灼烧法中有机质与总有机碳换算关系的重建及其在页岩分析中的应用

邱灵佳; 黄国林; 帅琴; 苏玉

doi:10.15898/j.cnki.11-2131/td.2015.02.011

灼烧法中有机质与总有机碳换算关系的重建及其在页岩分析中的应用

1.
东华理工大学化学生物与材料科学学院, 江西南昌 330013

2.
中国地质大学(武汉)材料与化学学院, 湖北武汉 430074

基金项目: 中国地质调查局油气科研专项(1211302108023-1);江西省自然科学基金项目(20132BAB203019)

详细信息

作者简介: 邱灵佳, 硕士, 主要从事页岩气有机地球化学评估研究.E-mail: Lingjiaqiu0701@sina.com

通讯作者: 黄国林, 博士, 主要从事绿色化学工艺研究.E-mail: guolinhuang@sina.com

中图分类号: P588.2

收稿日期: 2014-09-01

修回日期: 2015-03-05

录用日期: 2015-03-10

刊出日期: 2015-02-25

Reconstruction of the Conversion Relationship between Organic Matter and Total Organic Carbon in Calcination Method and Its Application in Shale Analysis

1.
Chemistry, Biology and Material Science, East China Institute of Technology, Nanchang 330013, China

2.
Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074, China

More Information

Corresponding author: HUANG Guo-lin, guolinhuang@sina.com

Received Date: 01 September 2014

Revised Date: 05 March 2015

Accepted Date: 10 March 2015

Publish Date: 25 February 2015

摘要

摘要:
有机质与总有机碳(TOC)的换算关系为w_o=1.724×w_TOC, 难以满足当前页岩气开发的现场测定要求, 需要作出修正。本文以鄂尔多斯盆地南部页岩样品为研究对象, 在传统灼烧法基础上, 采用X射线荧光光谱仪测定页岩组成, 得出影响烧失量的因素; 用热重-差热仪研究页岩灼烧情况, 确定了无机盐不分解而有机质分解的最佳灼烧温度和时间。通过线性拟合灼烧法测得的有机质含量与仪器法测得的有机碳含量间的换算关系, 建立了一种通过测定烧失量来换算总有机碳含量的新方法。在页岩最佳灼烧温度480℃, 灼烧时间1.5 h条件下线性拟合建立了两种新的换算关系, 获得TOC测定值与仪器法的标准值相对误差分别为1.691%、0.486%, 检出限分别为0.41%、1.60%。综合它们的优缺点, 可将测定页岩类样品的换算关系重建为w_o=2.125×w_TOC。重建的方法通过严格控制灼烧温度, 解决了传统灼烧法中烧失量因无机盐高温分解造成有机质代表性不足的问题, 可用于精确测定页岩中的有机质或有机碳含量。
- 页岩气 /
- 有机质 /
- 总有机碳 /
- 灼烧法 /
- 烧失量 /
- 换算系数
Abstract:
The current function relationship (w_o=1.724×w_TOC) between organic matter and total organic carbon needs a correction because it is not suitable for the new materials. As a significant index of shale gas exploitations, the determination of total organic carbon needs close attention. In this paper, a description of a modified calcination method that has been used to study samples from the south of Ordos Basin is described. X-ray Fluorescence Analysis (XRF) has been applied to determine the compositions of shale in order to reveal the factor controlling the ignition loss of the calcination method. TG-DTA analysis has been used to determine the calcination conditions, which could distinguish mineral salt whether decomposed or not. A linear relationship could be established by fitting the ignition loss value of the calcination method and standard total organic carbon value (TOC) of the CS analyzer method, which could be applied to determine TOC by the conversion relationship between loss on ignition and TOC. Results show that the best calcination temperature is 480℃, and the preferred reaction time is 1.5 h. Two function conversion relationships have been established at the above-mentioned conditions. The relative errors between values from the conversion relationship and from the equipment analysis are 1.691% and 0.486% with detection limits of 0.41% and 1.60%, respectively. The traditional conversion relationship could be corrected to w_o=2.125×w_TOC. The proposed method avoids the ignition loss in traditional calcination method that results in under-representation of organic matters for the decomposition of mineral salt at high temperature, and can precisely measure the organic matters or organic carbon in shale.
- shale gas /
- organic matter /
- total organic carbon /
- calcination method /
- loss on ignition /
- conversion factor

HTML全文

图 1 页岩样品主要组成

Figure 1.

下载: 全尺寸图片幻灯片

图 2 热重-差热分析(TG-DTA)曲线

Figure 2.

下载: 全尺寸图片幻灯片

图 3 (a)不同灼烧温度下的页岩灰分碳含量，(b)不同灼烧温度下灼烧法测定样品的有机质含量

Figure 3.

下载: 全尺寸图片幻灯片

图 4 线性拟合Ⅰ和Ⅱ：(a)有机质与TOC函数关系的线性拟合；(b)有机质与TOC线性拟合关系的验证

Figure 4.

下载: 全尺寸图片幻灯片

表 1 灼烧法与湿烧法和仪器法的比较

Table 1. A Comparison of RSD, detection limit and accuracy between calcination method, volumetric method and instrument method

测定方法	重现性RSD(%)					检出限	平均绝对误差 (%)
测定方法	1-Y1	1-Y2	1-Y3	1-Y4	平均值	(%)	平均绝对误差 (%)
灼烧法	1.038	0.657	3.667	3.432	2.198	0.41(拟合Ⅰ) 1.60(拟合Ⅱ)	1.686
湿烧法仪器法	5.763 1.635	1.897 2.411	3.846 1.933	3.995 1.755	3.875 1.934	0.26 0.643	2.790 1.397

下载: 导出CSV

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