N2-CH4（CO2）混合气体在线标样制备及其拉曼定量因子测定

席斌斌; 施伟军; 蒋宏; 钱一雄

N₂-CH₄（CO₂）混合气体在线标样制备及其拉曼定量因子测定

中国石化石油勘探开发研究院无锡石油地质研究所, 中国石化油气成藏重点实验室, 江苏无锡 214151

基金项目: 中国石油化工股份有限公司科技攻关项目（P12009）

详细信息

作者简介: 席斌斌, 工程师, 研究方向为流体包裹体地质学.E mail:xibb.syky@sinopec.com

中图分类号: P571;P575.4

收稿日期: 2013-12-09

修回日期: 2014-07-18

录用日期: 2014-07-28

刊出日期: 2014-05-25

Synthesis of N₂-CH₄ and N₂-CO₂ Gas Mixtures as an Online Standard and Determination of Their Raman Quantification Factors of CH₄ and CO₂

Wuxi Research Institute of Petroleum Geology, SINOPEC, Wuxi 214151, China

Received Date: 09 December 2013

Revised Date: 18 July 2014

Accepted Date: 28 July 2014

Publish Date: 25 May 2014

摘要

摘要:
利用混合气体的标准样品对激光拉曼探针进行标定, 可以快速准确地对包裹体中的无机及有机气相组分进行定量分析。而常用的商用钢瓶装混合气体标样, 存在费用高、气体组成单一固定等缺点。本文设计了一套在线标样制备装置, 提出一种在线配置不同浓度和压力条件下混合气体标样的方法。利用高纯度（纯度>99.999%）的N₂、CH₄以及CO₂钢瓶气, 经过在线混合增压, 在5 MPa和10 MPa条件下制备了N₂摩尔浓度为30%、50%和70%的N₂-CH₄以及N₂-CO₂混合气体在线标样。该方法制备的标样与70%N₂+30%CO₂的商用钢瓶气标样对比表明, CO₂与N₂的拉曼相对峰高以及相对峰面积值的误差在4%以内, 具有较高的准确度和重现性。通过不同压力和浓度条件下CH₄以及CO₂的拉曼相对定量因子测定表明, 气体的相对定量因子在5~10 MPa压力条件下与压力及组成无关。地质样品应用结果表明, 本方法可以方便、灵活、准确地按任意比例将两瓶及两瓶以上纯气体钢瓶样品进行混合及增压, 为激光拉曼标定、气体组成原位测量等提供了一种新的技术思路。
- 气体混合 /
- 激光拉曼探针 /
- 拉曼定量因子
Abstract:
Organic and/or inorganic gas composition can be measured quickly and accurately by using a Laser Raman Microprobe with an online standard of gas mixtures. The accuracy of the standard sample plays an important role in this method, but the commercial standard mixed gas cylinders are expensive with fixed composition that cannot be modified arbitrarily. A new method to synthesize the gas mixtures in different compositions under different pressures has been developed. The N₂-CH₄ and N₂-CO₂ gas mixtures with varied N₂ mol contents of 30%, 50% and 70% were synthesized. The pressure of these gas mixtures were increased to 5 and 10 MPa. Both the synthesized and commercial gas mixtures of 70% N₂ and 30% CO₂ have similar relative peak heights and peak areas of N₂ and CO₂. The error of this method is less than 4%. The Raman quantification factor of CH₄ and CO₂ are determined. In this study, the Raman quantification factor is insensitive to composition and pressure under 5 MPa and 10 MPa. This new method is relatively simple, easy and accurate, and only two or more kinds of pure gas cylinders are used to synthesize gas mixtures with different composition and under different pressure, which provides a new way for laser Raman calibration and gas composition measurement in situ.
- gas mixture /
- Laser Raman Microprobe /
- Raman quantification factor

HTML全文

图 1 在线标样制备装置简图

Figure 1.

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图 2 商用标样与在线样品拉曼谱图

Figure 2.

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图 3 N₂-CO₂以及N₂-CH₄在线混合气体拉曼谱图

Figure 3.

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图 4 CH₄-N₂拉曼参数相关图解

Figure 4.

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图 5 CO₂-N₂拉曼参数相关图解

Figure 5.

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图 6 包裹体拉曼光谱分析结果

Figure 6.

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表 1 包裹体样品分析结果

Table 1. The analytical composition of gas in fluid inclusions

包裹体	A_CO_₂	H_CO_₂	A_CH_₄	H_CH_₄	C_CH_₄(%)		C_CO_₂(%)
包裹体	A_CO_₂	H_CO_₂	A_CH_₄	H_CH_₄	据公式(3)	据公式(4)	据公式(3)	据公式(4)
包裹体a	3461.54	594.541	17891.2	4115.24	31.63	31.25	68.37	68.75
包裹体b	3137.87	732.481	14694.8	4251.27	29.54	27.60	70.46	72.40

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