CN108169179B - Method for determining effective conditions for evaluating biogenic source constitution of hydrocarbon source rock by using n-alkanes - Google Patents
Method for determining effective conditions for evaluating biogenic source constitution of hydrocarbon source rock by using n-alkanes Download PDFInfo
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Abstract
The invention relates to a method for determining effective conditions of n-alkane distribution characteristics in evaluation of hydrocarbon source rock formation application. The invention provides a method for determining effective conditions for evaluating the constitution of a hydrocarbon source rock biogenesis by using n-alkanes, which comprises the following steps: firstly, sampling representative hydrocarbon source rocks; (ii) performing kerogen vitrinite reflectance on all source rock samples: (R o) Determining the maturity of the sample; thirdly, determining the biogenic composition of all the hydrocarbon source rock samples quantitatively by utilizing the kerogen organic microscopic component data; fourthly, evaluating the biogenic composition of the sample according to the distribution of the normal alkane; fifthly, verifying the biogenic source composition result determined in the fourth step by using the biogenic source composition result determined in the third step; and sixthly, determining effective maturity conditions for evaluating the biogenic formation of the hydrocarbon source rock by the n-alkanes according to the effective maturity range of the sample. The invention provides a basis for accurately determining the organic matter source of the hydrocarbon source rock by utilizing the distribution characteristics of the normal paraffin.
Description
Technical Field
The invention belongs to the field of oil and gas geochemistry research, and particularly relates to a method for determining effective conditions of n-alkane distribution characteristics in evaluation of hydrocarbon source rock biogenesis application.
Background
N-alkanes are the most prominent organic components of source rocks and their carbon number distribution characteristics have an indicating role in the source of the organic matrix of source rocks (lushuang et al, 2008). High carbon number n-alkanes with odd and even dominance are generally considered (>nC23) Input that may be indicative of land-sourced organic matter; with nC15、nC17Medium relative molecular weight n-alkanes (nC) which are dominant and have insignificant odd-even dominance15—nC21) Possibly indicating the source of aquatic organisms such as algae (lushuang boats et al, 2008; b.p. sesamol et al, 1982). The predecessors have used n-alkanes extensively in research to determine the source of organic matter, whether modern or ancient, whether crude or source, whether mature or immature.
The inventor finds that the normal paraffin distribution characteristics of all the hydrocarbon source rock samples are not allThe organic matter source of the hydrocarbon source rock can be well indicated, the distribution of the normal paraffin is controlled by the type of the organic matter, and the influence of the maturity of the organic matter on the organic matter is not ignored. The normal paraffins of immature source rock usually have strong odd-even preponderance and abnormally high Pr/nC17Ratio and Ph/nC18This is because the distribution characteristics of the normal paraffins in the immature source rock are of little significance to the indication of the source, because the unsaturated hydrocarbons such as isoprenoid alkanes in the immature source rock are converted into saturated hydrocarbons in a limited amount, resulting in a low overall normal paraffin content, mostly "burr-like" distribution peaks, and difficult recognition of the main peak carbon (Zhi Jia Sheng et al, 1995; Sun Yongji et al, 1995). For mature-over mature source rock, the higher degree of thermal evolution leads to the cleavage of part of the normal paraffins, the long-chain normal paraffins becoming low-medium chain normal paraffins due to C — C bond cleavage (Qin xiaometii et al, 2013). The distribution characteristics of the normal paraffins in the petroleum cracking process are analyzed by simulation experiments (2009) of Tangxiaoqiang et al, and the results show that the normal paraffins with high molecular weight in the crude oil begin to be pyrolyzed before the crude oil is cracked to generate a large amount of gaseous hydrocarbons, and C15Cracking of hydrocarbons predominantly to C6—C14With increasing maturity, C6—C14Further converted into C1—C5. With the increase of the thermal evolution degree, the normal paraffin of the source rock should have the cracking process, so that the normal paraffin of the mature-over-mature source rock is mainly medium-chain normal paraffin, the distribution characteristics of the normal paraffin are mostly in a single peak type, and if the normal paraffin data is used alone to obtain wrong biogenic conclusions, the distribution characteristics of the normal paraffin of the source rock also have no indication significance on biogenic formation. Therefore, only within a certain maturity range does the distribution characteristics of the normal paraffins of the source rock have an indication for the biogenic composition. In practical work, the influence of maturity on the distribution characteristics of normal alkanes is often ignored, and then the distribution characteristics of the normal alkanes are used for determining biogenic composition, so that an incorrect conclusion is obtained.
