CN114563518B - Method for tracing leakage of underground water oil products - Google Patents
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for tracing leakage of underground water oil products. The method comprises the following steps: 1) Measuring fingerprint characteristics of an oil sample to be measured by gas chromatography-mass spectrometry to obtain a saturated hydrocarbon total ion flow chromatogram and an aromatic hydrocarbon total ion flow chromatogram, respectively drawing an n-alkane concentration distribution map and a polycyclic aromatic hydrocarbon concentration distribution map, and calculating to obtain a diagnosis ratio; 2) And judging the type of the oil sample to be detected according to the saturated hydrocarbon total ion flow chromatogram, the aromatic hydrocarbon total ion flow chromatogram, the normal alkane concentration distribution map and the polycyclic aromatic hydrocarbon concentration distribution map and the combination diagnosis ratio. The invention fully plays the advantages of high speed and high sensitivity of the gas chromatography-mass spectrometry technology, obtains the oil component information quickly, has strong practicability and good reproducibility, realizes the accurate identification of the oil samples in the atmospheric and vacuum devices and the catalytic cracking device, and provides an identification method for tracing the leakage of the atmospheric and vacuum devices and the catalytic cracking device of the oil refinery.
Description
Technical Field
The invention relates to the technical field of pollution sources of leaked oil products, in particular to a method for tracing leakage of underground water oil products.
Background
The petroleum may leak and leak during the process of processing, refining, transporting and the like and enter the soil and groundwater environment. The underground water petroleum pollution process is complex and has great hazard, once the underground water of a refinery is polluted, effective measures are required to be quickly taken, the pollution range is reduced, the vehicle is generally required to be stopped for maintenance, and a leakage source is searched, so that huge economic loss can be caused to enterprises.
The compositions of normal paraffins, polycyclic aromatic hydrocarbons, and steroids in different oils have their own characteristics, the so-called "oil fingerprint". The oil fingerprint identification method can rapidly determine the source and the type of the spilled oil by identifying and removing other suspicious oil sources, and can verify the reliability of other evidences by the identification result, effectively make up the defects of other investigation means, provide more scientific and reliable evidence for the identification of the spilled oil sources, and more effectively judge and identify the responsibility attribution of the spilled oil pollution event.
The oil analysis technology is divided into a characteristic method and a non-characteristic method, wherein the non-characteristic method is used for measuring total petroleum hydrocarbon, and the common method is a weight method. The characteristic method is used for determining the concentration of oil components, calculating characteristic values and the like to carry out oil spill identification, and the common method is a chromatographic method. The non-characteristic method has the advantages of less sample treatment time consumption, convenient oil degradation degree research, and suitability for spectrogram scanning qualitative analysis, and has the defect of oil identification and hypodynamia. The feature method has the advantages of containing the information of the components required for identification and having to perform feature analysis when analyzing oil spill.
Refined petroleum products are obtained through crude oil distillation, each finished oil sample has a characteristic chemical fingerprint due to the difference of crude oil raw materials and refining processes, and after petroleum enters the environment, the petroleum is affected by the environment, and the effects of weathering, dissolution, adsorption, degradation and the like are finally formed to form unique characteristics. These features can be used to distinguish product oil categories and to source identify product oil leakage.
However, fingerprint identification of spilled oil is mostly concentrated on crude oil and fuel oil, and research on fingerprint differences among oil samples of refinery devices is less, so that when oil leakage occurs in a refinery, special technology and data are lacking, and the fingerprint identification method is mostly concentrated on weathering and degradation effects in sea water and surface water on changes of the oil after the oil enters the environment, and has less research on fingerprint tracing of the oil leakage into a groundwater environment.
Disclosure of Invention
The invention aims to provide a method for tracing leakage of underground water oil products, and provides a rapid tracing method for oil products of a refinery atmospheric and vacuum device and a catalytic cracking device to leak into underground water.
