单个油包裹体和微区沥青显微红外光谱分峰拟合技术及应用

王倩茹; 陈红汉; 胡守志; 赵玉涛; 陈慧钦

doi:10.3799/dqkx.2016.133

单个油包裹体和微区沥青显微红外光谱分峰拟合技术及应用

doi: 10.3799/dqkx.2016.133

1.
中国地质大学构造与油气资源教育部重点实验室，湖北武汉 430074
2.
中国石油天然气股份有限公司吉林油田分公司勘探开发研究院，吉林松原 138001

基金项目:

中国地质大学(武汉)教学实验室开放基金项目 skj2014001

国家重点基础研究发展计划“973”项目 2012CB214804

详细信息

作者简介:
王倩茹(1989-)，女，博士，主要从事油气成藏机理研究.E-mail：qrwang@126.com

通讯作者:
陈红汉, E-mail：hhchen@cug.edu.cn

中图分类号: P632;P575.4
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出版历程
- 收稿日期: 2016-01-10
- 刊出日期: 2016-11-15

Curve-Fitting Analysis of Micro FT-IR and Its Application on Individual Oil Inclusion and Micro-Area Bitumens

1.
Key Laboratory of Tectonics and Petroleum Resources of Ministry of Education, China University of Geosciences, Wuhan 430074, China
2.
Jilin Oil Field Exploitation Research Institute, PetroChina, Songyuan 138001, China

摘要

摘要: 针对单个油包裹体和储层沥青等结构复杂样品傅里叶变换显微红外光谱吸收峰严重重叠的问题，基于高斯、洛伦茨函数或其组合(高斯-洛伦茨)模型理论，采用显微红外分峰拟合技术，对塔中北坡顺托果勒地区单个油包裹体成熟度和储层沥青成因进行了系统分析，并取得了4点认识：(1) 通过与Pironon对合成油包裹体的峰位坐标区域化划分吸收峰对比，认为分峰拟合技术更为真实地反映各子峰的面积，而且能够识别重叠区“隐蔽”的吸收峰，有助于准确判别有机质的结构组成；(2) 高斯、洛伦茨函数或其组合(高斯-洛伦茨)模型拟合子峰时，高斯-洛伦茨函数分布拟合的吸收峰与实测光谱吻合度较高，噪音目标越低拟合效果越好，但计算耗时越长，故优选噪音目标在1~10高斯-洛伦茨函数分布拟合各子峰；(3) 结合流体包裹体系统分析和均一温度-埋藏史投影法，单个油包裹体显微红外参数(CH_2a/CH_3a、X_inc、X_std等)揭示塔中北坡顺托果勒地区存在3期油充注，分别为加里东晚期、晚海西期和喜山期；(4) 显微红外光谱定量化分析是研究储层沥青多成因化和多期次油气充注叠加作用的有效手段，分析结果说明塔中北坡顺托果勒地区储层沥青经历了生物降解、氧化降解和水洗淋滤作用.
- 显微红外光谱 /
- 分峰拟合 /
- 单个油包裹体 /
- 微区沥青 /
- 志留系 /
- 塔里木盆地 /
- 石油地质
Abstract: Curve-fitting analysis of micro FT-IR, in the theory of Gaussian, Lorentz function or their combination (Gaussian-Lorentz) model, can break through the limit of overlapping spectra resulting from complicated structures of samples (e.g. individual oil inclusion and bitumens). Hence, curve-fitting analysis of micro FT-IR was used for analyzing maturity of individual oil inclusion and the origin of bitumens in Shuntuoguole area of Tazhong northeastern slope systematically, and four conclusions have been obtained: firstly, curve-fitting analysis of micro FT-IR may be more accurate for calculating absorption peaks, and some easily neglected peaks can be detected by this method in contrast with the method of interval oriented by Pironon. Secondly, Gaussian-Lorentz fitting is more approaching to actual spectra and the lower noise level is corresponding to better fit but requiring longer computation time. As a result, Gaussian-Lorentz fitting with 1~10 noise level is preferred. Thirdly, based on inclusion system analysis and burial history projection with homogenization temperature, infrared parameters (e.g. CH_2a/CH_3a, X_inc and X_std) reveal three hydrocarbon charging events occurred, including Late Caledonian, Late Hercynian and the Himalaya. Finally, micro FT-IR is an effective means for analyzing multi-hydrocarbon charging events and complicated origin of bitumens undergoing biodegradation, oxidative degradation and water eluviation quantitatively in study area.
- micro FT-IR /
- curve-fitting analysis /
- individual oil inclusion /
- micro-area bitumen /
- the Silurian /
- Tarim basin /
- petroleum geology

