CN110763773A - Analysis method of biomarker compounds in crude oil asphaltenes - Google Patents
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Abstract
The invention relates to a method for analyzing biomarker compounds in crude oil asphaltenes, which comprises the following steps: extracting crude oil to obtain asphaltene; in the hydrogen atmosphere, leading the asphaltene to have hydrodesulfurization reaction in the presence of a catalyst to obtain a desulfurization product; carrying out asphaltene precipitation treatment on the desulfurization product to obtain a deasphalted product; carrying out column chromatography separation treatment on the deasphalted product to obtain saturated hydrocarbon; and carrying out GC-MS analysis on the saturated hydrocarbon to obtain the biomarker compounds in the crude oil asphaltenes. The method can quickly and effectively analyze the biomarker compounds in the asphaltenes of the crude oil (particularly the biodegradable crude oil and the high and over mature crude oil), and the analysis process is simple. The method widens the analysis method of the steroids and the hopane compounds in the petroleum geological sample.
Description
Technical Field
The invention belongs to the technical field of petroleum exploration and development and oil gas organic geochemistry research application, and particularly relates to an analysis method of a biomarker compound in crude oil asphaltene.
Background
The prior art is quite mature for researching the biomarker compounds in normal crude oil, and the biomarker compounds in petroleum are generally analyzed by using the national standard gas chromatography-mass spectrometry for detecting precipitates and the biomarkers in the crude oil (GB/T18606-2001). The new quantitative analysis method for the biomarker compounds sterane and hopane [ J ] Chinese science: geoscience, 2014,44(8):1713-1722) firstly separates the geological sample to obtain saturated hydrocarbon, aromatic hydrocarbon, non-hydrocarbon and asphaltene of the geological sample, then analyzes the obtained saturated hydrocarbon by adopting full two-dimensional gas chromatography-time-of-flight mass spectrometry, and then analyzes the hopane and the sterane in the sample by combining with the ion chromatograms of m/z191 and m/z 217.
For organic matters in a high maturity stage or under strong biodegradation, common hydrocarbons (especially saturated hydrocarbons and aromatic hydrocarbons) and biomarkers are low in abundance or damaged, and conventional analysis means cannot effectively acquire molecular organic geochemical information. The asphaltene is less influenced in the thermal evolution and degradation process due to the complex structure of macromolecules, especially the asphaltene macromolecules are often bonded with original ecological biomarker micromolecules, and the biomarkers are protected by peripheral macromolecules and are not damaged, so that the original appearance of organic matters of the hydrocarbon source rock is reserved, and the possibility is provided for extracting valuable original hydrocarbon source rock information from the original hydrocarbon source rock.
In order to extract biomarker compounds in the asphaltene, Maanlai and the like (Maanlai, Zhang Shuichang, Zhang Dajiang and the like, crude oil asphaltene in a Tarim basin is subjected to ruthenium ion catalytic oxidation and oil source [ J ] oil exploration and development, 2004,31(3):54-58) to separate the asphaltene from the crude oil, and then Ruthenium Ion Catalytic Oxidation (RICO) reaction is adopted to obtain crude oil asphaltene RICO products, wherein the crude oil asphaltene RICO products mainly comprise monoacid, dibasic acid, tricyclic terpene alkanoic acid, hopane acid, gamma paraffin alkanoic acid, pregnane, steroid alkanoic acid and the like. The literature indicates that these are biomarkers bound in the asphaltene aromatic nucleus structure. The method has certain limitations, namely the reaction process is complicated, the RICO reaction is carried out, the methyl esterification and separation of the reaction product are also required, and the complicated analysis steps can cause the loss of the generated biomarker compound; secondly, the acid formed by the reaction is difficult to characterize due to the lack of standard.
Wu Yinqin and the like (Wu Yinqin, Xiyanqing, Wang Yongli and the like, research on the biological standard in the serious biodegradation heavy oil asphaltene inclusion [ J ] oil experimental geology 2010,32(3):480-483) carry out ultrasonic extraction on crude oil asphaltene, and extract is separated out saturated hydrocarbon to carry out chromatographic analysis to obtain a biomarker composition, but the analysis method can only obtain the biomarker adsorbed on the asphaltene, and the physical action can not interrupt the biomarker compound bonded on the asphaltene.
