CN107345947B - Preparation method and application of crude oil asphaltene pyrolysis reaction sample - Google Patents
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Abstract
The invention provides a preparation method of a crude oil asphaltene pyrolysis reaction sample, which comprises the following steps: 1) dissolving crude oil asphaltene in a polar organic solvent, and adding an infusible mineral to obtain a mixture; 2) and removing the organic solvent in the mixture, and carrying out curing treatment to obtain a crude oil asphaltene pyrolysis reaction sample. The crude oil asphaltene prepared by the preparation method can provide chromatography-mass spectrometry online analysis for pyrolysis and catalytic hydrogenation. The invention also provides application of the preparation method in the field of petroleum processing.
Description
Technical Field
The invention belongs to the technical field of application of petroleum exploration and development and oil refining chemical research, and particularly relates to a preparation method of a crude oil asphaltene pyrolysis reaction sample. The invention also relates to the application of the preparation method in the field of petroleum processing.
Background
Crude oil asphaltenes are small nonpolar molecules (C) insoluble in crude oil5-C7) Normal alkane and can be dissolved in polar solvents such as benzene, toluene and the like. It is generally considered to be a fragment molecule of kerogen and has some structural similarity to kerogen. Under geological conditions, asphaltenes have various occurrence forms, and a large amount of asphaltenes can be contained in crude oil liquid systems of oil reservoirs, dispersed liquid hydrocarbons remained in hydrocarbon source rocks, solid asphaltum or tar sands and other organic matters in the reservoirs. The existing asphaltene preparation method is represented by a petroleum soluble organic matter in rock and crude oil group component analysis standard of the petroleum and natural gas industry standard of the people's republic of China (SY/T5119-.
Asphaltenes in crude oil or rock extracts need to be characterized by means of pyrolysis. The pyrolysis process of asphaltenes is widely used in many areas of petrogeochemistry, including oil/source and oil/oil contrast, parent nature and environment of formation, maturity, crude oil formation temperature, crude oil drainage and migration, etc. (giandru, 2004). With the emergence of energy crisis and the increasing proportion of non-traditional resources such as heavy oil in crude oil production worldwide, research on the physical and chemical properties of asphaltenes is more and more important. The fine molecular structure information about geological macromolecules such as asphaltenes comes mainly from research results of various degradation methods.
The pyrolysis method mainly comprises two types of closed systems and open systems, such as a muffle furnace or a gold tube system (bear warrior et al, 1998; King copper mountain et al, 2010), and directly pyrolyzes the crude oil asphaltene sample, and then carries out purification analysis on the pyrolyzed product. The disadvantages of this method are the following: in the heating process, the asphaltene is heated unevenly, the asphaltene on the surface is heated for a long time, products are not easy to discharge in time and other influence factors, secondary degradation and other secondary processes can occur to pyrolysis products, the composition of the pyrolysis products obtained under the condition has certain difference with the original composition of functional groups in geological macromolecular structures such as the asphaltene and the like, and the repeatability is poor; secondly, the pyrolysis product is complex to process, light hydrocarbon components are easy to lose in the processing process, and meanwhile, pyrolysis-chromatography (Py-GC) and pyrolysis-chromatography-mass spectrometry (Py-GC-MS) online analysis processing cannot be carried out; the existing thermal degradation method is mainly applied to analysis of solid asphaltenes, but is rarely applied to analysis of crude oil asphaltenes, and the main reason is that the solid asphaltenes are not melted when heated to the temperature of more than 300 ℃ and only decomposed into gas and coke, and no fraction is available. However, asphaltenes extracted from kerogen and crude oil by organic solvents such as chloroform bitumen A, which contain a high H/C atomic ratio (usually greater than 2), tend to melt at temperatures above 300 ℃ and cause plugging of reaction equipment, especially analytical test lines, by crude oil asphaltenes which melt at high temperatures.
In view of the above problems, there are no reports and patent techniques for treating asphaltenes purified from crude oil prior to pyrolysis reactions. The asphaltene precipitation exists in each link of crude oil production, and accounts for a higher proportion of unconventional resources such as heavy oil. Production practices require a more thorough understanding of the thermodynamic behavior of asphaltenes. Therefore, the field has urgent need for establishing a pretreatment technology of a crude oil asphaltene pyrolysis reaction sample, which can ensure that the asphaltene is not melted under the high-temperature condition, and simultaneously, the surface of the crude oil asphaltene is uniformly heated, and the pyrolysis-chromatographic analysis repeatability is good.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a crude oil asphaltene pyrolysis reaction sample. The method effectively solidifies the asphaltene on the surface of the infusible mineral, increases the heating specific surface area of the asphaltene, improves the pyrolysis reaction efficiency of the asphaltene, ensures the reproducibility of pyrolysis products, provides scientific basis for analyzing the asphaltene structure, biogenesis and other information, and provides new technical support for oil and gas exploration and development.