In order to achieve the above purpose, according to one aspect of the present invention, a method for tracing leakage of groundwater oil is provided. The method comprises the following steps: 1) Measuring fingerprint characteristics of an oil sample to be measured by gas chromatography-mass spectrometry to obtain a saturated hydrocarbon total ion flow chromatogram and an aromatic hydrocarbon total ion flow chromatogram, respectively drawing an n-alkane concentration distribution map and a polycyclic aromatic hydrocarbon concentration distribution map, and calculating to obtain a diagnosis ratio; 2) And judging the type of the oil sample to be detected according to the saturated hydrocarbon total ion flow chromatogram, the aromatic hydrocarbon total ion flow chromatogram, the normal alkane concentration distribution map and the polycyclic aromatic hydrocarbon concentration distribution map and the combination diagnosis ratio.
Further, in step 1), the method further comprises the step of preprocessing the oil sample to be detected before the gas chromatography-mass spectrometry is carried out to determine the oil sample to be detected, and separating the oil sample to be detected into saturated hydrocarbon and aromatic hydrocarbon.
Further, the pretreatment specifically includes: when the oil sample to be detected is a pure oil sample, directly separating the oil sample to be detected into saturated hydrocarbon and aromatic hydrocarbon by using a chromatographic column; when the oil sample to be detected contains moisture, the oil sample to be detected is extracted by using an organic solvent, and then the concentrated oil sample to be detected is separated into saturated hydrocarbon and aromatic hydrocarbon by using a chromatographic column.
Further, the organic solvent is dichloromethane.
Further, the diagnostic ratios include, in order, Σchr/Σpah, Σfluos/Σpah, LMW/HMW, C17/Pr, (c21+c22)/(c28+c29), Σphens/Σfluos, and Σphens/Σpyr, wherein LMW/HMW is less than Σc21/greater than Σc21.
Further, step 2) specifically includes: obtaining the peak type of chromatographic peaks, the retention time of the chromatographic patterns and the type of polycyclic aromatic hydrocarbon according to the saturated hydrocarbon total ion flow chromatogram, the aromatic hydrocarbon total ion flow chromatogram, the normal alkane concentration distribution map and the polycyclic aromatic hydrocarbon concentration distribution map, and primarily judging the type of the oil sample to be detected; determining the type of the oil sample to be detected by combining the data ranges of the diagnostic ratios of sigma Chu/sigma PAH, sigma Fluos/sigma PAH, LMW/HMW, C17/Pr, (C21+C22)/(C28+C29), sigma Phens/sigma Fluos and sigma Phens/sigma Pyr; preferably, leakage sources are initially classified into two categories depending on whether chrysene material is present: (1) Hydrogenated wax oil, cycle oil and slurry oil containing chrysene substances; (2) Normal first-line oil, normal second-line oil, normal third-line oil, first-line oil reduced, second-line oil reduced, third-line oil reduced, crude oil, gasoline and diesel oil without chrysene substance.
Further, the judgment standard for preliminarily judging the type of the oil sample to be detected as the normal first line oil sample is as follows: the chromatographic peak is in the form of n-C 11 The normal paraffins at the two sides are symmetrically distributed; saturated hydrocarbon total ion flow chromatogramsThe retention time of the aromatic hydrocarbon total ion flow chromatogram is within 25 min; and the polycyclic aromatic hydrocarbon species include benzene and naphthalene, optionally containing dibenzothiophene; preferably, the judgment standard for preliminarily judging the type of the oil sample to be measured as the normal two-line oil sample is as follows: from n-C in the saturated hydrocarbons of the peak of the chromatographic peak 12 ~n-C 17 The aromatic hydrocarbon has UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 30 min; and the polycyclic aromatic hydrocarbon species include benzene, naphthalene and dibenzothiophene; preferably, the judgment standard for preliminarily judging the type of the oil sample to be detected as the normal three-line oil sample is as follows: from n-C in the saturated hydrocarbons of the peak of the chromatographic peak 14 ~n-C 29 The aromatic hydrocarbon has UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 45 min; and the polycyclic aromatic hydrocarbon must include benzene, naphthalene, optionally phenanthrene, dibenzothiophene and fluorene.
