阅读说明：本技术 根据石油组学判断稠油生物降解程度的方法 (Method for judging biodegradation degree of thick oil according to petromics ) 是由 王萌 朱光有 张志遥 陈志勇 于 2020-04-29 设计创作，主要内容包括：本发明提供了一种根据石油组学判断稠油生物降解程度的方法,所述根据石油组学判断稠油生物降解程度的方法包括：(1)向稠油中加入内标物后,对稠油中的非碱性氮化合物进行电离；(2)对稠油中的非碱性氮化合物进行定量分析；(3)根据步骤(2)中所得非碱性氮化合物含量判断稠油生物降解程度。本发明所提供的该方法对个人经验依赖程度低,能够从石油组学角度较为精确地确定不同稠油的生物降解程度差异。(The invention provides a method for judging the biodegradation degree of thick oil according to petromics, which comprises the following steps: (1) after an internal standard substance is added into the thickened oil, ionizing a non-basic nitrogen compound in the thickened oil; (2) carrying out quantitative analysis on non-basic nitrogen compounds in the thickened oil; (3) and (3) judging the biodegradation degree of the thickened oil according to the content of the non-basic nitrogen compound obtained in the step (2). The method provided by the invention has low degree of dependence on personal experience, and can accurately determine the biodegradation degree difference of different heavy oils from the angle of petromics.)

1. A method for judging the biodegradation degree of thick oil according to the petromics, which is characterized in that the method for judging the biodegradation degree of thick oil according to the petromics comprises the following steps:

(1) after an internal standard substance is added into the thickened oil, ionizing a non-basic nitrogen compound in the thickened oil;

(2) carrying out quantitative analysis on non-basic nitrogen compounds in the thickened oil;

(3) and (3) judging the biodegradation degree of the thickened oil according to the content of the non-basic nitrogen compound obtained in the step (2).

2. The method according to claim 1, characterized in that the thick oil is used in an amount of less than 100 mg.

3. The method of claim 1 or 2, wherein the internal standard comprises d 8-carbazole or d 10-benzo [ C ] carbazole.

4. The method according to claim 3, wherein the mass ratio of the internal standard substance to the thickened oil is 1:1000000-1: 10000000.

5. The method of claim 1, wherein in step (1), the non-basic nitrogen compounds in the thickened oil are ionized by a negative ion electrospray ionization source.

6. The method as claimed in claim 5, wherein the evaporation temperature of the negative ion electrospray ionization source is 200-250 ℃.

7. The method of claim 1, wherein in step (2), the non-basic nitrogen compounds in the thickened oil are quantitatively analyzed by Fourier transform ion trap mass spectrometry.

8. The method of claim 7, wherein the molecular weight range detected by the Fourier transform ion trap mass spectrometry is 200-700.

9. The method of claim 7 or 8, wherein the ion transfer tube temperature of the fourier transform ion trap mass spectrometer is 200-250 ℃.

10. The method according to claim 7 or 8, characterized in that the time of quantitative analysis is less than 30 min.

11. The method according to claim 7 or 8, wherein the detection lower limit of the non-basic nitrogen compound during the quantitative analysis is 0.01 ppm.

12. The method according to any one of claims 1 to 11, wherein the step (3) of judging the biodegradation degree of the thickened oil according to the content W of the non-basic nitrogen compounds obtained in the step (2) comprises the following steps:

when W <3.0ppm, the thick oil is not biodegraded, i.e. its degree of biodegradation is none;

when W is more than or equal to 3.0ppm and less than 9.0ppm, the biodegradation degree of the thickened oil is slight;

when W is more than or equal to 9.0ppm and less than 20.0ppm, the biodegradation degree of the thickened oil is medium;

when W is more than or equal to 20.0ppm and less than or equal to 30.0ppm, the biodegradation degree of the thickened oil is serious;

when W >30.0ppm, the extent of biodegradation of the thick oil is extremely severe.

Technical Field

The invention relates to a method for judging the biodegradation degree of thick oil according to petromics, belonging to the technical field of petroleum sample analysis.

Background

The petromics technology is a basic technology for analyzing and predicting the composition, physical properties and reactivity of crude oil and petroleum products which are regarded as an aggregate of molecules through a detailed composition analysis technology and a molecular reaction modeling technology from a molecular level (see: Song brocade, established; the petromics technology and the trend thereof, the contemporary chemical industry, 2014, 43 (8): 1498-1501).

In most cases, the changes in the thick oil composition are mainly caused by biodegradation. According to Hunt statistics, approximately 1/5 of the thick oil is destroyed by bacteria in the world, and approximately 1/5 of the thick oil has been transformed by bacteria (see Hunt JM. petroleum chemistry and genetics [ M ] San Franciso,1979: 617-618). The investigation of the mechanism of thickened oil biodegradation has been a focus of attention since Williams et al (see: Rubinstein J A, Winters J C. microbiological evaluation of crop oil in thermal energy [ A ].158th National Meeting of the American Chemical Society [ C ], New York,1969,86:22-31) first recognized the biodegradation of thickened oils under natural conditions. Most researchers believe that heavy oil degradation is primarily a function of aerobic microorganisms, and anaerobic microorganisms, such as sulfate-reducing bacteria, are also capable of oxidizing hydrocarbons, but much slower than aerobic microorganisms (see: Chenpingping, Meibor et al, simulation of heavy oil microbial degradation in sandstone reservoirs [ J ], depositional bulletin, 1997, 15(1): 135-.