The invention provides a preparation method of a crude oil asphaltene pyrolysis reaction sample, which comprises the following steps:
1) dissolving crude oil asphaltene in a polar organic solvent, and adding an infusible mineral to obtain a mixture;
2) and removing the organic solvent in the mixture, and carrying out curing treatment to obtain a crude oil asphaltene pyrolysis reaction sample.
The prepared pyrolytic reaction sample is filled into a chromatographic bottle and is sealed and stored by nitrogen for later use. The crude oil asphaltene obtained by the preparation method can provide chromatographic-mass spectrometric online analysis for pyrolysis and catalytic hydrogenation.
According to the invention, the crude oil asphaltene in the step 1) is derived from rock or crude oil extract, and is usually obtained by separating and enriching rock or crude oil by adopting a method commonly used in the field.
In step 1), the polar organic solvent preferably comprises a halogenated C1-C9At least one of alkanes and aromatic hydrocarbons, more preferably C1-C6At least one of chloroalkanes, benzene and toluene, most preferably dichloromethane. The weight ratio of crude oil asphaltenes to polar organic solvent is preferably (1.0-6.0):1, more preferably (3.0-5.0):1, most preferably (3.8-4.6): 1. Within this weight ratio range of the present invention,can completely dissolve the asphaltene and is beneficial to subsequent curing treatment.
According to the invention, in step 1), the weight ratio of the total weight of crude oil asphaltenes and polar organic solvent to the weight of the infusible mineral is preferably 1 (2.0-6.0), more preferably 1 (3.0-5.0), most preferably 1 (4.2-4.8). The infusible mineral preferably comprises at least one of fused silica sand, high purity silica sand and natural silica sand, more preferably fused silica sand. The fused quartz sand, the high-purity quartz sand and the natural quartz sand used in the invention are all commonly used in the field. The non-fusible mineral and the asphaltene selected by the invention do not generate thermochemical reaction, and in the weight ratio range, the heating specific surface area of the asphaltene can be effectively increased, so that the asphaltene is uniformly attached to the surface of the non-fusible mineral, the reaction efficiency is high, and the repeatability is good.
In the present invention, the term "infusible mineral" refers to a mineral material that does not deform and melt below 1000 ℃. The term "high purity silica sand" refers to SiO299.9-99.99 wt% of Fe2O3Natural crystal or natural silica with the content less than or equal to 0.001 wt%.
According to the invention, in step 2), the organic solvent is removed, preferably by rotary evaporation, while the curing treatment is carried out to obtain a completely homogeneous adhesion of the asphaltenes to the surface of the infusible mineral. The temperature of the rotary evaporation is preferably 200-800 ℃, more preferably 300-650 ℃. The time of the rotary evaporation is preferably 20 to 60min, more preferably 30 to 50 min. The rotational speed of the rotary evaporation is preferably 40 to 100r/min, more preferably 60 to 90 r/min. Within the range of the rotating speed, the invention is beneficial to removing the organic solvent and simultaneously further enabling the asphaltene to be uniformly adhered to the surface of the infusible mineral and carrying out cementation and solidification.
Aiming at the characteristic that crude oil asphaltene components are easy to melt in the high-temperature pyrolysis process, the crude oil asphaltene is effectively solidified on the infusible mineral, and the weight ratio of the asphaltene to the organic solvent, the weight ratio of the total weight of the crude oil asphaltene and the polar organic solvent to the infusible mineral and the rotation speed are optimized, so that the preparation method is simple and quick, the good pyrolysis reaction analysis effect is obtained, the preparation method is simple and quick, and the test conditions of high-temperature pyrolysis, catalytic hydrogenation and the like can be well met.
The invention also provides application of the preparation method in the field of petroleum processing. The invention can also be applied to the fields related to geology, oil gas storage and transportation and the like, and can also be used for effectively treating the asphaltene in the crude oil sample, thereby providing a proper sample for subsequent instrument analysis.
The invention provides a preparation method of a crude oil asphaltene pyrolysis reaction sample, the obtained sample can be directly subjected to pyrolysis or catalytic hydrogenation chromatography-mass spectrometry, the analysis requirement is met, and a foundation is laid for the composition research and geochemical application of asphaltene in a petroleum geological sample.