Therefore, there is a need to develop a method for analyzing biomarker compounds in crude oil asphaltenes, which is simple in operation and widely applicable (particularly to high and over mature crude oil or biodegradable crude oil).
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for analyzing the biomarker compounds in crude oil asphaltenes, aiming at the defects of the prior art. Existing conventional analytical methods are not effective for obtaining molecular organic geochemical information due to low or impaired abundance of hydrocarbons (especially saturated and aromatic hydrocarbons) and biomarker compounds in crude oils that undergo severe biodegradation or high, over-mature crude oils. The inventor of the invention has conducted extensive and intensive research in the technical field of analysis methods of biomarker compounds in crude oil asphaltenes, and found that by adopting a normal-pressure reaction device different from a conventional high-pressure catalytic hydrodesulfurization device (generally consisting of a high-pressure hydrogenation reaction kettle and a metal pipeline) in the analysis method of the biomarker compounds in crude oil asphaltenes, the biomarker compounds in the asphaltenes can be released under mild conditions, and the reaction devices all adopt chemical glass reactors (no special high-pressure hydrogenation reaction kettle is needed), so that the asphaltenes can be subjected to hydrodesulfurization under mild reaction conditions, C-S bonds in the asphaltenes are broken, and the biomarker compounds bonded on the asphaltenes are released, thereby effectively analyzing the composition distribution characteristics of the asphaltenes and further carrying out geochemical application research.
To this end, the present invention provides in a first aspect a method for analyzing biomarker compounds in crude oil asphaltenes, comprising the steps of:
s1, extracting crude oil to obtain asphaltene;
s2, in a hydrogen atmosphere, leading the asphaltene to have hydrodesulfurization reaction in the presence of a catalyst to obtain a desulfurization product;
s3, carrying out asphaltene precipitation treatment on the desulfurization product to obtain a deasphalted product;
s4, carrying out column chromatography separation treatment on the deasphalted product to obtain saturated hydrocarbon;
and S5, carrying out GC-MS analysis on the saturated hydrocarbon to obtain the biomarker compounds in the crude oil asphaltenes.
According to some embodiments, the method for extracting and processing crude oil to obtain asphaltene comprises the following steps:
t1, dissolving crude oil in an organic solvent to form a mixed solution;
t2, carrying out ultrasonic oscillation treatment on the mixed solution, standing for precipitation, and filtering to obtain filter residue;
t3, treating the filter residue with an eluent to obtain the asphaltene.
According to some specific embodiments, the organic solvent is selected from C5-C8One or more of the normal alkanes of (a); and/or
The eluent is selected from one or more of benzene, toluene, methanol, dichloromethane, chloroform and n-hexane.
According to other specific embodiments, the catalyst is selected from one or more of nickel metal, raney nickel, and palladium on carbon.
In some embodiments, in step S2, the mass ratio of the catalyst to the asphaltenes is (0.1-100):1, preferably (10-50): 1.
In other embodiments, in step S2, the hydrodesulfurization reaction is performed using an atmospheric pressure reactor; and/or the reaction temperature of the hydrodesulfurization is 40-100 ℃, preferably 40-80 ℃; the reaction time of the hydrodesulfurization is 1 to 24 hours, preferably 8 to 24 hours.
In the present invention, an atmospheric pressure reactor for conducting hydrodesulfurization of asphaltenes is shown in FIG. 1. The device includes:
a magnetic stirrer 1 with a built-in rotor 2 and heating;
a three-neck flask 3 arranged above the magnetic stirrer 1;
a condenser pipe 5 inserted into the middle opening of the three-mouth flask 3, wherein the upper end and the lower end of the side surface of the condenser pipe 5 are respectively provided with a cooling water interface 6, and the top end of the condenser pipe 5 is communicated with a hydrogen bag interface 7;
a vacuum pump interface 8 communicated with one side of the two side openings of the three-mouth flask 3;
a thermometer 4 inserted into the other of the two side ports of the three-necked flask 3.
