CN119023372B - Method for oil source comparison by using platinum-palladium ratio - Google Patents
Method for oil source comparison by using platinum-palladium ratio Download PDFInfo
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Abstract
本发明公开了一种利用铂钯比值进行油源对比的方法，涉及石油地质勘探技术领域。一种利用铂钯比值进行油源对比的方法，包括如下步骤：采集原油样品和烃源岩样品；分别对原油样品和烃源岩样品进行预处理，从原油样品中分离出沥青质和可溶有机质；将沥青质或预处理后的烃源岩样品进行铂族元素测定；根据烃源岩样品的铂族元素测定结果，模拟目标烃源岩样品的铂/钯概率分布，预测原油铂/钯比值范围；将原油样品测定得到的铂/钯比值结果与模拟得到的原油铂/钯比值范围进行对比。本发明通过利用烃源岩中的微量元素铂族元素进行油源比较，提高了油源对比结果的准确度和可信度。
The present invention discloses a method for oil source comparison using a platinum-palladium ratio, and relates to the technical field of petroleum geological exploration. A method for oil source comparison using a platinum-palladium ratio comprises the following steps: collecting crude oil samples and source rock samples; pre-treating the crude oil samples and source rock samples respectively, and separating asphaltene and soluble organic matter from the crude oil samples; performing platinum group element determination on the asphaltene or the pre-treated source rock samples; simulating the platinum/palladium probability distribution of the target source rock samples according to the platinum group element determination results of the source rock samples, and predicting the crude oil platinum/palladium ratio range; comparing the platinum/palladium ratio results obtained by the crude oil sample determination with the crude oil platinum/palladium ratio range obtained by simulation. The present invention improves the accuracy and credibility of the oil source comparison results by using trace platinum group elements in source rocks to compare oil sources.
Description
Technical Field
The invention relates to the technical field of petroleum geological exploration, in particular to a method for comparing oil sources by using a platinum-palladium ratio.
Background
The oil source comparison plays a core role in petroleum geology research, and the importance of the oil source comparison is represented in a plurality of aspects, namely the oil source comparison provides scientific basis for formulating accurate exploration strategy, the exploration success rate is remarkably improved by identifying main force source rocks and favorable hydrocarbon generation areas, the oil gas migration rule is revealed, the key migration channels and the main aggregation areas are helped to be identified, important clues are provided for predicting favorable trap and enrichment areas, and the oil source comparison is used as an important tool for basin evolution analysis and is helpful for reconstructing hydrocarbon generation and hydrocarbon discharge history of basins.
However, conventional oil source comparison methods, such as biomarker and stable carbon isotope analysis, tend to exhibit significant limitations in the face of crude oils that have a high degree of evolution or undergo strong secondary reformation. Biomarkers are susceptible to secondary processes such as thermal evolution, biodegradation and the like, and the characteristics of the biomarkers can be changed obviously to lose the parent source indication significance. Also, the stable carbon isotope ratio may be changed due to modification of secondary effects such as thermal cracking and Thermochemical Sulfate Reduction (TSR), which affects the reliability of the stable carbon isotope ratio as an oil source index. These factors reduce the accuracy and reliability of the comparison results of conventional oil source methods under complex geological conditions.
Therefore, it is urgently needed to provide an oil source comparison method with high accuracy and feasibility, so as to make up for the defects of the traditional organic geochemistry research method, and particularly, the research of supporting crude oil with high deep-ultra deep thermal evolution degree and secondary transformation effect is of great significance in identifying the main force source rock of a complex oil-gas-containing basin, revealing the oil-gas migration rule and improving the exploration success rate.
Disclosure of Invention
The technical problem to be solved by the invention is that the existing oil source comparison method has obvious limitation when facing crude oil with high evolution degree or undergoing strong secondary transformation, has lower accuracy and reliability of results, the purpose is to provide a method for oil source comparison by using a platinum-palladium ratio, and the accuracy and the reliability of oil source comparison results are improved by using trace element platinum group elements in hydrocarbon source rock to perform oil source comparison.
