甾烷和藿烷的国产X型分子筛分离制备实验研究

李二庭; 向宝力; 李际; 迪丽达尔·肉孜; 王汇彤; 马万云; 刘翠敏; 张晓刚

doi:10.11781/sysydz202104713

甾烷和藿烷的国产X型分子筛分离制备实验研究

doi: 10.11781/sysydz202104713

李二庭^{1, 2,},
向宝力^{1, 2},
李际^{1, 2},
迪丽达尔·肉孜^{1, 2},
王汇彤³,
马万云^{1, 2},
刘翠敏^{1, 2},
张晓刚^{1, 2}

1.
新疆砾岩油藏实验室, 新疆克拉玛依 834000
2.
中国石油新疆油田分公司实验检测研究院, 新疆克拉玛依 834000
3.
中国石油勘探开发研究院, 北京 100083

基金项目:

新疆维吾尔自治区重点实验室开放课题 2017D04023

详细信息

作者简介:
李二庭(1988-), 男, 博士, 高级工程师, 从事油气地球化学研究工作。E-mail: lierting@petrochina.com.cn

中图分类号: TE135
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出版历程
- 收稿日期: 2020-10-27
- 修回日期: 2021-05-17
- 刊出日期: 2021-07-28

Separation of steranes and hopanes by domestic X-type molecular sieves

LI Erting^{1, 2
,},
XIANG Baoli^{1, 2},
LI Ji^{1, 2},
ROUZI Dilidaer^{1, 2},
WANG Huitong³,
MA Wanyun^{1, 2},
LIU Cuimin^{1, 2},
ZHANG Xiaogang^{1, 2}

1.
Xinjiang Laboratory of Petroleum Reserve in Conglomerate, Karamay, Xinjiang 834000, China
2.
Research Institute of Experiment and Testing, Xinjiang Oilfield Company, PetroChina, Karamay, Xinjiang 834000, China
3.
Institute of Petroleum Exploration and Development, PetroChina, Beijing 100083, China

摘要

摘要: 采用国产10X和13X型分子筛对甾烷和藿烷类生物标志物进行吸附和脱附实验，探讨两种分子筛在制备甾烷和藿烷类化合物过程中的稳定碳同位素分馏效应，为甾烷和藿烷单体化合物的分离技术提供一种可靠方法。结果表明，两种分子筛对不同类型化合物的吸附作用不同，对甾烷化合物中的5α，14α，17α-20S、5α，14β，17β-20R、5α，14β，17β-20S三种构型吸附能力最弱，其次是5α，14α，17α-20R构型的甾烷系列、β-胡萝卜烷和伽马蜡烷。13X型分子筛对藿烷组分吸附能力强于10X型分子筛，可用于藿烷类化合物的分离；而10X型分子筛对甾烷组分吸附能力强于13X型分子筛。通过控制淋洗液的用量，能够分别分离不同构型的甾烷化合物。获得的甾烷和藿烷化合物单体烃稳定碳同位素分析结果显示，分离过程中无碳同位素分馏现象，重复性非常好，说明国产10X和13X型分子筛可用于甾烷和藿烷类化合物的分离富集及其单体烃碳同位素研究。
- 分子筛 /
- 甾烷 /
- 藿烷 /
- 单体烃碳同位素 /
- 生物标志化合物 /
- 油气地球化学
Abstract: Domestic 10X-type and 13X-type molecular sieves were used for the adsorption and desorption experiments of steranes and hopanes, and their stable carbon isotopic fractionation by the two kinds of molecular sieves during separation process was discussed in detail. These two kinds of molecular sieves have various adsorption effects on different types of compounds. They both have the weakest adsorption capacities for 5α, 14α, 17α-20S steranes, 5α, 14β, 17β-20R steranes and 5α, 14β, 17β-20S steranes, followed by 5α, 14α, 17α-20R steranes, β-carotane, and gammacerane. The 13X-type molecular sieve has stronger adsorption capacity for hopanes than that of the 10X-type molecular sieve, which can be used for the separation of hopanes. The 10X-type molecular sieve has stronger adsorption capacity for steranes than that of the 13X-type molecular sieve. By controlling the amount of eluent, different configuration of steranes can be further separated. The stable carbon isotopes of steranes and hopanes showed that no carbon isotopic fractionation occurred during separation process and the repeatability was very good, indicating that domestic 10X-type and 13X-type molecular sieves can be used for steranes and hopanes separation.
- molecular sieve /
- steranes /
- hopanes /
- compound specific carbon isotope /
- biomarkers /
- petroleum geochemistry

HTML全文

图 1 国产13X型分子筛柱淋洗下不同馏分总离子流图

Figure 1. Total ion current of different fractions eluted from domestic 13X molecular sieve column

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图 2 异辛烷抽提13X分子筛残留馏分总离子流和m/z 191图

Figure 2. Total ion current and m/z 191 of residual fractions of domestic 13X molecular seive extracted by isooctane

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图 3 国产10X型分子筛柱淋洗下不同馏分总离子流图

Figure 3. Total ion current of different fractions eluted from domestic 10X molecular sieve column

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图 4 异辛烷抽提10X分子筛残留馏分色谱/质谱TIC和m/z 191图

Figure 4. Total ion current and m/z 191 of residual fractions of domestic 10X molecular seive extracted by isooctane

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图 5 国产10X型分子筛制备甾烷化合物馏分的总离子流图

Figure 5. Total ion current of steranes fraction prepared by domestic 10X molecular sieve

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表 1 国产10X型分子筛分离出的甾烷化合物单体烃碳同位素测定结果

Table 1. Carbon isotopic values of steranes separated by domestic 10X molecular sieve

