CN114428127A - Method for identifying petroleum products - Google Patents
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- CN114428127A CN114428127A CN202011187241.3A CN202011187241A CN114428127A CN 114428127 A CN114428127 A CN 114428127A CN 202011187241 A CN202011187241 A CN 202011187241A CN 114428127 A CN114428127 A CN 114428127A
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Abstract
The method comprises the steps of correcting chromatograms of a known petroleum product and a petroleum product to be detected respectively to obtain retention indexes, determining a standard chromatographic peak and a corresponding peak area corresponding to a measured chromatographic peak of the petroleum product to be detected in the chromatogram of the known petroleum product by using the retention indexes obtained by correction, determining the similarity between the measured chromatographic peak and the standard chromatographic peak, and determining the type of the petroleum product to be detected according to the similarity.
Description
Technical Field
The present disclosure relates to the field of petrochemical technology, and in particular, to a method for identifying petroleum products.
Background
The chemical composition of petroleum products is complex and the difference between the chemical compositions of different kinds of petroleum products is large. In order to facilitate the management and circulation of petroleum products, it is generally necessary to identify the type of petroleum product.
In the related technology, chromatographic analysis is performed on a petroleum product to be detected to obtain retention time and peak area or peak height of each chemical component in the petroleum product, and then the retention time and peak area or peak height of each chemical component are compared with standard chromatographic maps of various petroleum products, so that the type of the petroleum product to be detected is determined.
However, in the course of implementing the disclosed concept, the inventors found that there are at least the following technical problems in the prior art: the existing chromatographic technology is difficult to realize the chromatographic separation of hydrocarbon compounds with the carbon number more than 12, chromatographic peaks of the hydrocarbon compounds with the carbon number more than 12 in petroleum products can overlap with other chromatographic peaks, and chemical components in the petroleum products are difficult to be distinguished through retention time, so that the accuracy of the existing petroleum product identification method is low.
Disclosure of Invention
In order to overcome the problem of low accuracy of the existing petroleum product identification method, the present disclosure provides a method of identifying a petroleum product.
In order to achieve the above object, the present disclosure provides a method of identifying a petroleum product, the method comprising:
obtaining a determination map of a petroleum product to be determined, wherein the determination map comprises at least one determination chromatographic peak ExiEach of said determined chromatographic peaks ExiWith corresponding assay retention time tR(xi)And determining the peak area xi；
For each of said determined chromatographic peaks ExiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index Ixi；
A standard profile for at least one known petroleum product, the standard profile comprising at least one standard chromatographic peak, each standard chromatographic peak having a corresponding standard retention time and standard peak area:
-correcting the standard retention time of each of said standard chromatographic peaks to obtain a standard retention index corresponding to each of said standard chromatographic peaks, and determining the retention index I from said measured retention indexxiAnd said standard retention index determination is compared to said assay chromatographic peak ExiCorresponding standard chromatographic peak Eyi；
- -according to each of said determined chromatographic peaks ExiArea x of measurement ofiAnd each of said corresponding standard chromatographic peaks EyiStandard peak area y ofiDetermining the similarity S between the measured spectrum and the standard spectrum;
and determining the type of the petroleum product to be detected according to the similarity S.
Optionally, said determining a chromatographic peak E for each of saidxiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index IxiThe method comprises the following steps:
selecting a corrected retention time set, and aligning the measurement chromatographic peak E according to the corrected retention time setxiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index Ixi(ii) a Wherein the set of corrected retention times contains a first corrected retention time tR(N)And a second correction retention time tR(N+m)And t isR(N)≤tR(xi)＜tR(N+m)(ii) a Said t isR(N)Correcting retention time of chromatographic peak corresponding to normal paraffin standard sample with carbon number N in the chromatogram, wherein t isR(N+m)The retention time of a chromatographic peak corresponding to the normal paraffin standard sample with the carbon number of N + m in the correction map is shown; n is an integer, and 5-43, when N is 10, m is 1, when N is>10，2≤m≤4。
Optionally further comprising: obtaining the calibration profile from a standard sample mixture; wherein the standard sample mixture comprises N-alkanes with carbon atoms of N and N + m, and the test conditions for obtaining the calibration map are the same as the test conditions for obtaining the measurement map.
