CN106770845A - A kind of aromatic hydrocarbons method of purification suitable for Compound-specific isotope analysis - Google Patents
A kind of aromatic hydrocarbons method of purification suitable for Compound-specific isotope analysis Download PDFInfo
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- CN106770845A CN106770845A CN201611053249.4A CN201611053249A CN106770845A CN 106770845 A CN106770845 A CN 106770845A CN 201611053249 A CN201611053249 A CN 201611053249A CN 106770845 A CN106770845 A CN 106770845A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
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Abstract
The present invention relates to a kind of aromatic hydrocarbons method of purification suitable for Compound-specific isotope analysis, the method is comprised the following steps：(1) crude oil is added in the clean glass tube for the treatment of, is then vacuumized and sealed with after three removing air of helium replacement；By the step (1) in equipped with crude oil glass tube be placed in Muffle furnace heat, obtain thermal decomposition product；(3) after the thermal decomposition product is cooled to room temperature, with dichloromethane supersonic extraction 2 ~ 4 times, merging obtains extract；(4) (GC IRMS) is tested with directly carrying out aromatic component analysis (GC MS) and individual carbon isotope after n-hexane precipitation bitumens matter after the extract is concentrated.The present invention is with low cost, it is easy to implement, applied widely, can provide effective technological means for Deep Oil And Gas Exploration area unsubstituted aromatic monomer carbon isotope composition OIL SOURCE CORRELATION.
Description
Technical field
It is the present invention relates to a kind of aromatic hydrocarbons method of purification more particularly to a kind of suitable for the unsubstituted of Compound-specific isotope analysis
Base aromatic hydrocarbons method of purification.
Background technology
As economic society is fast-developing, energy resource consumption is continued to increase, and oil-gas exploration is gradually prolonged to oil-gas bearing basin deep layer
Stretch（Zhu Guangyou etc., 2006;Zhang Shuichang etc., 2007）.However, Deep Oil And Gas Exploration exploration and development encounters greater difficulties than ever, its
One of be OIL SOURCE CORRELATION（An ancient unit of weight of gold etc., 2007; Huang et al., 2016）.Because the hydrocarbon source rock on these stratum and
Crude oil is big all in height-post-mature stage, standard biologic mark（Isoprenoid alkenes, steroid terpane etc.）Distribution tends to one
Cause, lose the function of indicating original source of students feature（Peters et al.,1993;Wu He is brave etc., and 2003;Beam Di Gang etc.,
2005）, therefore in the urgent need to finding new efficiency index.
Aromatic hydrocarbons is important part in crude oil and deposit Soluble Organic Matter, contains abundant geology, geochemical
Information.Aromatic hydrocarbons has the structure of stabilization, and its carbon isotope composition is influenceed smaller by secondary actions such as biodegradations（O’
Malley et al., 1994; Mazeas et al., 2002;Lin Junfeng etc., 2011）.In the research work of early stage,
It is found by the applicant that the Changing Pattern of aromatic compound individual carbon isotope has generality（Chen et al., 2016）, it is various
Aromatic compound is because of the difference of heat endurance, and carbon isotope composition Changing Pattern is different：Unsubstituted aromatic hydrocarbons is because with higher
Heat endurance, its isotopics will not substantially change；And containing substitution base aromatic hydrocarbons can occur the fracture or isomerization that replace base
So as to cause carbon isotope to become weight.Therefore, the aromatic compound of unsubstituted is more suitable for deep layer OIL SOURCE CORRELATION index.
However, to realize application of the unsubstituted aromatic hydrocarbons in OIL SOURCE CORRELATION, first have to ensure the essence of its isotopics
Really determine.But the base aromatic compound isomer containing substitution and homology species are more, and spillover is serious (Fig. 1) altogether, interference
The isotope assay of unsubstituted aromatic compound.Prior art is mainly based upon chromatographic principles, to owning in aromatic component
Compound is separated（Wang Huitong etc., 2003; Kim et al., 2005; Glaser et al., 2005;Chen Zulin
Deng 2012,2013; Jiang et al., 2013）.Because most of Research on Aromatic Chemistry properties are similar, the separation between component
It is difficult to distinguish, separating effect is easily influenceed by filler activity, sample concentration, eluant, eluent polarity, and controllability is poor.