Methods for determining the composition of the source of the hydrocarbon rock are many, such as the kerogen organic micro-component method, the n-alkane distribution characteristic method, C27-C29Regular sterane relative content method, etc., wherein the organic micro-components of kerogen can more intuitively and accurately react with the biogenic formation of the hydrocarbon source rock.
Disclosure of Invention
The invention aims to provide a method for determining effective conditions for evaluating the formation of a hydrocarbon source rock biogenesis source by using n-alkanes, which is used for determining the influence degree of the maturity of a hydrocarbon source rock on the distribution of the n-alkanes, determining the effective conditions for evaluating the formation of the hydrocarbon source rock biogenesis source by using the distribution characteristics of the n-alkanes and providing a basis for accurately determining the organic matter source of the hydrocarbon source rock by using the distribution characteristics of the n-alkanes.
The invention provides a method for determining effective conditions for evaluating the constitution of a hydrocarbon source rock biogenesis by using n-alkanes, which comprises the following steps:
step one, sampling a representative source rock, wherein the source rock sample has the following 2 aspects: firstly, the organic matter type is abundant, and the type I, the type II and the type III are all related; secondly, the sample needs to cover the hydrocarbon source rock at all thermal evolution stages of immature, low maturity, high maturity, over maturity and the like;
step two, carrying out kerogen vitrinite reflectivity (R) on all the hydrocarbon source rock sampleso) Determining the maturity of the sample;
thirdly, carrying out the identification of organic microscopic components of the kerogen, and quantitatively determining the biogenic composition of all the hydrocarbon source rock samples;
step four, carrying out saturated hydrocarbon gas chromatography analysis on the asphalt extracts of all the hydrocarbon source rock samples, and evaluating the biogenic composition of the samples according to the distribution of normal paraffin;
step five, verifying the biogenic source composition result determined in the step four by using the biogenic source composition result determined in the step three: when the results evaluated in the third step and the fourth step are consistent, the distribution characteristics of the normal alkane are effective in the application of determining the biogenic source of the hydrocarbon source rock, and the distribution characteristics of the normal alkane of the sample have good indication effect on the biogenic source; when the results evaluated in the third step and the fourth step are inconsistent, the distribution characteristics of the normal alkane are invalid or have poor effect in the application of determining the biogenic rock formation of the hydrocarbon source, and the distribution characteristics of the normal alkane of the sample have no indication significance on the biogenic rock formation;
and step six, determining effective maturity conditions for evaluating the formation of the hydrocarbon source rock by the n-alkanes according to the maturity range of the effective sample in the step five.
More preferably, the invention establishes the following calculation formula (1) and formula (2) for quantitatively calculating the biogenic composition of the sample for the first time:
t is the percentage of terrestrial biogenic sources of the sample in unit, W is the percentage of aquatic biogenic sources of the sample in unit, ∑ V is the total number of vitrinites, ∑ I is the total number of inerts, ∑ E is the total number of chitins, and ∑ S is the total number of sapropel groups.
Further preferably, the identification and quantitative determination of the biogenic composition of all the hydrocarbon source rock samples by carrying out the organic kerogen microscopic components in the third step comprises the following steps:
(1) removing inorganic minerals and soluble organic matters in rocks by adopting chemical and physical methods to the sample, enriching insoluble organic matters, and preparing kerogen;
(2) identifying the kerogen microscopic components in the rock by using a biological microscope with functions of white light transmission and epi-fluorescence transmission, and respectively calculating the percentage content (percentage of the total amount of all the microscopic components) of the 4 groups of organic microscopic components of the sapropel group, the chitin group, the vitrinite group and the inert group;
(3) in the classification of the kerogen micro-component composition of the Fujian Qi (1998), the vitrinite, inertinite and chitin groups of the 4 organic micro-components are mainly derived from terrestrial organisms, while the sapropel group is mainly derived from aquatic organisms.
