CN102636609B - Full two-dimensional gas chromatography analysis method for hydrocarbons in crude oil or deposited organic matters - Google Patents
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Abstract
The invention discloses a full two-dimensional gas chromatography analysis method for hydrocarbons in crude oil or deposited organic matters, which directly analyzes crude oil or deposited organic matter samples by using a full two-dimensional gas chromatography (GC x GC-FID) to obtain hydrocarbon (saturated hydrocarbons, aromatic hydrocarbons and the like) data, and qualitatively calculates to obtain the localization parameters of the saturated hydrocarbons and the aromatic hydrocarbons by using GC x GC-TOFMS software and a method and full two-dimensional gas chromatography hydrocarbon separation characteristics. The invention takes the two-dimensional gas chromatography analysis of the Daqing Sael diagram oil field, the peripheral basin square positive and negative trap and the sea tower basin crude oil and deposited organic matter sample as examples to carry out the method verification. The invention discloses a full two-dimensional gas chromatography analysis method for hydrocarbons in crude oil or deposited organic matters, which creates a new method for analyzing the hydrocarbons in the crude oil or the deposited organic matters and has important significance for deeply understanding the process of reservoir formation, migration, aggregation, preservation, oil source comparison and oil reservoir geochemistry research of the crude oil, exploring new geochemistry indexes of the crude oil and exploration and development.
Description
Technical field
The present invention relates to the analytical approach of hydro carbons in a kind of crude oil or deposition organic matter, be specifically related to the comprehensive two dimensional gas chromatography analytical approach (GC * GC-FID) to hydro carbons in crude oil or deposition organic matter, belong to organic geochemistry field in oil-gas exploration and development.
Background technology
Crude oil or deposition organic matter are a kind of complexity, multi-component uniform homogeneous blend, and main composition is hydro carbons (alkane, naphthenic hydrocarbon, aromatic hydrocarbons), also have a small amount of non-hydrocarbon component (sulfur-bearing, contain oxygen, nitrogen-containing compound) and resin and asphalt etc.Crude oil or deposit organic materialization and form to have preserved in hydrocarbon composition especially and form the information that changes etc. in oil generation matrix and crude oil converted product or oil extraction process, thereby, study crude oil or deposit organic materialization and form especially hydrocarbon composition and monomeric compound thereof, for formation, maturation, migration, gathering, preservation, OIL SOURCE CORRELATION and the reservoir geochemistry research etc. of deep understanding crude oil, and it is all significant to explore new petroleum geochemistry index.
The gas chromatography analysis method of hydro carbons in existing crude oil or deposition organic matter, referring to Xiao Tingrong, Li Li, Zhang Ju and etc. " oil and deposition organic hydro carbons gas chromatography analysis method " (People's Republic of China's oil and gas industry standard, 2008), use one dimension gas chromatographic technique (GC-FID), comprising respectively for the analytical approach of three kinds of hydro carbons: the stable hydrocarbon analytical approach in rock chloroform extract and crude oil, crude oil total hydrocarbon gas chromatography analysis method, aromatic hydrocarbons gas chromatography analysis method, wherein to obtain stable hydrocarbon and aromatic hydrocarbons and change parameter, at least need two kinds of corresponding hydro carbons gas chromatography analysis methods, and the stable hydrocarbon sample used with analysis of aromatics is all crude oil or deposits organic matter sample process loaded down with trivial details separated the obtaining of group composition before, in separation, there is the loss of component, can not guarantee primitiveness and the hydrocarbon component overall picture of crude oil or deposition organic matter sample, also there is resolution simultaneously, column capacity, sensitivity, quantitative and qualitative analysis reliability is relatively low, detected components is few, the problems such as ground parameter kind that a kind of analytical approach detects is single.Crude oil total hydrocarbon gas chromatography analysis method can not obtain aromatic hydrocarbons changes parameter (weak point that crude oil total hydrocarbon is analyzed).
Comprehensive two dimensional gas chromatography technology (GC * GC-FID) is the analytical technology growing up nineteen ninety, within 1999, produced the commercial comprehensive two dimensional gas chromatography instrument of First in the world, its cardinal principle be separating mechanism different and mutually independently two chromatographic columns with series system, be combined into two-dimensional gas chromatography, between these two chromatographic columns, a modulator is housed, this modulator plays trapping and transmits, each cut after first chromatographic column separation, all need to be introduced into modulator, after focusing on, with pulse mode, deliver in second chromatographic column and carry out further separation again, all components enters detecting device from second chromatographic column, signal is after data handling system is processed, the retention time that obtains take on the first pillar is the first horizontal ordinate, retention time on the second pillar is the second horizontal ordinate, signal intensity is three-dimensional or the two-dimensional chromatogram of ordinate.
