CN103592380B - Quantitative analysis method of liquid-state products of hydrocarbon generation and expulsion simulation experiment - Google Patents
Quantitative analysis method of liquid-state products of hydrocarbon generation and expulsion simulation experiment Download PDFInfo
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Abstract
The invention provides a quantitative analysis method of liquid-state products of a hydrocarbon generation and expulsion simulation experiment. The method comprises the following steps: collecting and treating the liquid-state products of the hydrocarbon generation and expulsion simulation experiment, wherein the step comprises light hydrocarbon collecting, heavy hydrocarbon collecting, standard sample adding, dehydrating, filtering and concentrating; carrying out quantitative analysis on the liquid-state products of the hydrocarbon generation and expulsion simulation experiment by utilizing a comprehensive two-dimensional gas chromatography-hydrogen flame ionization detector, wherein the step comprises primary comprehensive two-dimensional analysis, natural volatilization for constant weight as well as secondary comprehensive two-dimensional analysis; calculating full-component quantitative result of the liquid-state products of the hydrocarbon generation and expulsion simulation experiment. The quantitative analysis method disclosed by the invention can be used for avoiding volatilization of light hydrocarbon, has better experiment result repeatability and simple and easy-to-learn operation, and provides a reliable technical method for the quantitative analysis of the liquid-state products of the hydrocarbon generation and expulsion simulation experiment, so that estimation on basin oil and gas resource amount is more objective.
Description
Technical field
The present invention relates to the quantitative analysis method of a kind of generation and expulsion modeling experiment liquid product, belong to oil and gas geochemistry technical field.
Background technology
Sedimentary basin Hydrocarbon Generation potentiality and resource evaluation are one of Scientific problems at the cores during petroleum gas is studied, and generation and expulsion modeling experiment is the Hydrocarbon Generation potentiality of current widespread use and the important technical of region oil and gas resource evaluation.The product of generation and expulsion modeling experiment comprises gaseous products and liquid product.Gaseous products is the composition of gas under referring to normal temperature and pressure, comprises methane, ethane, propane, butane and carbon dioxide etc.Liquid product refers to that carbon number distribution is from C
5to C
40hydro carbons and resin and asphalt.C
5-C
15hydrocarbon component be called lighter hydrocarbons, collect via cooled with liquid nitrogen; C
15above component is trapped in the pipeline of generation and expulsion modeling experimental system, inwall, or is adsorbed by the clay mineral in hydrocarbon source rock, with organic solvent rinse, extracting obtains.Utilize all kinds of hydrocarbon source rock at gas, the liquid hydrocarbon productivity of different evolution stages, in conjunction with the concrete geologic condition (the raw hydrocarbon history of burial history, thermal histories and thermal evolution) of sedimentary basin, carry out basin modelling, the oil in basin, gas growing amount can be estimated, on this basis further predicting oil/gas resource.In recent years in the exploration and development practice of the shale gas developed rapidly, the tight sand oil unconventional petroleum resources such as gentle, the estimation of unconventionaloil pool in place resources is in the urgent need to solving evaluation and the key issue such as estimation, hydrocarbon source rock oil extraction efficiency of irreducible oil in rich organic hydrocarbon source rock by generation and expulsion modeling experiment.Therefore, the product of generation and expulsion modeling experiment is carried out to accurate quantitative analysis in oil-gas exploration, has important practical significance, especially seem even more important to based on the coal measures humus type matrix generating lighter hydrocarbons and high maturation and post-mature hydrocarbon source rock.