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图 1 单个油包裹体显微红外光谱重叠吸收峰处理方法

据Pironon and Barres(1990)

Fig. 1. Processing method of micro FT-IR overlapping absorptive peaks for individual oil inclusion

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图 2 塔里木盆地顺9井区志留系柯坪塔格组油包裹体及其红外光谱特征

a₁.顺901井，5 301.44 m，柯坪塔格组，石英颗粒内裂纹中见油包裹体，透射光；a₂.顺901井，5 301.44 m，柯坪塔格组，石英颗粒内裂纹中见油包裹体，荧光；a₃.顺901井，5 301.44 m，柯坪塔格组，石英颗粒内裂纹中油包裹体荧光光谱；a₄.顺901井，5 301.44 m，柯坪塔格组，石英颗粒内裂纹中油包裹体显微红外光谱，A所示2 947 cm^-1处并非为波谷，B区域内并无吸收峰；b₁.顺904H井，5 369.06 m，柯坪塔格组，穿石英颗粒裂纹中见油包裹体，透射光；b₂.顺904H井，5 369.06 m，柯坪塔格组，穿石英颗粒裂纹中见油包裹体，荧光；b₃.顺904H井，5 369.06 m，柯坪塔格组，穿石英颗粒裂纹中油包裹体荧光光谱；b₄.顺904H井，5 369.06 m，柯坪塔格组，穿石英颗粒裂纹中油包裹体显微红外光谱，A所示2 947 cm^-1处并非为波谷，C处显示图 1原则所忽略的“隐蔽”吸收峰

Fig. 2. Oil inclusions and their micro FT-IR spectra of the Silurian Kepingtage Formation in well Shun 9 area, Tarim basin

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图 3 利用高斯-洛伦茨函数分布拟合的各个子峰及拟合效果

a.顺901井，5 301.44 m，柯坪塔格组，石英颗粒内裂纹中油包裹体显微红外光谱拟合效果图；b.顺904H井，5 369.06 m，柯坪塔格组，穿石英颗粒裂纹中油包裹体显微红外光谱.绿色线为拟合的子峰，红色线和蓝色线分别为实测光谱和合成光谱，两者几乎重合说明拟合效果较好，黄色线为实测光谱的二阶导数，理论上其波谷位置为吸收峰的波峰，紫色线为实测光谱与合成光谱的差值(差减光谱)

Fig. 3. Curve-fitting analysis by Gaussian-Lorentz function and its fitting effect

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图 4 储层沥青的显微红外光谱重叠谱图和分峰拟合效果

a.储层沥青显微红外光谱3 000~2 800 cm^-1重叠吸收峰；b.3 000~2 800 cm^-1重叠吸收峰拟合后的效果图，其中绿色吸收峰为拟合之后的各个子峰，蓝色吸收峰为合成光谱，基本与实测光谱(红色线)重合，黄色线为二阶导数，二阶导数波谷理论上对应实测光谱的吸收峰波峰；c.储层沥青的显微红外透射光谱

Fig. 4. Micro FT-IR spectra of bitumen in reservoir and its effect by curve-fitting analysis

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图 5 不同函数分布子峰拟合效果

红色线为样品的实测红外光谱，蓝色线为合成光谱，绿色线为拟合的子峰，黄色线为实测光谱的二阶导数，紫线为实测光谱与合成光谱的差值(差减光谱)

Fig. 5. Effect spectra by Curve-fitting analysis

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图 6 不同类型函数分布、不同噪音目标重叠峰拟合效果

Fig. 6. Fitting effect in the control of different parameters by curve-fitting analysis

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图 7 顺托果勒地区志留系柯坪塔格组油气成藏时期(以顺9井为例)

Fig. 7. Hydrocarbon charging periods of Kepingtage Formation in Shuntuoguole

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图 8 顺托果勒地区柯坪塔格组沥青的典型产状

a.顺10井，5 694.87 m，沥青顺层理分布；b.顺904H井，5 372.18 m，斑点状沥青；c.顺901井，5 301.44 m，块状沥青；d.顺9井，5 591.95 m，裂缝充填沥青；e.顺904H井，5 374.12 m，纯沥青充填于孔隙；f.顺901井，5 296.92 m，沥青零星分布于孔隙

Fig. 8. Typical occurrences of solid bitumen of Kepingtage Formation in Shuntuoguole area