The invention is realized by the following technical scheme:
a method for comparing oil sources by using a platinum-palladium ratio comprises the following steps:
Collecting a crude oil sample and a hydrocarbon source rock sample;
Respectively preprocessing a crude oil sample and a hydrocarbon source rock sample, and separating asphaltenes and soluble organic matters from the crude oil sample;
carrying out platinum group element measurement on an asphaltene or pretreated hydrocarbon source rock sample;
Simulating the platinum/palladium probability distribution of crude oil generated by the target source rock sample according to the platinum group element measurement result of the source rock sample, and predicting the platinum/palladium ratio range of the crude oil;
And comparing the platinum/palladium ratio result obtained by measuring the crude oil sample with the crude oil platinum/palladium ratio range obtained by simulation.
In some embodiments of the invention, the crude oil sample may be crude oil or an oil-containing core,
When the crude oil sample is crude oil, the crude oil is a midway test sample in a drilling stage or a single-layer stable-output sample in a production stage, the collected crude oil is stored in a light-resistant container, and air in the container is discharged;
When the crude oil sample is an oil-containing core, the oil-containing core is a freshly collected core segment with high oil saturation, and the oil-containing core is wrapped by aluminum foil paper and then sealed and packaged.
Preferably, the oil-containing core with high oil saturation has dark color and obvious fluorescence characteristic under white light.
Preferably, the known source rock sample can be a core sample obtained by drilling, or can be a field outcrop sample. The source rock lithology is typically organic-containing dark-black mudstone, limestone or marlite. The outdoor outcrop is subjected to weathering, so that a exploring groove is required to be newly dug during collection, and then a fresh, weatherproof and pollution-free hydrocarbon source rock sample is collected.
Preferably, during core sample collection, the influence of hydrothermal fluid, an abnormal mineralization area, a remarkable diagenetic action zone, a structural deformation zone and the like is avoided, a stable hydrocarbon source rock development interval is selected, and the sample covers the whole hydrocarbon source rock development interval as much as possible, so that the change in the vertical direction can be reflected. The core sample is collected by taking care to avoid the peripheral part possibly polluted by the drilling fluid. And wrapping the sample by using tinfoil paper, and placing the sample into a sealing bag for preservation.
As a possible design, the above-mentioned pretreatment of the crude oil sample includes the steps of:
and (3) separating the group components from the crude oil sample to obtain asphaltenes.
Preferably, the solvent is n-hexane.
Preferably, the chromatographic column is a silica gel-alumina chromatographic column, and the volume ratio of the silica gel to the alumina is 3:1.
In some embodiments of the present invention, when the crude oil sample is an oil core, the oil core sample is crushed, dried at low temperature, extracted with dichloromethane to obtain an oil core extract, and asphaltene separation is performed.
Preferably, the oil core sample is broken to a particle size of <2mm.
As one possible design, the pretreatment of the hydrocarbon source rock sample is specifically to clean and dry the hydrocarbon source rock sample, and grind the hydrocarbon source rock sample to 100-200 meshes.
As one possible design, the platinum group element measurement includes the steps of:
Weighing a certain weight of asphaltene (generally 100 mg) or hydrocarbon source rock sample (generally 150-200 mg), adding the asphaltene or pretreated hydrocarbon source rock sample into an Ir-Ru-Pt-Pd mixed diluent, adding a sample dissolving reagent, heating and dissolving the platinum group elements enriched in the sample and the Ir-Ru-Pt-Pd mixed diluent to reach isotope balance, separating the platinum group elements and the matrix elements by adopting anion exchange resin, eluting the matrix elements by eluent, and then measuring the platinum group elements.
Preferably, the sample dissolving reagent is reverse aqua regia, the reverse aqua regia comprises concentrated hydrochloric acid (12 mol/L) and concentrated nitric acid (16 mol/L), and the volume ratio of the concentrated hydrochloric acid to the concentrated nitric acid is 1:2.
Preferably, the above-mentioned heated dissolution is specifically a treatment at 220 ℃ for 72 hours.
Preferably, the anion exchange resin is 2.5mL, 100-200 mesh AG 1X 8 anion exchange resin.
Preferably, the above eluent is used for eluting the matrix element, specifically, 1 mol/L HCl and 0.8 mol/L HNO 3 are used for eluting the matrix element.
As a possible design, after the above elution of the matrix element, ru is eluted with 12 mol/L HNO 3, ir, pt are eluted with 15 mL 13.5 mol/L HNO 3, and Pd is finally eluted with 15 mL 10 mol/L HCl.