Drawings
FIG. 1 is a chromatogram-mass spectrum of saturated hydrocarbon after pyrolysis reaction at 300 ℃ of a crude oil sample in comparative example 1.
FIG. 2 is a chromatogram-mass spectrum of saturated hydrocarbon obtained by pyrolysis of crude oil asphaltenes at 300 ℃ in example 1.
FIG. 3 is a chromatogram-mass spectrum of saturated hydrocarbons of the crude oil asphaltene catalytic hydropyrolysis product in example 2.
Fig. 2 and fig. 3 are chromatogram-mass spectra of saturated hydrocarbon in catalytic hydrogenation and pyrolysis, and it can be seen from the graphs that, compared with fig. 1, the crude oil asphaltene pyrolysis product obtained by the preparation method provided by the invention has a good saturated hydrocarbon peak.
Detailed Description
The invention will now be further illustrated by means of specific examples, but it will be understood that the scope of the invention is not limited thereto.
The method for separating crude oil asphaltenes from crude oil is referred to "determination of wax, colloid, asphaltene content in crude oil" (SY/T7550-2012).
Saturated hydrocarbon-chromatography-mass spectrometry on-line analysis method referring to GB/T18340.5-2010 geological sample organic geochemical analysis method part 5-rock extract and crude oil saturated hydrocarbon analysis gas chromatography.
Example 1
10g of crude oil asphaltenes separated from crude oil were taken and dissolved well in 2g of methylene chloride. 40g of fused silica sand was added and stirred well. And removing the dichloromethane to constant weight by rotary evaporation, wherein the temperature of the rotary evaporation is 300 ℃, the time is 40min, and the rotating speed is 75r/min, so as to prepare the asphaltene sample for the pyrolysis reaction. It was transferred to a chromatographic flask and stored sealed with nitrogen.
And (3) placing the obtained pyrolysis reaction asphaltene sample in a muffle furnace, heating for 72h at 300 and 340 ℃, and analyzing a pyrolysis product on line by using saturated hydrocarbon-chromatography-mass spectrometry.
Example 2
10g of crude oil asphaltenes separated from crude oil were taken and dissolved well in 6g of methylene chloride. 80g of fused silica sand was added and stirred well. And (3) removing the dichloromethane to constant weight by rotary evaporation, wherein the temperature of the rotary evaporation is 450 ℃, the time is 50min, and the rotating speed is 90r/min, so that the pyrolysis reaction asphaltene sample is prepared. It was transferred to a chromatographic flask and stored sealed with nitrogen.
And carrying out hydrogenation reaction on the obtained asphaltene sample for the pyrolysis reaction under the action of a catalyst. The hydrogenation product is placed in a muffle furnace, heated for 72h at 300 and 340 ℃, and the catalytic hydropyrolysis product is analyzed on line by saturated hydrocarbon-chromatography-mass spectrometry.
Example 3
10g of crude oil asphaltenes separated from crude oil were taken and dissolved well in 10g of methylene chloride. 80g of fused silica sand was added and stirred well. And (3) removing the dichloromethane to constant weight by rotary evaporation, wherein the temperature of the rotary evaporation is 600 ℃, the time is 60min, and the rotating speed is 90r/min, so that the pyro lysis reaction asphaltene sample is prepared. It was transferred to a chromatographic flask and stored sealed with nitrogen.
And (3) placing the obtained pyrolysis reaction asphaltene sample in a muffle furnace, heating for 72h at 300 and 340 ℃, and analyzing a pyrolysis product on line by using saturated hydrocarbon-chromatography-mass spectrometry.
Comparative example 1
10g of crude oil asphaltenes separated from crude oil were taken and dissolved well in 20g of methylene chloride. 40g of fused silica sand was added and stirred well. And removing the dichloromethane to constant weight by rotary evaporation, wherein the temperature of the rotary evaporation is 300 ℃, the time is 40min, and the rotating speed is 75r/min, so as to prepare the asphaltene sample for the pyrolysis reaction. It was transferred to a chromatographic flask and stored sealed with nitrogen.
And (3) placing the obtained pyrolysis reaction asphaltene sample in a muffle furnace, heating for 72h at 300 and 340 ℃, and analyzing a pyrolysis product on line by using saturated hydrocarbon-chromatography-mass spectrometry. The result shows that the obtained spectrogram has obviously increased impurity peaks.
Comparative example 2
10g of crude oil asphaltenes separated from crude oil were taken and dissolved well in 2g of methylene chloride. 100g of fused silica sand was added and sufficiently stirred. And removing the dichloromethane to constant weight by rotary evaporation, wherein the temperature of the rotary evaporation is 300 ℃, the time is 40min, and the rotating speed is 75r/min, so as to prepare the asphaltene sample for the pyrolysis reaction. It was transferred to a chromatographic flask and stored sealed with nitrogen.
