CN111505105A - Trace element-based crude oil producing area tracing method - Google Patents
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Abstract
The invention discloses a trace element-based crude oil producing area tracing method, which comprises the following steps of: step 1, dissolving crude oil samples of different producing areas; step 2, analyzing the trace element content of each crude oil sample; and 3, establishing a producing area tracing model according to the content of the trace elements. The method can identify adulterated crude oil, block cross-environment propagation of fake and inferior products and improve the control capability of technical trade measures.
Description
Technical Field
The invention relates to the technical field of trace element fingerprint identification crude oil analysis. More particularly, the invention relates to a crude oil producing area tracing method based on trace elements.
Background
Crude oil is the most important energy consumer and chemical raw material in the world, is known as 'industrial blood', and plays an important role in modern economic life. As the second economic entity in the world, the demand of China for crude oil is increasing, and the supply in China is short, the import of crude oil from abroad is an important way to meet the demand. The import of crude oil shipping in China increases from 2.54 million tons (510 million barrels per day) in 2013 to 4.12 million tons (830 million barrels per day) in 2018. Since 2015, China has replaced the United states to become the largest crude oil entry country in the world, and the external dependence of crude oil has broken through by 70% at present. In recent years, with the activation of crude oil import market and the continuous improvement of trade volume in China, illegal vendors mix crude oil in export of China to pursue higher benefits, trade fraud is carried out, market order is destroyed, and energy safety in China is greatly damaged. Therefore, a rapid, simple and accurate technical method for identifying crude oil in different producing areas is urgently needed to be established, and the method has important significance and application value for ensuring energy safety in China, knowing the producing areas of the crude oil, ensuring no adulteration of imported crude oil and the like.
Crude oil mainly comprises hydrocarbons, non-hydrocarbon compounds and a plurality of trace elements, and is controlled by multiple factors such as climate, structure and deposition, crude oil from different regional sources has unique fingerprint information, and the content of chemical components (such as mineral elements, organic elements, isotopes and the like) in the crude oil is different from the composition. The fingerprint features with origin information provide possibility for researching the origin identification of the crude oil.
At present, no relevant patent for identifying the origin of crude oil exists at home and abroad, and no relevant research for identifying the origin of crude oil by utilizing a trace element fingerprint analysis technology is reported. The prior art has the problems of scattered production area traceability indexes, incomplete system and the like.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.
The invention also aims to provide a crude oil producing area tracing method based on trace elements, which is used for identifying crude oil imported from different countries by establishing a model, identifying adulterated crude oil, blocking cross-environment propagation of fake and inferior products, improving the control capability of technical trade measures and ensuring the energy safety of China.
To achieve these objects and other advantages in accordance with the present invention, there is provided a trace element-based crude oil producing region tracing method, comprising the steps of:
step 1, dissolving crude oil samples of different producing areas;
step 2, analyzing the trace element content of each crude oil sample;
and 3, establishing a producing area tracing model according to the content of the trace elements.
Preferably, the step of dissolving the treated crude oil sample comprises:
step 1.1, putting a crude oil sample into a sample dissolving bomb, adding inverted aqua regia and hydrofluoric acid in a volume ratio of 20:1, tightly covering, and putting into an oven;
step 1.2, baking for 2 hours at 120 ℃, taking out and deflating, adding 15 times volume of inverted aqua regia in hydrofluoric acid, tightly covering, and putting into an oven again;
step 1.3, repeating the operation of step 1.2;
step 1.4, drying for 15h at 190 ℃, taking out and evaporating to dryness, adding nitric acid with the volume being 10 times of that of hydrofluoric acid, evaporating to dryness again, adding nitric acid, high purity water and an internal standard solution with the volume ratio of 1:1:1 and the volume being 10 times of that of the hydrofluoric acid respectively, covering tightly and placing into a drying oven;
and (3) drying at 190 ℃ for 4h, taking out, and fixing the volume by using dilute nitric acid with the mass fraction of 2%.
Preferably, the analysis of the crude oil sample in step 2 is by inductively coupled plasma mass spectrometry.
Preferably, the radio frequency power of the inductively coupled plasma mass spectrometry is 1350W, the temperature of the atomizing chamber is 2 ℃, the flow rate of the carrier gas is 1.06L/min, and the flow rate of the compensation gas is 4.3m L/min.
Preferably, in the step 3, the data of the trace element content of each crude oil sample is analyzed by adopting a principal component analysis method, a Fisher function method and a cross validation combination mode.
Preferably, the trace elements include V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Cs, Ba.
Preferably, the score aggregation areas of the crude oil of different production places are preliminarily distinguished by utilizing principal component analysis according to 14 element content data of V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Cs and Ba, the information of the V, Co, Ni, Zn, Ga, Rb, Y and Cs elements is selected, and the distinguishing analysis is carried out through cross inspection according to a Fisher function, so that the distribution rule of the crude oil of different production places is accurately distinguished.