As one possible design, the above platinum group element measurement specifically uses a plasma mass spectrometer to measure the Pt content and Pd content of the platinum group element.
Preferably, the detection accuracy is 0.1ppb.
Preferably, the plasma mass spectrometer is a Neptune multi-receiving inductively coupled plasma mass spectrometer (Neptune MC-ICP-MS).
In some embodiments of the invention, the above-described platinum/palladium probability distribution for modeling a target hydrocarbon source rock sample to produce crude oil is specifically modeled by monte carlo.
According to the invention, through Monte Carlo simulation, a statistical method based on random sampling is used for simulating the change of Pt/Pd ratio in the process of converting hydrocarbon source rock into crude oil, and uncertainty of a geological process is considered. Through a large number of random sampling and calculation, a predicted crude oil Pt/Pd ratio range can be obtained, and a theoretical basis is provided for subsequent oil source comparison.
Preferably, the probability distribution characteristics of the individual parameters must be specified before Monte Carlo (Monte Carlo) simulation. Since the number of source rock data may be small, a continuous probability distribution curve of the Pt/Pd ratio of the source rock is created by a method of nuclear density Estimation (KDE) for the source rock data before Monte Carlo simulation. The bandwidth is determined during the calculation using the Scott method. The newly obtained probability distribution curve effectively predicts the probability distribution characteristics of the missing data portions as compared to the original data. Based on geological awareness and judgment, the possible range and distribution of K is defined. After the simulation parameter setting is completed, monte Carlo simulation is performed, the simulation times are generally set to ten thousand times or more, and the obtained simulation results are distributed in the percentiles of 5% and 95% as predicted crude oil Pt/Pd ratio ranges.
Because the Pt/Pd values of the source rock are not exactly the same as the Pt/Pd values of the crude oil from which they were derived. In estimating the Pt/Pd of crude oil produced from a target source rock, the Pt/Pd of the crude oil is estimated by multiplying by a coefficient K. The K value reflects various geologic factors that may lead to changes in the Pt/Pd ratio during hydrocarbon source rock hydrocarbon production, crude oil migration, and aggregation.
In some embodiments of the invention, the above range of predicted crude Pt/Pd ratios is performed by the following formula:
Pt/Pd Crude oil = Pt/Pd Hydrocarbon source rock *K
In the formula,
Pt/Pd Crude oil is the Pt/Pd ratio of crude oil generated by a known hydrocarbon source rock layer;
Pt/Pd Hydrocarbon source rock is hydrocarbon source rock Pt/Pd;
K is a geological process influence factor.
Preferably, the geological process influencing factor is mainly used for simulating the possible change of the Pt/Pd ratio in the process of converting the hydrocarbon source rock into the crude oil, and the setting is obtained by comprehensively judging regional geological awareness. Preferably, the K value ranges from 0.5 to 1.5, and more preferably, the K value ranges from 0.8 to 1.2.
As one possible design, the crude oil sample is considered to be from a hydrocarbon source rock sample if the platinum/palladium ratio results of the crude oil sample fall within the simulated range of 5-95% of the platinum/palladium ratio of the crude oil.
And if the platinum/palladium ratio result of the crude oil sample is not within the range of 5-95% of the simulated crude oil platinum/palladium ratio, the crude oil sample is not considered to be from the hydrocarbon source rock sample or the crude oil sample has the contribution of other hydrocarbon source rocks.
Compared with the prior art, the invention has the following advantages and beneficial effects:
The inventor performs oil source comparison by utilizing a platinum-palladium ratio, is different from the traditional oil source comparison method based on biomarker compounds and stable carbon isotopes, solves the defects of large influence of thermal evolution and secondary action and strong polynary property of parameters of the traditional comparison method, has the advantages of small influence of thermal evolution and secondary action of source rock, has an important role in judging the source process of crude oil subjected to secondary transformation, and has an important guiding role in the exploration of the ancient sea-phase carbonate reservoir subjected to complex migration, aggregation and adjustment transformation.