And (3) placing the obtained pyrolysis reaction asphaltene sample in a muffle furnace, heating for 72h at 300 and 340 ℃, and analyzing a pyrolysis product on line by using saturated hydrocarbon-chromatography-mass spectrometry. The result shows that the spectrogram plotting time is too long, and more miscellaneous peaks appear.
Comparative example 3
10g of crude oil asphaltenes separated from crude oil were taken and dissolved well in 2g of methylene chloride. 40g of fused silica sand was added and stirred well. And removing the dichloromethane to constant weight by rotary evaporation, wherein the temperature of the rotary evaporation is 300 ℃, the time is 60min, and the rotating speed is 110r/min, so as to prepare the asphaltene sample for the pyrolysis reaction. It was transferred to a chromatographic flask and stored sealed with nitrogen.
And (3) placing the obtained pyrolysis reaction asphaltene sample in a muffle furnace, heating for 72h at 300 and 340 ℃, and analyzing a pyrolysis product on line by using saturated hydrocarbon-chromatography-mass spectrometry. The result shows that the obtained spectrogram has obviously increased impurity peaks.
As can be seen from FIGS. 1-3, the present invention achieves a good pyrolysis reaction effect by effectively solidifying asphaltenes in crude oil. The cured crude oil asphaltene sample has a good saturated hydrocarbon peak, and can be subjected to pyrolysis saturated hydrocarbon-chromatography-mass spectrometry on-line analysis. The asphaltene spectrograms obtained in the comparative examples 1 to 3 have obvious swelling and impurity peak characteristics, and the online analysis cannot be carried out due to too many impurity peaks. The crude oil asphaltene pyrolysis reaction sample obtained in example 1 still had a similar pattern at 340 ℃ to that at 300 ℃, whereas the crude oil asphaltene pyrolysis reaction sample obtained in comparative example 3 blocked the test line at 340 ℃ making analysis impossible. This shows that the preparation method of the invention can provide excellent samples for on-line analysis of chromatography-mass spectrometry for pyrolysis and catalytic hydrogenation.
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Further, it should be understood that the various aspects recited herein, portions of different embodiments, and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.
Claims (11)
1. A preparation method of a crude oil asphaltene pyrolysis reaction sample comprises the following steps:
1) dissolving crude oil asphaltene in a polar organic solvent, and adding an infusible mineral to obtain a mixture;
2) removing the organic solvent in the mixture, and carrying out curing treatment to obtain a crude oil asphaltene pyrolysis reaction sample;
wherein the weight ratio of the crude oil asphaltene to the polar organic solvent is (1.0-6.0):1, and the weight ratio of the total weight of the crude oil asphaltene and the polar organic solvent to the infusible mineral is 1: (2.0-6.0); the polar organic solvent comprises C1-C6At least one of chlorinated alkane, benzene and toluene, and the infusible mineral comprises at least one of fused silica sand, high-purity silica sand and natural silica sand.
2. The method of claim 1, wherein in step 1), the weight ratio of crude oil asphaltenes to polar organic solvent is (3.0-5.0): 1.
3. The preparation method of claim 1, wherein in the step 1), the weight ratio of the total weight of the crude oil asphaltenes and the polar organic solvent to the non-fusible minerals is 1 (3.0-5.0).
4. The method of claim 1, wherein in step 2), the organic solvent is removed by rotary evaporation.
5. The method of claim 4, wherein the rotary evaporation is performed at a rotation speed of 40 to 100 r/min.
6. The method of claim 4, wherein the rotary evaporation is performed at a rotation speed of 60 to 90 r/min.
7. The method of claim 5 or 6, wherein the time of the rotary evaporation is 20 to 80 min.
8. The method of claim 5 or 6, wherein the time of the rotary evaporation is 30-50 min.
9. The method as claimed in claim 4, wherein the temperature of the rotary evaporation is 200-800 ℃.
10. The method as claimed in claim 4, wherein the temperature of the rotary evaporation is 300-650 ℃.
11. Use of the preparation process according to any one of claims 1 to 10 in the field of petroleum processing.
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| CN111927441B (en) * | 2019-05-13 | 2023-10-31 | 中国石油天然气股份有限公司 | Crude oil component simulation method for oil-water transition zone |
| CN110243957B (en) * | 2019-05-29 | 2022-05-10 | 中国石油天然气股份有限公司 | Method for extracting biomarker compounds in high/over-mature asphalt |
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