At present, the gaseous product of generation and expulsion modeling experiment is collected and quantivative approach comparative maturity, but the quantitatively never good method of liquid product full constituent, mainly because of caused by the difficult quantitation to light hydrocarbon component.After light hydrocarbon component is collected via cooled with liquid nitrogen, often containing a large amount of water (about 10 milliliters), and the amount of lighter hydrocarbons is generally about hundreds of milligram, how to make that profit is separated completely, lighter hydrocarbons again non-volatile loss be a difficult problem.(the Zhang Wenzheng such as Zhang Wenzheng, Pei Ge. the collection of lighter hydrocarbons and Petroleum geological significance in thermal simulation. Natural Gas Geology research paper collection. Beijing: petroleum industry publishing house, oil and water separation Weighing method operation easier 1989:118-125) proposed is high, lighter hydrocarbons volatilize seriously in oil water separation process and constant weight process, and profit is separated very difficult completely.The water or a little lighter hydrocarbons that are mixed into trace in lighter hydrocarbons are stayed in water and all can be brought very large error, so experimental result is difficult to repeat, the lighter hydrocarbons quantitative result accuracy obtained cannot be determined.In the container collecting lighter hydrocarbons, add the organic solvents such as methylene chloride can avoid the lighter hydrocarbons of oil water separation process to escape, but the existence of solvent cannot be quantitative to lighter hydrocarbons with Weighing method.(the Zheng Lunju such as Zheng Lunju, Malaysia and China are good, Wang Qiang etc. the raw And Hydrocarbon Potential quantitative evaluation research of hydrocarbon source rock finite space pyrolysis. oil experiment geology, 2011,33 (5): 452-459) by the quantitative lighter hydrocarbons of gas chromatography of routine, but owing to containing the compositions such as colloid in collected light hydrocarbon component, the overlap of peaks condistillation of stable hydrocarbon and aromatic hydrocarbons simultaneously, there is interference in various degree to standard specimen peak, also cannot obtain lighter hydrocarbons quantitative result accurately.Even if there is a lighter hydrocarbons (C
15following hydro carbons) quantitative result, due to containing C in heavy hydrocarbon
15the fractions of following hydro carbons, the amount of liquid hydrocarbon still cannot be determined.Therefore, in the generation and expulsion modeling experiment of reality, often the lighter hydrocarbons collected and other liquid product are mixed and analyze, due to C
15following hydrocarbon component volatilization escapes, and the liquid product result obtained is imperfect, thus have impact on the estimation to stock number.
Comprehensive two dimensional gas chromatography (GC × GC) is the brand-new means of one of the separate complex potpourri grown up the nineties in last century, and its two-dimensional quadrature piece-rate system can be separated the compound that cannot be separated on conventional gas phase chromatogram-flame ionization ditector (GC-FID) in the second dimension chromatographic column.
Therefore, how to utilize comprehensive two dimensional gas chromatography, develop the quantitative analysis method of a kind of generation and expulsion modeling experiment liquid product, be still one of this area problem demanding prompt solution.
Summary of the invention
For solving the problems of the technologies described above, a kind of generation and expulsion modeling is the object of the present invention is to provide to test the quantitative analysis method of liquid product.Method of the present invention is a kind of method of the effective quantitative test generation and expulsion modeling experiment liquid product utilizing comprehensive two dimensional gas chromatography to set up the separation characteristic of opposed polarity compound.
For reaching above-mentioned purpose, the invention provides the quantitative analysis method of a kind of generation and expulsion modeling experiment liquid product, it comprises following step:
The collection of A, generation and expulsion modeling experiment liquid product and process:
A1, lighter hydrocarbons are collected: make lighter hydrocarbons collection container be connected to the kettle of generation and expulsion modeling experimental provision, the methylene chloride of 20-30mL is contained with and described lighter hydrocarbons collection container is placed in liquid nitrogen cold trap in described lighter hydrocarbons collection container, the kettle temperature of generation and expulsion modeling experimental provision is remained on 210-220 DEG C, open the product exit valve of generation and expulsion modeling experimental provision, light hydrocarbon component in liquid product enters lighter hydrocarbons collection container with gaseous products, gaseous products enters gas collection vessel, after gas dosing balance, lighter hydrocarbons are collected and are terminated, obtain the dichloromethane solution (this solution comprises water) containing lighter hydrocarbons,
A2, heavy hydrocarbon are collected: after lighter hydrocarbons are collected and terminated, the kettle temperature of generation and expulsion modeling experimental provision is down to room temperature, with each three times of the pipeline of the methylene chloride of 20-50mL cleaning generation and expulsion modeling experimental provision, inner wall of kettle and generation and expulsion modeling laboratory sample, obtain the dichloromethane solution (this solution comprises water) containing heavy hydrocarbon;