According to some embodiments, in step S3, the solvent used for asphaltene precipitation treatment of the desulfurization product is selected from C5-C8Preferably n-hexane.
According to other specific embodiments, in step S4, the column chromatography packing used for the column chromatography separation of the deasphalted product is selected from alumina and/or silica gel, preferably silica gel; the deasphalted product is separated by column chromatographyThe eluent used is selected from C5-C8Preferably n-hexane.
According to some embodiments, the GC-MS analysis is a selective ion scan analysis; the GC-MS analysis was performed on a chromatograph-mass spectrometer.
In some preferred embodiments, the GC-MS analysis uses a (20-60) mx (250-) 320 μm × 0.25 μm, preferably 30m × 250 μm × 0.25 μm or 30m × 320 μm × 0.25 μm DB-5MS or HP-5MS quartz fused elastic capillary chromatography column with He as carrier gas and split and/or undivided injection.
In some embodiments, a method for analyzing biomarkers in crude oil asphaltenes comprises the steps of:
1) preparation of asphaltenes from crude oil using C5-C8Dissolving appropriate amount of crude oil in normal alkane, ultrasonically vibrating, standing for precipitation, filtering with quantitative filter paper, and eluting filter residue on the filter paper with dichloromethane to obtain asphaltene;
2) dissolving asphaltene with one or more of organic solvents such as benzene, toluene, methanol, dichloromethane, chloroform, n-hexane, etc. by using the device of FIG. 1, adding metal catalyst (such as nickel metal, Raney nickel, palladium carbon, etc.), and performing hydrodesulfurization reaction on asphaltene under hydrogen atmosphere under heating condition at 40-100 deg.C, preferably 40-80 deg.C; the reaction time is 1-24 hours, preferably 8-24 hours;
3) precipitating asphaltene in the desulfurization product to obtain a reaction product after removing the asphaltene;
4) subjecting the deasphalted reaction product to silica gel column chromatography, and taking n-hexane as an eluent to obtain a saturated hydrocarbon component of the reaction product;
5) the saturated hydrocarbon component is subjected to solvent volatilization to 0.1-5.0mg/mL, and selective ion scanning analysis is carried out by GC-MS (gas chromatography-mass spectrometry) which is carried out on an Agilent 7890B-5977MSD type chromatograph-mass spectrometer in USA, the chromatographic column is a DB-5MS or HP-5MS fused quartz fused elastic capillary chromatographic column with (20-60) m multiplied by (250-320) mu m multiplied by 0.25 mu m (liquid film thickness), preferably 30m multiplied by 250 mu m multiplied by 0.25 mu m (liquid film thickness) or 30m multiplied by 320 mu m multiplied by 0.25 mu m (liquid film thickness), the carrier gas is He, and the sample injection mode is flow division sample injection and/or non-flow division sample injection. By selecting the characteristic ions m/z191 and m/z 217 of the biomarker compounds, the composition distribution of the hopane and the sterane is finally obtained.
In a second aspect, the invention provides the use of a method according to the first aspect of the invention in the analysis of biomarker compounds in crude oil asphaltenes, in particular in the analysis of biomarker compounds in high, over mature or biodegradable crude oil asphaltenes.
The analysis method of the biomarker compounds in the crude oil asphaltenes provided by the invention can directly analyze and research the biomarker compounds in the biodegradable crude oil or the high and over mature crude oil asphaltenes. The method can carry out hydrodesulfurization reaction under mild reaction conditions by only using a simple reaction device, break C-S bonds and release the biomarker compounds bonded on the asphaltene. Therefore, the method can quickly and effectively analyze the biomarker compounds in the asphaltenes of the crude oil (particularly the biodegradable crude oil and the high and over mature crude oil), has simple analysis process and low cost, and is more favorable for industrial popularization and application. The method widens the analysis method of the steroids and the hopane compounds in the petroleum geological sample.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings.