Comprehensive two dimensional gas chromatography technology is in the application of petrochemical industry, Ruan Chunhai, Ye Fen, grand " stalling characteristic that oil sample comprehensive two dimensional gas chromatography the is analyzed " (analytical chemistry that waits in hole, 2002) in, adopted comprehensive two dimensional gas chromatography technology (GC * GC-FID), the sample of its analysis is the chemical products diesel oil that petroleum refining obtains, kerosene, the application of this technology for petroleum refining after product, the composition of sample is relatively simple, the specificity of analysis condition is stronger, also exist and analyze that hydrocarbon component is few qualitatively, the problems such as a large amount of standard models of needs are qualitative, and the required classes of compounds of obtaining, data message neither be former exploration activity pay close attention to, be unsuitable for directly to complexity, comprise stable hydrocarbon, aromatic hydrocarbons, nonhydrocarbon, the crude oil of bituminous matter family component or deposit organic primary sample and analyze.The domestic report of not seeing comprehensive two dimensional gas chromatography (GC * GC-FID) analytical approach of hydro carbons in crude oil or deposition organic matter.
Summary of the invention
The object of the invention is to analyze the problems such as resolution, column capacity, sensitivity that hydrocarbon compound exists, quantitative and qualitative analysis reliability is relatively low, detected components is few, a kind of analytical approach detects ground parameter kind are single in order to solve one dimension vapor-phase chromatography (GC-FID), and a kind of comprehensive two dimensional gas chromatography analytical approach (GC * GC-FID) that can not need the separated direct injected of group composition to detect hydro carbons (stable hydrocarbon, aromatic hydrocarbons etc.) in crude oil or deposition organic matter is provided.
The comprehensive two dimensional gas chromatography analytical approach of hydro carbons in crude oil provided by the invention or deposition organic matter, comprises following steps:
1) gather crude oil or rock (reservoir rock or hydrocarbon source rock) sample, take from the crude oil of well mouth of oil well or test former wet goods and detect sample as crude oil, by the mensuration > > of the imitative pitch of oil and gas industry standard < < CHLORINE IN ROCKS, extracting in rock sample organic as the organic quality inspection test sample product of deposition;
2) to step 1) crude oil that obtains detects sample or deposits organic quality inspection test sample product, adds carbon disulphide (chromatographically pure) solvent, and obtain crude oil and detect solution or deposit organic quality inspection and survey solution;
3) by step 2) the detection solution that obtains carries out comprehensive two dimensional gas chromatography detection, and the comprehensive two dimensional gas chromatography that obtains crude oil or deposit organic each component of hydro carbons is analyzed data;
4) by step 3) GC * GC-FID of obtaining analyzes data, utilizes the stalling characteristic of GC * GC-TOFMS analysis software and method and comprehensive two dimensional gas chromatography hydro carbons spectrogram to carry out hydrocarbon compound qualitative;
5) for step 4) hydrocarbon compound qualitatively that obtains, utilize step 3) in the analysis data of its correspondence calculate hydrocarbon compound in crude oil or deposition organic matter quantitative result and the ground parameter of stable hydrocarbon and aromatic hydrocarbons.
Wherein:
Step 1) depositing organic quality inspection test sample product extracts and obtains from rock specimens by the mensuration > > SY/T 5118-2005 of the imitative pitch of oil and gas industry standard < < CHLORINE IN ROCKS.
Step 3) the analysis data that obtain are spectrogram and spectrum peak data.
Step 3) described comprehensive two dimensional gas chromatography analysis condition is: 80 ℃ of one dimension chromatographic column initial temperature, 300 ℃ of final temperatures, constant temperature 30min; 90 ℃ of two dimension chromatographic column initial temperature, 310 ℃ of final temperatures, constant temperature 30min; 300 ℃ of injector temperatures; 320 ℃ of detecting device FID temperature.
Concrete, step 3) described comprehensive two dimensional gas chromatography analysis condition is: U.S. LECO company comprehensive two dimensional gas chromatography instrument (GC * GC), be furnished with Agilent7890 gas chromatograph and flame ionization ditector (FID) and the hot modulator of four spout twin-stages, control and data processing are Chroma TOF software; One dimension chromatographic column is DB-Petro:50m * 0.2mm * 0.5 μ m, 80 ℃ of initial temperature, and permanent 0.2min, is raised to 300 ℃ with 2 ℃/min heating rate, constant temperature 30min; Two dimension chromatographic column is DB-17ht:2m * 0.1mm * 0.1 μ m, 85 ℃ of initial temperature, and permanent 0.2min, is raised to 310 ℃ with 2 ℃/min heating rate, constant temperature 30min; 300 ℃ of injector temperatures, split sampling pattern; 320 ℃ of detecting device FID temperature, detecting device make-up gas is high-purity helium; Modulator temperature is higher 30 ℃ than one dimension furnace temperature; Be 10s modulation period, and wherein the hot blow time is 2.5s; Carrier gas is high-purity helium, and post flow is 1.8ml/min; Combustion gas is hydrogen, and flow is 45ml/min; Combustion-supporting gas is air, and flow is 450ml/min.
