WO2017181394A1

WO2017181394A1 - Oil-gas inclusion component sampling method

Info

Publication number: WO2017181394A1
Application number: PCT/CN2016/079902
Authority: WO
Inventors: 张丛
Original assignee: 深圳市樊溪电子有限公司
Priority date: 2016-04-21
Filing date: 2016-04-21
Publication date: 2017-10-26
Also published as: WO2017181445A1

Abstract

An oil-gas inclusion component sampling method comprising the following steps: a) providing a first container and a second container, where the outer diameter of the first container is smaller than the inner diameter of the second container, and the first container and the second container are transparent; b) placing a solvent into the first container and sealing the first container; c) loading an oil-gas inclusion sample into the second container, then loading the first container containing the solvent and sealed in step b) into the second container; d) utilizing laser to erode the oil-gas inclusion sample in the second container sealed in step c), and then utilizing laser to break open an extremity of the first container in proximity to the sample while keeping the second container intact, thus allowing the solvent in the first container to be introduced into the second container, and as such, fully dissolving the components of the oil-gas inclusion in the solvent.

Description

Method for sampling oil and gas inclusion components

Technical field

The invention belongs to the field of oil and gas exploration research and is used for collecting the components of oil and gas inclusions in geological samples.

Background technique

Oil and gas inclusions are geological paleo-fluid samples captured in minerals such as calcite and quartz during hydrocarbon accumulation. The analysis of the composition of oil and gas inclusions is one of the important means to understand the properties of oil and gas, source, and accumulation period, but because the inclusions themselves are small (the diameter is generally less than 20 microns) and the multi-period oil and gas inclusions are often Superimposed on the same mineral particle, so how to effectively collect the components of the target inclusion is the key and difficult point of inclusion composition analysis. In the current prior art, the collection of oil and gas inclusion components is generally divided into two steps: the first step destroys the main mineral around the inclusions and releases the inclusion components; the second step extracts the released inclusion components. Enrichment. The main methods for destroying the main minerals around the inclusions are laser ablation, mechanical crushing and thermal bursting. The laser ablation method has high precision and can destroy the main mineral around the inclusions on the micrometer scale, and can selectively encapsulate the inclusions. The components are released; the mechanical disruption and the thermal explosion method are not capable of selectively releasing the inclusion components, destroying the main mineral around the target inclusions, and destroying the main minerals around the non-target inclusions, resulting in the collected components. Being polluted. The enrichment of inclusion components is mainly composed of carrier gas purge cold trap enrichment and solvent extraction enrichment. The first method can effectively treat gas hydrocarbons in the inclusions and liquid hydrocarbons with low to medium carbon number. Extraction, but the disadvantage is that with the increase of the carbon number of the compound in the inclusion, the extraction efficiency will be lower and lower, and because the structure of the extraction device is more complicated, it is easy to introduce more external pollution; the second method is for the liquid hydrocarbon compound. (Liquid hydrocarbon compounds containing a higher carbon number) have higher extraction efficiency, but have the disadvantage of lower extraction efficiency for gaseous hydrocarbons. In summary, the existing method can effectively collect the gaseous hydrocarbons in the target inclusions and the liquid hydrocarbons with lower carbon numbers, but it cannot guarantee the high collection efficiency of the higher carbon number compounds in the oil and gas inclusions. Effectively reduce external pollution.

Summary of the invention

In view of the above-mentioned state of the art, in order to make up for the fact that the existing method cannot effectively collect the high carbon number compound in the target oil and gas inclusion and is vulnerable to external pollution, the present invention provides a method for sampling oil and gas inclusion components, including The following steps:

A method for sampling oil and gas inclusion components, comprising the following steps:

a) providing a first container and a second container, wherein the outer diameter of the first container is smaller than the inner diameter of the second container;

b) placing the solvent in the first container and sealing the first container;

c) loading the oil and gas inclusion sample into the second container, and then filling the solvent-filled sealed first container obtained in step b) into the second container, and then sealing the second container;

d) abrading the oil and gas inclusion sample in the sealed second container obtained by the step c) by using a laser to release the oil and gas inclusion component therein, and then using the laser to maintain the second container under the condition that the second container is intact The end near the sample breaks, allowing the solvent in the first container to enter the second container, thus fully dissolving the components of the oil and gas inclusions in the solvent.

The material of the first container and the second container in the above step a) is selected from the group consisting of an organic polymer and an inorganic glass.

The organic polymer is selected from the group consisting of at least one of polymethyl methacrylate, polypropylene, polycarbonate, polyethylene, polyamide, and polystyrene; the inorganic glass is selected from ordinary glass and/or quartz. glass.

The shape of the end faces of the first container and the second container is selected from one of a triangle, an ellipse, a circle, a semicircle, and a polygon, preferably a square.

In a preferred embodiment of the method of the invention, the ports of the first container and the second container are sealed with a hydrogen flame gun in steps c) and d).

In a preferred embodiment of the process of the invention, the solvent in step c) is selected from at least one of n-hexane, dichloromethane, cyclohexane, benzene, toluene, freon, chloroform and diethyl ether. N-hexane is preferred.