样品	单体烃碳同位素δ¹³C/‰
样品	α, α, α-C₂₇S甾烷	α, β, β-C₂₇R甾烷	α, β, β-C₂₇ S甾烷	α, α, α-C₂₇ R甾烷	C₂₉ S重排甾烷	α, α, α-C₂₈ S甾烷	α, β, β-C₂₈ R甾烷	α, β, β-C₂₈ S甾烷	α, α, α-C₂₈ R甾烷	α, α, α-C₂₉ S甾烷	α, β, β-C₂₉ R甾烷	α, β, β-C₂₉ S甾烷	α, α, α-C₂₉ R甾烷	伽马蜡烷	β-胡萝卜烷
馏分1	-	-36.19	-32.88	-	-	-	-33.84	-31.31	-	-32.66	-34.64	-33.12	-	-	-
馏分2	-31.41	-34.87	-32.53	-	-33.93	-33.59	-33.19	-32.64	-33.00	-32.08	-33.50	-33.70	-	-	-
馏分3	-31.46	-34.75	-31.61	-31.95	-35.51	-34.98	-	-34.56	-30.42	-31.19	-34.00	-32.86	-29.84	-	-31.92
馏分4	-	-	-	-30.79	-	-	-	-	-30.43	-	-	-	-29.29	-36.38	-32.06
馏分5	-	-	-	-30.52	-	-	-	-	-29.96	-	-	-	-30.31	-	-32.45
馏分6	-	-	-	-29.11	-	-	-	-	-30.41	-	-	-	-30.76	-37.24	-32.00
馏分7	-	-	-	-	-	-	-	-	-	-	-	-	-	-36.77	-32.35
馏分8	-	-	-	-	-	-	-	-	-	-	-	-	-	-36.53	-31.99

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表 2 国产10X型分子筛分离出的甾烷化合物单体烃碳同位素测定结果与平均值的误差

Table 2. Error of carbon isotope measurement and average values of sterane compounds separated by domestic 10X molecular sieve

样品	单体烃碳同位素测定结果与平均值的误差/‰
样品	α, α, α-C₂₇S甾烷	α, β, β-C₂₇R甾烷	α, β, β-C₂₇ S甾烷	α, α, α-C₂₇ R甾烷	C₂₉ S重排甾烷	α, α, α-C₂₈ S甾烷	α, β, β-C₂₈ R甾烷	α, β, β-C₂₈ S甾烷	α, α, α-C₂₈ R甾烷	α, α, α-C₂₉ S甾烷	α, β, β-C₂₉ R甾烷	α, β, β-C₂₉ S甾烷	α, α, α-C₂₉ R甾烷	伽马蜡烷	β-胡萝卜烷
馏分1	-	-	0.54	-	-	-	-0.31	-1.60	-	0.66	0.54	-0.10	-	-	-
馏分2	-0.30	0.06	0.19	-	-1.80	-0.79	0.31	-0.20	-	0.08	-0.60	0.53	-	-	-
馏分3	0.30	-0.06	-0.73	1.30	1.80	0.79	-	-1.80	0.12	-0.74	0.06	-0.43	-0.20	-	-0.21
馏分4	-	-	-	0.19	-	-	-	-	0.13	-	-	-	-0.71	-0.35	-0.07
馏分5	-	-	-	-0.08	-	-	-	-	-0.36	-	-	-	0.31	-	0.34
馏分6	-	-	-	-0.80	-	-			-0.11	-	-	-	0.60	0.51	-0.13
馏分7	-	-	-	-	-	-	-		-	-	-	-	-	0.04	0.24
馏分8	-	-	-	-	-	-			-	-	-	-	-	-0.20	-0.12

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表 3 国产10X分子筛分离出的甾烷化合物单体烃碳同位素重复性分析

Table 3. Repeatability analysis of carbon isotope of sterane compounds by domestic 10X molecular sieve

平行实验	单体烃碳同位素δ¹³C/‰
平行实验	α, α, α-C₂₇S甾烷	α, β, β-C₂₇R甾烷	α, β, β-C₂₇ S甾烷	α, α, α-C₂₇ R甾烷	C₂₉ S重排甾烷	α, α, α-C₂₈ S甾烷	α, β, β-C₂₈ R甾烷	α, β, β-C₂₈ S甾烷	α, α, α-C₂₈ R甾烷	α, α, α-C₂₉ S甾烷	α, β, β-C₂₉ R甾烷	α, β, β-C₂₉ S甾烷	α, α, α-C₂₉ R甾烷	伽马蜡烷	β-胡萝卜烷
第一次	-31.46	-34.87	-33.96	30.79	-33.53	-32.98	-33.84	-33.31	-30.52	-32.34	-34.43	-33.34	-29.36	-36.45	-32.06
第二次	-32.28	-32.41	-34.43	30.85	-34.51	-33.69	-33.19	-32.64	-30.42	-32.98	-33.65	-32.89	-29.87	-35.87	-32.43

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表 4 国产10X型和13X型分子筛分离出的藿烷化合物单体烃碳同位素测定结果

Table 4. Carbon isotope of hopane compounds separated by domestic 10X and 13X molecular sieves

分子筛	单体烃碳同位素δ¹³C/‰
分子筛	C₂₀三环萜烷	C₂₁三环萜烷	C₂₃三环萜烷	C₂₄三环萜烷	C₂₉藿烷	C₃₀藿烷	C₃₀莫烷	C₃₁藿烷S构型	C₃₁藿烷R构型	C₃₂藿烷S构型	C₃₂藿烷R构型
10X	-33.7	-31.4	-32.6	-30.2	-60.7	-60.3	-60.1	-60.0	-60.1	-60.4	-60.8
13X	-33.3	-31.4	-32.8	-30.3	-60.4	-60.3	-60.3	-60.7	-60.4	-60.7	-60.8

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