FIG. 1 is a diagram of an asphaltene hydrodesulfurization reaction apparatus according to the present invention. Wherein the reference numerals have the following meanings:
1-magnetic stirrer with heating; 2-a rotor; 3-three-neck flask; 4-a thermometer; 5-a condenser pipe; 6-cooling water interface; 7-hydrogen bag interface; 8-vacuum pump interface.
FIG. 2 is a diagram showing the distribution characteristics of the hopane compounds in the crude oil asphaltenes of Tahe.
FIG. 3 is a distribution characteristic diagram of sterane compounds in Tahe crude oil asphaltene. Wherein 1 to 4 represent C27A steroid; 5 to 8 represent C28A steroid; 9-12 represent C29A stanol.
Detailed Description
In order that the invention may be more readily understood, the following detailed description of the invention is given, with reference to the accompanying examples and drawings, which are given by way of illustration only and are not intended to limit the scope of the invention.
Examples
Example 1
The method is adopted to analyze and research the Tahe crude oil sample which is subjected to strong biodegradation.
(1) Dissolving crude oil by using normal hexane, ultrasonically oscillating, standing for 24 hours, filtering by using quantitative filter paper, and filtering filter residues on the filter paper by using dichloromethane to obtain asphaltene;
(2) dissolving the filtered asphaltene volatilized solvent into a toluene/methanol (V: V ═ 1:1) mixed solution in a device shown in figure 1, placing the dissolved solution into a three-neck flask, adding Raney Ni (Raney nickel) catalyst (the mass ratio of the Raney Ni catalyst to the asphaltene is 10:1) into the three-neck flask, and stirring and refluxing the mixture at 80 ℃ for 8 hours under a hydrogen atmosphere to obtain a desulfurization product;
(3) and filtering the desulfurization product by using toluene and n-hexane to remove the catalyst, dehydrating the filtrate by using anhydrous sodium sulfate, and then, spin-drying the filtrate by using a rotary evaporator. After the solvent is rotated and evaporated, n-hexane is used for precipitating unreacted asphaltene to obtain a deasphalted asphaltene product;
(4) separating the deasphalted product by using a silica gel chromatographic column to obtain saturated hydrocarbon;
(5) the saturated hydrocarbon is subjected to selective ion mode analysis by adopting Agilent 7890B-5977 GC-MS, and the chromatographic column is a DB-5MS quartz fused elastic capillary column with the thickness of 30m multiplied by 250 mu m multiplied by 0.25 mu m (liquid film thickness). The carrier gas is He, and the sample injection is not carried out by shunting. The mass chromatograms of the obtained hopane and sterane are shown in fig. 2 and 3, respectively.
As shown in figures 2 and 3, the method of the invention can obtain bonded biomarker compounds in the asphaltene, such as m/z191 (hopane) m/z 217 (sterane) with complete carbon number distribution, C29-C35Agastache and gamma-paraffin can be detected; m/z 217 (sterols) also have a complete carbon number distribution, C27-C29Sterane can be detected.
Example 2
The method is adopted to analyze and research the Tahe crude oil sample which is subjected to strong biodegradation.
(1) Dissolving crude oil by using normal hexane, ultrasonically oscillating, standing for 24 hours, filtering by using quantitative filter paper, and filtering filter residues on the filter paper by using dichloromethane to obtain asphaltene;
(2) dissolving the filtered asphaltene volatilized solvent into a toluene/methanol (V: V ═ 1:1) mixed solution in a device shown in figure 1, placing the dissolved solution into a three-neck flask, adding Raney Ni (Raney nickel) catalyst (the mass ratio of the Raney Ni catalyst to the asphaltene is 50:1) into the three-neck flask, and stirring and refluxing the mixture at 60 ℃ for 12 hours under a hydrogen atmosphere to obtain a desulfurization product;
(3) and filtering the desulfurization product by using toluene and n-hexane to remove the catalyst, dehydrating the filtrate by using anhydrous sodium sulfate, and then, spin-drying the filtrate by using a rotary evaporator. After the solvent is rotated and evaporated, n-hexane is used for precipitating unreacted asphaltene to obtain a deasphalted asphaltene product;
(4) separating the deasphalted product by using a silica gel chromatographic column to obtain saturated hydrocarbon;
(5) the saturated hydrocarbon is subjected to selective ion mode analysis by adopting Agilent 7890B-5977 GC-MS, and the chromatographic column is a DB-5MS quartz fused elastic capillary column with the thickness of 30m multiplied by 250 mu m multiplied by 0.25 mu m (liquid film thickness). The carrier gas is He, and the sample injection is not carried out by shunting. Mass chromatograms of hopane and stanol were obtained (not shown).