Further, the judgment standard for preliminarily judging the type of the oil sample to be measured as the first line of reduction oil sample is as follows: from n-C in the saturated hydrocarbons of the peak of the chromatographic peak 11 ~n-C 20 The aromatic hydrocarbon has UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 25 min; and the polycyclic aromatic hydrocarbon species include benzenes, naphthalenes, dibenzothiophenes, and fluorenes, optionally phenanthrenes; preferably, the preliminary judging of the type of the oil sample to be detected is that the two-line oil sample is subtracted: from n-C in the saturated hydrocarbons of the peak of the chromatographic peak 15 ~n-C 33 The aromatic hydrocarbon has UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 30 min; and the polycyclic aromatic hydrocarbon species include benzene, naphthalene, phenanthrene, dibenzothiophene, and fluorene; preferably, the preliminary judgment of the type of the oil sample to be measured is that the three-line oil sample is subtracted is as follows: from n-C in the saturated hydrocarbons of the peak of the chromatographic peak 22 ~n-C 36 The aromatic hydrocarbon has UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 36 min; and the polycyclic aromatic hydrocarbon includes phenanthrenes and dibenzothiophenes, optionally naphthalene; preferably, the method comprises the steps of,the judgment standard for preliminarily judging the type of the oil sample to be detected as crude oil is as follows: the chromatographic peak has a peak value from n-C 8 To n-C 32 The peak heights of the (C) are gradually reduced, and the saturated hydrocarbon and the aromatic hydrocarbon have almost no UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 35 min; and the polycyclic aromatic hydrocarbon species include benzene, naphthalene, phenanthrene, dibenzothiophene, and fluorene; preferably, the judgment standard for preliminarily judging that the type of the oil sample to be detected is the gasoline oil sample is as follows: the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 15 min; and the polycyclic aromatic hydrocarbon includes benzene and naphthalene only; preferably, the judgment standard for preliminarily judging that the type of the oil sample to be detected is the diesel oil sample is as follows: chromatographic peak-to-peak type of saturated hydrocarbon total ion flow chromatogram is n-C 14 Is distributed on the right side with the center; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 25 min; and polycyclic aromatic hydrocarbon species including benzene, naphthalene, phenanthrene, dibenzothiophene, fluorene, anthracene, and pyrene; preferably, the judgment standard for preliminarily judging the type of the oil sample to be detected as the hydrogenated wax oil sample is as follows: chromatographic peak-to-peak type of saturated hydrocarbon total ion flow chromatogram is n-C 20 As the center, normal paraffins on two sides are uniformly distributed, and the saturated hydrocarbon and the aromatic hydrocarbon have UCM bulges; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 40 min; and polycyclic aromatic hydrocarbon types including benzene, phenanthrene, fluorene, chrysene, anthracene and pyrene, optionally naphthalene, dibenzothiophene; preferably, the judging standard for preliminarily judging the type of the oil sample to be detected as the circulating oil sample is as follows: saturated and aromatic hydrocarbons have UCM bulges; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 30 min; and the polycyclic aromatic hydrocarbon includes benzene, naphthalene, phenanthrene, fluorene, chrysene, anthracene and pyrene, and optionally dibenzothiophene; preferably, the judgment standard for preliminarily judging the type of the oil sample to be measured as the oil slurry oil sample is as follows: saturated hydrocarbons are less abundant than aromatic hydrocarbons and both contain UCM bulges; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 35 min; the polycyclic aromatic hydrocarbon includes benzene and naphthalenePhenanthrenes, dibenzothiophenes, fluorenes, chrysene, anthracenes, and pyrenes.
Further, the diagnostic ratio for determining the type of the oil sample to be detected as being combined with the normal line oil sample is as follows: the value of Σchr/Σpah is 0, the value of Σfluos/Σpah is 0, the value of LMW/HMW is absent, the value of C17/Pr is absent; preferably, the diagnostic ratio for determining the type of the oil sample to be detected as the combination of the normal two-line oil sample is as follows: the value of Σchr/Σpah is 0, the value of Σfluos/Σpah is 0, the value of LMW/HMW is absent, the value of C17/Pr is present; preferably, the diagnostic ratio for determining the type of the oil sample to be detected as being combined with the normal three-line oil sample is as follows: the value of Σchr/Σpah is 0, and the value of (c21+c22)/(c28+c29) is larger than 10.