Step 4) GC described in * GC-FID analysis data are carried out hydrocarbon compound quilitative method and are: the retention time of utilizing the compounds such as GC * GC-TOFMS analysis software and method obtain n-alkane and naphthalene is serial, phenanthrene is serial, set up the qualitative template of relative position, the qualitative template of naphthalene series compound relative position, the qualitative template of series of phenanthrenes relative position of stable hydrocarbon and aromatic compound, in conjunction with stalling characteristics such as the quadrature of comprehensive two dimensional gas chromatography hydro carbons figure is separated, family is separated, tile effects, to the hydro carbons of comprehensive two dimensional gas chromatography analysis, carry out qualitative.
Step 5) quantitative result of described hydrocarbon compound is the relative mass mark of each hydrocarbon compound in qualitative hydrocarbon component; Change the oil and gas industry standard < < of parameter Shi An People's Republic of China (PRC) oil and the organic hydro carbons gas chromatography analysis method > > of deposition (SY/T 5779-2008) stipulates to calculate describedly.
The comprehensive two dimensional gas chromatography analytical approach of hydro carbons in crude oil of the present invention or deposition organic matter, also can comprise and utilize step 5) the ground parameter obtaining carries out the process of crude oil source and exploration value assessment.
This evaluation procedure can be for the ground parameter of single sample, according to < < oil and deposition organic hydro carbons gas chromatography analysis method > > (SY/T 5779-2008) index, evaluate the hydrocarbon source rock in its type, degree of ripeness, source etc., judgement extraction value.
This evaluation procedure also can be for the ground parameter of different specimens, carry out crude oil or deposit organic hydro carbons matrix and degree of ripeness, OIL SOURCE CORRELATION, for different basins petroleum geochemistry, studying and explore provides foundation, or the hydrocarbon source rock that provides crude oil to originate, the source of indication crude oil and exploration direction.
The present invention utilizes comprehensive two dimensional gas chromatography (GC * GC-FID) directly to enter crude oil or the analysis of deposition organic matter sample obtains hydro carbons (stable hydrocarbon, aromatic hydrocarbons etc.) data, utilize GC * GC-TOFMS software and method and comprehensive two dimensional gas chromatography separation of hydrocarbons characteristic qualitative, calculate stable hydrocarbon and aromatic hydrocarbons groundization parameter, solved the resolution that one dimension gas chromatography (GC-FID) exists, column capacity, sensitivity, quantitative and qualitative analysis reliability is relatively low, detected components is few, a kind of detection method obtains the problems such as groundization parameter kind is single, avoided crude oil or deposition organic matter sample can not guarantee its primitiveness and hydrocarbon component overall picture and the error of bringing and pollution through group composition separation, started hydrocarbon analysis new method in crude oil or sedimentogeneous rock, greatly enrich crude oil and deposited organic quality Geochemistry information, for exploring, petroleum geochemistry New Set and exploratory development are significant.
Accompanying drawing explanation
Fig. 1 side of being 402 well crude oil GC * GC-FID analysis site systems of battle formations;
Fig. 2 side of being 402 well crude oil GC-FID analysis of spectra;
Fig. 3 is the qualitative template of the relative position of stable hydrocarbon and aromatic compound;
Fig. 4 is the qualitative template of naphthalene series compound relative position;
Fig. 5 is the qualitative template of series of phenanthrenes relative position.
Embodiment
The present invention has mainly proposed the comprehensive two dimensional gas chromatography analytical approach (GC * GC-FID) of hydro carbons in crude oil or deposition organic matter, by to crude oil or deposition organic matter sample direct injection analysis, utilize GC * GC-TOFMS analysis software and comprehensive two dimensional gas chromatography separation of hydrocarbons characteristic qualitative, calculate stable hydrocarbon and aromatic hydrocarbons groundization parameter.
From several respects, describe the present invention in detail below.
