Pyrolysis method of crude oil or asphalt sample
By using muddy siltstone as matrix samples in Rock-eva l 6 pyrolysis instruments to isolate crude oil or asphalt samples, the problem that the existing technology cannot carry out pyrolysis experiments for crude oil or asphalt samples is solved, and high-accurate pyrolysis analysis and quantitative research of different fractions are achieved.
Patent Information
- Application Number
- CN202311286442.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-09-30
- Publication Date
- 2025-04-01
AI Technical Summary
The prior art cannot carry out pyrolysis experiments for crude oil or asphalt non-rock samples, resulting in limited application scope of pyrolysis experiments.
A pyrolysis method of crude oil or asphalt samples was used to isolate crude oil or asphalt samples by placing the sample in a nickel-based crucible and using a mud siltstone as the matrix sample, the matrix sample was used to isolate crude oil or asphalt samples to prevent sintering, and multi-temperature pyrolysis analysis was performed in a Rock-eva l 6 pyrolysis instrument.
The pyrolysis analysis of crude oil or asphalt samples is achieved, which reduces errors, improves the accuracy of the test data, and allows quantitative research on the content of different fractions.
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Figure CN119738246A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of oil and gas geochemical testing, and in particular to a pyrolysis method for crude oil or asphalt samples. Background Art
[0002] The principle of rock pyrolysis analysis is that the rock sample is programmed to heat in a pyrolysis furnace, the discharged hydrocarbons are detected by a hydrogen flame ionization detector, and the carbon monoxide and carbon dioxide generated by the pyrolysis of organic matter and the carbon dioxide generated by the heating and oxidation of residual organic matter after pyrolysis are detected by a thermal conductivity or infrared detector. It is fast, economical and effective in evaluating the hydrocarbon generation potential of source rocks and the oil content of reservoir rocks. Rock pyrolysis technology has been widely used in oil exploration. At present, the Rock EVA L 6 pyrolyzer jointly developed by France Vanchi Company and French Petroleum Research Institute is the mainstream product of domestic rock pyrolysis analysis.
[0003] The rock eva l 6 pyrolyzer is used as an analytical instrument. At present, laboratory pyrolysis experiments are mainly aimed at rock samples. Pyrolysis experiments on non-rock samples such as crude oil or asphalt cannot be carried out for the time being, which greatly limits the scope of application of pyrolysis experiments. The main reason why crude oil or asphalt cannot be subjected to pyrolysis experiments is that the sample container used in the experiment is a nickel-based crucible, and a partition is provided on the bottom and lid of the crucible. The mesh size is smaller than the sample particle size (rock samples are generally crushed to 100 meshes), which plays the role of circulating carrier gas and supporting samples. Crude oil or asphalt has a flowing property. When samples with good fluidity are weighed, the samples flow directly out of the crucible, resulting in the inability to conduct experiments; samples with poor fluidity are heated during the analysis process. The fluidity is enhanced, and the sample flows out of the crucible or blocks the crucible mesh, resulting in distortion of experimental data, damage to the crucible, and the experiment cannot be carried out effectively.
[0004] In order to expand the sample range of pyrolysis experiments and carry out pyrolysis experiments on crude oil or asphalt samples, it is necessary to establish a new pyrolysis method to ensure the feasibility of pyrolysis experiments on such special samples and the reliability of the data. Summary of the invention
[0005] The present application provides a pyrolysis method for crude oil or asphalt samples to solve the above-mentioned technical problem that the prior art cannot carry out pyrolysis experiments on crude oil or asphalt non-rock samples.
[0006] According to one aspect of the present application, an embodiment provides a method for pyrolyzing a crude oil or asphalt sample, comprising the following steps:
[0007] S1. Take a crude oil sample or an asphalt sample and place it in a crucible so that the crude oil sample or the asphalt sample is covered with a matrix sample on all sides, and obtain the mass of the crude oil sample or the asphalt sample; wherein the matrix sample is used to separate the matrix sample from the crude oil sample, or to separate the matrix sample from the asphalt sample, and the matrix sample is argillaceous siltstone, and the parameter values of the amount of liquid hydrocarbon S1, the amount of cracked hydrocarbon S2, the amount of carbon dioxide in organic matter cracking S3, and the residual carbon S4 in the argillaceous siltstone are all lower than 0.05 mg / g;
[0008] S2. Place the crucible in a pyrolyzer and perform pyrolysis of the crude oil sample or asphalt sample under set conditions.