Optionally, said determining chromatographic peak E from said corrected retention time setxiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index IxiThe method comprises the following steps:
according to the first correction retention time tR(N)And the second correction retention time tR(N+m)Determining the chromatographic peak E for each of said samples according to formula (1)xiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index IxiWherein, formula (1) is:
in the formula (1), t0The dead time of the measurement is shown.
Optionally, said retention index I according to said determinationxiAnd said standard retention index determination is compared to said assay chromatographic peak ExiCorresponding standard chromatographic peak EyiThe method comprises the following steps:
retention index I according to said determinationxiAnd said standard retention index, determining said assay retention index IxiA difference from the standard retention index;
when the absolute value of the difference value does not exceed a preset threshold value, determining the standard chromatographic peak indicated by the standard retention index as the standard retention index IxiIndicated determination of chromatographic Peak ExiCorresponding standard chromatographic peak Eyi。
Optionally, said determining a chromatographic peak E from each of saidxiArea x of measurement ofiAnd each of said corresponding standard chromatographic peaks EyiStandard peak area y ofiDetermining the similarity S of the measured spectrum and the standard spectrum, comprising:
according to each said determined chromatographic peak ExiArea x of measurement ofiAnd each of said corresponding standard chromatographic peaks EyiStandard peak area y ofiCalculating the similarity S by using an equation (2), wherein the equation (2) is:
in the formula (2), n represents the corresponding standard chromatographic peak E in the standard spectrumyiThe number of the cells.
Optionally, the method further comprises:
acquiring a standard map of the at least one known petroleum product, establishing a standard map library, and determining the similarity S for each standard map in the standard map library; wherein the test conditions for obtaining the standard map are the same as the test conditions for obtaining the assay map.
Optionally, determining the type of the petroleum product to be tested according to the similarity S includes:
sequentially judging the numerical value of the similarity S between the measured spectrum and each standard spectrum:
when S is equal to 1, the petroleum product to be detected is a known petroleum product corresponding to the standard map of the current similarity;
when S is0When S is less than or equal to 1, the petroleum product to be detected is a known petroleum product corresponding to the standard map with the largest similarity value;
when S is less than S0When the petroleum product to be detected does not belong to any known petroleum product;
wherein S is0Is any value of 0.90 to 0.95.
Optionally, the chromatographic method for measuring the determination pattern and the standard pattern is selected from one of high performance liquid chromatography, high performance capillary electrophoresis chromatography and gas chromatography.
Optionally, the known petroleum product has a boiling point of 30 ℃ to 550 ℃; the boiling point of the petroleum product to be detected is 30-550 ℃.
According to the technical scheme, in the method for identifying the petroleum product, the chromatograms of the known petroleum product and the petroleum product to be detected are respectively corrected to obtain the retention indexes, the retention indexes obtained through correction are utilized to determine the standard chromatographic peak and the corresponding peak area corresponding to the measured chromatographic peak of the petroleum product to be detected in the chromatogram of the known petroleum product, the similarity between the measured chromatographic peak and the standard chromatographic peak is determined, the type of the petroleum product to be detected is determined according to the similarity, and the method can improve the accuracy of petroleum product identification.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 schematically shows a schematic of a standard map of 3 known petroleum products in an embodiment of the disclosure.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a method of identifying a petroleum product, the method comprising: obtaining a determination map of a petroleum product to be determined, wherein the determination map comprises at least one determination chromatographic peak ExiEach of said determined chromatographic peaks ExiWith corresponding assay retention time tR(xi)And determining the peak area xi(ii) a For each of said determined chromatographic peaks ExiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index Ixi(ii) a A standard profile for at least one known petroleum product, the standard profile comprising at least one standard chromatographic peak, each standard chromatographic peak having a corresponding standard retention time and standard peak area:
-correcting the standard retention time of each of said standard chromatographic peaks to obtain a standard retention index corresponding to each of said standard chromatographic peaks, and determining the retention index I from said measured retention indexxiAnd said standard retention index determination is compared to said assay chromatographic peak ExiCorresponding standard chromatographic peak Eyi；
- -according to each of said determined chromatographic peaks ExiArea x of measurement ofiAnd each of said corresponding standard chromatographic peaks EyiStandard peak area y ofiDetermining the similarity S between the measured spectrum and the standard spectrum;
and determining the type of the petroleum product to be detected according to the similarity S.
