石油地质气相色谱及气相色谱-质谱实验室比对结果评价

魏彩云; 马行陟; 胡国艺; 许怀先; 柳少波; 魏金红; 翁娜; 吕玥

doi:10.11781/sysydz202303528

石油地质气相色谱及气相色谱-质谱实验室比对结果评价

doi: 10.11781/sysydz202303528

魏彩云^1,,
马行陟^1, ,,
胡国艺^{1, 2},
许怀先^{1, 2},
柳少波^{1, 2},
魏金红^{1, 2},
翁娜¹,
吕玥¹

1.
中国石油勘探开发研究院, 北京 100083
2.
石油地质勘探专业标准化委员会, 北京 100083

基金项目:

中国石油天然气股份有限公司科技项目 2021DJ0604

中国石油天然气股份有限公司科技项目 2021DJ0107

详细信息

作者简介:
魏彩云(1971—)，女，高级工程师，从事石油地质实验分析。E-mail: cywei@petrochina.com.cn

通讯作者:
马行陟(1984-), 男, 高级工程师, 从事油气地质综合研究。E-mail: maxingzhi@petrochina.com.cn

中图分类号: TE135
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出版历程
- 收稿日期: 2022-12-27
- 修回日期: 2023-04-19
- 刊出日期: 2023-05-28

Evaluation of laboratory comparison results of GC and GC-MS in petroleum geology industry

WEI Caiyun^1
,,
MA Xingzhi^{1
, ,},
HU Guoyi^{1, 2},
XU Huaixian^{1, 2},
LIU Shaobo^{1, 2},
WEI Jinhong^{1, 2},
WENG Na¹,
LÜ Yue¹

1.
Research Institute of Petroleum Exploration & Development, PetroChina, Beijing 100083, China
2.
Standardization Committee of Petroleum Geological Exploration, Beijing 100083, China

摘要

摘要: 为了解全国石油地质行业气相色谱及气相色谱—质谱实验室间的检测能力，提高检测水平，促进行业间交流，由石油地质勘探专业标准化委员会牵头，组织全国石油地质相关实验室开展了比对工作。气相色谱及气相色谱—质谱分析测试比对共有全国23家实验室参与，选取全油、饱和烃和芳烃3类样品，根据相关标准规定了统一的实验方法，利用四分位数稳健统计方法评价了各实验室数据质量。结果表明，各实验室数据稳定、可信，分析结果的重复性和再现性良好。气相色谱全油轻烃比对参数合格率为95%，饱和烃和芳烃参数合格率均为97%；气相色谱—质谱比对饱和烃参数合格率100%，芳烃参数合格率为95%，总体满意率较高。部分实验室相关参数出现问题数据及离群值主要原因与样品储存条件、保存时间、仪器型号、测试方法以及人员操作误差等相关，建议各实验室加强质量管控措施，进一步提升实验室气相色谱及气相色谱—质谱检测能力水平。
- 色谱—质谱 /
- 色谱 /
- 全油 /
- 饱和烃 /
- 芳烃 /
- 比对结果
Abstract: In order to learn about the detection capability of GC (gas chromatography) and GC-MS (gas chromato-graphy-mass spectrometry) laboratories in the petroleum geology industry of China, improve the detection level of the laboratories and promote inter-industry exchanges, the Standardization Committee of Petroleum Geological Exploration organized a comparison study among the petroleum geology laboratories throughout the country. A total of 23 laboratories participated in this study. Total hydrocarbons, saturated hydrocarbon and aromatic hydrocarbon samples were selected, and the experimental method was specified according to relevant standards. The data quality of each laboratory was evaluated using the quartile robust statistical method. The results show that the data of the laboratories are stable and reliable, and the analysis results have good repeatability and reproducibility. The qualification rate of total hydrocarbons light hydrocarbon ratio parameters of GC is 95%, and the qualification rate of saturated hydrocarbon and aromatic hydrocarbon parameters is 97%. The qualification rate of saturated hydrocarbon parameters of GC-MS is 100%, and the qualification rate of aromatic parameters is 95%. The overall satisfaction rate is high. The main reasons for the problematic data and outliers of relevant parameters of some laboratories are the storage conditions, storage time, instrument model, test method, personnel operation errors, etc. It is suggested that the laboratories should strengthen quality control measures to further improve the GC and GC-MS detection capabilities.
- GC-MS /
- GC /
- total hydrocarbons /
- saturated hydrocarbon /
- aromatic hydrocarbon /
- comparison results