The invention at least comprises the following beneficial effects: firstly, collecting crude oil samples of different producing areas, and carrying out inductively coupled plasma mass spectrometry analysis on the samples after dissolving treatment; and performing discriminant analysis by combining principal component analysis, Fisher function and cross validation, and performing origin tracing on crude oil in Brazil, Columbia, Iran, Saudiabar, Venezuela, Angola, Australia and other countries to construct an origin tracing model. The method is rapid and accurate, has the accuracy rate of 100 percent, and has important significance and great application prospect for quality control and risk tracing of the imported crude oil market in China.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a scatter plot of a crude oil sample of the present invention in three-dimensional space of a classification function.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1 trace element-based crude oil producing area tracing method
The invention particularly provides a crude oil origin tracing method, which is established by the following steps:
(1) crude oil samples from different producing areas are taken, and specific information of the sample collection is shown in table 1. Carrying out dissolution treatment on the sample;
TABLE 1 crude oil sample Collection information Table
(2) Carrying out multi-element analysis of ICP-MS (inductively coupled plasma mass spectrometry) on the treated solution to be detected to obtain the content of trace elements in the crude oil sample, wherein the unit is mu g/g;
(3) and (3) analyzing the trace element content data of the crude oil sample obtained in the step (2) by adopting a Principal Component Analysis (PCA) method, a Fisher function method and a cross validation combined mode, and establishing to obtain a production area traceability model.
Example 2 measurement of trace elements in crude oil
(1) Approximately 100mg of crude oil sample was weighed into a bomb, 2m L Invert and 0.1m L HF were added, covered tightly and placed in an oven.
(2) After the oven is taken out and deflated at 120 ℃ for 2 hours, 1.5m of L inverted aqua regia is added into the sample-dissolving bomb, and the sample-dissolving bomb is tightly covered and placed into the oven.
(3) And (4) repeating the step (2).
(4) The mixture is taken out and placed on an electric heating plate after being dried for 15 hours at 190 ℃ in an oven, then is dried by distillation, is added with 1m L nitric acid and is dried by distillation again, is added with 1m L nitric acid, 1m L high-purity water and 1m L internal standard solution (2% nitric acid solution containing Rh 500ppb concentration), and is covered tightly and placed in the oven.
(5) After the oven is taken out after 4 hours at 190 ℃, the volume is adjusted to 25g by 2 percent dilute nitric acid.
The content of L i, Be, Sc, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Cs, Ba, L a, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, L U, Hf, Ta, Tl, Pb, Th, U, 37 trace elements in the sample was determined by inductively coupled plasma mass spectrometry, the sample was analyzed under conditions of 1350W of RF power, 2 ℃ of atomizing chamber temperature, 1.06L/min of carrier gas flow rate, 4.3m L/min of compensation gas flow rate, 20ppb of Rh as an internal standard element was selected, wherein 23 elements were contained in most samples below the detection limit of the method and did not participate in the research of tracing the origin of crude oil.
TABLE 2 average content of trace elements in crude oil samples in different regions
Example 3 analysis of major Components of trace elements in crude oil
Based on the results of the element content measurement in example 2, the contents of 14 trace elements, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Cs, and Ba, in the crude oil were used for the main component analysis, and the analysis results are shown in Table 3.
TABLE 3 analysis results of main components of trace element contents
Through data analysis, components with characteristic values larger than 1 are selected as main components, and 5 effective main components are extracted. The 1 st principal component contribution rate is 28.726%, the 2 nd principal component contribution rate is 17.609%, the 3 rd principal component contribution rate is 12.901%, the 4 th principal component contribution rate is 10.871%, and the 5 th principal component contribution rate is 7.452%. The cumulative contribution rate of 5 principal components reaches 77.559%, which shows that 5 principal components already contain most information of the original 14 indexes, and the 3 principal components effectively reduce the influence caused by unimportant factors, so that the 5 principal components can be used as the data base for preliminarily distinguishing the crude oil producing areas.
The 5 principal components obtained by principal component analysis are each a linear combination of the original 14 trace element contents. According to the table 4, 8 trace element indexes with higher principal component contribution values are selected, and the crude oil producing area tracing model with ideal effects is finally obtained by combining gradual discriminant analysis.
Table principal component contribution values of 48 trace element indicators
Example 4 discrimination analysis of crude oil producing area Using 8 kinds of microelements
According to the principal component analysis results provided in the above example 3, in order to improve the reliability and stability of trace element indexes to the crude oil producing area tracing, 8 elements with significant differences among 7 countries, namely V, Co, Ni, Zn, Ga, Rb, Y, and Cs with high principal component contribution values, are selected as variables, a Fisher function is used to establish a model, and the crude oil producing area is subjected to discriminant analysis, and the results show that the discriminant accuracy reaches 100%, and are shown in fig. 1 and table 5.