Or more preferably, the step two of performing the kerogen vitrinite reflectance determination on all the hydrocarbon source rock samples comprises the following steps:
(1) removing inorganic minerals and soluble organic matters in rocks by adopting chemical and physical methods to the sample, enriching insoluble organic matters, and preparing kerogen;
(2) the reflectivity of the kerogen vitrinite is measured, the number of measuring points is required to be not less than 20, and the average reflectivity value is taken as R of the sampleo。
Still alternatively or more preferably, the step four of performing a saturated hydrocarbon gas chromatography analysis and biogenic signature analysis on the extract of the sample comprises the steps of:
(1) carrying out a trichloromethane asphalt extraction experiment on the sample to obtain an asphalt extract;
(2) carrying out gas chromatographic analysis on saturated hydrocarbon on the asphalt extract to obtain a normal paraffin distribution curve;
(3) determining biogenic characteristics of the hydrocarbon source rock sample according to a normal paraffin distribution curve peak type, wherein the 'unimodal front peak type' indicates biogenic characteristics with the aquatic organism input as a main part, the 'unimodal rear peak type' indicates biogenic characteristics with the land organism input as a main part, and the 'bimodal' indicates biogenic characteristics with the land organism and the aquatic organism mixed input.
The invention discloses a method for determining effective conditions for evaluating the biogenic formation of hydrocarbon source rocks by using n-alkanes, which comprises the following steps: firstly, establishing a quantitative biogenic composition calculation formula for the first time based on the kerogen organic micro-component data, wherein the quantitative biogenic composition calculation formula is used for quantitatively calculating the biogenic composition of the hydrocarbon source rock; secondly, qualitatively evaluating the biogenic characteristics of the hydrocarbon source rock based on the normal paraffin data; and finally, verifying whether the biogenic source composition result determined by the normal alkane distribution characteristic method is effective by using the biogenic source composition result determined by the kerogen obvious organic micro-component method, and quantitatively determining the effective condition of the normal alkane distribution characteristic in the application of determining the biogenic source formation of the hydrocarbon source rock. The method has important significance for determining the influence degree of maturity on the distribution of the normal paraffin of the source rock, more accurately determining the organic matter source of the source rock by using the distribution characteristics of the normal paraffin and the like.
The method has the advantages of defining the influence degree of the maturity of the hydrocarbon source rock on the distribution of the normal paraffin, determining the effective condition for evaluating the biogenic source composition of the hydrocarbon source rock by using the distribution characteristics of the normal paraffin, and providing a basis for accurately determining the organic matter source of the hydrocarbon source rock by using the distribution characteristics of the normal paraffin.
Drawings
Fig. 1 to 4 are schematic diagrams showing the flow of determining effective conditions for evaluating the formation of a hydrocarbon source rock by normal paraffins according to the present invention.
FIG. 5 is a silver-rated basin geographic location and structuring element division diagram.
FIG. 6 geochemical section of a source rock of a silver basin H-well.
Examples
Determination of effective conditions for evaluating constitution of hydrocarbon source rock biogenesis by silver frontal basin normal paraffin
The silver frontal basin is located in the west of inner Mongolia autonomous region (fig. 5), and the sedimentary strata are mainly of the lower chalky system and can be divided into Bartonege wall groups (K) from bottom to top1b) Suhong chart group (K)1s) and silver root group (K)1y), early chalkiness is the full development period of the depressed basin, developing the sectorial delta-lake sedimentary system (spagherwei et al, 2013; linderwondo et al, 2004; chenjiaping et al, 2001). The chalky source rocks of the system in the area develop comparatively, and the lithology of the source rocks mainly comprises dark gray-black argillaceous rocks, gray-dark gray argillaceous rocks, gray argillaceous mudstones, dark gray dolomitic mudstones, pozzolanic mudstones, argillaceous dolomite and the like (Chengzhou et al, 2017; Zhao Chun et al, 2017).