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图 9 塔里木盆地顺托果勒地区志留系不同成因储层沥青显微红外光谱特征

Fig. 9. Micro FT-IR spectra characteristic of different origin of bitumens in the Silurian Kepingtage Formation, Tarim basin

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图 10 储层沥青红外参数AR_H3000-3100/AL_2800-3000与CH_2a/CH_3a强度比值

Fig. 10. Relationship between AR_H3000-3100/AL_2800-3000 and CH_2a/CH_3a of different bitumens

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表 1 不同类型函数分布的子峰属性统计

Table 1. Statistic corresponding parameters of different fitting functions

谱峰类型	中心(cm^-1)	峰高	半峰宽(cm^-1)	峰面积	噪音目标	残差	相对误差
高斯	2 849.345	0.053 8	37.949	2.173 1	1	0.002 2	0.005 0
	2 864.613	0.101 1	38.167	4.107 6	1	-0.000 2	-0.000 5
	2 902.960	0.143 8	34.013	5.206 2	1	-0.000 3	-0.000 5
	2 924.208	0.170 4	24.540	4.452 2	1	-0.000 2	-0.000 2
	2 950.833	0.198 2	41.090	8.667 2	1	0.000 4	0.000 7
	3 030.408	0.022 2	59.478	1.407 1	1	-0.002 4	-0.006 4
	2 850.535	0.059 5	35.360	2.239 4	10	0.000 7	0.001 5
	2 864.172	0.090 5	36.723	3.539 4	10	0.000 8	0.001 8
	2 898.597	0.113 1	33.366	4.017 4	10	0.001 9	0.003 9
	2 924.064	0.226 7	30.055	7.253 7	10	0.002 6	0.004 2
	2 954.583	0.177 1	36.173	6.818 6	10	0.002 8	0.005 1
	3 032.623	0.016 6	40.071	0.706 5	10	-0.003 5	-0.009 2
	2 844.340	0.022 7	52.497	1.269 7	15	-0.001 0	-0.044 1
	2 857.752	0.112 3	35.932	4.295 7	15	-0.003 2	-0.028 5
	2 905.953	0.024 5	63.609	1.659 2	15	-0.009 7	-0.395 9
	2 927.919	0.238 0	67.572	17.122 5	15	0.020 9	0.087 8
	2 957.805	0.034 6	58.145	2.144 1	15	0.016 8	0.485 5
	3 042.629	0.034 0	66.783	2.415 4	15	-0.002 3	-0.067 7
	2 818.355	0.010 9	58.472	0.675 9	20	-0.000 2	-0.018 3
	2 858.814	0.133 9	40.093	5.712 7	20	-0.001 2	-0.008 9
	2 908.349	0.056 4	53.174	3.191 3	20	-0.007 5	-0.133 0
	2 932.459	0.231 1	65.023	15.994 4	20	-0.009 8	-0.042 4
	2 964.186	0.021 2	51.444	1.161 2	20	0.014 0	0.660 3
	3 041.014	0.032 5	59.539	2.062 7	20	-0.003 4	-0.104 6
洛伦茨	2 849.805	0.076 6	29.283	3.515 6	1	-0.001 1	-0.002 5
	2 865.159	0.081 5	31.716	4.049 3	1	-0.000 3	-0.000 6
	2 897.928	0.054 6	38.640	3.301 0	1	-0.000 6	-0.001 3
	2 924.770	0.253 6	42.096	16.709 0	1	-0.000 1	-0.000 2
	2 956.152	0.134 1	31.142	6.543 2	1	-0.004 6	-0.008 6
	3 049.290	0.043 8	71.914	4.920 4	1	-0.002 6	-0.006 8