A3, add standard specimen: merge dichloromethane solution containing lighter hydrocarbons with the dichloromethane solution containing heavy hydrocarbon in volumetric flask, obtain the dichloromethane solution containing lighter hydrocarbons and heavy hydrocarbon, then add the deuterated n-tetracosane hydrocarbon (C that 300-600 μ L concentration is 0.5454mg/mL wherein
24d
50) standard specimen (solvent is methylene chloride);
A4, to dewater: add methylene chloride wherein again, make to rise to more than volumetric flask neck containing the water in the dichloromethane solution of lighter hydrocarbons and heavy hydrocarbon after adding standard specimen, then with long-neck dropper, water is removed;
A5, filtration: cross in the funnel being plugged with absorbent cotton and filter the solid impurity contained in the dichloromethane solution of lighter hydrocarbons and heavy hydrocarbon after dewatering;
A6, concentrated: the dichloromethane solution containing lighter hydrocarbons and heavy hydrocarbon after filtering to be volatilized on Nitrogen evaporator, is concentrated into about 1.5mL, proceeds in the 2mL sample injection bottle of gas chromatography routine, obtain the sample of generation and expulsion modeling experiment liquid product quantitative test;
The quantitative test of B, generation and expulsion modeling experiment liquid product:
B1, the sample utilizing comprehensive two dimensional gas chromatography-flame ionization ditector (GC × GC-FID) analytical procedure A to obtain, go out the quality of stable hydrocarbon and the quality of aromatic hydrocarbons according to the calculated by peak area of comprehensive two dimensional gas chromatography figure, be designated as S1 and F1 respectively;
Wherein, the computing formula of S1 and F1 is respectively:
In formula, A
1for stable hydrocarbon integrating peak areas result, A
2for aromatic hydrocarbons integrating peak areas result, A
0for standard specimen integrating peak areas result, M
0for standard specimen quality;
B2, step B1 is analyzed after sample at room temperature naturally evaporate into constant weight (being equal to the constant weight condition of chloroform bitumen " A "), obtain the liquid product after lighter hydrocarbons volatilization (not containing methylene chloride, methylene chloride volatilizees this liquid product all) and quality W1 thereof;
B3, employing 1-2mL methylene chloride dissolve the liquid product after lighter hydrocarbons volatilization, then the dichloromethane solution of liquid product after utilizing comprehensive two dimensional gas chromatography-flame ionization ditector analysis to contain lighter hydrocarbons volatilization, go out the quality of stable hydrocarbon and the quality of aromatic hydrocarbons according to the calculated by peak area of comprehensive two dimensional gas chromatography figure, be designated as S2 with F2(S2 respectively consistent with the computing formula of S1 and F1 in step B1 with the computing formula of F2);
The calculating of C, generation and expulsion modeling experiment liquid product full constituent quantitative result:
Generation and expulsion modeling experiment liquid product gross mass W=W1+S1+F1-S2-F2, the quality N=W1-S2-F2 of the non-hydrocarbonaceous materials contained in generation and expulsion modeling experiment liquid product.
In the methods described above, preferably, comprehensive two dimensional gas chromatography condition in the analysis condition of described comprehensive two dimensional gas chromatography-flame ionization ditector is: one dimension chromatographic column is Petro post, the heating schedule of one dimension chromatogram is 50 DEG C and keeps 0.2min, is then raised to 305 DEG C with the speed of 10 DEG C/min and keeps 5min(to need 30.7min altogether); Two way chromatograms post is DB-17HT post, the heating schedule of Two way chromatograms is 60 DEG C and keeps 0.2min, then being raised to 315 DEG C with the speed of 10 DEG C/min keeps the heating schedule of 5min(Two way chromatograms to adopt the heating rates identical with one dimension chromatogram, difference be initial temperature and final temperature higher than one dimension chromatogram 10 DEG C); Gas chromatographic sample introduction mouth temperature is 300 DEG C, and using helium as carrier gas, flow rate of carrier gas is 2mL/min, and adopt split sampling pattern, split ratio is 400:1, and sample size is 1 μ L; The heating schedule of modulator is 85 DEG C and keeps 0.2min, then being raised to 335 DEG C with the speed of 10 DEG C/min keeps the heating schedule of 5min(modulator to adopt the heating rate identical with one dimension chromatogram, difference be initial temperature and final temperature higher than one dimension chromatogram 35 DEG C), modulation period is 6s, and the hot blow time in modulation period is 1.5s.This comprehensive two dimensional gas chromatography condition is the comprehensive two dimensional gas chromatography condition in said method step B1 and B3.
In the methods described above, preferably, flame ionization ditector (FID) condition in the analysis condition of described comprehensive two dimensional gas chromatography-flame ionization ditector is: using helium as carrier gas, the flow velocity of carrier gas, hydrogen, air is respectively 23mL/min, 60mL/min, 400mL/min, detector temperature is 310 DEG C, frequency acquisition is 200 spectrograms/s, and the solvent delay time is 0min.This flame ionization ditector condition is the step B1 in said method and the flame ionization ditector condition in B3.