The H well of the basin is selected as a research object, and systematic sampling is carried out on the chalky system source rock under the H well, wherein the number of the samples is 21, and the samples are numbered from H1 to H21. And carrying out geochemical test analysis such as kerogen vitrinite reflectivity determination, kerogen saturated hydrocarbon gas chromatographic analysis and the like on the hydrocarbon source rock sample.
The test results show (table 1): the total organic carbon content (TOC) of the source rock is 0.08-8.56 percent, and the average content is 2.37 percent; hydrocarbon generation potential (S)1+S2) 0.05-62.71 mg/g, and the average is 13.59 mg/g; the chloroform asphalt A is 0.001-0.466 percent, and the average is 0.133 percent; the abundance of the organic matters of the source rocks is very different, namely the source rocks with very low abundance and the source rocks with very high quality with very high abundance of the organic mattersA source rock. Kerogen H/C (atomic ratio) of 0.62 to 2.13, O/C (atomic ratio) of 0.05 to 0.53, carbon isotope delta13The C value is-29.9-20.4%, the whole hydrocarbon source rock is mixed (II)1Types II and II2Type) but with development of type i or type iii source rock in some sections of the well. Specular component reflectance (R)o) 0.49-2.34%, maximum pyrolysis peak temperature (T)max) The temperature is 429-533 ℃, the maturity span of the source rock is large, and the source rock with low maturity and the over-mature source rock exist. The above shows that these source rock samples are somewhat representative.
And (3) carrying out biogenic composition analysis on 21 samples by respectively utilizing 2 methods in the third step and the fourth step, wherein the samples can be divided into 3 types according to the indication of existence of biogenic composition by the distribution characteristics of the normal paraffin and the distribution characteristics of the normal paraffin, and the samples respectively represent 3 types of hydrocarbon source rocks.
The first category includes samples H-1 and H-2, Source rock RoThey had CPI (carbon dominance index) of 5.27 and 4.25, respectively, and OEP (parity dominance) of 4.51 and 4.22, respectively, indicating that the source rock had significant carbon dominance and was less mature ∑ nC21-/∑nC22+(light-to-heavy carbon ratio of n-alkane) 0.14 and 0.32, respectively, (nC)21+nC22)/(nC28+nC29) 0.36 and 1.21 respectively, and the relative content of the long-chain high-carbon-number normal alkane is obviously greater than that of the low-carbon-number normal alkane. Pr/nC17Respectively 2.13 and 0.81, Ph/nC189.65 and 15.05, Pr/Ph 0.36 and 0.22, respectively, with higher abundance of source rock isoprenoid. The overall distribution characteristics of the normal paraffin are in a burr shape, and the organic matter source of the hydrocarbon source rock is very difficult to determine by depending on the distribution of the normal paraffin alone (figure 6). The kerogen micro-fraction showed an absolute preponderance of the relative contents of the sapropel group, 80.8% and 87.2%, respectively, representing the biogenic characteristics of predominantly aquatic organisms (table 2). The source rock has low saturated hydrocarbon content, the distribution of the normal alkane is in a burr shape, and the distribution characteristics of the normal alkane have no indication significance on the biogenic source of the source rock.
The second category includes samples H-3-H-15, hydrocarbonsSource rock RoThe carbon content of the low-maturity and partially-mature hydrocarbon source rocks is 0.60-0.80%, and the low-maturity and partially-mature hydrocarbon source rocks have obvious carbon advantages, the CPI is 1.49-2.03 and is 1.65 on average, the OEP is 1.20-2.68 and is 1.63, ∑ nC on average21-/∑nC22+0.27-0.97, average 0.51; (nC)21+nC22)/(nC28+nC29) 0.30 to 8.43, and an average of 2.43. The distribution characteristics of the normal paraffin of the source rock are shown as 'unimodal rear peak type', and the main peak carbon is C23Mainly, secondly, C29And C25The n-alkane profile showed that the organic matter of this type of source rock was mainly derived from terrestrial organisms (fig. 6). The content of vitrinite or asphalt, inert component and chitin component from terrestrial organisms is 50.0-84.0%, and the average content is 63.6%; the content of sapropel from aquatic organisms is 16.0-50.0%, and the average content is 36.4%; organic matter indicative of hydrocarbon source rock originates mainly from terrestrial organisms (table 2). The distribution characteristics of the normal paraffin of the source rock are consistent with the biogenic characteristics determined by the kerogen micro-components, and the distribution characteristics of the normal paraffin have good indication effect on the biogenic composition of the source rock.