[0009] In one embodiment, the pyrolysis method of the crude oil or asphalt sample further comprises the following steps:
[0010] S0. Preparation of matrix samples.
[0011] In one embodiment, step S0 includes the following sub-steps:
[0012] S01. crushing the muddy siltstone to 40-60 mesh, wherein the selection conditions of the muddy siltstone are low organic matter content and low carbonate mineral content;
[0013] S02. The crushed mud siltstone is placed in a muffle furnace and fired at high temperature under set conditions to remove organic components and minerals in the mud siltstone within the instrument detection temperature range.
[0014] In one embodiment, in step S02, the setting conditions for high-temperature firing of the crushed mudstone siltstone are: firing temperature 850°C to 900°C, and firing time 45min to 60min.
[0015] In one embodiment, step S1 includes the following sub-steps:
[0016] S11. Weigh an appropriate amount of matrix sample and place it in a crucible, and weigh it to obtain a mass G1;
[0017] S12. Weigh an appropriate amount of crude oil sample or asphalt sample and place it on the matrix sample in the crucible, and weigh it to obtain the mass G2;
[0018] S13. Continue to weigh an appropriate amount of matrix sample and place it in a crucible to cover the crude oil sample or asphalt sample;
[0019] S14. Subtract G1 from G2 to obtain the mass G of the crude oil sample or asphalt sample.
[0020] In one embodiment, in step S12, the crude oil sample or the asphalt sample is placed at the center of the crucible to ensure that the crude oil sample is isolated from the crucible wall by the matrix sample, or the asphalt sample is isolated from the crucible wall by the matrix sample.
[0021] In one embodiment, after step S12 is completed, step S13 is quickly implemented to prevent the volatilization of light components in the crude oil sample or asphalt sample.
[0022] In one embodiment, in step S2, a multi-stage pyrolysis method is used to perform pyrolysis analysis on crude oil samples or asphalt samples.
[0023] In one embodiment, the pyrolyzer is a Rock-eva l 6 pyrolyzer.
[0024] In one embodiment, the crucible is a nickel-based crucible used in conjunction with a Rock-eva l 6 pyrolyzer.
[0025] The technical solution of the above embodiment of the present application, by selecting suitable argillaceous siltstone as the matrix sample, the matrix sample isolates the crude oil sample or asphalt sample from the crucible to prevent the crude oil sample or asphalt sample from sintering on the crucible wall during pyrolysis. The pyrolysis of the crude oil sample or asphalt sample is carried out under the isolation of the matrix sample, which realizes the feasibility of carrying out pyrolysis analysis of the crude oil sample or asphalt sample, reduces the error caused by objective reasons, and improves the accuracy of the test data. Through pyrolysis, the content of different fractions in the crude oil sample or asphalt sample is analyzed.
[0026] It should be noted that due to the special properties of crude oil or asphalt samples, crude oil will leak from the crucible screen, resulting in the inability to accurately weigh the sample volume, contaminating the operating table and instruments, and volatilization of light components causing data distortion. In addition, the products of samples with more heavy components such as heavy oil and asphalt after heating will block the pipeline and crucible of the pyrolysis instrument. Therefore, it is impossible to directly place such samples in the crucible for pyrolysis experiments. The pyrolysis method of crude oil or asphalt samples of the present invention avoids the occurrence of the above situation. BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Figure 1 is a schematic diagram of a sample placement method in a crucible in an embodiment;
[0028] Figure 2 It is a pyrolysis spectrum of crude oil fractions under different temperature conditions in an embodiment. DETAILED DESCRIPTION
[0029] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present application will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.