	2 852.791	0.085 8	35.911	4.815 2	10	0.000 5	0.001 2
	2 865.871	0.061 2	37.799	3.615 5	10	0.001 8	0.004 0
	2 900.611	0.060 8	38.531	3.663 1	10	-0.001 4	-0.002 9
	2 925.281	0.241 3	39.417	14.860 0	10	-0.001 4	-0.002 3
	2 955.602	0.134 8	30.679	6.466 5	10	-0.004 9	-0.009 2
	3 045.140	0.027 8	42.574	1.848 4	10	-0.004 4	-0.011 4
	2 850.675	0.074 4	27.932	3.251 2	15	-0.001 2	-0.016 1
	2 865.696	0.077 8	33.403	4.064 6	15	0.000 9	0.011 5
	2 900.234	0.058 9	39.518	3.637 1	15	-0.000 8	-0.013 6
	2 925.178	0.243 9	39.925	15.218 6	15	-0.001 9	-0.007 8
	2 956.139	0.132 7	30.050	6.241 9	15	-0.005 2	-0.039 2
	3 047.280	0.030 5	48.747	2.324 5	15	-0.004 0	-0.131 2
	2 855.444	0.108 4	34.913	5.917 2	20	-0.003 3	-0.030 2
	2 871.141	0.034 3	39.132	2.098 2	20	0.003 2	0.094 7
	2 900.667	0.056 5	38.976	3.437 8	20	0.000 1	0.001 2
	2 924.752	0.238 7	38.300	14.283 4	20	-0.002 2	-0.009 2
	2 955.416	0.138 1	31.657	6.839 0	20	-0.004 6	-0.033 5
	3 046.063	0.029 2	42.134	1.918 5	20	-0.004 7	-0.160 6
高斯-洛伦茨	2 850.190	0.076 3	32.728	3.3079	1	0.000 7	0.001 6
	2 865.969	0.081 5	33.737	3.647 7	1	0.000 6	0.001 3
	2 897.078	0.079 5	33.947	3.584 3	1	-0.000 7	-0.001 4
	2 924.370	0.243 5	35.523	11.462 2	1	0.000 2	0.000 4
	2 955.941	0.154 0	33.739	6.779 7	1	-0.001 2	-0.002 1
	3 039.386	0.023 7	55.219	1.719 9	1	-0.002 7	-0.007 1
	2 851.754	0.070 1	35.011	3.249 6	10	0.000 9	0.002 0
	2 864.191	0.074 7	37.471	3.704 4	10	0.000 8	0.001 8
	2 897.165	0.075 4	36.992	3.697 1	10	0.000 3	0.000 7
	2 924.793	0.241 0	36.565	11.672 7	10	0.001 0	0.001 7
	2 956.296	0.147 7	32.532	6.362 0	10	-0.001 9	-0.003 6
	3 038.757	0.019 6	40.722	1.054 2	10	-0.003 5	-0.009 1
	2 853.303	0.088 8	34.023	4.036 5	15	0.002 0	0.022 5
	2 868.599	0.059 9	40.111	3.213 4	15	0.003 3	0.055 1
	2 899.733	0.068 7	38.528	3.541 3	15	0.003 0	0.043 7
	2 924.922	0.236 1	37.191	11.797 3	15	0.001 8	0.007 6
	2 956.573	0.146 3	33.145	6.508 0	15	-0.001 9	-0.012 9
	3 044.623	0.024 3	41.216	1.338 8	15	-0.004 3	-0.176 9
	2 856.648	0.130 5	38.052	6.883 2	20	-0.007 6	-0.058 2
	2 914.059	0.056 4	59.676	4.715 7	20	-0.003 8	-0.067 3
	2 930.042	0.223 7	65.995	19.618 0	20	-0.008 0	-0.035 7
	2 960.401	0.034 6	57.355	2.779 9	20	0.022 3	0.644 5
	3 053.415	0.041 2	65.631	3.769 4	20	-0.002 7	-0.065 5