Further, the diagnostic ratio combined by determining the type of the oil sample to be detected as the line-subtracting oil sample is: the values of Σchr/Σpah are 0, Σfluos/Σpah are not 0, C17/Pr are not 0, and the value (c21+c22)/(c28+c29) is absent; preferably, the diagnostic ratio for determining the type of the oil sample to be tested as the combination of the two-wire oil sample is as follows: the values of Σchr/Σpah are 0, Σfluos/Σpah are not 0, C17/Pr are not 0, (c21+c22)/(c28+c29) are not 0, LMW/HMW are less than 1; preferably, the diagnostic ratio for determining the type of the oil sample to be detected as the combination of the three-line oil sample is as follows: the value of Σ Chur/ΣPAH is 0, the value of Σ Fluos/ΣPAH is 0, the value of LMW/HMW is smaller than 1; preferably, the diagnostic ratio for determining the type of the oil sample to be detected as being combined with the crude oil sample is as follows: the values of Σchr/Σpah are 0, Σfluos/Σpah are not 0, C17/Pr are not 0, (c21+c22)/(c28+c29) are not 0, LMW/HMW are greater than 1; preferably, the diagnostic ratio for determining the type of the oil sample to be tested as being combined with the gasoline oil sample is as follows: the value of Σ Chur/ΣPAH is 0, the value of Σ Fluos/ΣPAH is 0, the value of LMW/HMW is greater than 1; preferably, the diagnostic ratio for determining the type of the oil sample to be tested as being combined with the diesel oil sample is as follows: the values of Σchr/Σpah are 0, Σfluos/Σpah are not 0, the value of C17/Pr is not present; preferably, the diagnosis ratio for determining the type of the oil sample to be detected as the hydrogenated wax oil sample is: the value of Σ Chr/Σ PAH is not 0, the value of Σ Phens/Σ Fluos is less than 10; preferably, the diagnostic ratio for determining the type of the oil sample to be detected as the combination of the circulating oil sample is as follows: the value of Σ cr/Σ PAH is not 0, and the value of Σ Phens/Σ Pyr is greater than 0.8; preferably, the diagnostic ratio for determining the type of the oil sample to be detected as being combined with the oil slurry oil sample is as follows: the value of Σchr/Σpah is not 0, and the value of Σphens/Σpyr is smaller than 0.8.
The invention fully plays the advantages of high speed and high sensitivity of the gas chromatography-mass spectrometry technology, and obtains the oil component information faster, and has strong practicability and good reproducibility. The influence of underground water and aqueous medium on the fingerprint characteristics of the oil sample is taken into the factors to be examined, so that the accurate identification of the oil sample in the atmospheric and vacuum device and the catalytic cracking device is realized, and an identification method is provided for tracing the leakage of the atmospheric and vacuum device and the catalytic cracking device of the oil refinery.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 shows a saturated hydrocarbon total ion flow chromatogram of example 1;
FIG. 2 shows an aromatic hydrocarbon total ion flow chromatogram of example 1;
FIG. 3 shows the normal alkane concentration profile of example 1;
FIG. 4 shows the polycyclic aromatic hydrocarbon concentration profile of example 1;
FIG. 5 shows a saturated hydrocarbon total ion flow chromatogram of example 1;
FIG. 6 shows a total ion flow chromatogram of aromatic hydrocarbons of example 1;
FIG. 7 shows the normal alkane concentration profile of test example 1; and
FIG. 8 shows the polycyclic aromatic hydrocarbon concentration distribution chart of test example 1.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
The invention relates to a fingerprint tracing method for leakage of refined oil products in groundwater by an atmospheric and vacuum device and a catalytic cracking device of a refining enterprise, which is a method for identifying the oil products by utilizing gas chromatography-mass spectrometry, and can be used for tracing the pollution source field of the leaked oil products when the refined products of the refining enterprise leak into the groundwater environment.