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图 1 气相色谱峰不同峰形的积分方式

Figure 1. Integration methods for different GC peak shapes

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图 2 各实验室全油轻烃气相色谱Z值

Figure 2. GC Z values of whole oil light hydrocarbon

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图 3 各实验室饱和烃气相色谱Z值

Figure 3. GC Z values of saturated hydrocarbon

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图 4 各实验室芳烃气相色谱Z值

Figure 4. GC Z values of aromatic hydrocarbon

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图 5 各实验室饱和烃气相色谱—质谱Z值

Figure 5. GC-MS Z values of saturated hydrocarbon

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图 6 各实验室芳烃气相色谱—质谱Z值

Figure 6. GC-MS Z values of aromatic hydrocarbon

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图 7 各气相色谱及气相色谱—质谱实验室所用的气相色谱仪器品牌统计

Figure 7. Brands of the GC and GC-MS instruments of the laboratories

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图 8 各气相色谱及气相色谱—质谱实验室实验操作人员情况

Figure 8. Operators of the GC and GC-MS laboratories

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表 1 用于石油地质气相色谱及气相色谱—质谱实验室比对的样品情况

Table 1. Samples for laboratory comparison of GC and GC-MS in petroleum geology industry

序号	地区	井号	层位	样品
1	塔里木盆地	大宛126	康村组(N_1-2k)	原油
2	柴达木盆地	狮45	干柴沟组(E₃²)	饱和烃
3	柴达木盆地	狮45	干柴沟组(E₃²)	芳烃

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表 2 石油地质气相色谱及气相色谱—质谱实验室比对样品均匀性验证结果

Table 2. Uniformity verification of samples for laboratory comparison of GC and GC-MS in petroleum geology industry

样品	参数	统计量F	临界值Fα
原油轻烃	正庚烷值I₅	1.118 660	3.682
原油轻烃	异庚烷值I₆	0.196 993	3.682
饱和烃	P_r/P_h	0.028 250	3.682
饱和烃	CPI	0.472 700	3.682
芳烃	MNR	1.134 528	3.682
芳烃	MPI	0.446 326	3.682

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表 3 气相色谱检测条件

Table 3. GC detection conditions

项目	参考标准	检测条件
原油轻烃气相色谱	《石油和沉积有机质烃类气相色谱分析方法：SY/T 5779—2008》^[19]	色谱柱：HP-PONA柱(50 m×0.2 mm×0.5 μm)。进样口：进样量为0.1 μL，分流进样(150∶1)，温度300 ℃，载气流速1 mL/ min。程序升温：初温35 ℃，保持5 min，以1 ℃/min升至70 ℃，再以4 ℃/min升至310 ℃，保持30 min。检测器：温度320 ℃，氢气流量为40 mL/min，空气流量为400 mL/min，尾吹气流量为25 mL/min。
饱和烃气相色谱	《石油和沉积有机质烃类气相色谱分析方法：SY/T 5779—2008》^[19]	色谱柱：DB-5或HP-5柱(60 m×0.25 mm×0.25 μm)。进样口：进样量为2 μL，分流进样(5∶1)，温度300 ℃，载气流速1 mL/min。程序升温：初温80 ℃，保持2 min，以5 ℃/min升至310 ℃，保持30 min。检测器：温度320 ℃，氢气流量为40 mL/min，空气流量为400 mL/min，尾吹气流量为25 mL/min。
芳烃气相色谱	《石油和沉积有机质烃类气相色谱分析方法：SY/T 5779—2008》^[19]	色谱柱：DB-5或HP-5柱(60 m×0.25 mm×0.25 μm)。进样口：进样量为2 μL，不分流进样，温度300 ℃，载气流速1 mL/min。程序升温：初温60 ℃，以4 ℃/min升至310 ℃，保留30 min。检测器：温度320 ℃，氢气流量为40 mL/min，空气流量为400 mL/min，尾吹气流量为25 mL/min。

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表 4 气相色谱—质谱检测条件

Table 4. GC-MS detection conditions

项目	参考标准	检测条件
饱和烃气相色谱—质谱	《气相色谱—质谱法测定沉积物和原油中生物标志物：GB/T 18606—2017》^[20]	色谱柱：DB-5MS或HP-5MS柱(60 m×0.25 mm×0.25 μm) 进样口：进样量为1 μL，不分流进样，进样口温度300 ℃，载气流速为1.0 mL/min。程序升温：初温为60 ℃，然后以6 ℃/min的速度升至260 ℃，再以1.5 ℃/min升至320 ℃，保留20 min。质谱部分：EI电离源，离子源温度为250~310 ℃，电离电压为70 eV。
芳烃气相色谱—质谱	《气相色谱—质谱法测定沉积物和原油中生物标志物：GB/T 18606—2017》^[20]	色谱柱：DB-5MS或HP-5MS柱(60 m×0.25 mm×0.25 μm) 进样口：进样量为1 μL，不分流进样，进样口温度300 ℃，载气流速为1.0 mL/min。程序升温：初温为60 ℃，然后以3 ℃/min的速度升至320 ℃，保留20 min。质谱部分：EI电离源，离子源温度为250~310 ℃，电离电压为70 eV。