One, crude oil or deposit organic hydro carbons comprehensive two dimensional gas chromatography analytical approach
In present embodiment crude oil or deposition organic matter, the comprehensive two dimensional gas chromatography analytical approach of hydro carbons completes in the steps below:
1) gather crude oil or rock (reservoir rock or hydrocarbon source rock) sample, using and take from well mouth of oil well or test former wet goods and test sample as crude oil, the organic test of deposition sample extracts and obtains from rock sample by the mensuration > > of the imitative pitch of oil and gas industry standard SY/T 5118-2005 < < CHLORINE IN ROCKS;
2) by step 1) crude oil that obtains or the organic test of deposition sample, add the appropriate (ratio of by volume 1: 1 for example, these data can change) carbon disulphide (chromatographically pure) solvent, obtain crude oil and detect solution or deposit organic quality inspection survey solution;
3) to step 2) the detection solution that obtains carries out comprehensive two dimensional gas chromatography analysis, and the comprehensive two dimensional gas chromatography that obtains crude oil or deposit organic hydro carbons is analyzed data (spectrogram and spectrum peak data); Wherein comprehensive two dimensional gas chromatography analysis condition is: U.S. LECO company comprehensive two dimensional gas chromatography (GC * GC), be furnished with Agilent7890 gas chromatograph and flame ionization ditector (FID) and the hot modulator of four spout twin-stages, control and data processing are Chroma TOF software; One dimension chromatographic column is DB-Petro:50m * 0.2mm * 0.5 μ m, 80 ℃ of initial temperature, and permanent 0.2min, is raised to 300 ℃ with 2 ℃/min heating rate, constant temperature 30min; Two dimension chromatographic column is DB-17ht:2m * 0.1mm * 0.1 μ m, 90 ℃ of initial temperature, and permanent 0.2min, is raised to 310 ℃ with 2 ℃/min heating rate, constant temperature 30min; 300 ℃ of injector temperatures, split sampling pattern; 320 ℃ of detecting device FID temperature, detecting device make-up gas is high-purity helium; Modulator temperature is higher 30 ℃ than one dimension furnace temperature; Be 10s modulation period, and wherein the hot blow time is 2.5s; Carrier gas is high-purity helium, and post flow is 1.8ml/min; Combustion gas is hydrogen, and flow is 45ml/min; Combustion-supporting gas is air, and flow is 450ml/min.
Here, 80 ℃ of one dimension chromatographic column initial temperature, 300 ℃ of final temperatures, constant temperature 30min; 90 ℃ of two dimension chromatographic column initial temperature, 310 ℃ of final temperatures, constant temperature 30min; 300 ℃ of injector temperatures; 320 ℃ of detecting device FID temperature are for adapting to crude oil or depositing the comprehensive two dimensional gas chromatography analysis condition that organic quality inspection is surveyed.
4) by step 3) GC * GC-FID of obtaining analyzes data, (these compounds are relevant to former exploration activity to utilize GC * GC-TOFMS analysis software and method to obtain the compounds such as n-alkane is serial with naphthalene, luxuriant and rich with fragrance series, determining of qualitative classes of compounds is also feature of the present invention) retention time, set up the qualitative recognition template of compound, in conjunction with stalling characteristics such as the quadrature of comprehensive two dimensional gas chromatography hydro carbons figure is separated, family is separated, tile effects, GC * GC-FID is analyzed to data, and to carry out hydrocarbon compound qualitative, obtains compound title qualitatively;
5) for step 4) the qualitative hydrocarbon compound obtaining, utilize step 2) corresponding spectrum peak data calculates quantitative result (the relative mass mark of each compound in hydrocarbon component), and calculate in crude oil or deposition organic matter, change parameter stable hydrocarbon and aromatic hydrocarbons (can be according to People's Republic of China's oil and gas industry standard, oil and the organic hydro carbons gas chromatography analysis method of deposition, SY/T 5779-2008).
Two, embodiment
Take below the upright rift of Saertu Oilfield in Daqing, Its Peripheral Basins, pinnacle basin crude oil and deposition organic be the implementation process of example explanation the inventive method.
1, experimental specimen
Saar oil field is one of Daqing oil field main force oil producing area, gathers 1-k03 well mouth of oil well crude oil sample in Saar; The upright rift of Its Peripheral Basins is efforts will be concentrated on prospecting area, Daqing Oil Field basin, in side 4, side's 6 well former exploration activity obtains after important breakthrough, successively in side 10, the exploration such as side 402, side's 403 wells obtains commercial oil, the Exploration Potential of having shown upright rift, collection side 4 (3214.0-3234.0m, E1w), side 402 (3299.7-3276.3m, E1x-w), side's 403 (3328.0-3334.0m, E1w) crude oil are tested sample as crude oil;
It is grand celebration efforts will be concentrated on prospecting basins that Hailaer-Ta wood is examined lattice basin, gathers tower 21-59 mud stone (1727m, Klt) and oil-sand (1523m, Klnl), tower 21-46 mud stone (2442m, Klnl) sample, for extracting the organic test of deposition sample.
2, experiment, result and discussion
2.1 GC * GC-FID analyzes hydrocarbon compound
By step 3) operation each sample is carried out to comprehensive two dimensional gas chromatography analysis, obtain comprehensive two dimensional gas chromatography and analyze data." the side's 402 well crude oil " sample of take is example, and GC * GC-FID analysis can detect 4126 spectrum peaks, and (factor data is huge, and whole component raw data are not provided for this reason in present specification.Table 2 has been listed the data for reference of qualitative part component).