In the prior art, when identifying petroleum products, chromatographic analysis needs to be performed on the petroleum products to be detected to obtain retention time of chromatographic peaks corresponding to each chemical component in the petroleum products, and then the retention time of the chromatographic peaks corresponding to each chemical component is compared with the retention time of each chromatographic peak in a standard spectrum of known petroleum products, so as to determine the type of the petroleum products to be detected. However, hydrocarbon compounds with a large number of carbon atoms in petroleum products are difficult to separate in a chromatographic system, and therefore, hydrocarbon compounds with a large number of carbon atoms in petroleum products are difficult to distinguish by retention time of each chromatographic peak, resulting in low accuracy of the existing petroleum product identification method.
According to the petroleum product identification method provided by the disclosure, the similarity between the measurement spectrum and the standard spectrum is determined by utilizing the peak areas of the measurement spectrum peak with the same retention index and the corresponding standard spectrum peak, the type of the petroleum product to be detected is determined according to the similarity, each chemical component in the petroleum product does not need to be accurately distinguished according to retention time, and the similarity between the measurement spectrum and the standard spectrum can be accurately determined under the condition that the spectrum peaks corresponding to various chemical components are overlapped, so that the accuracy of petroleum product identification can be remarkably improved by the method.
The petroleum product identification method disclosed by the invention has a wide application range, can be used for identifying petroleum products with larger boiling point ranges, and can be used for identifying known petroleum products with the boiling points of 30-550 ℃ for example; the boiling point of the petroleum product to be detected can be 30-550 ℃.
Optionally, said determining a chromatographic peak E for each of saidxiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index IxiAt least can include: selecting a corrected retention time set, and aligning the measurement chromatographic peak E according to the corrected retention time setxiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index Ixi(ii) a Wherein the set of corrected retention times contains a first corrected retention time tR(N)And a second correction retention time tR(N+m)And t isR(N)≤tR(xi)＜tR(N+m)(ii) a Said t isR(N)Correcting retention time of chromatographic peak corresponding to normal paraffin standard sample with carbon number N in the chromatogram, wherein t isR(N+m)The retention time of a chromatographic peak corresponding to the normal paraffin standard sample with the carbon number of N + m in the correction map is shown; n is an integer, and 5-43, when N is 10, m is 1, when N is>10，2≤m≤4。
Optionally further comprising: obtaining the calibration profile from a standard sample mixture; wherein the standard sample mixture may include at least N-alkanes having carbon atoms of N and N + m, and the test conditions for obtaining the calibration pattern are the same as the test conditions for obtaining the assay pattern.
Preferably, the standard sample mixture may include at least a normal alkane having 5 to 44 carbon atoms. The correction retention time set at least comprises retention time of corresponding chromatographic peaks of the normal alkanes with the carbon number of 5-44 in the correction spectrum.
Further, said determining chromatographic peak E from said corrected retention time setxiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index IxiThe method comprises the following steps: according to the first correction retention time tR(N)And the second correction retention time tR(N+m)Determining the chromatographic peak E for each of said samples according to formula (1)xiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index IxiWherein, formula (1) is:
in the formula (1), t0The dead time of the measurement is shown. Dead time is a common term for gas chromatography and refers to the time from the introduction of the sample until the peak of the inert gas appears to be at a maximum, reflecting the time for the carrier gas to flow through the system.