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表 5 各实验室气相色谱检测参数平均值

Table 5. Average values of GC detection parameters of the laboratories

实验室代码	全油轻烃参数平均值		饱和烃参数平均值		芳烃参数平均值
实验室代码	甲基环己烷指数I₁	正庚烷值I₅	C_(21+22)/C_(28+29)	Pr/Ph	MNR	MPI
1	52.92	24.67	2.351 4	0.422 6	1.836 5	0.946 7
2	52.19	25.00			1.627 5	0.904 5
3	52.75	24.57	2.185 2	0.392 7	1.811 7	0.934 3
4	52.87	24.73	2.343 0	0.416 8	1.745 6	0.924 9
5	53.12	24.32	2.171 1	0.447 9	1.837 4	0.847 5
6	53.20	24.55	1.866 9	0.424 8	1.826 1	0.887 1
7	52.93	24.67	2.252 2	0.376 7	1.841 3	0.984 0
8	53.40	24.36	2.371 2	0.394 6	1.847 2	0.969 0
9	53.35	24.96	2.211 1	0.411 9	1.870 9	0.915 3
10	53.34	24.40	2.369 9	0.419 3	1.717 6	0.899 0
11	53.22	24.77	2.421 7	0.407 6	1.849 1	0.962 8
12	52.76	25.52	2.251 5	0.419 7
13	53.07	25.11	2.124 0	0.420 6	1.713 9	0.917 2
14	53.61	24.37	2.215 6	0.417 7	1.880 0	0.969 1
15	52.96	24.63	2.385 1	0.386 3	1.832 6	0.860 7
16	53.04	24.66	2.361 7	0.403 8	1.876 0	0.921 2
17			2.648 2	0.383 7
18	53.16	24.65	2.297 0	0.416 9
19	53.05	24.34
20	52.83	24.58	2.123 8	0.353 2	1.845 2	0.976 9
21
22	53.04	24.60	2.282 0	0.425 2	1.794 0	0.940 1
23	53.09	24.86	2.308 1	0.417 7	1.702 0	0.940 6
注：表中空白处指实验室未参与该项目比对工作，表 6同。

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表 6 各实验室气相色谱—质谱检测参数平均值

Table 6. Average values of GC-MS detection parameters of the laboratories

实验室代码	饱和烃参数平均值			芳烃参数平均值
实验室代码	C₂₁TT/C₂₃TT	Ts/(Ts+Tm)	C₃₁H22S/(22S+22R)	MDR	MPI
1	0.771 0	0.511 4	0.518 4	18.206 5	0.748 2
2	0.730 4	0.491 5	0.511 8	19.761 3	0.816 1
3	0.697 0	0.435 4	0.597 0	17.252 7	0.575 2
4	0.718 2	0.479 8	0.503 1	13.608 8	0.757 7
5	0.694 8	0.497 0	0.502 2	19.658 0	0.736 6
6	0.736 0	0.501 3	0.544 8	20.154 0	0.813 9
7	0.751 5	0.533 3	0.537 2	20.241 5	0.829 3
8
9	0.703 8	0.510 3	0.519 6	18.560 5	0.785 0
10	0.731 2	0.496 2	0.528 2	20.021 1	0.764 0
11	0.715 8	0.491 3	0.506 5	19.271 8	0.806 4
12
13	0.752 9	0.474 6	0.602 4	20.239 5	0.783 7
14	0.748 4	0.513 0	0.575 4	17.159 2	0.764 6
15	0.683 9	0.475 7	0.519 6	16.717 9	0.749 6
16	0.738 4	0.530 5	0.531 4	19.659 4	0.777 7
17	0.725 3	0.483 1	0.602 3
18	0.727 7	0.474 2	0.584 3	18.639 7	0.778 6
19	0.769 1	0.441 1	0.530 4	18.218 5	0.802 6
20	0.696 1	0.501 8	0.506 3	17.432 3	0.705 1
21	0.738 5	0.514 1	0.632 6	18.896 2	0.750 5
22	0.781 5	0.520 9	0.517 3	17.369 3	0.759 7
23	0.701 6	0.503 2	0.508 9	18.673 5	0.814 5

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表 7 剔除离群值后所有比对参数平均值

Table 7. Average values of all comparison parameters after removing outliers

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