According to an exemplary embodiment of the invention, a method for tracing leakage of underground water oil products is provided. The method comprises the following steps: 1) Measuring fingerprint characteristics of an oil sample to be measured by gas chromatography-mass spectrometry to obtain a saturated hydrocarbon total ion flow chromatogram and an aromatic hydrocarbon total ion flow chromatogram, respectively drawing an n-alkane concentration distribution map and a polycyclic aromatic hydrocarbon concentration distribution map, and calculating to obtain a diagnosis ratio; 2) And judging the type of the oil sample to be detected according to the saturated hydrocarbon total ion flow chromatogram, the aromatic hydrocarbon total ion flow chromatogram, the normal alkane concentration distribution map and the polycyclic aromatic hydrocarbon concentration distribution map and the combination diagnosis ratio.
The invention fully plays the advantages of high speed and high sensitivity of the gas chromatography-mass spectrometry technology, and obtains the oil component information faster, and has strong practicability and good reproducibility. The influence of underground water and aqueous medium on the fingerprint characteristics of the oil sample is taken into the factors to be examined, so that the accurate identification of the oil sample in the atmospheric and vacuum device and the catalytic cracking device is realized, and an identification method is provided for tracing the leakage of the atmospheric and vacuum device and the catalytic cracking device of the oil refinery.
Preferably, the step 1) further comprises the step of preprocessing the oil sample to be detected before the gas chromatography-mass spectrometry is carried out to determine the oil sample to be detected, and separating the oil sample to be detected into saturated hydrocarbon and aromatic hydrocarbon; further, the method specifically comprises the following steps: when the oil sample to be measured is a pure oil sample, the oil sample to be measured is directly separated into saturated hydrocarbon (F 1 ) And aromatic hydrocarbons (F) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the When the oil sample to be measured contains moisture, the oil sample to be measured is extracted by using an organic solvent preferentially, and then the concentrated oil sample to be measured is separated into saturated hydrocarbon (F) 1 ) And aromatic hydrocarbons (F) 2 ). More preferably, the organic solvent is methylene chloride. Dichloromethane is the least toxic of methane chloride, and its toxicity is only 0.11% of carbon tetrachloride toxicity.Dichloromethane is slightly soluble in water and is mutually soluble with most common organic solvents, and has broad-spectrum dissolving capacity, low boiling point, relatively lowest toxicity and relatively best reaction inertia; the petroleum ether and diethyl ether are mainly used for replacing inflammable petroleum ether and diethyl ether and are used as extracting agents of fat and oil. In addition, methylene chloride may also be used as an eluent for the aromatic hydrocarbon component.
In a preferred embodiment of the invention, the diagnostic ratio comprises in order Σ Chr/Σ PAH, Σ Fluos/Σ PAH, LMW/HMW (smaller than Σ C21/larger than Σ C21), C17/Pr, (c21+c22)/(c28+c29), Σ Phens/Σ Fluos, Σ Phens/Σpyr. Wherein Σchr/Σpah represents chrysene and its alkylated series sum/measured total polycyclic aromatic hydrocarbon ratio, Σfluos/Σpah represents fluorene and its alkylated series sum/measured total polycyclic aromatic hydrocarbon ratio; LMW/HMW represents the sum of n-alkanes less than n-di-undecane/the sum of n-alkanes greater than or equal to n-di-undecane; C17/Pr represents n-heptadecane/pristane; (C21+C22)/(C28+C29) represents (n-heneicosane+n-docosyl)/n-octacosyl+n-nonacosyl), ΣPhens/ΣFluos represents phenanthrene and its alkylated series sum/fluorene and its alkylated series sum, ΣPhens/Σpyr represents phenanthrene and its alkylated series sum/pyrene and its alkylated series sum.
Preferably, step 2) specifically comprises: obtaining the peak type of chromatographic peaks, the retention time of the chromatographic patterns and the type of polycyclic aromatic hydrocarbon according to the saturated hydrocarbon total ion flow chromatogram, the aromatic hydrocarbon total ion flow chromatogram, the normal alkane concentration distribution map and the polycyclic aromatic hydrocarbon concentration distribution map, and primarily judging the type of the oil sample to be detected; and determining the type of the oil sample to be detected by combining the data ranges of the diagnostic ratios of Σchr/Σpah, Σfluos/Σpah, LMW/HMW (smaller than Σc21/larger than Σc21), C17/Pr, (c21+c22)/(c28+c29), Σphens/Σfluos and Σphens/Σpyr. By adopting the step, firstly, the oil products with obvious differences can be initially separated according to the visual presentation of the total ion flow chromatogram, so that fewer samples are identified for the follow-up, and the labor is saved; secondly, the concentration profile can provide the types of components and the content thereof as the basis for further sieving; and finally, extracting a representative more stable diagnosis ratio to identify the oil product.