In the present disclosure, the method and principle of obtaining the standard retention index corresponding to each of the standard chromatographic peaks by correcting the standard retention time of each of the standard chromatographic peaks is in accordance with the method and principle of determining each of the measured chromatographic peaks E described abovexiCorresponding assay retention index IxiThe method and principle are the same, and refer to the foregoing description, and are not repeated herein.
Optionally, said retention index I according to said determinationxiAnd said standard retention index determination is compared to said assay chromatographic peak ExiCorresponding standard chromatographic peak EyiThe method comprises the following steps: retention index I according to said determinationxiAnd said standard retention index, determining said assay retention index IxiA difference from the standard retention index; when the absolute value of the difference value does not exceed a preset threshold value, determining the standard chromatographic peak indicated by the standard retention index as the standard retention index IxiIndicated determination of chromatographic Peak ExiCorresponding standard chromatographic peak Eyi。
Alternatively, when there are multiple standard retention indices and the assay retention index IxiWhen the absolute value of the difference is smaller than a preset threshold value, determining the standard chromatographic peak indicated by the standard retention index corresponding to the difference with the minimum absolute value as the standard retention index IxiIndicated determination of chromatographic Peak ExiCorresponding standard chromatographic peak Eyi。
The preset threshold value is used for representing experiment errors allowed to occur in the repeated chromatographic analysis process, and the experiment errors can be caused by factors such as instrument equipment, experiment environment and personal operation. Statistical analysis can be performed on historical data generated by the multiple chromatographic analyses, so that experimental errors allowed to occur in the multiple chromatographic analyses can be determined, and specific values of the preset threshold can be determined according to the experimental errors. Illustratively, the preset threshold value can be 0.5-10.0, preferably 0.5-5, and more preferably 2.
In the actual identification process, the type of the petroleum product to be detected is not necessarily the same as that of the selected known petroleum product, and the determination chartDetermination of the chromatographic Peak E in the SpectrumxiThe standard spectrum peak is not necessarily in one-to-one correspondence with the standard spectrum peak in the standard spectrum, therefore, the corresponding standard spectrum peak E in the standard spectrumyiThe number of the standard chromatographic peaks is less than or equal to the number of the standard chromatographic peaks. At the same time, partial measurement of chromatographic peak E may also occurxiAbsence of corresponding standard chromatographic peak E in standard chromatogramyiIn this case, the chromatographic peak E will not be determined for this portion in the subsequent calculationxiThe peak area of (a) is taken into account.
Optionally, said determining a chromatographic peak E from each of saidxiArea x of measurement ofiAnd each of said corresponding standard chromatographic peaks EyiStandard peak area y ofiDetermining the similarity S between the measured spectrum and the standard spectrum at least comprises the following steps: according to each said determined chromatographic peak ExiArea x of measurement ofiAnd each of said corresponding standard chromatographic peaks EyiStandard peak area y ofiCalculating the similarity S by using an equation (2), wherein the equation (2) is:
in the formula (2), n represents the corresponding standard chromatographic peak E in the standard spectrumyiThe number of the cells.
In the process of implementing the concept of the present disclosure, the inventors of the present disclosure found that different kinds of petroleum products are similar in component composition, and thus the difference of retention time of corresponding chromatographic peaks of each component in a chromatogram is small, and it is difficult to accurately distinguish different kinds of petroleum products by the retention time of the chromatographic peaks. The inventor of the present disclosure further finds that the content difference of each component in different types of petroleum products is large, specifically, the peak area or peak height difference of the corresponding chromatographic peak of each component in the chromatogram is large, so that the peak area of each chromatographic peak is used to calculate the similarity of different chromatograms, and further, whether the petroleum products corresponding to the two chromatograms are the same type of petroleum product is determined according to the similarity, and the accuracy of petroleum product identification can be significantly improved.