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表 2 两种拟合方法对红外参数结果的影响

Table 2. The differences of calculation results from above two fitting methods

	υCH_3a	υCH_2a	υCH_3s	υCH_2s	CH_2a/CH_3a	X_inc	X_std
分峰拟合	1.36	2.55	0.32	1.27	1.88	16.38	8.79
区域面积	0.56	1.31	0.10	0.45	2.34	10.67	10.25

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表 3 顺托果勒地区柯坪塔格组(S₁k)单个油包裹体显微红外光谱参数

Table 3. Micro FT-IR parameters of individual oil inclusion of Kepingtage Formation in Shuntuoguole area(S₁k)

井号	深度(m)	产状	X_inc	X_std	CH_2a/CH_3a	油包裹体均一温度(℃)	同期盐水包裹体均一温度(℃)	充注年龄(Ma)	时期
顺9	5 600.46	石英颗粒内裂纹	3.16	4.39	0.99	26.9	58.8	410.0	加里东晚期
顺9	5 599.59	石英颗粒内裂纹	3.61	4.54	1.02	23.5	61.7	403.3
顺10	5 694.27	石英颗粒内裂纹	3.60	4.53	1.29	16.4	55.3	418.2
顺10	5 693.11	石英颗粒内裂纹	3.74	4.58	1.23	16.0	54.2	415.6
顺10	5 693.11	石英颗粒内裂纹	3.98	4.66	1.20	15.6	44.8	416.9
顺10	5 693.11	石英颗粒内裂纹	4.11	4.70	1.22	19.8	70.6	408.4
顺9	5 597.27	石英颗粒内裂纹	8.31	6.10	2.15	77.8	92.5	265.1	晚海西期
顺9	5 600.46	石英颗粒内裂纹	10.64	6.88	1.62	75.9	93.8	264.7
顺9	5 600.46	穿石英颗粒裂纹	10.00	6.67	1.45	75.6	110.3	253.8
顺9	5 600.46	穿石英颗粒裂纹	10.21	6.74	1.86	82.5	108.2	256.2
顺9	5 597.95	石英颗粒内裂纹	12.15	7.38	1.78	65.6	90.6	272.3
顺10	5 694.27	石英颗粒内裂纹	9.59	6.53	1.63	79.5	102.3	270.5
顺10	5 694.27	穿石英颗粒裂纹	10.40	6.80	1.63	83.8	106.7	254.8
顺901	5 497.00	石英颗粒内裂纹	7.17	5.72	1.67	79.1	102.4	260.0
顺901	5 497.00	穿石英颗粒裂纹	10.50	6.83	1.93	84.6	112.5	252.0
顺901	5 497.00	穿石英颗粒裂纹	11.46	7.15	1.71	83.9	110.3	253.1
顺902H	5 301.62	石英颗粒内裂纹	9.94	6.65	1.62	75.4	96.5	265.4
顺902H	5 301.62	石英颗粒内裂纹	11.97	7.32	1.78	68.7	89.4	268.7
顺9	5 600.46	穿石英颗粒裂纹	14.85	8.28	1.66	97.3	126.2	10.2	喜山期
顺9	5 597.95	穿石英颗粒裂纹	16.36	8.79	2.04	99.0	130.0	8.4
顺9	5 599.59	穿石英颗粒裂纹	17.79	9.26	2.00	101.5	127.7	9.6
顺9	5 600.46	石英颗粒内裂纹	18.72	9.57	2.39	96.5	125.4	9.9

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表 4 顺托果勒地区志留系柯坪塔格组(S₁k)沥青显微红外光谱数据

Table 4. Micro FT-IR parameters of bitumens in Kepingtage Formation (S₁k)

井号	深度(m)	沥青产状	AR_H3000-3100/AL_2800-3000	X_inc	X_std	CH_2a/CH_3a
顺9	5 336.56	块状沥青	0.00	17.10	9.03	1.98
顺9	5 336.56	块状沥青	0.00	14.37	8.12	1.89
顺901	5 516.19	块状沥青	0.00	22.31	10.77	3.89
顺901	5 298.56	块状沥青	0.00	12.94	7.65	1.70
顺901	5 294.78	顺层理分布	0.16	0.88	3.63	3.04
顺901	5 294.78	顺层理分布	0.05	12.24	7.41	2.19
顺902H	5 517.07	块状沥青	0.02	13.61	7.87	2.05
顺902H	5 527.28	块状沥青	0.05	13.15	7.72	2.00
顺902H	5 527.28	块状沥青	0.04	9.22	6.41	1.65
顺902H	5 527.28	块状沥青	0.07	7.54	5.85	1.69
顺902H	5 517.07	块状沥青	0.04	6.78	5.59	1.71
顺902H	5 543.05	块状沥青	0.05	5.84	5.28	1.73
顺902H	5 527.28	块状沥青	0.07	4.90	4.97	1.48
顺902H	5 543.05	块状沥青	0.05	4.82	4.94	1.66
顺902H	5 543.05	块状沥青	0.08	4.71	4.90	1.71
顺902H	5 527.28	块状沥青	0.08	4.54	4.85	1.33
顺903H	5 590.88	块状沥青	0.04	15.17	8.39	2.17
顺903H	5 590.88	块状沥青	0.05	12.95	7.65	2.43
顺903H	5 590.88	块状沥青	0.07	8.78	6.26	1.63
顺903H	5 590.88	块状沥青	0.00	19.58	9.86	2.51
顺903H	5 590.88	块状沥青	0.00	17.02	9.01	2.34
顺904H	5 372.18	斑点状沥青	0.00	20.36	10.12	2.00
顺904H	5 577.10	块状沥青	0.00	15.81	8.60	1.77
顺10	5 694.87	顺层理分布	0.11	7.25	5.75	1.66
顺10	5 689.00	顺层理分布	0.07	2.34	4.11	1.45

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