According to a preferred embodiment of the present invention, leakage sources are primarily classified into two categories depending on whether chrysene (Chrysene) material is contained or not: (1) Hydrogenated wax oil, circulating oil and slurry oil containing chrysene (Chrysene) substance; (2) Normal first-line oil, normal second-line oil, normal third-line oil, first-line oil reduced, second-line oil reduced, third-line oil reduced, crude oil, gasoline, diesel oil which does not contain chrysene (Chrysene) substance.
Preferably, the judgment standard for preliminarily judging the type of the oil sample to be measured as the normal line oil sample is: the chromatographic peak is in the form of n-C 11 The normal paraffins at the two sides are symmetrically distributed; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 25 min; and the polycyclic aromatic hydrocarbon species include benzene and naphthalene, optionally containing dibenzothiophene.
Preferably, the judgment standard for preliminarily judging the type of the oil sample to be measured as the normal two-line oil sample is as follows: from n-C in the saturated hydrocarbons of the peak of the chromatographic peak 12 ~n-C 17 The aromatic hydrocarbon has UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 30 min; and the polycyclic aromatic hydrocarbon species include benzene, naphthalene and dibenzothiophene.
Preferably, the judgment standard for preliminarily judging the type of the oil sample to be measured as the normal three-line oil sample is as follows: from n-C in the saturated hydrocarbons of the peak of the chromatographic peak 14 ~n-C 29 The aromatic hydrocarbon has UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 45 min; and the polycyclic aromatic hydrocarbon must include benzene, naphthalene, optionally phenanthrene, dibenzothiophene and fluorene.
Preferably, the judgment standard for preliminarily judging the type of the oil sample to be measured as the first line subtracting oil sample is: from n-C in the saturated hydrocarbons of the peak of the chromatographic peak 11 ~n-C 20 The aromatic hydrocarbon has UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 25 min; and the polycyclic aromatic hydrocarbon species include benzenes, naphthalenes, dibenzothiophenes, and fluorenes, optionally phenanthrenes.
Preferably, preliminary judgmentThe judgment standard for judging the type of the oil sample to be tested is two-line oil sample reduction: from n-C in the saturated hydrocarbons of the peak of the chromatographic peak 15 ~n-C 33 The aromatic hydrocarbon has UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 30 min; and the polycyclic aromatic hydrocarbon species include benzene, naphthalene, phenanthrene, dibenzothiophene, and fluorene.
Preferably, the judgment standard for preliminarily judging the type of the oil sample to be measured as the three-line subtracting oil sample is as follows: from n-C in the saturated hydrocarbons of the peak of the chromatographic peak 22 ~n-C 36 The aromatic hydrocarbon has UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 36 min; and the polycyclic aromatic hydrocarbon species include phenanthrenes and dibenzothiophenes, optionally including naphthalenes.
Preferably, the judgment standard for preliminarily judging the type of the oil sample to be detected as the crude oil is as follows: the chromatographic peak has a peak value from n-C 8 To n-C 32 The peak heights of the (C) are gradually reduced, and the saturated hydrocarbon and the aromatic hydrocarbon have almost no UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 35 min; and the polycyclic aromatic hydrocarbon species include benzene, naphthalene, phenanthrene, dibenzothiophene, and fluorene.
Preferably, the judgment standard for preliminarily judging that the type of the oil sample to be measured is the gasoline oil sample is: the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 15 min; and the polycyclic aromatic hydrocarbon species include only benzene and naphthalene.