TABLE 57 national crude oil microelement discrimination results
Note: a. 100.0% of the original grouped cases were correctly classified. b. Only the cases under analysis are cross-validated, in which each case is classified by a derivative function of all cases other than that case. c. 85.7% of the cross-validated grouped cases were correctly classified.
Wherein, Fisher linear discriminant functions of the trace elements of the crude oil of 7 countries are respectively as follows:
Ybar＝-0.226*V-3.351*Co+0.776*Ni+140219*Zn-8.589*Ga+3354.189*Rb-
266.622*Y+9420.943*Cs-17.734
YBrother (a kind of toy)＝5.938*V-0.788*Co-4.980*Ni+45.422*Zn-212.275*Ga-9541.572*Rb-
15220.999*Y+222119.600*Cs-437.470
YYi＝1.472*V-4.723*Co-1.041*Ni+24.381*Zn-81.994*Ga-1792.764*Rb-
3946.164*Y+66100.565*Cs-39.327
YSaudi＝0.407*V-3.175*Co-0.097*Ni+8.560*Zn-41.830*Ga+103.398*Rb-
1177.144*Y+22432.579*Cs-7.230
YCommission＝12.992*V+68.618*Co-17.063*Ni+28.647*Zn+596.969*Ga-15725.668*Rb
-32504.702*Y+207159.733*Cs-1274.732
YAn＝-1.276*V+14.225*Co+2.661*Ni+14.957*Zn-218.679*Ga+3595.663*Rb+
2822.165*Y+18165.060*Cs-36.483
YAo De＝-0.266*V-11.349*Co+1.315*Ni+29.571*Zn+206.330*Ga+885.268*Rb+
394.29*Y+5464.763*Cs-29.121
7 national crude oil samples are successfully identified by using 8 mineral element indexes, and the accuracy is 100%. The accuracy of one cross validation is also 85.7%, which shows that the 8 elements can effectively identify crude oil samples of 9 countries, interference elements are removed by a stepwise discrimination method, and key element fingerprints for distinguishing crude oil samples of different countries are screened out, so that the origin tracing analysis is effectively carried out.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the embodiments shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (7)
1. A crude oil producing area tracing method based on trace elements is characterized by comprising the following steps:
step 1, dissolving crude oil samples of different producing areas;
step 2, analyzing the trace element content of each crude oil sample;
and 3, establishing a producing area tracing model according to the content of the trace elements.
2. The trace-element-based crude oil source tracing method according to claim 1, wherein the step of dissolving the crude oil sample comprises:
step 1.1, putting a crude oil sample into a sample dissolving bomb, adding inverted aqua regia and hydrofluoric acid in a volume ratio of 20:1, tightly covering, and putting into an oven;
step 1.2, baking for 2 hours at 120 ℃, taking out and deflating, adding 15 times volume of inverted aqua regia in hydrofluoric acid, tightly covering, and putting into an oven again;
step 1.3, repeating the operation of step 1.2;
step 1.4, drying for 15h at 190 ℃, taking out and evaporating to dryness, adding nitric acid with the volume being 10 times of that of hydrofluoric acid, evaporating to dryness again, adding nitric acid, high purity water and an internal standard solution with the volume ratio of 1:1:1 and the volume being 10 times of that of the hydrofluoric acid respectively, covering tightly and placing into a drying oven;
and (3) drying at 190 ℃ for 4h, taking out, and fixing the volume by using dilute nitric acid with the mass fraction of 2%.
3. The trace-element-based crude oil source tracing method of claim 1, wherein the crude oil sample analysis in step 2 is performed by inductively coupled plasma mass spectrometry.
4. The trace-element-based crude oil producing region tracing method according to claim 3, wherein the inductively coupled plasma mass spectrometry has a radio frequency power of 1350W, the atomizing chamber temperature is 2 ℃, the carrier gas flow rate is 1.06L/min, and the offset gas flow rate is 4.3m L/min.
5. The trace element-based crude oil producing region tracing method according to claim 1, wherein in step 3, the trace element content data of each crude oil sample is analyzed by adopting a principal component analysis method, a Fisher function method and a cross validation combination mode.
6. The trace-element-based crude oil origin tracing method according to claim 1, wherein the trace elements comprise V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Cs, Ba.
7. The trace element-based crude oil producing area tracing method according to claim 5, wherein the score gathering areas of crude oils of different producing areas are preliminarily discriminated by principal component analysis according to 14 element content data of V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Cs and Ba, information of V, Co, Ni, Zn, Ga, Rb, Y and Cs elements is selected, discrimination analysis is performed by cross inspection according to a Fisher function, and the distribution rule of crude oils of different producing areas is accurately discriminated.
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