Bound biomarker compounds in asphaltenes can also be obtained from mass chromatograms of hopanes and stanols, e.g. m/z191 (hopanes) m/z 217 (sterols) show a complete carbon number distribution, C29-C35Agastache and gamma-paraffin can be detected; m/z 217 (sterols) also have a complete carbon number distribution, C27-C29Sterane can be detected.
Example 3
The method is adopted to analyze and research the Tahe crude oil sample which is subjected to strong biodegradation.
(1) Dissolving crude oil by using normal hexane, ultrasonically oscillating, standing for 24 hours, filtering by using quantitative filter paper, and filtering filter residues on the filter paper by using dichloromethane to obtain asphaltene;
(2) dissolving the filtered asphaltene volatilized solvent into a toluene/methanol (V: V ═ 1:1) mixed solution in a device shown in figure 1, placing the dissolved solution into a three-neck flask, adding Raney Ni (Raney nickel) catalyst (the mass ratio of the Raney Ni catalyst to the asphaltene is 30:1) into the three-neck flask, and stirring and refluxing for 6 hours at 100 ℃ in a hydrogen atmosphere to obtain a desulfurization product;
(3) and filtering the desulfurization product by using toluene and n-hexane to remove the catalyst, dehydrating the filtrate by using anhydrous sodium sulfate, and then, spin-drying the filtrate by using a rotary evaporator. After the solvent is rotated and evaporated, n-hexane is used for precipitating unreacted asphaltene to obtain a deasphalted asphaltene product;
(4) separating the deasphalted product by using a silica gel chromatographic column to obtain saturated hydrocarbon;
(5) the saturated hydrocarbon is subjected to selective ion mode analysis by adopting Agilent 7890B-5977 GC-MS, and the chromatographic column is a DB-5MS quartz fused elastic capillary column with the thickness of 30m multiplied by 250 mu m multiplied by 0.25 mu m (liquid film thickness). The carrier gas is He, and the sample injection is not carried out by shunting. Mass chromatograms of hopane and stanol were obtained (not shown).
Bound biomarker compounds in asphaltenes can also be obtained from mass chromatograms of hopanes and stanols, e.g. m/z191 (hopanes) m/z 217 (sterols) show a complete carbon number distribution, C29-C35Agastache and gamma-paraffin can be detected; m/z 217 (sterols) also have a complete carbon number distribution, C27-C29Sterane can be detected.
Comparative example 1
The method is adopted to analyze and research the Tahe crude oil sample which is subjected to strong biodegradation.
(1) Dissolving crude oil by using normal hexane, ultrasonically oscillating, standing for 24 hours, filtering by using quantitative filter paper, and filtering filter residues on the filter paper by using dichloromethane to obtain asphaltene;
(2) dissolving the asphaltene obtained by filtration into a toluene/methanol (V: V ═ 1:1) mixed solution after volatilizing the solvent in a device shown in figure 1, placing the dissolved solution into a three-neck flask, adding an excessive Raney Ni (Raney nickel) catalyst (the mass ratio of the Raney Ni catalyst to the asphaltene is 10:1) into the three-neck flask, and stirring and refluxing the mixture at 80 ℃ for 8 hours under a hydrogen atmosphere to obtain a desulfurization product;
(3) and filtering the desulfurization product by using toluene and n-hexane to remove the catalyst, dehydrating the filtrate by using anhydrous sodium sulfate, and then, spin-drying the filtrate by using a rotary evaporator.