[0030] In order to enable those skilled in the art to better understand the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only embodiments of a part of the present application, not all embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without creative work should fall within the scope of protection of the present application.
[0031] It should be noted that the terms "first", "second" etc. in the present application are used to distinguish similar objects, and need not be used to describe a specific order or sequential order. It should be understood that the data used in this way can be interchanged in appropriate circumstances, so that the embodiments of the present application described here. In addition, the terms "including" and "having" and any of their variations are intended to cover non-exclusive inclusions, for example, the process, method, system, product or equipment comprising a series of steps or units need not be limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or equipment.
[0032] It should be understood that when an element (such as a layer, film, region, or substrate) is described as being "on" another element, the element may be directly on the other element, or there may be an intermediate element. Moreover, in this application, when an element is described as being "connected" to another element, the element may be "directly connected" to the other element, or "connected" to the other element through a third element.
[0033] Embodiment 1
[0034] Please refer to Figure 1 , one embodiment provides a method for pyrolyzing a crude oil or asphalt sample, comprising the following steps:
[0035] S0. Prepare matrix sample;
[0036] S1. Take an appropriate amount of crude oil sample or asphalt sample and place it in a crucible so that the crude oil sample or asphalt sample is covered with matrix sample on all sides, and obtain the mass of the crude oil sample or asphalt sample; wherein the matrix sample is used to separate the matrix sample from the crude oil sample, or to separate the matrix sample from the asphalt sample, and the matrix sample is argillaceous siltstone, and the parameter values of the amount of liquid hydrocarbon S1, the amount of cracked hydrocarbon S2, the amount of carbon dioxide in organic matter cracking S3, and the residual carbon S4 in the argillaceous siltstone are all lower than 0.05 mg / g;
[0037] S2. Place the crucible in a pyrolyzer and perform pyrolysis of the crude oil sample or asphalt sample under set conditions.
[0038] In one embodiment, step S0 includes the following sub-steps:
[0039] S01. crushing the muddy siltstone to 40-60 mesh, wherein the selection conditions of the muddy siltstone are low organic matter content (TOC < 0.5%) and low carbonate mineral content;
[0040] S02. The crushed argillaceous siltstone is placed in a muffle furnace and fired at high temperature under set conditions to remove organic components and minerals in the argillaceous siltstone within the instrument detection temperature range. Preferably, the set conditions are: firing temperature of 850°C to 900°C, and firing time of 45min to 60min.
[0041] In one embodiment, step S1 includes the following sub-steps:
[0042] S11. Weigh an appropriate amount of matrix sample and place it in a crucible, and weigh it to obtain a mass G1;
[0043] S12. Weigh an appropriate amount of crude oil sample or asphalt sample and place it on the matrix sample in the crucible, and weigh it to obtain the mass G2; preferably, the crude oil sample or asphalt sample is placed in the center of the crucible to ensure that the crude oil sample is isolated from the crucible wall by the matrix sample, or the asphalt sample is isolated from the crucible wall by the matrix sample to prevent the crude oil sample or asphalt sample from sintering on the crucible wall;
[0044] After step S12 is completed, step S13 is quickly implemented to prevent the light components in the crude oil sample or the asphalt sample from volatilizing;
[0045] S13. Continue to weigh an appropriate amount of matrix sample and place it in a crucible to cover the crude oil sample or asphalt sample;
[0046] S14. Subtract G1 from G2 to obtain the mass G of the crude oil sample or asphalt sample.
[0047] In one embodiment, in step S2, a multi-temperature pyrolysis method is used to perform pyrolysis analysis on a crude oil sample or an asphalt sample. Pyrolysis analysis of the crude oil sample can obtain crude oil fractions at different temperature stages. Crude oil fractions refer to petroleum components distilled within a certain temperature range, and different fractions have different boiling point ranges. Among them, the sum of fractions PF1 and PF2 is a gasoline fraction, PF3 is a diesel fraction, and PF4 is a lubricating oil fraction.