Drawings
In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present invention, the drawings that are needed in the examples will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and that other related drawings may be obtained from these drawings without inventive effort for a person skilled in the art. In the drawings:
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a graph showing the distribution of the Pt/Pd ratio and the estimated nuclear density of the hydrocarbon source rock in the research area according to the present invention;
FIG. 3 is a graph showing the probability distribution of K factors for the steps of the method of the present invention;
FIG. 4 is a graph showing the Pt/Pd probability distribution of crude oil predicted by the Monte Carlo method in the steps of the method of the invention;
FIG. 5 is a graph showing sample asphaltene content versus Pt/Pd profile for a process step of the present invention.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present invention and the descriptions thereof are for illustrating the present invention only and are not to be construed as limiting the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
It should be further noted that, for convenience of description, only some, but not all of the matters related to the present invention are shown in the accompanying drawings.
The inventor considers that the crude oil contains inorganic microelements (such as rare earth elements, platinum group elements and the like) with certain abundance and indicating significance besides organic compounds, and the hydrocarbon source kerogen is enriched with microelements with certain abundance, so that the generated oil gas can inherit the composition of the organic matters and microelements in the sedimentary diagenetic environment thereof, is not easily influenced by the heat maturity, migration and secondary effects, and has potential oil source comparison significance. Based on the method, the inventor performs oil source comparison by utilizing the platinum-palladium ratio, so that the influence of the thermal evolution of the source rock and the secondary effect is small, the method has an important effect in judging the source process of the crude oil subjected to the secondary transformation effect, and has an important guiding effect on the exploration of the ancient sea-phase carbonate reservoir subjected to complex migration, aggregation and adjustment transformation.
The embodiment of the invention specifically describes samples in Y-layer hydrocarbon source rocks and O-system reservoirs of a Tarim basin. The former agree based on the hydrocarbon source rock spreading and the hydrocarbon source rock evaluation results revealed by real drilling, and crude oil in O-series reservoirs comes from Y-layer hydrocarbon source rocks.
Referring to fig. 1, the specific method comprises the steps of:
s1, collecting a crude oil sample and a hydrocarbon source rock sample.
The known source rock sample can be a core sample obtained by drilling, or can be a field outcrop sample. The source rock lithology is typically organic-containing dark-black mudstone, limestone or marlite. During core sample collection, the key point is to avoid the influences of hydrothermal fluid, abnormal mineralization areas, remarkable diagenetic action zones, structural deformation zones and the like, select stable hydrocarbon source rock development intervals, and the sample should cover the whole hydrocarbon source rock development intervals as much as possible so as to reflect the change in the vertical direction.
The outdoor outcrop is subjected to weathering, so that a exploring groove is required to be newly dug during collection, and then a fresh, weatherproof and pollution-free hydrocarbon source rock sample is collected.
The core sample is collected by taking care to avoid the peripheral part possibly polluted by the drilling fluid. And wrapping the sample by using tinfoil paper, and placing the sample into a sealing bag for preservation.
The crude oil sample to be compared can be crude oil collected at a wellhead or an oil core. The wellhead crude oil is collected from a wellhead oil-gas separator, and the sample is a test sample (DST) in the middle of a drilling stage or a sample produced stably in a single layer in a production stage so as to avoid mutual pollution of crude oil samples in different layers. The residual liquid in the pipeline should be removed before collection. The crude oil is collected and stored in a brown glass bottle, and is filled as much as possible, so that air oxidation is avoided. The fresh core section with high oil saturation is selected from the oil core, and is wrapped by aluminum foil paper and then placed into a sealing plastic bag.
Because the system drills few wells meeting the Y-layer hydrocarbon source rock, the sample acquisition difficulty is high, the known Y-layer hydrocarbon source rock is exposed in partial areas, and the hydrocarbon source rock sample is selected from typical stratum sections with complete exposure of the northwest margin of the basin. The target layer (Y layer) and the upper and lower strata are exposed completely, and are representative. From the field observation result, the method can be divided into an upper section, a middle section and a lower section. The lower section is the phosphorus-containing thin layer silicalite (early hydrothermal action), which is changed into the thin layer silicalite and black mudstone interbedded, and the uppermost developing thick layer dolomite. The sample collection selects a middle stable shale section, and 16 black shale samples are collected from a bottom-up system. And wrapping the sample by using tinfoil paper, and placing the sample into a sealing bag for preservation.