Optionally, the method further comprises: acquiring a standard map of the at least one known petroleum product, establishing a standard map library, and determining the similarity S for each standard map in the standard map library; wherein the test conditions for obtaining the standard map are the same as the test conditions for obtaining the assay map.
Optionally, determining the type of the petroleum product to be tested according to the similarity S includes: sequentially judging the numerical value of the similarity S between the measured spectrum and each standard spectrum: when S is equal to 1, the petroleum product to be detected is a known petroleum product corresponding to the standard map of the current similarity; when S is0When S is less than or equal to 1, the petroleum product to be detected is a known petroleum product corresponding to the standard map with the largest similarity value; when S is less than S0When the petroleum product to be detected does not belong to any known petroleum product; wherein S is0Is any value of 0.90 to 0.95. That is, S0And judging whether the similarity S is an effective judgment threshold, wherein the similarity S not less than the judgment threshold can be used for effectively identifying the type of the petroleum product to be detected. Wherein S is0Can be determined according to actual needs, and in order to further improve the accuracy of petroleum product identification, S in the disclosure0For example, the value of (d) may be 0.95.
Optionally, the chromatographic method for measuring the determination pattern and the standard pattern is selected from one of high performance liquid chromatography, high performance capillary electrophoresis chromatography and gas chromatography. Preferably, the chromatographic method is gas chromatography.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
The starting materials, reagents, instruments and equipment referred to in the examples of the present disclosure may be obtained by purchase, unless otherwise specified. The experimental methods mentioned in the examples of the present disclosure are all conventional in the art unless otherwise specified.
In the embodiments of the present disclosure, all samples for chromatography are sample solutions, or test solutions obtained by diluting each sample solution by the same factor.
In the disclosed embodiment, the chromatographic methods used for chromatographic analysis are all gas chromatography, and the chromatographic conditions include: the gas chromatography column may be an HP-5 column having a length of 30m, an internal diameter of 0.32mm and a coating thickness of 0.5. mu.m. The temperature of a sample inlet of the chromatograph can be 250-280 ℃, the pressure of the sample inlet under a pressure stabilizing mode can be 75-95 kPa, and the split ratio can be 10: 1-60: 1, the sample injection volume can be 0.5-1 mu L, the sample injection is carried out in a constant flow mode, the flow rate can be 0.3-2 mL/min, and the carrier gas can be nitrogen. The operating conditions of the column were: the initial temperature is 30-40 ℃, the heating rate is 1-3/min, the final temperature is 150-200 ℃, and the temperature is kept for 5-20 min.
Example 1
This example serves to illustrate the petroleum product identification method of the present disclosure.
Step 101, taking straight-run gasoline 1 (with the boiling point range of 35-195 ℃) as a petroleum product to be detected, performing chromatographic analysis by adopting the chromatographic conditions to obtain a determination map of the petroleum product to be detected, and determining a chromatographic peak E in the determination mapxiAnd each measured chromatographic peak ExiCorresponding measured retention time tR(xi)And determining the peak area xiAs shown in table 2.
Step 102, selecting a corrected retention time set and determining a chromatographic peak E for each chromatographic peak according to the corrected retention time setxiCorresponding measured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index Ixi。
Wherein, the correction retention time set can be determined in advance by the following method: and (3) performing chromatographic analysis on the standard sample mixture by adopting the chromatographic conditions to obtain a correction map, wherein the retention time of each standard sample in the standard sample mixture in a chromatographic peak corresponding to the correction map forms a correction retention time set. The standard sample mixture comprises normal alkanes with 5-44 carbon atoms, so that the correction retention time set comprises retention times of corresponding chromatographic peaks of the normal alkanes with 5-44 carbon atoms in a correction spectrum. The set of corrected retention times determined in this example is shown in table 1.