The third category includes samples H-16-H-21, Source rock Ro0.95 to 2.11 percent of the total weight of the rock, which represents mature-over-mature source rock, the source rock has no obvious odd-even advantages, the CPI is 1.08 to 1.60, the average value is 1.26, the OEP is 0.91 to 1.20, the average value is 1.04, ∑ nC21-/∑nC22+0.58-3.76, average 2.58; (nC)21+nC22)/(nC28+nC29) 2.90 to 5.95, and an average of 4.72. The distribution characteristics of the normal paraffin of the source rock show a single-peak front-peak type, and the main peak carbon is mainly C14、C15And C16(FIG. 6). If the biogenic composition is determined by using the distribution characteristics of the normal paraffin, the conclusion that the organic matter of the hydrocarbon source rock mainly originates from aquatic organisms can be obtained. The kerogen microscopic component shows that the content of vitrinite or asphalt, inertia component and chitin component from terrestrial organisms is 50.0-90.0%, and the average content is 68.4%; the content of the sapropel group from aquatic organisms is only 10.0-50.0%, and the average content is 31.6%; indicating that the organic matter of the source rock is mainly originated from the landSource organisms (table 2). Such source rocks usually contain medium-short chain normal paraffins of relatively high specific gravity, so that the distribution of normal paraffins tends to appear "unimodal, and the distribution characteristics of normal paraffins are not indicative of the formation of the source rock.
Therefore, the distribution characteristics of the n-alkanes of the source rock have no indication effect on the source composition under the conditions of overhigh maturity and overlow maturity, the distribution characteristics of the n-alkanes of the source rock have indication significance on the source composition only within a certain maturity range, and the research on the chalky lake-phase source rock under the silver basin H well shows that only the condition that R is metoWhen the content is 0.60-0.80%, the normal alkane has good indication effect on the biogenic source.
TABLE 1 geochemical test data for source rock of H-wells
TABLE 2 organic micro-components and biogenic composition of kerogen in H-well hydrocarbon source rock
And V is the total number of vitrinite groups, I is the total number of inert groups, E is the total number of chitin groups, and S is the total number of sapropel groups.
Claims (5)
1. A method for determining effective conditions for evaluating the formation of a hydrocarbon source rock by normal paraffins, comprising the steps of:
sampling representative hydrocarbon source rocks;
step two, carrying out kerogen vitrinite reflectivity (R) on all the hydrocarbon source rock sampleso) Determining the maturity of the sample;
thirdly, carrying out the identification of organic microscopic components of the kerogen, and quantitatively determining the biogenic composition of all the hydrocarbon source rock samples;
step four, carrying out saturated hydrocarbon gas chromatography analysis on the asphalt extracts of all the hydrocarbon source rock samples, and evaluating the biogenic composition of the samples according to the distribution of normal paraffin;
step five, verifying the biogenic source composition result determined in the step four by using the biogenic source composition result determined in the step three: when the results evaluated in the third step and the fourth step are consistent, the distribution characteristics of the normal alkane are effective in the application of determining the biogenic source of the hydrocarbon source rock, and the distribution characteristics of the normal alkane of the sample have good indication effect on the biogenic source; when the results evaluated in the third step and the fourth step are inconsistent, the distribution characteristics of the normal alkane are invalid or have poor effect in the application of determining the biogenic rock formation of the hydrocarbon source, and the distribution characteristics of the normal alkane of the sample have no indication significance on the biogenic rock formation;
and step six, determining effective maturity conditions for evaluating the formation of the hydrocarbon source rock by the n-alkanes according to the maturity range of the effective sample in the step five.