In comparative analysis, side's 402 well crude oil total hydrocarbon gas chromatographies (GC-FID) are analyzed (Fig. 2) can only detect 197 peaks and component, how separation detects 3929 spectrum peaks to visible above-mentioned comprehensive two dimensional gas chromatography, illustrate that comprehensive two dimensional gas chromatography is compared with the resolution of one dimension gas chromatography, column capacity, highly sensitive, the good separating effect of component, the component of detection are many, and quantitative and qualitative analysis reliability is just high.
Repeated experiment
With regard to same sample for step 3) comprehensive two dimensional gas chromatography analytic process carries out repeated experiment, and calculates to analyze data the quantitative result that (with reference to 2.3.1) obtains different hydrocarbons compound in sample.Result shows: same laboratory sample is the difference of replicate analysis relative mass mark repeatedly, all meet the oil and gas industry standard < < of People's Republic of China (PRC) oil and the organic hydro carbons gas chromatography analysis method > > of deposition (SY/T 5779-2008) regulation, illustrate of the present invention reproducible.It is example that table 1 be take " middle 1-k03 well crude oil " sample, list it and repeated quantitative result, the maximum difference that shows parallel analysis relative mass mark is 0.19%, be less than and allow repeated maximal value 0.3857%, all meet < < oil and the requirement of the organic hydro carbons gas chromatography analysis method > > of deposition (SY/T 5779-2008) regulation.
The repeated experiment data that table 1 comprehensive two dimensional gas chromatography is analyzed
2.2 GC * GC-FID analyzes hydrocarbon compound separation characteristic and qualitative
4126 components that general side's 402 well crude oil GC * GC-FID analyzing and testing go out for raw data comprehensive two dimensional gas chromatography-flight time mass spectrum (GC * GC-TOFMS) software and method carry out qualitative, result is qualitative altogether 61 stable hydrocarbon and aromatic compound (in Table 2 listed compounds).According to qualitative results, below one band of side's 402 well crude oil GC * GC-FID analysis site systems of battle formations (Fig. 1) is the most weak saturated alkane of polarity, top is naphthenic hydrocarbon, monocycle series, dicyclo, thrcylic aromatic hydrocarbon series etc. successively, the substituent compound of same carbon number of being with of the same clan is linear array, the substituent same compounds of group of different carbon numbers is tile and arranges, whole like this spectrogram has been divided into different regions, represents compound not of the same clan.
According to GC * GC-TOFMS software and method qualitative results, qualitative the first dimension, the second repair and maintenance that go out component are stayed to time data mapping, obtain the qualitative template of relative position (Fig. 3) of stable hydrocarbon and aromatic compound, n-alkane in Fig. 3, the handsome alkane of grand-mother, phytane, gammacerane, naphthalene series, luxuriant and rich with fragrance series, dibenzothiophene, alkane series compound lays respectively at different relative retention positions suddenly.
According to oil and the organic hydro carbons gas chromatography analysis method of deposition (SY/T 5779-2008), require the aromatic hydrocarbons parameter of analyzing, adopt identical method to make respectively the qualitative template of relative retention position (Fig. 4, Fig. 5) to aromatic hydrocarbons naphthalene series, luxuriant and rich with fragrance series and dibenzothiophene (dibenzothiophene is changed common counter with being), in Fig. 4, naphthalene series compound is: 1: naphthalene; 2:2-methylnaphthalene; 3:1-methylnaphthalene; 4:2-ethyl naphthalene; 5:1-ethyl naphthalene; 6:2,6-dimethylnaphthalene; 7:2,7-dimethylnaphthalene; 8:1,7+1,3+1,6-dimethylnaphthalene; 9:1,4-dimethylnaphthalene; 10:2,3-dimethylnaphthalene; 11:1,5-dimethylnaphthalene; 12:1,2-dimethylnaphthalene; 13:1,3,7-trimethylnaphthalene; 14:1,3,6-trimethylnaphthalene; 15:1,4,6-trimethylnaphthalene; 16:2,3,6-trimethylnaphthalene; 17:1,2,7-trimethylnaphthalene; 18:2,3,5-trimethylnaphthalene; 19:1,2,4-trimethylnaphthalene; 20:1,2,5-trimethylnaphthalene.The Sino-Philippines series of Fig. 5 and dibenzothiophene compound are: 21: phenanthrene; 22:3-methylphenanthrene; 23:2-methylphenanthrene; 24:9-methylphenanthrene; 25:1-methylphenanthrene; 26:C2-luxuriant and rich with fragrance-1; 27:C2-luxuriant and rich with fragrance-2; 28:C2-luxuriant and rich with fragrance-3; 29:C2-luxuriant and rich with fragrance-4; 30:C2-luxuriant and rich with fragrance-5; 31:C2-luxuriant and rich with fragrance-6; 32:C2-luxuriant and rich with fragrance-7; 33:C2-luxuriant and rich with fragrance-8; 34: dibenzothiophene; 35:4-methyldibenzothiophene; 36:C2-dibenzothiophene-1; 37:C2-dibenzothiophene-2; 38:C2-dibenzothiophene-3).