[0048] In the implementation of the above-mentioned pyrolysis method of crude oil or asphalt sample, the pyrolyzer is selected as Rock-eva 1 6 pyrolyzer. Preferably, the crucible is selected as a nickel-based crucible used in conjunction with the Rock-eva 1 6 pyrolyzer.
[0049] The pyrolysis method of crude oil or asphalt samples of the present invention uses Rockeva L 6 pyrolyzer as an analytical instrument, which can be used to carry out pyrolysis experimental methods of special crude oil or asphalt samples, realize quantitative research on the content of different fractions in crude oil or asphalt, and provide reliable parameters for evaluating the properties of crude oil in reservoirs.
[0050] Embodiment 2
[0051] Please refer to Figure 1 An embodiment provides a pyrolysis method for crude oil samples or asphalt samples. The following will explain the technical solution of the present invention with the ideas of the inventor, which will help those skilled in the art to be familiar with the ideas of the present invention. Among them, some technical points are explained in detail so that those skilled in the art can fully understand the technical solution of the present invention.
[0052] Explain in detail.
[0053] 1. Select a mud siltstone with low organic matter content (TOC < 0.5%) and low carbonate mineral content, crush the mud siltstone sample to 40-60 mesh, place it in a muffle furnace and sinter it at 850°C-900°C for 45-60 minutes to remove the organic components and minerals in the sample within the instrument detection temperature range.
[0054] 2. Use a pyrolysis instrument to detect the amount of liquid hydrocarbons S1, cracked hydrocarbons S2, carbon dioxide in organic matter cracking S3, and residual carbon S4 in the sample after firing. The above parameter values are required to be less than 0.05 mg / g. The organic components and carbon dioxide in the sample have been basically removed and can be used as a matrix sample. If the requirements cannot be met in one firing, multiple firings are required until the parameter content is less than 0.05 mg / g.
[0055] 3. Weigh 18mg~20mg of matrix sample and place it in the nickel-based crucible dedicated to the Rock-eva l 6 pyrolyzer, and weigh to obtain the mass G1 (mg). Weigh 1mg~5mg of crude oil sample or asphalt sample and place it on the matrix sample in the nickel-based crucible, and weigh to obtain the mass G2 (mg). When placing the crude oil or asphalt sample, try to place it in the center of the crucible. The crude oil or asphalt cannot contact the crucible wall, otherwise the crude oil or asphalt sample will sinter on the crucible wall.
[0056] The mass difference obtained by subtracting G1 from G2 is the mass G of the crude oil or asphalt sample. Since the light components in the crude oil or asphalt sample are volatile, after adding the sample, 18 mg to 20 mg of the matrix sample needs to be weighed quickly and added to the nickel-based crucible to cover the crude oil or asphalt sample ( Figure 1 ).
[0057] 4. After weighing the sample, place the crucible in the Rockeva L 6 pyrolyzer for testing, set the pyrolysis analysis conditions, and carry out pyrolysis of crude oil or asphalt. And according to the pyrolysis data, conduct quantitative research on the content of different fractions in the sample.
[0058] Embodiment 3
[0059] Please refer to Figure 1 , Figure 2 An embodiment provides a method for pyrolysis of crude oil or asphalt samples, which is described below through a case to facilitate further understanding of the technical solution.
[0060] A crude oil sample from a domestic oil field was selected and pyrolysis analysis was performed using the method provided by the present invention. Specifically: an appropriate amount of matrix sample was weighed and placed in a nickel-based crucible, and the mass G1 was weighed to be 21.15 mg; an appropriate amount of crude oil sample was extracted with a microinjection needle and injected onto the matrix sample in the crucible, and the mass G2 was weighed to be 25.81 mg; the mass difference between G2 and G1 yielded a crude oil mass of 4.66 mg. To prevent the crude oil from volatilizing, about 20 mg of the matrix sample was quickly weighed and added to the nickel-based crucible to cover the crude oil sample.