11 Crude oil samples and 3 oil-containing core samples to be compared were collected from multiple areas of the north tower ridge of the tariff basin, sample types including extra heavy oil, normal oil, light oil and reservoir bitumen, and sample densities are shown in table 1. The crude oil maturity of the AD-YQ region to the TH region to the TP region is different, and the degradation degree is gradually reduced due to obvious biodegradation. The higher the degradation, the greater the crude oil density. In the development and fracture zone of SB oil-containing rock core, asphalt enrichment is the product of physical alteration of early-stage filling crude oil, and after early-stage hydrocarbon filling, the fracture zone is re-activated to reduce the temperature and pressure of stratum, so that local asphalt enrichment is caused.
Because of the density and high viscosity of crude oil produced by partial heavy oil wells, light oil is injected into a reservoir in the current exploitation process. Therefore, crude oil samples collected at the wellhead are all midway test (DST) samples, are not affected by dilution in the later production process, and are stored in a brown glass bottle after being collected and are filled as much as possible. The oil-containing core sample is prepared by selecting a fresh core part which is not polluted by drilling fluid, wrapping the fresh core part by using tinfoil paper after collection, and storing the fresh core part in a sealing bag.
S2, respectively preprocessing a crude oil sample and a hydrocarbon source rock sample, and separating asphaltene and soluble organic matters from the crude oil sample.
Because the metal elements in the crude oil are mainly enriched in asphaltene in the form of organic metal complex, the crude oil and the core sample containing oil need to be separated from asphaltene before platinum group element test. The core sample containing oil needs to be extracted before separation. The samples were crushed to the appropriate particle size (< 2 mm) and then low temperature dried. And (3) placing the dried sample into a Soxhlet extractor, and extracting crude oil in a reservoir by using methylene dichloride as an extracting solution. And (3) separating asphaltenes from the oil-containing core extract and the crude oil, taking a certain amount of reservoir extract or crude oil, and precipitating asphaltenes after dissolving the reservoir extract or crude oil by using an n-hexane solution.
The following description will take a sample of crude oil from Y-layer hydrocarbon source rock and O-system reservoir in a Tarim basin as an example. Asphaltene separation was performed on 14 crude oil samples collected at the wellhead. The relative asphaltene content (asphaltene mass to crude oil or extract mass) of each sample is shown in table 1.
Table 1 crude oil sample physical asphaltene relative content characterization
| Region of | Sample type | Sample number | Density (20 ℃ C., g/cm 3) | Asphaltenes (%) |
| AD-YQ | Ultra heavy crude oil | AD1 | 1.01 | 33.3 |
| AD2 | 0.91 | 41.9 | ||
| AD3 | 1.05 | 55.2 | ||
| YQ1 | 1.04 | 43 | ||
| YQ2 | 1.04 | 47.3 | ||
| TH | Heavy oil | TH1 | 0.97 | 2.8 |
| TH2 | 0.91 | 3.7 | ||
| TH3 | 0.96 | 4.1 | ||
| TH4 | 0.96 | 2.6 | ||
| TP | Light oil-normal oil | TP1 | 0.81 | 1.4 |
| TP2 | 0.88 | 2.4 | ||
| SB | Oil core (reservoir bitumen) | SB1 | / | 23.9 |
| SB2 | / | 19.1 | ||
| SB3 | / | 29.9 |
In some embodiments of the present invention, the pre-treating the hydrocarbon source rock sample specifically includes cleaning and drying the hydrocarbon source rock sample, and grinding the hydrocarbon source rock sample to 100-300 mesh.
S3, measuring platinum group elements of the asphaltene or the pretreated hydrocarbon source rock sample.
The Platinum Group Elements (PGEs) of the organic matter-rich samples (black shale and crude oil asphaltenes obtained by pretreatment) are all measured by adopting an acid dissolution method (4 mL concentrated HCl+8 mL concentrated HNO 3).
The specific experimental steps are as follows:
S31, weighing black shale of about 200 mg or crude oil asphaltene samples obtained by 100 mg pretreatment, and adding a certain amount of Ir-Ru-Pt-Pd mixed diluent;
S32, adopting a Carius tube sample-dissolving method, taking reverse aqua regia as a sample-dissolving reagent, and heating 72 h at 240 ℃ to completely dissolve the enriched platinum group elements in the sample and reach isotope balance with a diluent;
S33, after the platinum group element (Ir, ru, pt, pd) dissolved in the aqua regia phase is converted into chloride, AG 1X 8 anion exchange resin (2.5 mL; 100-200 meshes) is adopted to realize the separation of the platinum group element and the matrix element, 1 mol/L HCl and 0.8 mol/L HNO 3 are used for eluting the matrix element, 12 mol/L HNO 3 is used for eluting Ru and 15 mL 13.5 mol/L HNO 3 are used for eluting Ir and Pt, and 15 mL 10 mol/L HCl is used for eluting Pd. The content of Pt and Pd elements in the platinum group elements is measured by Neptune MC-ICP-MS, and the measurement precision is 0.1ppb.