TABLE 1
Wherein each chromatographic peak E is determined according to the formula (1)xiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index IxiThe formula (1) is:
in the formula (1), N and N + m represent the number of carbon atoms of the standard sample, N is an integer of 5. ltoreq. N.ltoreq.43, and when N.ltoreq.10, m is 1, and when N is 10>10，2≤m≤4；tR(xi)Represents the measured retention time; t is tR(N)Representing a first corrected retention time; t is tR(N+m)Denotes a second correction retention time, and tR(N)≤tR(xi)＜tR(N+m)；t0The dead time of the measurement is shown.
Each measurement chromatogram Peak E obtained by calibration in this examplexiCorresponding retention index IxiAs shown in table 2.
TABLE 2
| Determination of chromatographic Peak ExiNumbering | Determination of the Retention time tR(xi) | Measurement ofPeak area xi | Retention index Ixi |
| 1 | 3.58 | 386.05 | 605.099 |
| 2 | 4.11 | 219.00 | 632.75 |
| 3 | 4.61 | 62.72 | 655.743 |
| 4 | 4.83 | 213.09 | 665.08 |
| 5 | 5.02 | 121.66 | 672.808 |
| 6 | 5.23 | 143.02 | 681.016 |
| 7 | 5.38 | 68.58 | 686.679 |
| 8 | 5.45 | 70.75 | 689.268 |
| 9 | 5.51 | 110.93 | 691.461 |
| 10 | 5.82 | 372.05 | 703.623 |
| 11 | 6.33 | 434.80 | 728.774 |
| 12 | 7.15 | 184.84 | 765.246 |
103, acquiring standard spectrums of 15 known petroleum products, wherein each standard spectrum comprises a standard spectrum peak, and each standard spectrum peak has corresponding standard retention time and standard peak area; and correcting the standard retention time of each standard chromatographic peak for each standard chromatogram to obtain the standard retention index corresponding to each standard chromatographic peak.
Wherein, the standard map of the known petroleum product can be predetermined by the following method: and (3) taking the known petroleum product, and performing chromatographic analysis by adopting the chromatographic conditions to obtain a standard map of the known petroleum product. Fig. 1 schematically shows a standard map of 3 known petroleum products in this example.
The method for obtaining the standard retention index corresponding to each standard chromatographic peak by correcting the standard retention time of each standard chromatographic peak is the same as the method described in step 102. Taking straight run gasoline as an example, the standard retention index corresponding to each standard chromatographic peak obtained by calibration in this example is shown in table 3.
TABLE 3
| Standard chromatographic peak numbering | Standard retention time | Standard peak area | Standard retention index |
| 1 | 3.60 | 391.1 | 606.215 |
| 2 | 4.12 | 220.0 | 633.237 |
| 3 | 4.62 | 64.7 | 656.177 |
| 4 | 4.84 | 211.1 | 665.495 |
| 5 | 5.03 | 118.7 | 673.206 |
| 6 | 5.24 | 143.0 | 681.398 |
| 7 | 5.39 | 64.6 | 687.051 |
| 8 | 5.46 | 73.8 | 689.635 |
| 9 | 5.52 | 109.9 | 691.824 |
| 10 | 5.82 | 369.0 | 703.623 |
| 11 | 6.34 | 432.8 | 729.247 |
| 12 | 7.16 | 184.8 | 765.665 |
104, according to the determination of retention index IxiAnd a standard retention index, determining the assay retention index IxiDifference from standard retention index; when the absolute value of the difference value does not exceed a preset threshold value, determining a standard chromatographic peak indicated by the standard retention index as the standard retention index IxiIndicated determination of chromatographic Peak ExiCorresponding standard chromatographic peak EyiIn this embodiment, the value of the preset threshold is 2.0, and when there are multiple standard retention indexes and measurement retention index IxiIs less than 2.0, the standard chromatographic peak indicated by the standard retention index corresponding to the difference with the smallest absolute value is determined as the standard retention index IxiIndicated determination of chromatographic Peak ExiCorresponding standard chromatographic peak Eyi。
The measured chromatographic peak E determined in this example is taken as the peak of the straight-run gasolinexiCorresponding to the standard chromatographic peak EyiThe correspondence of (2) is shown in Table 4.