In the methods described above, preferably, described Petro post is of a size of 10m × 0.2mm × 0.5 μm.
In the methods described above, preferably, described DB-17HT post is of a size of 2m × 0.1mm × 0.1 μm.
Generation and expulsion modeling test whole liquid products of collecting after add standard specimen, dewater etc. processes by the quantivative approach of generation and expulsion modeling of the present invention experiment liquid product, adopt the quality of stable hydrocarbon and aromatic hydrocarbons in comprehensive two dimensional gas chromatography-flame ionization ditector analyzing liquid product, obtained the quality of whole liquid hydrocarbon by the volatilization constant weight of reagent and secondary comprehensive two dimensional gas chromatography-flame ionization ditector analysis.The orthogonal separation system of comprehensive two dimensional gas chromatography can eliminate the interference at condistillation peak and colloid, bitum interference, does not affect, can obtain the exact level of stable hydrocarbon and aromatic hydrocarbons in liquid hydrocarbon to standard specimen peak.Secondary comprehensive two dimensional gas chromatography-flame ionization ditector analysis, eliminates part hydrocarbon repeating in lighter hydrocarbons and in heavy hydrocarbon and measures, can calculate the quality of whole liquid hydrocarbon (comprising colloid, bituminous matter), make quantitative result more accurately and reliably.Quantitative analysis method of the present invention avoids the volatilization of lighter hydrocarbons, and experimental result repeatability is better and simple to operate easy to learn, and the liquid product quantitative test of simulating hydrocarbons expulsion experiment of making a living provides reliable technical method, and it is more objective to make the estimation of basin hydrocarbon resources amount.
Accompanying drawing explanation
Fig. 1 is the full two-dimensional lattice spectrogram in the step B1 of embodiment 1.
Fig. 2 is the complete two-dimentional 3D spectrogram in the step B1 of embodiment 1.
Fig. 3 is the full two-dimensional lattice spectrogram in the step B3 of embodiment 1.
Fig. 4 is the complete two-dimentional 3D spectrogram in the step B3 of embodiment 1.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
The present embodiment provides a kind of generation and expulsion modeling to test the quantitative analysis method of liquid product.Under getting Zhangjiakou, area, garden black shale sample carries out generation and expulsion modeling experiment (this sample message is as shown in table 1), the liquid product this sample being carried out generation and expulsion modeling experiment carries out collecting, process, analyze and calculating according to following step, obtains quantitative result.
Table 1
The quantitative analysis method of the generation and expulsion modeling experiment liquid product of the present embodiment comprises following step:
The collection of A, generation and expulsion modeling experiment liquid product and process:
A1, lighter hydrocarbons are collected: make lighter hydrocarbons collection container be connected to the kettle of generation and expulsion modeling experimental provision, the methylene chloride of 20mL is contained with and described lighter hydrocarbons collection container is placed in liquid nitrogen cold trap in described lighter hydrocarbons collection container, the kettle temperature of generation and expulsion modeling experimental provision is remained on 220 DEG C, open the product exit valve of generation and expulsion modeling experimental provision, light hydrocarbon component in liquid product enters lighter hydrocarbons collection container with gaseous products, gaseous products enters gas collection vessel, after gas dosing balance, lighter hydrocarbons are collected and are terminated, obtain the dichloromethane solution (this solution comprises water) containing lighter hydrocarbons,
A2, heavy hydrocarbon are collected: after lighter hydrocarbons are collected and terminated, the kettle temperature of generation and expulsion modeling experimental provision is down to room temperature, with the pipeline of the methylene chloride of 20-50mL cleaning generation and expulsion modeling experimental provision, inner wall of kettle and each three substandard products of generation and expulsion modeling experiment sample, obtain the dichloromethane solution (this solution comprises water) containing heavy hydrocarbon;