The following description will take a sample of crude oil from Y-layer hydrocarbon source rock and O-system reservoir in a Tarim basin as an example. The crude oil, oil core asphaltene component obtained in step S2 was subjected to a platinum group element test, and the test results are shown in table 2.
TABLE 2 results of testing platinum group elements for source rock and crude oil samples
| Sample numbering | Sample type | Pt(ppb) | Pd(ppb) | Pt/Pd | Sample numbering | Sample type | Pt(ppb) | Pd(ppb) | Pt/Pd |
| A1 | Hydrocarbon source rock | 2.1 | 6.8 | 0.31 | S16 | Hydrocarbon source rock | 1.9 | 6 | 0.31 |
| A2 | Hydrocarbon source rock | 2.5 | 5.4 | 0.46 | AD1 | Ultra heavy crude oil | 0.5 | 1 | 0.55 |
| A3 | Hydrocarbon source rock | 3.2 | 7.1 | 0.45 | AD2 | Ultra heavy crude oil | 0.8 | 2.2 | 0.38 |
| A4 | Hydrocarbon source rock | 2.4 | 6.9 | 0.35 | AD3 | Ultra heavy crude oil | 0.7 | 1.7 | 0.38 |
| A5 | Hydrocarbon source rock | 4 | 5.2 | 0.77 | YQ1 | Ultra heavy crude oil | 0.5 | 1.3 | 0.36 |
| A6 | Hydrocarbon source rock | 4 | 11.2 | 0.36 | YQ2 | Ultra heavy crude oil | 0.4 | 1.4 | 0.33 |
| A7 | Hydrocarbon source rock | 4.8 | 12.5 | 0.39 | TH1 | Heavy oil | 0.3 | 0.8 | 0.41 |
| A8 | Hydrocarbon source rock | 4.9 | 12.9 | 0.38 | TH2 | Heavy oil | 0.3 | 0.9 | 0.4 |
| A9 | Hydrocarbon source rock | 2.5 | 4.4 | 0.57 | TH3 | Heavy oil | 0.3 | 0.9 | 0.35 |
| A10 | Hydrocarbon source rock | 3.1 | 9.7 | 0.31 | TH4 | Heavy oil | 0.3 | 0.9 | 0.34 |
| A11 | Hydrocarbon source rock | 3.5 | 10.3 | 0.34 | TP1 | Light oil-normal oil | 1.7 | 1.9 | 0.52 |
| A12 | Hydrocarbon source rock | 2.9 | 9 | 0.32 | TP2 | Light oil-normal oil | 1.7 | 1.1 | 0.44 |
| A13 | Hydrocarbon source rock | 1.9 | 4.8 | 0.4 | SB1 | Reservoir bitumen | 0.8 | 1.4 | 0.53 |
| A14 | Hydrocarbon source rock | 2.7 | 5.5 | 0.49 | SB2 | Reservoir bitumen | 0.8 | 1.3 | 0.62 |
| A15 | Hydrocarbon source rock | 1.5 | 6.8 | 0.22 | SB3 | Reservoir bitumen | 2.3 | 3.4 | 0.68 |
S4, simulating the platinum/palladium probability distribution of the target source rock sample according to the platinum group element measurement result of the source rock sample, and predicting the crude oil platinum/palladium ratio range.
And according to the platinum group element result obtained by the source rock test, simulating the target source rock by Monte Carlo to generate the possible Pt/Pd probability distribution of the crude oil, and predicting the Pt/Pd ratio range of the crude oil. According to the formula:
Pt/Pd Crude oil = Pt/Pd Hydrocarbon source rock *K
In the formula,
Pt/Pd Crude oil is the Pt/Pd ratio of the crude oil produced by the known hydrocarbon source rock layer,
Pt/Pd Hydrocarbon source rock is hydrocarbon source rock Pt/Pd,
K is a geological process influence factor, and is mainly used for simulating the possible change of the Pt/Pd ratio in the process of converting hydrocarbon source rock into crude oil, and the setting of the K is obtained by comprehensively judging regional geological awareness.