2. The method of claim 1, wherein the step three comprises quantitatively calculating the biogenic composition of the sample by using the following formula (1) and formula (2):
t is the percentage of terrestrial biogenic sources of the sample in unit, W is the percentage of aquatic biogenic sources of the sample in unit, ∑ V is the total number of vitrinites, ∑ I is the total number of inerts, ∑ E is the total number of chitins, and ∑ S is the total number of sapropel groups.
3. The method for determining effective conditions for evaluating biogenic formation of hydrocarbon source rocks by using n-alkanes according to claim 2, wherein the step three of carrying out the identification of organic kerogen micro-components and the quantitative determination of biogenic formation of all hydrocarbon source rock samples comprises the following steps:
(1) removing inorganic minerals and soluble organic matters in rocks by adopting chemical and physical methods to the sample, enriching insoluble organic matters, and preparing kerogen;
(2) identifying the kerogen microscopic components in the rock by using a biological microscope with functions of white light transmission and epi-fluorescence transmission, and respectively calculating the percentage content of the 4 groups of organic microscopic components of the sapropel group, the chitin group, the vitrinite group and the inert group;
(3) according to the classification mode of the composition of the kerogen microscopic components of the Fujian Qi 1998, the vitrinite group, the inertness group and the chitin group in 4 organic microscopic components are mainly derived from terrestrial organisms, and the sapropel group is mainly derived from aquatic organisms;
(4) and (3) quantitatively calculating the biogenic composition of the sample by using a calculation formula (1) and a formula (2).
4. The method for determining effective conditions for evaluating biogenic source constitution of n-alkanes according to claim 1, 2 or 3, wherein said step two of performing a keratidine reflectivity measurement on all samples of said source rock comprises the steps of:
(1) removing inorganic minerals and soluble organic matters in rocks by adopting chemical and physical methods to the sample, enriching insoluble organic matters, and preparing kerogen;
(2) the reflectivity of the kerogen vitrinite is measured, the number of measuring points is required to be not less than 20, and the average reflectivity value is taken as R of the sampleo。
5. The method for determining effective conditions for evaluating biogenic formation of hydrocarbon source rock by using n-alkanes according to claim 1, 2 or 3, wherein the step four of performing gas chromatography analysis of saturated hydrocarbon and biogenic feature analysis on the extract of the sample comprises the following steps:
(1) carrying out a trichloromethane asphalt extraction experiment on the sample to obtain an asphalt extract;
(2) carrying out gas chromatographic analysis on saturated hydrocarbon on the asphalt extract to obtain a normal paraffin distribution curve;
(3) determining biogenic characteristics of the hydrocarbon source rock sample according to a normal paraffin distribution curve peak type, wherein the 'unimodal front peak type' indicates biogenic characteristics with the aquatic organism input as a main part, the 'unimodal rear peak type' indicates biogenic characteristics with the land organism input as a main part, and the 'bimodal' indicates biogenic characteristics with the land organism and the aquatic organism mixed input.
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| CN112179806B (en) * | 2019-07-03 | 2024-05-31 | 中国石油化工股份有限公司 | Method for evaluating hydrocarbon potential of hydrocarbon source rock |
| CN110470762B (en) * | 2019-08-22 | 2021-11-02 | 陕西延长石油(集团)有限责任公司研究院 | Method for improving accuracy of quantitative evaluation of maturity of hydrocarbon source rock by aromatic hydrocarbon parameters |
| CN114137180A (en) * | 2020-09-04 | 2022-03-04 | 中国石油化工股份有限公司 | Method for recovering original organic matter type of high-over mature hydrocarbon source rock |
| CN113281308B (en) * | 2021-05-25 | 2022-04-12 | 中国石油大学(北京) | Method for quantitatively identifying organic matter source of hydrocarbon source rock based on normal paraffin C22 +/C21-ratio |
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