热解峰温度Tmax标准值及不确定度(℃) 残余有机碳S4标准值及不确定度(mg/g) GBW(E)070323(RJ1) (0.16) 2.01±0.21 440±2 9.5±0.8 GBW(E)070324(RJ2) (0.62) 3.70±0.40 442±2 17.7±1.4 GBW(E)070325(RJ3) (0.16) 5.85±0.50 437±2 15.5±1.3 GBW(E)070326(RJ4) (0.31) 7.39±0.50 440±2 12.5±1.2 GBW(E)070327(RJ5) (1.81) 11.90±0.80 441±2 29.9±3.0
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表 4 标准物质验证结果
Table 4. Verification results of the reference materials
样品编号 S2(mg/g) Tmax(℃) S4(mg/g) 实测值 标准值及不确定度 实测值 标准值及不确定度 实测值 标准值及不确定度 GBW(E)070323
(RJ1)1.91 2.01±0.21 441 440±2 9.30 9.5±0.8 GBW(E)070324 (RJ2) 3.58 3.70±0.40 443 442±2 17.25 17.7±1.4 GBW(E)070325 (RJ3) 5.74 5.85±0.50 437 437±2 15.21 15.5±1.3 GBW(E)070326 (RJ4) 7.26 7.39±0.50 442 440±2 12.04 12.5±1.2 GBW(E)070327 (RJ5) 12.15 11.90±0.80 441 441±2 29.33 29.9±3.0
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