A3, add standard specimen: merge dichloromethane solution containing lighter hydrocarbons with the dichloromethane solution containing heavy hydrocarbon in volumetric flask, obtain the dichloromethane solution containing lighter hydrocarbons and heavy hydrocarbon, then add the deuterated n-tetracosane hydrocarbon (C that 300 μ L concentration are 0.5454mg/mL wherein
24d
50) standard specimen;
A4, to dewater: add methylene chloride wherein again, make to rise to more than volumetric flask neck containing the water in the dichloromethane solution of lighter hydrocarbons and heavy hydrocarbon after adding standard specimen, then with long-neck dropper, water is removed;
A5, filtration: cross in the funnel being plugged with absorbent cotton and filter the solid impurity contained in the dichloromethane solution of lighter hydrocarbons and heavy hydrocarbon after dewatering;
A6, concentrated: the dichloromethane solution containing lighter hydrocarbons and heavy hydrocarbon after filtering to be volatilized on Nitrogen evaporator, is concentrated into about 1.5mL, proceeds in the 2mL sample injection bottle of gas chromatography routine, obtain the sample of generation and expulsion modeling experiment liquid product quantitative test;
The quantitative test of B, generation and expulsion modeling experiment liquid product:
B1, the sample utilizing comprehensive two dimensional gas chromatography-flame ionization ditector (GC × GC-FID) analytical procedure A to obtain, the quality of stable hydrocarbon and the quality of aromatic hydrocarbons is gone out according to the calculated by peak area of comprehensive two dimensional gas chromatography figure, be designated as S1 and F1 respectively, wherein, the computing formula of S1 and F1 is respectively:
in formula, A
1for stable hydrocarbon integrating peak areas result, A
2for aromatic hydrocarbons integrating peak areas result, A
0for standard specimen integrating peak areas result, M
0for standard specimen quality; As shown in Figure 1, complete two-dimentional 3D spectrogram as shown in Figure 2, Fig. 1 marked the full two-dimensional lattice spectrogram obtained normal octane (nC
8), toluene, methylnaphthalene and standard specimen (C
24d
50) go out peak position, and stable hydrocarbon and the distribution of aromatic hydrocarbons on full two-dimensional lattice spectrogram, Fig. 2 solid reflects stable hydrocarbon and the distribution situation of aromatic hydrocarbons on complete two-dimentional spectrogram intuitively;
Wherein, comprehensive two dimensional gas chromatography condition in the analysis condition of described comprehensive two dimensional gas chromatography-flame ionization ditector is: one dimension chromatographic column is Petro post (being of a size of 10m × 0.2mm × 0.5 μm), the heating schedule of one dimension chromatogram is 50 DEG C and keeps 0.2min, is then raised to 305 DEG C with the speed of 10 DEG C/min and keeps 5min(to need 30.7min altogether); Two way chromatograms post is DB-17HT post (being of a size of 2m × 0.1mm × 0.1 μm), the heating schedule of Two way chromatograms is 60 DEG C and keeps 0.2min, then being raised to 315 DEG C with the speed of 10 DEG C/min keeps the heating schedule of 5min(Two way chromatograms to adopt the heating rates identical with one dimension chromatogram, difference be initial temperature and final temperature higher than one dimension chromatogram 10 DEG C); Gas chromatographic sample introduction mouth temperature is 300 DEG C, and using helium as carrier gas, flow rate of carrier gas is 2mL/min, and adopt split sampling pattern, split ratio is 400:1, and sample size is 1 μ L; The heating schedule of modulator is 85 DEG C and keeps 0.2min, then being raised to 335 DEG C with the speed of 10 DEG C/min keeps the heating schedule of 5min(modulator to adopt the heating rate identical with one dimension chromatogram, difference be initial temperature and final temperature higher than one dimension chromatogram 35 DEG C), modulation period is 6s, and the hot blow time in modulation period is 1.5s;