In a preferred embodiment of the method of the present invention, the solvent in step c) is injected into the first container through a dedicated syringe for chromatography, then centrifuged to the end of the first container by a centrifuge, and the solvent is frozen to a solid. The first container is then vacuum sealed.

In a preferred embodiment of the method of the invention, the solvent in the first container is centrifuged into the sample end of the second container using a centrifuge in step d).

In a preferred embodiment of the method of the invention, the analysis in step d) is carried out by gas chromatography-mass spectrometry.

In a preferred embodiment of the present invention, the effect of the rock sample of the invention and the solvent package is as shown in FIG. 1 , and the double-layered square capillary structure maintains the relative independence of the sample and the n-hexane solvent, and It is in the same confined space, and the sample is better viewed under a microscope in a square capillary with respect to a circular capillary.

The beneficial effects of the invention:

The method of the invention is simple and convenient to operate, adopts a multi-layer capillary structure, not only maintains the relative independence of the sample and the solvent, but also ensures that the two are in the same closed container, and the high-precision excimer laser can specifically ablate the target inclusion body. In this way, the external pollutants can be effectively reduced, and the organic solvent extraction method used in the present invention can facilitate the enrichment of the inclusion components having a higher carbon number. Compared with the prior art, the method provided by the invention can simultaneously satisfy the target oil and gas inclusions Compounds with higher carbon numbers are efficiently collected and reduce external pollution.

DRAWINGS

1 is a schematic view showing a sampling method of oil and gas inclusion components of the present invention.

LIST OF REFERENCE NUMERALS 1 - oil and gas inclusion sample, 2-second quartz capillary square tube, 3-n-hexane (about 10 ul), 4-first quartz capillary square tube.

Fig. 2(a) is a diagram showing the effect of the first quartz capillary tube before ablation, and the magnification is 200 times.

Fig. 2(b) is a diagram showing the effect of the first quartz capillary tube after ablation, the magnification is 200 times.

Fig. 3(a) is the effect diagram of the ingot before the erosion of the Luo 63 well, with a magnification of 200 times.

Figure 3 (b) is the effect of the erosion of the Luo 63 well, with a magnification of 200 times.

Figure 4 is a graph showing the results of gas chromatography-mass spectrometry analysis of the inclusion components of Luo 63 well.

Fig. 5 is a graph showing the results of gas chromatography-mass spectrometry analysis of the components collected in the background of the inclusion components in Example 2.

Figure 6 is a graph showing the results of gas chromatography-mass spectrometry analysis of the inclusion components in Example 2 collected by the method of the present invention.

detailed description

The present invention will be described in detail below with reference to the embodiments, but the scope of the invention is not limited to the following examples.

In the examples, gas chromatography-mass spectrometry analysis of oil and gas inclusion components was carried out by using Agilent's GC (7890A)-MS (5975C) component analyzer.

The chromatographic conditions are: column type DB-5ms, size 30m×0.32mm×0.25μm; inlet temperature 300°C, transmission line temperature 300°C; column temperature programmed: 80°C (3min)—3°C/min→210 °C—2°C/min→310°C (15min); the carrier gas is He, and the flow rate is 1.5ml/min. The mass spectrometry conditions were: ion source EI+, scan mode TIC/SIM, TIC scan range 50-800, scan period 0.87 c/s.

The hydrogen flame gun is an OH100 hydrogen flame gun manufactured by Walker Energy. The maximum temperature is up to 2800 °C.

The centrifuge is an IEC MB model manufactured by Block Scientific of the United States with a rated speed of 14,000 rpm.

The 193 nm laser is a GEO-Laser type laser produced by Coherent Corporation of the United States.

Example 1

Steps:

(1) Take a certain amount of calcite cement sample 1 in the breccia fracture zone of the Luo 63 well in Zhanhua Depression, and smash the sample 1 into a section with a section of less than 1 mm*1 mm, then dry the pellet and solvent. The surface adsorbed hydrocarbon component is removed.

(2) Take two quartz capillary tubes, the first quartz capillary tube 4 has an inner diameter of 0.7 mm*0.7 mm, an outer diameter of 0.9 mm*0.9 mm, a length of about 50 mm, and a second quartz capillary tube 2 inner diameter of 1 mm. *1mm, outer diameter is 1.2mm*1.2mm, length is about 60mm. First, put two square tubes in methylene chloride solvent for 48 hours, then take out and dry, then seal one end of the two square tubes with a hydrogen flame gun, and finally put the two square tubes into the oven at 100 Bake for about 30 minutes at °C to remove moisture.

(3) First, inject about 10 ul of n-hexane 3 into the first quartz capillary tube 4 with a special syringe for chromatography, and then centrifuge the n-hexane to the sealing end with a centrifuge, and then connect the open end of the first quartz capillary tube 4 Vacuum pump, the other end is immersed in liquid nitrogen to freeze the n-hexane 3 into a solid, start the vacuum pump to draw the vacuum on the first quartz capillary tube 4, and finally seal with a flame gun at the end of the first quartz capillary tube 4 near the vacuum pump and It is taken out of liquid nitrogen.