Because the determination of the biodegradation degree of thickened oil is one of the bases of oil and gas exploration, in addition to the research on the biodegradation mechanism of thickened oil, the concern of those skilled in the art on the biodegradation degree of thickened oil is getting more and more compact, but the existing methods for determining the biodegradation degree of thickened oil in the field basically rely on the personal experience of different professionals for judgment, and because the complexity and the variability of the biodegradation degree of thickened oil, the determination of the biodegradation degree of thickened oil through empirical judgment often leads to inaccurate judgment, so that a method for determining the biodegradation degree of thickened oil with low dependence on personal experience is urgently needed to be established in the field at present.

Disclosure of Invention

In order to solve the above-mentioned disadvantages and shortcomings, the present invention aims to provide a method for judging the biodegradation degree of heavy oil according to petromics. The method has low dependence on personal experience, and can accurately determine the biodegradation degree difference of different heavy oils from the angle of petromics.

In order to achieve the above object, the present invention provides a method for judging the biodegradation degree of heavy oil according to petromics, wherein the method for judging the biodegradation degree of heavy oil according to petromics comprises:

(1) after an internal standard substance is added into the thickened oil, ionizing a non-basic nitrogen compound in the thickened oil;

(2) carrying out quantitative analysis on non-basic nitrogen compounds in the thickened oil;

(3) and (3) judging the biodegradation degree of the thickened oil according to the content of the non-basic nitrogen compound obtained in the step (2).

In the above-described method, preferably, the amount of the thick oil is less than 100 mg.

In the above-described method, preferably, the internal standard comprises d 8-carbazole or d 10-benzo [ C ] carbazole.

In the above-described method, preferably, the mass ratio of the internal standard substance to the thick oil is 1:1000000-1: 10000000.

In the above-mentioned method, preferably, in the step (1), the non-basic nitrogen compounds in the heavy oil are ionized by using a negative ion electrospray ionization source.

In the above-described method, the evaporation temperature of the anion electrospray ionization source is preferably 200-250 ℃. Wherein, the evaporation temperature of the anion electrospray ionization source is set to 200-250 ℃, so that the condensation reaction of the non-basic nitrogen compound at the temperature of over 250 ℃ can be avoided as much as possible, and the analysis result is influenced.

In the method described above, preferably, in the step (2), the non-basic nitrogen compounds in the thick oil are quantitatively analyzed by fourier transform ion trap mass spectrometry.

In the above method, the molecular weight detected by the Fourier transform ion trap mass spectrum is preferably 200-700. The molecular weight range detected by the Fourier transform ion trap mass spectrum is 200-700, so that the interference of the surfactant with the molecular weight less than 200 can be avoided.

In the method described above, the ion transfer tube temperature of the Fourier transform ion trap mass spectrometer is preferably 200 ℃ to 250 ℃. Wherein, the temperature of an ion transmission tube of the Fourier transform ion trap mass spectrum is set to 200-250 ℃, so that the condition that the condensation reaction of the non-basic nitrogen compound is generated at the temperature of more than 250 ℃ to influence the analysis result can be avoided as much as possible.

In the above-described method, preferably, the time for the quantitative analysis is less than 30 min.

In the above-mentioned method, preferably, the detection lower limit of the non-basic nitrogen compound during the quantitative analysis is 0.01 ppm.

In the above-mentioned method, preferably, in the step (3), the determination of the biodegradation degree of the thick oil based on the content W of the non-basic nitrogen compound obtained in the step (2) comprises:

when W <3.0ppm, the thick oil is not biodegraded, i.e. its degree of biodegradation is none;

when W is more than or equal to 3.0ppm and less than 9.0ppm, the biodegradation degree of the thickened oil is slight;

when W is more than or equal to 9.0ppm and less than 20.0ppm, the biodegradation degree of the thickened oil is medium;

when W is more than or equal to 20.0ppm and less than or equal to 30.0ppm, the biodegradation degree of the thickened oil is serious;

when W >30.0ppm, the extent of biodegradation of the thick oil is extremely severe.

In the method, the used negative ion electrospray ionization source and the fourier transform ion trap mass spectrum are conventional devices, and besides the evaporation temperature of the negative ion electrospray ionization source, the molecular weight range detected by the fourier transform ion trap mass spectrum and the ion transmission tube temperature of the fourier transform ion trap mass spectrum, a person skilled in the art can reasonably set other parameters of the negative ion electrospray ionization source and the fourier transform ion trap mass spectrum according to actual needs on site to carry out ionization and quantitative analysis, so long as the purpose of the invention can be realized.

The method for judging the biodegradation degree of the thick oil according to the petromics has low dependence degree on personal experience, and can accurately determine the biodegradation degree difference of different thick oils from the angle of the petromics.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a mass spectrum obtained in example 8 of the present invention.

FIG. 2 is a graph showing the relationship between DBE and the number c of carbon atoms of a non-basic nitrogen compound in example 8 of the present invention.

Detailed Description

In order to clearly understand the technical features, objects and advantages of the present invention, the following detailed description of the technical solutions of the present invention will be made with reference to the following specific examples, which should not be construed as limiting the implementable scope of the present invention.