TABLE 4
Step 105, for each standard spectrum, determining the chromatographic peak E according to each measured chromatographic peakxiArea x of measurement ofiAnd each corresponding standard chromatographic peak EyiStandard peak area y ofiAnd determining the similarity S between the measured spectrum and the standard spectrum.
Specifically, the similarity S is calculated by using equation (2), where equation (2) is:
in the formula (2), n represents a corresponding standard chromatographic peak E in a standard spectrumyiThe number of the cells.
And step 106, determining the type of the petroleum product to be detected according to the similarity S.
Specifically, the numerical value of the similarity S between the measured spectrum and each standard spectrum is sequentially judged: when S is equal to 1, the petroleum product to be detected is a known petroleum product corresponding to the standard map of the current similarity, and at the moment, the judgment of other known petroleum products can be stopped; when S is0When S is less than or equal to 1, the similarity obtained by all standard maps is less than 1 and is S0In the above, the petroleum product to be detected is the known petroleum product corresponding to the standard map with the largest similarity value; when S is less than S0In the meantime, the petroleum product to be tested does not belong to any known petroleum product, wherein S in the embodiment0Is 0.95. In this example, the similarity between the measurement pattern and 15 feature patterns is shown in table 5.
TABLE 5
| Characteristic map | Similarity S |
| Straight run gasoline No. 1 | 1.000 |
| Straight run gasoline No. 2 | 0.926 |
| Reformed feedstock No. 1 | 0.767 |
| Reformed feedstock No. 2 | 0.704 |
| Reformed feedstock oil No. 3 | 0.371 |
| Catalytic gasoline No. 1 | 0.381 |
| Catalytic gasoline No. 2 | 0.383 |
| Catalytic gasoline No. 3 | 0.738 |
| Reformate No. 1 | 0.035 |
| Reformate No. 2 | 0.013 |
| Shengli diesel oil | 0.176 |
| Liaohe diesel oil | 0.175 |
| Tahe diesel oil | 0.141 |
| Daqing diesel oil | 0.024 |
| Raw oil | 0.025 |
As can be seen from table 5, the similarity between the petroleum product to be detected and the straight-run gasoline 1 in this embodiment is 1 through identification, that is, the method of this embodiment identifies that the petroleum product to be detected is the straight-run gasoline 1, thereby demonstrating that the method for identifying a petroleum product of the present disclosure is accurate and reliable.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. A method of identifying a petroleum product, the method comprising:
obtaining a determination map of a petroleum product to be determined, wherein the determination map comprises at least one determination chromatographic peak ExiEach of said determined chromatographic peaks ExiWith corresponding assay retention time tR(xi)And determining the peak area xi；
For each of said determined chromatographic peaks ExiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index Ixi；
A standard profile for at least one known petroleum product, the standard profile comprising at least one standard chromatographic peak, each standard chromatographic peak having a corresponding standard retention time and standard peak area:
-correcting the standard retention time of each of said standard chromatographic peaks to obtain a standard corresponding to each of said standard chromatographic peaksQuasi retention index and retention index I according to said determinationxiAnd said standard retention index determination is compared to said assay chromatographic peak ExiCorresponding standard chromatographic peak Eyi；
- -according to each of said determined chromatographic peaks ExiArea x of measurement ofiAnd each of said corresponding standard chromatographic peaks EyiStandard peak area y ofiDetermining the similarity S between the measured spectrum and the standard spectrum;
and determining the type of the petroleum product to be detected according to the similarity S.