Before Monte Carlo simulation, the probability distribution characteristics of each parameter should be defined. Since the number of source rock data may be small, a continuous probability distribution curve of the Pt/Pd ratio of the source rock is created by a method of nuclear density Estimation (KDE) for the source rock data before Monte Carlo simulation. The bandwidth is determined during the calculation using the Scott method. The newly obtained probability distribution curve effectively predicts the probability distribution characteristics of the missing data portions as compared to the original data. Based on geological awareness and judgment, the possible range and distribution of K is defined. After the simulation parameter setting is completed, monte Carlo simulation is performed, the simulation times are generally set to ten thousand times or more, and the obtained simulation results are distributed in the percentiles of 5% and 95% as predicted crude oil Pt/Pd ratio ranges.
The following description will take a sample of crude oil from Y-layer hydrocarbon source rock and O-system reservoir in a Tarim basin as an example.
From the distribution characteristics of the actually measured source rock samples Pt/Pd, peaks appear in 0.3117-0.4033, and nuclear density estimation (KDE) is performed on the existing data to obtain the distribution characteristics of the source rock Pt/Pd (refer to the curve in FIG. 2). In the present invention, a continuous probability distribution curve is obtained by processing limited source rock Pt/Pd ratio data with a KDE. The curve not only reflects the characteristics of the existing data, but also reasonably estimates possible data gaps, and provides a reliable basis for subsequent simulation analysis.
When designing the K factor model, since the number of hydrocarbon source rock samples is currently known to be small, it is considered that the variation from the hydrocarbon source rock to the crude oil Pt/Pd is relatively small, and the distribution of K is set to conform to the normal distribution, the mean value (μ) is 1.0, the standard deviation (σ) is 0.05, and the cut-off range is 0.8 to 1.2 (refer to fig. 3).
Monte Carlo simulation was performed after determining the probability of the distribution of Pt/Pd Hydrocarbon source rock and the distribution of the K factor.
The simulation was set to 10 ten thousand times, and the simulated Pt/Pd Hydrocarbon source rock values were multiplied by the randomly generated K factor to obtain the predicted Pt/Pd Crude oil distribution.
The 5% and 95% percentiles of this distribution were calculated to be 0.2022 and 0.7052, respectively, and the Pt/Pd ratio of the target source rock-produced crude oil was considered to be within this range (the two dashed line ranges in fig. 4).
S5, comparing a platinum/palladium ratio result obtained by measuring the crude oil sample with a platinum/palladium ratio range of crude oil generated by the target hydrocarbon source rock obtained through simulation.
The Pt/Pd results from the crude oil sample testing were compared to the crude oil Pt/Pd range from the Monte Carlo simulation, and if they were within the 5% -95% range of the Monte Carlo simulation, the crude oil sample was considered to be from the target hydrocarbon source rock, and if they were not, the crude oil sample was considered to be from the other hydrocarbon source rock sample.