(4) First, the prepared particles are loaded into the first quartz capillary tube 4, and then the first quartz capillary tube 4 is loaded into the second quartz capillary tube 2, and then the second quartz is irradiated with a flame gun. The open end of the capillary tube 2 is sealed, and the second quartz capillary tube 2 is placed under the laser lens to find the inclusion sample 1 to be collected for the component and the main mineral surrounding the inclusion sample 1 is abraded by a laser. The inclusion component is released, and after the target inclusion is denuded, the first quartz capillary tube 4 is broken near the sample end by a 193 nm laser, and the second quartz capillary tube 2 is placed in a centrifuge to make The n-hexane 3 was centrifuged to the sample end.

(5) Correlate experimental analysis of the composition of oil and gas inclusions by gas chromatography-mass spectrometry.

After the above method is processed, the released inclusion component has been sufficiently dissolved into the n-hexane solvent, and only the second quartz capillary tube 2 is broken during component analysis, and the solution therein can be taken out.

The effect of the laser on the quartz capillary square first quartz capillary tube 4 before and after the sample end is as shown in Fig. 2(a) and Fig. 2(b), the 193nm laser can close the capillary first quartz capillary tube 4 The sample end is ablated and the n-hexane solvent is released.

From the comparison of the photographs before and after the ablation of the sample, Fig. 3(a) and Fig. 3(b), it can be seen that the inclusions in the sample are selectively ablated without affecting other surrounding inclusions. From the analysis results of the sample, it can be seen that the hydrocarbon components in the inclusions are dominated by normal paraffins, the main peak carbon is C15, and the highest hydrocarbon content can be detected. The hydrocarbons in the inclusions are light, in the inclusions. Light oil or condensate is captured.

Example 2

Take another oil and gas inclusion for component analysis. Before collecting and analyzing the inclusions, the sample is collected for the background (ie, except for the main minerals around the inclusions, the other operations and inclusions are collected. The components collected under exactly the same conditions were analyzed and the results are shown in Fig. 5.

After the background composition and analysis of the sample is completed, the same sample is collected for inclusion (ie, steps 1-5 are repeated) and analyzed, and the results are shown in FIG. 6.

As can be seen from the comparison of Fig. 5 and Fig. 6, the background component analysis results are in the number of peaks (numbers 1 to 4 in Fig. 5). Peak) is still much smaller than the inclusion composition in terms of response intensity (in Figure 5, the intensity of the highest peak 1 is only 10,000), indicating that the pollution introduced by the method itself has less impact on the analysis results.

The results show that the method is simple and flexible, and the introduction of less external pollution can effectively collect the components with higher carbon number in the target inclusions, which has high scientific research and practical value.

Claims

A method for sampling oil and gas inclusion components, comprising the following steps:

a) providing a first container and a second container, wherein the outer diameter of the first container is smaller than the inner diameter of the second container;

b) placing the solvent in the first container and sealing the first container;

c) loading the oil and gas inclusion sample into the second container, and then filling the solvent-filled sealed first container obtained in step b) into the second container, and then sealing the second container;

d) abrading the oil and gas inclusion sample in the sealed second container obtained by the step c) by using a laser to release the oil and gas inclusion component therein, and then using the laser to maintain the second container under the condition that the second container is intact The end near the sample breaks, allowing the solvent in the first container to enter the second container, thus fully dissolving the components of the oil and gas inclusions in the solvent.
The method for sampling an inclusion component according to claim 1, wherein the material of the first container and the second container in the step a) is selected from the group consisting of an organic polymer and an inorganic glass.
The method for sampling inclusion composition according to claim 1 or 2, wherein the organic polymer is selected from the group consisting of polymethyl methacrylate, polypropylene, polycarbonate, polyethylene, polyamide, and polystyrene. At least one of the constituent glasses; the inorganic glass is selected from the group consisting of ordinary glass and/or quartz glass.
The method for sampling inclusion components according to claim 1, wherein the shape of the end faces of the first container and the second container is selected from one of a triangle, an ellipse, a circle, a semicircle, and a polygon. It is preferably square.
The method of sampling an inclusion component according to claim 1, wherein the ports of the first container and the second container are sealed by the hydrogen flame gun in the steps c) and d).
The method for sampling inclusion components according to claim 1, wherein the solvent in the step c) is selected from the group consisting of n-hexane, dichloromethane, cyclohexane, benzene, toluene, freon, chloroform and diethyl ether. At least one of them.
The method for sampling inclusion composition according to claim 1, wherein the solvent in step c) is injected into the first container through a special syringe for chromatography, and then centrifuged to the end of the first container by a centrifuge, and The solvent is frozen to a solid and the first container is then vacuum sealed.
The method of sampling inclusion composition according to claim 1, wherein in step d), the solvent in the first container is centrifuged into the sample end of the second container using a centrifuge.
The method for sampling an inclusion component according to claim 1, wherein the sample obtained by obtaining the oil and gas inclusion obtained in the step d) is analyzed by gas chromatography-mass spectrometry.