In enforcement, Fig. 3 template is for the classification of stable hydrocarbon and aromatic hydrocarbons, main qualitative to the n-alkane in stable hydrocarbon, and Fig. 4 and Fig. 5 are qualitative for aromatic hydrocarbons naphthalene series, luxuriant and rich with fragrance series and dibenzothiophene.Fig. 4 and Fig. 5 template are that the naphthalene series (Fig. 4) in Fig. 3, luxuriant and rich with fragrance series and dibenzothiophene (Fig. 5) are listed separately, and the retention time of each component is consistent with Fig. 3's, is convenient to accurately qualitative.Fig. 3-Fig. 5 is altogether qualitative 61 stable hydrocarbon and aromatic compound (listed referring to table 2).
Crude oil or to deposit the relative position that peak in organic GC * GC-FID hydrocarbon analysis occurs stable, as long as find the peak position of a kind of compound in Liao Ge family, relative position with other compound component in gang just can determine, this is that comprehensive two dimensional gas chromatography is than one of advantage of one dimension gas chromatography analysis method.
The quantitative calculating of 2.3 hydrocarbon compounds and groundization calculation of parameter
2.3.1 the quantitative result of hydrocarbon compound: side 402 well oil sample GC * GC-FID analyzes 61 stable hydrocarbon and aromatic compound qualitative altogether, utilizing in 2.1 the spectrum peak data to should 61 hydrocarbon compounds obtaining to calculate (with reference to the existing algorithm of industry) obtains each compound quantitative result (the relative mass mark of each compound in qualitative hydrocarbon compound) and lists in table 2, table 2 has shown the first dimension of measuring for the first time, the second dimension retention time and relative mass mark, parallel analysis relative mass mark difference, allow maximum repeatability (identical with 2.1 repeated experiment quantivative approach, sample is different).As shown in Table 2, the parallel analysis component relative mass mark difference that constituent mass mark is less than 0.5wt% is not more than 0.0358%, the parallel analysis component relative mass mark difference of 0.5wt%～1wt% is not more than 0.0555%, the parallel analysis component relative mass mark difference of constituent mass mark 1wt%～2wt% is not more than 0.0730%, the parallel analysis component relative mass mark difference that constituent mass mark is less than 2wt%～3wt% is not more than 0.1134%, the parallel analysis component relative mass mark difference of 3wt%～4wt% is not more than 0.1596%, the parallel analysis component relative mass mark difference of 4wt%～5wt% is not more than 0.1936%, the parallel analysis component relative mass mark difference of 5wt%～6wt% is not more than 0.2370%, all meet the repeated requirement of the oil and gas industry standard < < of People's Republic of China (PRC) oil and the organic hydro carbons gas chromatography analysis method > > of deposition (SY/T 5779-2008) regulation.
Table 2 side 402 crude assay quantitative results
Table 2 data also show, in side's 402 Hydrocarbons In Crude Oils qualitative component, n-alkane accounts for 90.5378%, pristane and phytane account for 3.6548%, naphthalene series accounts for 5.4168%, luxuriant and rich with fragrance series accounts for 0.3895%, visible, n-alkane has comparative advantage and reflects the hydro carbons feature of sapropel type matrix, the hydro carbons feature of the high reflection of pristane content humus type matrix, comprehensive evaluation has sapropel humic mixed type feature, for crude oil feature, raw hydrocarbon matrix and explore provide foundation.
2.3.2 the ground calculation of parameter of hydrocarbon compound:
According to table 2 quantitative data, or according to 61 kinds of original spectrum peak data that compound is corresponding qualitatively, calculate (with reference to existing industry standard algorithm) side's 402 well crude oil groundization parameters.The results are shown in Table 3, show: main peak carbon and the carbon number range of twice replicate determination are all identical, the difference of 6 stable hydrocarbon groundization parameters is all not more than 0.121%, the difference of 9 aromatic hydrocarbons groundization parameters is all not more than 0.131%, groundization parameter is (by 61 compounds qualitatively, press SY/T5779-2008 industry standard regulation etc., calculate 15 stable hydrocarbon and aromatic hydrocarbons and change parameter) quantitative result meets the repeated requirement of industry standard (SY/T 5779-2008 industry standard) regulation.