The content of the invention
The technical problems to be solved by the invention be to provide it is a kind of it is simple to operate, with low cost, be fast and effectively applied to
The aromatic hydrocarbons method of purification of Compound-specific isotope analysis.
To solve the above problems, a kind of aromatic hydrocarbons method of purification suitable for Compound-specific isotope analysis of the present invention,
Comprise the following steps：
(1) 0.1 ~ 0.2g crude oil is added in the clean glass tube for the treatment of, takes out true after then removing air for three times with helium replacement
Sky is simultaneously sealed；
By the step (1) in equipped with crude oil glass tube be placed in Muffle furnace heat, obtain thermal decomposition product；
(3) after the thermal decomposition product is cooled to room temperature, with dichloromethane supersonic extraction 2 ~ 4 times, merging obtains extract；
(4) with directly carrying out aromatic component analysis (GC-MS) and monomer after n-hexane precipitation bitumens matter after the extract is concentrated
Carbon isotope tests (GC-IRMS).
(2) middle heating condition refers to that heating-up temperature is 500 DEG C ~ 550 DEG C to the step, and the heat time is 12 h ~ 48 h.
The condition of the step (3) middle supersonic extraction refer to temperature for 30 ~ 33 DEG C, frequency be 15 ~ 25 kHz, time be 20 ~
30min。
The condition of the step (4) middle concentration refer to temperature be 30 ~ 33 DEG C, under conditions of pressure is 0.04 ~ 0.06MPa
3 ~ 5min of vacuum distillation to the mL of solvent residue 1 ~ 2 is 50 DEG C, air-distillation to the mL of solvent residue 1 ~ 2 in temperature.
The present invention has advantages below compared with prior art：
1st, it is of the invention according to aromatic compound thermal stability difference and unsubstituted aromatic monomer carbon isotope stability, by height
The mode of temperature heating eliminates the aromatic hydrocarbons of the base containing substitution to realize the enrichment of unsubstituted aromatic hydrocarbons, makes aromatic component further
Separation just can directly carry out the Accurate Analysis of carbon isotope（Fig. 2）, so as to reach the mesh for operating more convenient, data more reliable
's.
2nd, using the inventive method to Caidamu Basin CX0642 crude oil（Aromatic hydrocarbons carries out Compound-specific isotope analysis in crude oil
Before need reference literature Chen et al., the method in 2016 is finely separated）And its 500 DEG C（Heat 24 h）Thermal decomposition product
Carry out aromatic monomer carbon isotope test（GC-IRMS）Analysis finds：With unsubstituted naphthalene and nothing in CX0642 Aromatic Hydrocarbon From Oil components
The luxuriant and rich with fragrance contrast discovery of substitution, the change for not causing unsubstituted aromatic hydrocarbons carbon isotope is processed by the high temperature of the process（Table 1）.
Unsubstituted aromatic compound carbon isotope composition in the CX0642 crude oil of table 1. and 500 DEG C of thermal decomposition products
Test condition：Aromatic monomer carbon isotope is tested（GC-IRMS）In match Mo Feishier companies of the U.S.（Thermo-Fisher
Scientific）It is analyzed on the MAT253 mass spectrographs of production, is connected to using vario PYRO cube elemental analysers
ISOPRIME-100 is carried out13C isotope analyses.Using HP-5 capillary columns（60 m×0.32 mm×0.25 μm,
Agilent, USA）, carrier gas is high-purity helium, and carrier gas flux is 1.1 mL/min, heating schedule：80 DEG C of initial temperature, constant 2
Min, then 300 DEG C, constant temperature 30min are risen to 4 DEG C/min.Sample duplicate measurements at least 2 times, stability of instrument is same using known carbon
The n-compound of position element composition is detected that every 5 samples are demarcated once.