Flame ionization ditector (FID) condition in the analysis condition of described comprehensive two dimensional gas chromatography-flame ionization ditector is: using helium as carrier gas, the flow velocity of carrier gas, hydrogen, air is respectively 23mL/min, 60mL/min, 400mL/min, detector temperature is 310 DEG C, frequency acquisition is 200 spectrograms/s, and the solvent delay time is 0min;
B2, by step B1 analyze after sample at room temperature naturally evaporate into constant weight (being equal to the constant weight condition of chloroform bitumen " A "), obtain lighter hydrocarbons volatilization after liquid product and quality W1;
B3, employing methylene chloride dissolve the liquid product after lighter hydrocarbons volatilization, the dichloromethane solution of the liquid product after then utilizing comprehensive two dimensional gas chromatography-flame ionization ditector analysis (analysis condition of this comprehensive two dimensional gas chromatography-flame ionization ditector is identical with step B1) to volatilize containing lighter hydrocarbons, go out the quality of stable hydrocarbon and the quality of aromatic hydrocarbons according to the calculated by peak area of comprehensive two dimensional gas chromatography figure, be designated as S2 with F2(S2 respectively consistent with the computing formula of S1 and F1 in step B1 with the computing formula of F2); As shown in Figure 3, complete two-dimentional 3D spectrogram as shown in Figure 4, marked n-tridecane (nC to the full two-dimensional lattice spectrogram obtained in Fig. 3
13), methylnaphthalene and standard specimen (C
24d
50) go out peak position, and stable hydrocarbon and the distribution of aromatic hydrocarbons on full two-dimensional lattice spectrogram, Fig. 4 solid reflects stable hydrocarbon and the distribution situation of aromatic hydrocarbons on complete two-dimentional spectrogram intuitively, as can be seen from Figure 3, through constant weight of naturally volatilizing, in sample, remove the compound of boiling point lower than n-tridecane hydrocarbon and methylnaphthalene;
The calculating of C, generation and expulsion modeling experiment liquid product full constituent quantitative result:
Generation and expulsion modeling experiment liquid product gross mass W=W1+S1+F1-S2-F2, the quality N=W1-S2-F2 of the non-hydrocarbonaceous materials contained in generation and expulsion modeling experiment liquid product;
Wherein, the data of S1, F1, W1, S2, F2, W and N are as shown in table 2.
Table 2
| S1(mg) | 28.44 |
| F1(mg) | 263.04 |
| S2(mg) | 1.19 |
| F2(mg) | 42.34 |
| W1(mg) | 446.67 |
| W(mg) | 694.61 |
| N(mg) | 403.14 |
Embodiment 2
The present embodiment provides a kind of generation and expulsion modeling to test the quantitative analysis method of liquid product.Get the sample identical with embodiment 1, the method identical with embodiment 1 is adopted to carry out generation and expulsion modeling experiment, the quantitative analysis method that the liquid hydrocarbon product that generation and expulsion modeling is tested tests liquid product according to the generation and expulsion modeling identical with embodiment 1 is analyzed, obtains quantitative result.Adopt the quantitative result of the present embodiment and the quantitative result of embodiment 1 to contrast, investigate the repeatability of the quantitative analysis method of generation and expulsion modeling of the present invention experiment liquid product.
The data of S1, F1, W1, S2, F2, W and N of the present embodiment are as shown in table 3.
Table 3
| S1(mg) | 27.64 |
| F1(mg) | 331.00 |
| S2(mg) | 8.06 |
| F2(mg) | 190.45 |
| W1(mg) | 563.33 |
| W(mg) | 723.47 |
| N(mg) | 364.82 |
From the data of table 3, the generation and expulsion modeling experiment liquid product gross mass W that the method for the present embodiment obtains is 723.47mg, and the quality N of the non-hydrocarbonaceous materials contained in generation and expulsion modeling experiment liquid product is 364.82mg.The quantitative result of the present embodiment and the quantitative result of embodiment 1 is adopted to compare, the result error of the liquid product gross mass that twice experiment obtains is 2.03%, the result error of the quality of non-hydrocarbonaceous materials is 4.99%, all in the scope of experimental technique permissible error 5%.Therefore, the quantitative result of the generation and expulsion modeling experiment liquid product adopting quantitative analysis method of the present invention to obtain is true, reliable, have repeatability.