2. The method of claim 1, wherein said determining a chromatographic peak E for each of said measured chromatographic peaksxiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index IxiThe method comprises the following steps:
selecting a corrected retention time set, and aligning the measurement chromatographic peak E according to the corrected retention time setxiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index Ixi(ii) a Wherein the set of corrected retention times contains a first corrected retention time tR(N)And a second correction retention time tR(N+m)And t isR(N)≤tR(xi)＜tR(N+m)(ii) a Said t isR(N)Correcting retention time of chromatographic peak corresponding to normal paraffin standard sample with carbon number N in the chromatogram, wherein t isR(N+m)The retention time of a chromatographic peak corresponding to the normal paraffin standard sample with the carbon number of N + m in the correction map is shown; n is an integer, and 5-43, when N is 10, m is 1, when N is>10，2≤m≤4。
3. The method of claim 2, further comprising: obtaining the calibration profile from a standard sample mixture; wherein the standard sample mixture comprises N-alkanes with carbon atoms of N and N + m, and the test conditions for obtaining the calibration map are the same as the test conditions for obtaining the measurement map.
4. The method of claim 2, wherein said determining a chromatographic peak E based on said corrected retention time setxiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index IxiThe method comprises the following steps:
according to the first correction retention time tR(N)And the second correction retention time tR(N+m)Determining the chromatographic peak E for each of said samples according to formula (1)xiMeasured retention time tR(xi)Correcting to obtain each measured chromatographic peak ExiCorresponding assay retention index IxiWherein, formula (1) is:
in the formula (1), t0The dead time of the measurement is shown.
5. The method of claim 1, wherein said retention index I is determined according to said assayxiAnd said standard retention index determination is compared to said assay chromatographic peak ExiCorresponding standard chromatographic peak EyiThe method comprises the following steps:
retention index I according to said determinationxiAnd said standard retention index, determining said assay retention index IxiA difference from the standard retention index;
when the absolute value of the difference value does not exceed a preset threshold value, determining the standard chromatographic peak indicated by the standard retention index as the standard retention index IxiIndicated determination of chromatographic Peak ExiCorresponding standard chromatographic peak Eyi。
6. The method of claim 1, wherein said determining a chromatographic peak E from each of said plurality of chromatographic peaksxiMeasured peak of (2)Area xiAnd each of said corresponding standard chromatographic peaks EyiStandard peak area y ofiDetermining the similarity S of the measured spectrum and the standard spectrum, comprising:
according to each said determined chromatographic peak ExiArea x of measurement ofiAnd each of said corresponding standard chromatographic peaks EyiStandard peak area y ofiCalculating the similarity S by using an equation (2), wherein the equation (2) is:
in the formula (2), n represents the corresponding standard chromatographic peak E in the standard spectrumyiThe number of the cells.
7. The method of claim 1, further comprising:
acquiring a standard map of the at least one known petroleum product, establishing a standard map library, and determining the similarity S for each standard map in the standard map library; wherein the test conditions for obtaining the standard map are the same as the test conditions for obtaining the assay map.
8. The method according to claim 1 or 7, wherein the determining the type of the petroleum product to be tested according to the similarity S comprises:
sequentially judging the numerical value of the similarity S between the measured spectrum and each standard spectrum:
when S is equal to 1, the petroleum product to be detected is a known petroleum product corresponding to the standard map of the current similarity;
when S is0When S is less than or equal to 1, the petroleum product to be detected is a known petroleum product corresponding to the standard map with the largest similarity value;
when S is less than S0When the petroleum product to be detected does not belong to any known petroleum product;
wherein S is0Is 0.90 to 0Any value of.95.
9. The method according to claim 8, wherein the chromatography method by which the determination pattern and the standard pattern are measured is selected from one of high performance liquid chromatography, high performance capillary electrophoresis chromatography, and gas chromatography.
10. The method according to any one of claims 1 to 9, wherein the known petroleum product has a boiling point of 30 ℃ to 550 ℃; the boiling point of the petroleum product to be detected is 30-550 ℃.
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| RU2804172C1 (en) * | 2022-12-21 | 2023-09-26 | Общество с ограниченной ответственностью "Газпромнефть Научно-Технический Центр" (ООО "Газпромнефть НТЦ") | Method for processing chromatographic data to determine composition of hydrocarbon fluid, system and machine-readable medium for its implementation |
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