From the Pt/Pd distribution characteristics of crude oil and oil-containing core samples (see fig. 4), pt/Pd of each region and different types of samples are in the range of 5% -95% according to Monte Carlo simulation, all from known hydrocarbon source rocks, consistent with the previous understanding, and it is illustrated that the oil source comparison method based on the Pt/Pd ratio of the platinum group element is feasible. In addition, as can be seen from the plot of Pt/Pd versus asphaltenes for the samples (see fig. 5), the Pt/Pd ratios for the samples collected for the different regions do not show regular changes with asphaltene content, but are relatively consistent. The Pt/Pd ratio is not affected by secondary effects such as crude oil migration (polar compounds are adsorbed by reservoir minerals, the asphaltene content is reduced), biodegradation (the asphaltene content is increased) and the like, and has very good stability.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. The method for comparing oil sources by using the platinum-palladium ratio is characterized by comprising the following steps of:
Collecting a crude oil sample and a hydrocarbon source rock sample;
Respectively preprocessing a crude oil sample and a hydrocarbon source rock sample, and separating asphaltenes from the crude oil sample;
Carrying out platinum group element measurement on asphaltene and the pretreated hydrocarbon source rock sample;
Simulating the platinum/palladium probability distribution of crude oil generated by the target source rock sample according to the platinum group element measurement result of the source rock sample, and predicting the platinum/palladium ratio range of the crude oil;
Comparing a platinum/palladium ratio result obtained by measuring a crude oil sample with a crude oil platinum/palladium ratio range obtained by simulation;
The platinum/palladium probability distribution of crude oil generated by simulating a target hydrocarbon source rock sample is specifically that a continuous probability distribution curve of Pt/Pd ratio of the hydrocarbon source rock is created by a nuclear density estimation method for hydrocarbon source rock data, a Scott method is used for determining bandwidth in the calculation process, after simulation parameter setting is completed, monte Carlo simulation is executed based on a random sampling statistical method, and the obtained simulation result is distributed in a percentile of 5% and 95% and is used as a predicted range of Pt/Pd ratio of the crude oil;
The predicted crude oil Pt/Pd ratio range is carried out by the following formula:
Pt/Pd Crude oil = Pt/Pd Hydrocarbon source rock *K
In the formula,
Pt/Pd Crude oil is the Pt/Pd ratio of crude oil generated by a known hydrocarbon source rock layer;
Pt/Pd Hydrocarbon source rock is hydrocarbon source rock Pt/Pd;
K is a geological process influence factor.
2. The method for oil source comparison according to claim 1, wherein the crude oil sample is crude oil or an oil-containing core,
When the crude oil sample is crude oil, the crude oil is a midway test sample in a drilling stage or a single-layer stable-output sample in a production stage, the collected crude oil is stored in a light-resistant container, and air in the container is discharged;
When the crude oil sample is an oil-containing core, the oil-containing core is a freshly collected core segment with high oil saturation, and the oil-containing core is wrapped by aluminum foil paper and then sealed and packaged.
3. A method for oil source comparison using platinum to palladium ratios according to claim 1, wherein the crude oil sample pretreatment comprises the steps of:
And (3) performing group component separation on the crude oil sample to obtain a reservoir extract, dissolving the reservoir extract by using a solvent, and separating out precipitated asphaltenes and soluble organic matters.
4. A method for comparing oil sources by utilizing a platinum-palladium ratio according to claim 3, wherein when the crude oil sample is an oil-containing core, the oil-containing core sample is crushed, dried at a low temperature, extracted to obtain an oil-containing core extract, and asphaltene is separated.
5. The method for oil source comparison by using the platinum-palladium ratio according to claim 1, wherein the pretreatment of the hydrocarbon source rock sample is specifically to clean and dry the hydrocarbon source rock sample and grind the hydrocarbon source rock sample to 100-300 meshes.
6. The method for oil source comparison using platinum-palladium ratio according to claim 1, wherein the platinum group element measurement comprises the steps of:
Adding asphaltene or pretreated hydrocarbon source rock sample into Ir-Ru-Pt-Pd mixed diluent, adding sample dissolving reagent, heating to dissolve enriched platinum group element in the sample and mixing with Ir-Ru-Pt-Pd mixed diluent to reach isotope balance, separating platinum group element and matrix element by anion exchange resin, eluting matrix element by eluent, and measuring platinum group element.
7. The method of claim 6, wherein after elution of the matrix element, the Ru is eluted with 12 mol/L HNO 3, the Ir and Pt are eluted with 15 mL 13.5 mol/L HNO 3, and the Pd is eluted with 15 mL 10 mol/L HCl.
8. The method for oil source comparison by using a platinum-palladium ratio according to claim 6 or 7, wherein the platinum group element measurement is specifically to measure the Pt content and the Pd content of the platinum group element by using a plasma mass spectrometer.
9. The method for oil source comparison by using a platinum-palladium ratio according to claim 1, wherein if the platinum/palladium ratio of the crude oil sample falls within a range of 5-95% of the platinum/palladium ratio of the crude oil obtained by simulation, the crude oil sample is considered to be from a hydrocarbon source rock sample;
and if the platinum/palladium ratio result of the crude oil sample is not within the range of 5-95% of the simulated crude oil platinum/palladium ratio, the crude oil sample is not considered to be from the target hydrocarbon source rock sample or the crude oil sample has the contribution of other hydrocarbon source rocks.
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