Claims (3)
1. a quantitative analysis method for generation and expulsion modeling experiment liquid product, it comprises the following steps:
The collection of A, generation and expulsion modeling experiment liquid product and process:
A1, lighter hydrocarbons are collected: make lighter hydrocarbons collection container be connected to the kettle of generation and expulsion modeling experimental provision, the methylene chloride of 20-30mL is contained with and described lighter hydrocarbons collection container is placed in liquid nitrogen cold trap in described lighter hydrocarbons collection container, the kettle temperature of generation and expulsion modeling experimental provision is remained on 210-220 DEG C, open the product exit valve of generation and expulsion modeling experimental provision, light hydrocarbon component in liquid product enters lighter hydrocarbons collection container with gaseous products, gaseous products enters gas collection vessel, after gas dosing balance, lighter hydrocarbons are collected and are terminated, obtain the dichloromethane solution containing lighter hydrocarbons,
A2, heavy hydrocarbon are collected: after lighter hydrocarbons are collected and terminated, the kettle temperature of generation and expulsion modeling experimental provision is down to room temperature, with each three times of the pipeline of the methylene chloride of 20-50mL cleaning generation and expulsion modeling experimental provision, inner wall of kettle and generation and expulsion modeling laboratory sample, obtain the dichloromethane solution containing heavy hydrocarbon;
A3, add standard specimen: merge dichloromethane solution containing lighter hydrocarbons with the dichloromethane solution containing heavy hydrocarbon in volumetric flask, obtain the dichloromethane solution containing lighter hydrocarbons and heavy hydrocarbon, then add the deuterated n-tetracosane hydrocarbon standard specimen that 300-600 μ L concentration is 0.5454mg/mL wherein;
A4, to dewater: add methylene chloride wherein again, make to rise to more than volumetric flask neck containing the water in the dichloromethane solution of lighter hydrocarbons and heavy hydrocarbon after adding standard specimen, then with long-neck dropper, water is removed;
A5, filtration: cross in the funnel being plugged with absorbent cotton and filter the solid impurity contained in the dichloromethane solution of lighter hydrocarbons and heavy hydrocarbon after dewatering;
A6, concentrated: the dichloromethane solution containing lighter hydrocarbons and heavy hydrocarbon after filtering to be volatilized on Nitrogen evaporator, is concentrated into 1.5mL, proceeds in the 2mL sample injection bottle of gas chromatography routine, obtain the sample of generation and expulsion modeling experiment liquid product quantitative test;
The quantitative test of B, generation and expulsion modeling experiment liquid product:
B1, the sample utilizing comprehensive two dimensional gas chromatography-flame ionization ditector analytical procedure A to obtain, go out the quality of stable hydrocarbon and the quality of aromatic hydrocarbons according to the calculated by peak area of comprehensive two dimensional gas chromatography figure, be designated as S1 and F1 respectively;
B2, by step B1 analyze after sample at room temperature naturally evaporate into constant weight, obtain lighter hydrocarbons volatilization after liquid product and quality W1;
B3, employing 1-2mL methylene chloride dissolve the liquid product after lighter hydrocarbons volatilization, then the dichloromethane solution of liquid product after utilizing comprehensive two dimensional gas chromatography-flame ionization ditector analysis to contain lighter hydrocarbons volatilization, go out the quality of stable hydrocarbon and the quality of aromatic hydrocarbons according to the calculated by peak area of comprehensive two dimensional gas chromatography figure, be designated as S2 and F2 respectively;
The calculating of C, generation and expulsion modeling experiment liquid product full constituent quantitative result:
Generation and expulsion modeling experiment liquid product gross mass W=W1+S1+F1-S2-F2, the quality N=W1-S2-F2 of the non-hydrocarbonaceous materials contained in generation and expulsion modeling experiment liquid product;
Wherein, comprehensive two dimensional gas chromatography condition in the analysis condition of described comprehensive two dimensional gas chromatography-flame ionization ditector is: one dimension chromatographic column is Petro post, the heating schedule of one dimension chromatogram is 50 DEG C and keeps 0.2min, is then raised to 305 DEG C with the speed of 10 DEG C/min and keeps 5min; Two way chromatograms post is DB-17HT post, and the heating schedule of Two way chromatograms is 60 DEG C and keeps 0.2min, is then raised to 315 DEG C with the speed of 10 DEG C/min and keeps 5min; Gas chromatographic sample introduction mouth temperature is 300 DEG C, and using helium as carrier gas, flow rate of carrier gas is 2mL/min, and adopt split sampling pattern, split ratio is 400:1, and sample size is 1 μ L; The heating schedule of modulator is 85 DEG C and keeps 0.2min, and be then raised to 335 DEG C with the speed of 10 DEG C/min and keep 5min, modulation period is 6s, and the hot blow time in modulation period is 1.5s;
Flame ionization ditector condition in the analysis condition of described comprehensive two dimensional gas chromatography-flame ionization ditector is: using helium as carrier gas, the flow velocity of carrier gas, hydrogen, air is respectively 23mL/min, 60mL/min, 400mL/min, detector temperature is 310 DEG C, frequency acquisition is 200 spectrograms/s, and the solvent delay time is 0min.
2. method according to claim 1, wherein, described Petro post is of a size of 10m × 0.2mm × 0.5 μm.
3. method according to claim 1, wherein, described DB-17HT post is of a size of 2m × 0.1mm × 0.1 μm.
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