Table 3 side 402 crude assay groundization parameters
The ground parameter that table 3 provides also shows, main peak carbon nC
15reflection be take algae as main organic matter, C
21+ C
22/ C
28+ C
29be 3.289 reflections to take the raw biology in lake be main organic matter, Pr/Ph 3.652 is reflected as humus type, Pr/nC
17, Ph/nC
18be 0.493 and 0.141 to be reflected as sapropel type, OEP is that 1.069 reflection degree of ripeness are high, ∑ C
21 -/ ∑ C
22 +be that 2.544 reflection degree of ripeness are high, equally, the aromatic hydrocarbons parameter values such as methylnaphthalene ratio, methylphenanthrene ratio, methylphenanthrene index are seen, crude maturity is high, comprehensive evaluation side's 402 well crude oil have sapropel humic mixed type feature, degree of ripeness is high, should derive from degree of ripeness higher or bury darker hydrocarbon source rock, for crude oil Source Study and exploration provide foundation.From former exploration activity result, side's 402 well crude oil belong to lightweight oil (oil density 0.82g.cm
-3), be convenient to exploitation.
2.4 crude oil and deposit the ground parameter comparison that organic GC * GC-FID analyzes
With above same method obtain respectively each crude oil and deposit the stable hydrocarbon of organic quality inspection test sample product comprehensive two dimensional gas chromatography analysis and aromatic hydrocarbons change parameter (table 4).Therefrom visible, 15 stable hydrocarbon and the aromatic hydrocarbons groundization parameter of the side 4 of the upright rift of Its Peripheral Basins, side 402, side's 403 crude oil samples (upright rift crude oil) mostly approach, do not have obvious difference, and reflection has sapropel humic mixed type feature; In the distant basin of pine, the geochemical index reflection of 1-k03 well and pinnacle basin tower 21-59 well crude oil has sapropel type feature; From main peak carbon, OEP, ∑ C
21-/∑ C
22+ wait the aromatic hydrocarbons parameters such as stable hydrocarbon parameter and methylnaphthalene ratio, methylphenanthrene ratio, methylphenanthrene index to see, the degree of ripeness of upright rift crude oil is the highest, and the crude oil of pinnacle basin tower 21-59 well takes second place, and in loose distant basin, the crude oil of 1-k03 well is relatively minimum.From former exploration activity result, the side 4 of upright rift, side 402, side's 403 crude oil all belong to lightweight oil (oil density 0.82g.cm
-3), in loose distant basin, 1-k03 well crude oil belongs to middle matter oil (oil density 0.87g.cm
-3), for different basins petroleum geochemistry, studying and explore provides foundation.
From pinnacle basin oil-sand and the organic quality parameter comparison of mud stone (table 4), the approaching of tower 21-59 well 1523m crude oil and tower 21-59 well 1727m mud stone, with tower 21-46 well 2442m mud stone differ larger, illustrate that crude oil may, mainly from 1727m mud stone (oil source rock), indicate the source of crude oil and the direction of exploration.
Table 4 crude oil and deposit organic GC * GC-FID and analyze groundization supplemental characteristic
By example, understand that specifically the present invention carries out the overall process that in crude oil or deposition organic matter, hydro carbons comprehensive two dimensional gas chromatography is analyzed above, the result that the method records can be used for petroleum geochemistry and exploratory development research.The present invention has following feature:
(1) propose and set up the comprehensive two dimensional gas chromatography analytical approach of hydro carbons in crude oil or deposition organic matter, can directly enter crude oil or deposition organic matter sample analysis acquisition stable hydrocarbon and aromatic hydrocarbons and change parameter, analyze and obtain the reproducible of component and groundization parameter, solved resolution, column capacity, sensitivity that one dimension gas chromatography (GC-FID) exists, quantitative and qualitative analysis reliability is relatively low, detected components is few, a kind of detection method obtains the problems such as groundization parameter kind is single, avoided crude oil or deposited error and the pollution that organic matter sample brings through group composition separation.
(2) utilize the method in Saertu Oilfield in Daqing, upright rift, the application of pinnacle basin, 6 mouthfuls of oil well crude oils and organic stable hydrocarbon and the aromatic hydrocarbons groundization parameter of deposition (oil-sand, mud stone) have been measured, result shows that oil generation matrix, sedimentary environment and the crude maturity in loose distant basin, Its Peripheral Basins, pinnacle basin exist difference, for crude oil generates, becomes Tibetan process, migration, gathering, preservation, OIL SOURCE CORRELATION and reservoir geochemistry research etc., provides new foundation.