3rd, the mode of this high-temperature process of the invention need not carry out the fine separation of aromatic hydrocarbons, can preferably retain nothing and take
For naphthalene compounds, and carry out the measure of its isotope, it is to avoid being placed for a long time because of sample cannot naphthalene compounds volatilize
The phenomenon being measured, so that many reliable OIL SOURCE CORRELATION indexs.
4th, the inventive method applicability is wide.Respectively to 1 crude oil of Tarim Basin（TP17CX）, Crude Oils From Qaidam Basin
The extract that 1 (CX0745), Ordos Basin crude oil 1 (LFP) and corresponding high temperature treatment are obtained carries out GC-
IRMS is analyzed, and finds do not have by the high temperature processing procedure by unsubstituted naphthalene in both contrasts and unsubstituted luxuriant and rich with fragrance contrast
Cause the change of unsubstituted aromatic hydrocarbons carbon isotope（Fig. 3 ~ 5, table 2）.
Unsubstituted aromatic compound carbon isotope composition in the different crude oils of table 2. and 500 DEG C of thermal decomposition products
5th, the present invention is with low cost, it is easy to implement, applied widely, can be same for Deep Oil And Gas Exploration area unsubstituted aromatic monomer carbon
Position element composition OIL SOURCE CORRELATION provides effective technological means.
Brief description of the drawings
Specific embodiment of the invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is crude oil S26 aromatic component total ion currents（TIC）Figure（MN, monomethyl naphthalene；DMN, dimethylnaphthalene；TMN, three
Methyl naphthalene；TeMN, tetramethyl naphthalene；P, it is luxuriant and rich with fragrance）.
Fig. 2 is Compound-specific isotope analysis figure in 500 DEG C of thermal decomposition products of CX0642 crude oil of the present invention.
Fig. 3 is list in 500 DEG C of thermal decomposition products (abbreviation TP17CX-500) of crude oil TP17CX (Tarim Basin) of the present invention
Body carbon isotope analysis figure.
Fig. 4 is 500 DEG C of thermal decomposition products of crude oil CX0745 (Caidamu Basin) of the present invention（Abbreviation CX0745-500）Middle list
Body carbon isotope analysis figure.
Fig. 5 is 500 DEG C of thermal decomposition products of crude oil LFP (Ordos Basin) of the present invention（Abbreviation LFP-500）Middle free carbon
Isotope analysis figure.
Specific embodiment
A kind of aromatic hydrocarbons method of purification suitable for Compound-specific isotope analysis of embodiment 1, comprises the following steps：
(1) 0.1g crude oil is added in the clean glass tube for the treatment of, is vacuumized simultaneously after then removing air three times with helium replacement
Sealing；
By step (1) in be placed in Muffle furnace equipped with the glass tube of crude oil, heat 48 h in 500 DEG C, obtain thermal decomposition product；
(3) after thermal decomposition product is cooled to room temperature, with dichloromethane in 30 DEG C, frequency be 15 kHz, the time be 20 min under the conditions of surpass
Sound is extracted 2 times, and merging obtains extract；
Extract be 30 DEG C in temperature, pressure be 0.04MPa under conditions of 3 ~ 5min of vacuum distillation to solvent residue 1 ~ 2
(GC- is tested with directly carrying out aromatic component analysis (GC-MS) and individual carbon isotope after n-hexane precipitation bitumens matter after mL
IRMS).