[0061] The multi-stage pyrolysis method was used for analysis. Experimental conditions: initial temperature 100℃, final temperature 650℃, heating rate 25℃ / min. Maintain temperature at 100℃, 200℃, 300℃, 650℃ for 5min, 5min, 2min, 2min respectively. After the test, the crude oil fractions at different temperature stages were PF1 61.1mg / g, PF2 257.75mg / g, PF3 231.01mg / g, and PF4 333.27mg / g.
[0062] Crude oil fractions refer to the components of petroleum distilled within a certain temperature range, and different fractions have different boiling point ranges. For this sample, the sum of fractions PF1 and PF2 is the gasoline fraction, PF3 is the diesel fraction, and PF4 is the lubricating oil fraction.
[0063] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims
1. A method for pyrolyzing crude oil or asphalt samples, characterized in that: The following steps are involved: S1. Take a crude oil sample or an asphalt sample and place it in a crucible so that the crude oil sample or the asphalt sample is covered with a matrix sample on all sides, and obtain the mass of the crude oil sample or the asphalt sample; wherein the matrix sample is used to separate the matrix sample from the crude oil sample, or to separate the matrix sample from the asphalt sample, and the matrix sample is argillaceous siltstone, and the parameter values of the amount of liquid hydrocarbon S1, the amount of cracked hydrocarbon S2, the amount of carbon dioxide in organic matter cracking S3, and the residual carbon S4 in the argillaceous siltstone are all lower than 0.05 mg / g; S2. Place the crucible in a pyrolyzer and perform pyrolysis of the crude oil sample or asphalt sample under set conditions.
2. The pyrolysis method of a crude oil or asphalt sample according to claim 1, characterized in that: The pyrolysis method of the crude oil or asphalt sample further comprises the following steps: S0. Preparation of matrix samples.
3. The pyrolysis method of a crude oil or asphalt sample according to claim 2, characterized in that: Step S0 includes the following sub-steps: S01. crushing the muddy siltstone to 40-60 mesh, wherein the selection conditions of the muddy siltstone are low organic matter content and low carbonate mineral content; S02. The crushed mud siltstone is placed in a muffle furnace and fired at high temperature under set conditions to remove organic components and minerals in the mud siltstone within the instrument detection temperature range.
4. The pyrolysis method of a crude oil or asphalt sample according to claim 3, characterized in that: In step S02, the setting conditions for high-temperature firing of the crushed mudstone siltstone are: firing temperature 850°C to 900°C, and firing time 45min to 60min.
5. The pyrolysis method of a crude oil or asphalt sample according to claim 1, characterized in that: Step S1 includes the following sub-steps: S11. Weigh an appropriate amount of matrix sample and place it in a crucible, and weigh it to obtain a mass G1; S12. Weigh an appropriate amount of crude oil sample or asphalt sample and place it on the matrix sample in the crucible, and weigh it to obtain the mass G2; S13. Continue to weigh an appropriate amount of matrix sample and place it in a crucible to cover the crude oil sample or asphalt sample; S14. Subtract G1 from G2 to obtain the mass G of the crude oil sample or asphalt sample.
6. The pyrolysis method of crude oil or asphalt sample according to claim 5, characterized in that: In step S12, the crude oil sample or the asphalt sample is placed at the center of the crucible to ensure that the crude oil sample is isolated from the crucible wall by the matrix sample, or the asphalt sample is isolated from the crucible wall by the matrix sample.
7. The pyrolysis method of crude oil or asphalt sample according to claim 5, characterized in that: After step S12 is completed, step S13 is quickly implemented to prevent the light components in the crude oil sample or asphalt sample from volatilizing.
8. The pyrolysis method of crude oil or asphalt sample according to claim 1, characterized in that: In step S2, a multi-temperature-step pyrolysis method is used to perform pyrolysis analysis on the crude oil sample or the asphalt sample.
9. A method for pyrolyzing a crude oil or asphalt sample according to any one of claims 1 to 8, characterized in that: The pyrolyzer used was Rock-eval 6 pyrolyzer.
10. A method for pyrolyzing a crude oil or asphalt sample according to claim 9, characterized in that: The crucible used is a nickel-based crucible used with the Rock-eval 6 pyrolyzer.