(3) along with explore Daqing exploration area and the raising of oilfield exploitation degree, the new discovery of oil gas and remaining oil are exploited the progress of main dependence technology and increasing of hydrocarbon information, and the comprehensive two dimensional gas chromatography analytical approach of hydro carbons in crude oil or deposition organic matter, greatly enrich crude oil or deposited organic geochemical information, for exploring petroleum geochemistry New Set and exploratory development, provide Information base and technical support, had a extensive future.
Claims (3)
1. crude oil or deposit an organic hydro carbons comprehensive two dimensional gas chromatography analytical approach, is characterized in that, comprises following steps:
1) gather crude oil or reservoir rock or hydrocarbon source rock sample, crude oil or the test crude oil of taking from well mouth of oil well detect sample as crude oil, by the mensuration > > of the imitative pitch of oil and gas industry standard < < CHLORINE IN ROCKS, extract in rock sample organic as the organic quality inspection test sample product of deposition;
2) crude oil obtaining to step 1) detects sample or deposits organic quality inspection test sample product, adds carbon disulphide solvent, obtains crude oil and detects solution or deposit organic quality inspection survey solution;
3) by step 2) the detection solution that obtains carries out comprehensive two dimensional gas chromatography detection, and the comprehensive two dimensional gas chromatography that obtains crude oil or deposit organic each component of hydro carbons is analyzed data;
4) GC step 3) being obtained * GC-FID analyzes data, utilizes the stalling characteristic of GC * GC-TOFMS analysis software and method and comprehensive two dimensional gas chromatography hydro carbons spectrogram to carry out hydrocarbon compound qualitative;
5) hydrocarbon compound qualitatively obtaining for step 4), utilize the analysis data of its correspondence in step 3) calculate hydrocarbon compound in crude oil or deposition organic matter quantitative result and the ground parameter of stable hydrocarbon and aromatic hydrocarbons;
Wherein: the analysis data that step 3) obtains are spectrogram and spectrum peak data; Comprehensive two dimensional gas chromatography analysis condition described in step 3) is: U.S. LECO company comprehensive two dimensional gas chromatography instrument (GC * GC), be furnished with Agilent7890 gas chromatograph and flame ionization ditector (FID) and the hot modulator of four spout twin-stages, control and data processing are Chroma TOF software; One dimension chromatographic column is DB-Petro:50m * 0.2mm * 0.5 μ m, 80 ℃ of initial temperature, and permanent 0.2min, is raised to 300 ℃ with 2 ℃/min heating rate, constant temperature 30min; Two dimension chromatographic column is DB-17ht:2m * 0.1mm * 0.1 μ m, 85 ℃ of initial temperature, and permanent 0.2min, is raised to 310 ℃ with 2 ℃/min heating rate, constant temperature 30min; 300 ℃ of injector temperatures, split sampling pattern; 320 ℃ of detecting device FID temperature, detecting device make-up gas is high-purity helium; Modulator temperature is higher 30 ℃ than one dimension furnace temperature; Be 10s modulation period, and wherein the hot blow time is 2.5s; Carrier gas is high-purity helium, and post flow is 1.8ml/min; Combustion gas is hydrogen, and flow is 45ml/min; Combustion-supporting gas is air, and flow is 450ml/min;
GC described in step 4) * GC-FID analysis data are carried out hydrocarbon compound quilitative method and are: utilize GC * GC-TOFMS analysis software and method to obtain C
10-C
36the retention time of n-alkane and naphthalene series, series of phenanthrenes, set up the qualitative template of relative position, the qualitative template of naphthalene series compound relative position, the qualitative template of series of phenanthrenes relative position of stable hydrocarbon and aromatic compound, in conjunction with the quadrature of comprehensive two dimensional gas chromatography hydro carbons figure is separated, family is separated, tile effect stalling characteristic, to the hydro carbons of comprehensive two dimensional gas chromatography analysis, carry out qualitative.
2. the comprehensive two dimensional gas chromatography analytical approach of hydro carbons in crude oil according to claim 1 or deposition organic matter, it is characterized in that, described step 1) deposits organic quality inspection test sample product and extracts and obtain from rock specimens by the mensuration > > SY/T5118-2005 of the imitative pitch of oil and gas industry standard < < CHLORINE IN ROCKS.
3. the comprehensive two dimensional gas chromatography analytical approach of hydro carbons in crude oil according to claim 1 and 2 or deposition organic matter, it is characterized in that, the quantitative result of hydrocarbon compound is the relative mass mark of each hydrocarbon compound in qualitative hydrocarbon component described in step 5); Change the oil and gas industry standard < < of parameter Shi An People's Republic of China (PRC) oil and the organic hydro carbons gas chromatography analysis method > > of deposition describedly, standard No. SY/T5779-2008, regulation calculates.
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| 王汇彤 等.国家发展和改革委员会.《石油勘探与开发》.2012,第39卷(第1期),第123－128页. |
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