Aromatic component is analyzed（GC-MS）Test condition：Gc/ms Analyser is by the limited public affairs of U.S.'s Agilent Technologies
Department's production.Gas chromatograph is Hewlett-Packard 6890N types, chromatographic condition：Injector temperature：280℃；Carrier gas is
High pure nitrogen, flow：0.8 ml/min,；Chromatographic column：SE-54 fused-silica capillary columns（30m × 0.32 mm × 0.25 μm,
The Lanzhou Chemistry and Physics Institute of the Chinese Academy of Sciences, China）；Heating schedule：Begin 80 DEG C of temperature（held 0 min）, 290 DEG C, constant temperature are risen to 3 DEG C/min
30 min.Mass spectrograph is 5973 N quadrupole rod mass spectrums, and ion gun is EI sources, and ion source temperature is 230 DEG C, and quadrupole rod temperature is
150 DEG C, ion gun ionization energy is 70ev；280 DEG C of interface temperature；Acquisition mode：Full scan；Mass range：33~650amu；Spectrum
Storehouse is U.S. NIST02L.
Individual carbon isotope (GC-IRMS) test condition：Aromatic monomer carbon isotope is tested（GC-IRMS）In the U.S., match is silent
Fly generation that company（Thermo-Fisher Scientific）It is analyzed on the MAT253 mass spectrographs of production, uses vario
PYRO cube elemental analysers are connected to ISOPRIME-100 and carry out13C isotope analyses.Using HP-5 capillary columns（60 m
× 0.32 mm × 0.25 μm, Agilent, USA）, carrier gas is high-purity helium, and carrier gas flux is 1.1 mL/min, is heated up
Program：80 DEG C of initial temperature, constant 2 min, then 300 DEG C, constant temperature 30min are risen to 4 DEG C/min.Sample duplicate measurements at least 2
Secondary, stability of instrument is detected that every 5 samples are demarcated once using the n-compound of known carbon isotope composition.
A kind of aromatic hydrocarbons method of purification suitable for Compound-specific isotope analysis of embodiment 2, comprises the following steps：
(1) 0.2g crude oil is added in the clean glass tube for the treatment of, is vacuumized simultaneously after then removing air three times with helium replacement
Sealing；
By step (1) in be placed in Muffle furnace equipped with the glass tube of crude oil, heat 12 h in 550 DEG C, obtain thermal decomposition product；
(3) after thermal decomposition product is cooled to room temperature, with dichloromethane in 33 DEG C, frequency be 25 kHz, the time be 30 min under the conditions of surpass
Sound is extracted 4 times, and merging obtains extract；
Extract be 33 DEG C in temperature, pressure be 0.06MPa under conditions of 3 ~ 5min of vacuum distillation to solvent residue 1 ~ 2
(GC- is tested with directly carrying out aromatic component analysis (GC-MS) and individual carbon isotope after n-hexane precipitation bitumens matter after mL
IRMS).Test condition is with embodiment 1.
A kind of aromatic hydrocarbons method of purification suitable for Compound-specific isotope analysis of embodiment 3, comprises the following steps：
(1) 0.15g crude oil is added in the clean glass tube for the treatment of, is vacuumized after then removing air three times with helium replacement
And seal；
By step (1) in be placed in Muffle furnace equipped with the glass tube of crude oil, heat 24 h in 515 DEG C, obtain thermal decomposition product；
(3) after thermal decomposition product is cooled to room temperature, with dichloromethane in 32 DEG C, frequency be 20 kHz, the time be 24 min under the conditions of surpass
Sound is extracted 3 times, and merging obtains extract；
Extract be 32 DEG C in temperature, pressure be 0.05MPa under conditions of 3 ~ 5min of vacuum distillation to solvent residue 1 ~ 2
(GC- is tested with directly carrying out aromatic component analysis (GC-MS) and individual carbon isotope after n-hexane precipitation bitumens matter after mL
IRMS).Test condition is with embodiment 1.