(4) The product after spin drying is dissolved by dichloromethane, and then subjected to selective ion mode analysis by Agilent 7890B-5977 GC-MS, wherein a chromatographic column is a DB-5MS quartz fused elastic capillary column with the thickness of 30m multiplied by 250 μm multiplied by 0.25 μm (liquid film thickness). The carrier gas is He, no shunt sample injection is carried out, and the mass chromatogram of the hopane and the sterane is not obtained.
It can be seen from the examples and comparative examples that the method of the present invention does not need to use a conventional high pressure catalytic hydrodesulfurization device, but only uses a simple normal pressure reaction device, hydrodesulfurization is performed on the asphaltenes under mild reaction conditions, and the bonded biomarker compounds in the asphaltenes can be completely detected through deepening treatment (asphaltene precipitation and deasphalted asphaltene product column chromatography separation) on the desulfurization products. The method has the advantages of simple device and mild conditions, greatly reduces the analysis and detection cost of the biomarker compounds in the crude oil asphaltenes, and has wide application prospect.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method for analyzing biomarker compounds in crude oil asphaltenes, comprising the following steps:
s1, extracting crude oil to obtain asphaltene;
s2, in a hydrogen atmosphere, leading the asphaltene to have hydrodesulfurization reaction in the presence of a catalyst to obtain a desulfurization product;
s3, carrying out asphaltene precipitation treatment on the desulfurization product to obtain a deasphalted product;
s4, carrying out column chromatography separation treatment on the deasphalted product to obtain saturated hydrocarbon;
and S5, carrying out GC-MS analysis on the saturated hydrocarbon to obtain the biomarker compounds in the crude oil asphaltenes.
2. The method as claimed in claim 1, wherein the method for extracting and processing crude oil to obtain asphaltene comprises the following steps:
t1, dissolving crude oil in an organic solvent to form a mixed solution;
t2, carrying out ultrasonic oscillation treatment on the mixed solution, standing for precipitation, and filtering to obtain filter residue;
t3, treating the filter residue with an eluent to obtain the asphaltene.
3. The method according to claim 2, wherein the organic solvent is selected from C5-C8One or more of the normal alkanes of (a); and/or
The eluent is selected from one or more of benzene, toluene, methanol, dichloromethane, chloroform and n-hexane.
4. A process according to any one of claims 1 to 3, wherein the catalyst is selected from one or more of nickel metal, raney nickel and palladium on carbon.
5. The method according to any one of claims 1 to 4, wherein in step S2, the mass ratio of the catalyst to the asphaltenes is (0.1-100):1, preferably (10-50): 1.
6. The method according to any one of claims 1 to 5, wherein in step S2, the hydrodesulfurization reaction is carried out using an atmospheric pressure reaction device; and/or
The reaction temperature of the hydrodesulfurization reaction is 40-100 ℃, and preferably 40-80 ℃; the reaction time of the hydrodesulfurization is 1 to 24 hours, preferably 8 to 24 hours.
7. The method according to any one of claims 1 to 6, wherein in step S3, the solvent used for the asphaltene precipitation treatment of the desulfurization product is selected from C5-C8Preferably n-hexane.
8. The method according to any one of claims 1 to 7, wherein in step S4, the column chromatography packing used for the column chromatography separation of the deasphalted product is selected from alumina and/or silica gel, preferably silica gel; the eluent used for the column chromatography separation treatment of the deasphalted product is selected from C5-C8Preferably n-hexane.
9. The method according to any one of claims 1 to 8, wherein in step S5, the GC-MS analysis is a selective ion scan analysis; the GC-MS analysis is carried out on a chromatograph-mass spectrometer;
preferably, the GC-MS analysis adopts a DB-5MS or HP-5MS quartz fused elastic capillary chromatographic column with the size of (20-60) mx (250-320) mu m multiplied by 0.25 mu m, the carrier gas is He, and the sample injection mode is divided flow injection and/or non-divided flow injection.
10. Use of a method according to any one of claims 1 to 9 in the analysis of biomarker compounds in crude oil asphaltenes, in particular in the analysis of high, over mature or biodegradable crude oil asphaltenes.
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