A kind of aromatic hydrocarbons method of purification suitable for Compound-specific isotope analysis of embodiment 4, comprises the following steps：
(1) 0.18g crude oil is added in the clean glass tube for the treatment of, is vacuumized after then removing air three times with helium replacement
And seal；
By step (1) in be placed in Muffle furnace equipped with the glass tube of crude oil, heat 36 h in 530 DEG C, obtain thermal decomposition product；
(3) after thermal decomposition product is cooled to room temperature, with dichloromethane in 31 DEG C, frequency be 18 kHz, the time be 28 min under the conditions of surpass
Sound is extracted 3 times, and merging obtains extract；
(4) under the conditions of extract is 50 DEG C in temperature, with after n-hexane precipitation bitumens matter after air-distillation to the mL of solvent residue 1 ~ 2
Directly carry out aromatic component analysis (GC-MS) and individual carbon isotope test (GC-IRMS).Test condition is with embodiment 1.
Claims (4)
1. a kind of aromatic hydrocarbons method of purification suitable for Compound-specific isotope analysis, comprises the following steps：
(1) 0.1 ~ 0.2g crude oil is added in the clean glass tube for the treatment of, takes out true after then removing air for three times with helium replacement
Sky is simultaneously sealed；
By the step (1) in equipped with crude oil glass tube be placed in Muffle furnace heat, obtain thermal decomposition product；
(3) after the thermal decomposition product is cooled to room temperature, with dichloromethane supersonic extraction 2 ~ 4 times, merging obtains extract；
(4) with directly carrying out aromatic component analysis and the same position of free carbon after n-hexane precipitation bitumens matter after the extract is concentrated
Element test.
2. a kind of aromatic hydrocarbons method of purification suitable for Compound-specific isotope analysis as claimed in claim 1, it is characterised in that：Institute
(2) middle heating condition refers to that heating-up temperature is 500 DEG C ~ 550 DEG C to state step, and the heat time is 12 h ~ 48 h.
3. a kind of aromatic hydrocarbons method of purification suitable for Compound-specific isotope analysis as claimed in claim 1, it is characterised in that：Institute
The condition for stating step (3) middle supersonic extraction refer to temperature for 30 ~ 33 DEG C, frequency be 15 ~ 25 kHz, time be 20 ~ 30min.
4. a kind of aromatic hydrocarbons method of purification suitable for Compound-specific isotope analysis as claimed in claim 1, it is characterised in that：Institute
The condition for stating step (4) middle concentration refer to temperature be 30 ~ 33 DEG C, pressure be 0.04 ~ 0.06MPa under conditions of vacuum distillation 3 ~
5min to the mL of solvent residue 1 ~ 2 is 50 DEG C, air-distillation to the mL of solvent residue 1 ~ 2 in temperature.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107500266A (en) * | 2017-09-29 | 2017-12-22 | 浙江旺林生物科技有限公司 | A kind of method for removing polycyclic aromatic hydrocarbon in plant powdered carbon |
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| CN104250568A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Treatment process for coal tar-residual oil hydrocracking, catalytic cracking and aromatics extraction |
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2016
- 2016-11-25 CN CN201611053249.4A patent/CN106770845A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250568A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Treatment process for coal tar-residual oil hydrocracking, catalytic cracking and aromatics extraction |
| CN105018138A (en) * | 2014-04-27 | 2015-11-04 | 中石化南京工程有限公司 | Method and system for producing aromatic hydrocarbon, asphalt and high-octane gasoline through inferior crude oil |
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| Title |
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| YONGXIN CHEN ET AL.: "Influence of thermal maturity on carbon isotopic composition of individual aromatic hydrocarbons during anhydrous closed-system pyrolysis", 《FUEL》 * |
| 张敏等: "塔里木盆地海相烃源岩与原油芳烃单体烃碳同位素分布特征及其意义", 《中国科学》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107500266A (en) * | 2017-09-29 | 2017-12-22 | 浙江旺林生物科技有限公司 | A kind of method for removing polycyclic aromatic hydrocarbon in plant powdered carbon |
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Application publication date: 20170531 |