Preferably, the judgment standard for preliminarily judging the type of the oil sample to be tested as the diesel oil sample is as follows: chromatographic peak-to-peak type of saturated hydrocarbon total ion flow chromatogram is n-C 14 Is distributed on the right side with the center; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 25 min; and the polycyclic aromatic hydrocarbon species include benzene, naphthalene, phenanthrene, dibenzothiophene, fluorene, anthracene, and pyrene.
Preferably, the judgment standard for preliminarily judging the type of the oil sample to be detected as the hydrogenated wax oil sample is as follows: chromatographic peak-to-peak type of saturated hydrocarbon total ion flow chromatogram is n-C 20 As the center, two sides normal alkaneUniformly distributed, wherein the saturated hydrocarbon and the aromatic hydrocarbon have UCM bulges; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 40 min; and polycyclic aromatic hydrocarbon types including benzene, phenanthrene, fluorene, chrysene, anthracene and pyrene, optionally naphthalene, dibenzothiophene.
Preferably, the judging standard for preliminarily judging the type of the oil sample to be detected as the circulating oil sample is as follows: saturated and aromatic hydrocarbons have UCM bulges; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 30 min; and polycyclic aromatic hydrocarbons including benzene, naphthalene, phenanthrene, fluorene, chrysene, anthracene, and pyrene, optionally dibenzothiophene.
Preferably, the judgment standard for preliminarily judging the type of the oil sample to be measured as the oil slurry oil sample is as follows: the content of saturated hydrocarbon is less than that of aromatic hydrocarbon, and the saturated hydrocarbon and the aromatic hydrocarbon have UCM bulge; the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 35 min; and polycyclic aromatic hydrocarbons including benzene, naphthalene, phenanthrene, dibenzothiophene, fluorene, chrysene, anthracene, and pyrene.
In a further preferred embodiment of the invention, the diagnostic ratio combined to determine the type of oil sample to be tested as a normal line oil sample is: the values of Σchr/Σpah are 0, Σfluos/Σpah are 0, LMW/HMW (less than Σc21/greater than Σc21) are absent, C17/Pr are absent.
Preferably, the diagnostic ratio for determining the type of the oil sample to be tested as being combined with the normal two-line oil sample is: the values of Σchr/Σpah are 0, Σfluos/Σpah are 0, LMW/HMW (less than Σc21/greater than Σc21) are absent, C17/Pr are present.
Preferably, the diagnostic ratio for determining the type of the oil sample to be detected as being combined with the normal three-line oil sample is as follows: the value of Σchr/Σpah is 0, and the value of (c21+c22)/(c28+c29) is larger than 10.
Preferably, the diagnostic ratio combined to determine the type of the oil sample to be tested as a minus line oil sample is: the values of Σchr/Σpah are 0, Σfluos/Σpah are not 0, C17/Pr are not 0, and the value (c21+c22)/(c28+c29) is not present.
Preferably, the diagnostic ratio to determine the type of the oil sample to be tested as the combination of the two-wire oil sample is: the values of Σchr/Σpah are 0, Σfluos/Σpah are not 0, C17/Pr are not 0, (c21+c22)/(c28+c29) are not 0, and LMW/HMW (less than Σc21/greater than Σc21) are less than 1.
Preferably, the diagnostic ratio to determine the type of the oil sample to be tested as the subtracted line oil sample is: the values of Σchr/Σpah are 0, Σfluos/Σpah are 0, LMW/HMW (less than Σc21/greater than Σc21) are less than 1.
Preferably, the diagnostic ratio for determining the type of the oil sample to be tested as being combined with the crude oil sample is: the values of Σchr/Σpah are 0, Σfluos/Σpah are not 0, C17/Pr are not 0, (c21+c22)/(c28+c29) are not 0, and LMW/HMW (less than Σc21/greater than Σc21) are greater than 1.
Preferably, the diagnostic ratio to determine the type of the oil sample to be tested as being combined with the gasoline oil sample is: the values of Σchr/Σpah are 0, Σfluos/Σpah are 0, LMW/HMW (less than Σc21/greater than Σc21) are greater than 1.
Preferably, the diagnostic ratio to determine the type of the oil sample to be tested as being combined with the diesel oil sample is: the values of Σchr/Σpah are 0, Σfluos/Σpah are not 0, and the value of C17/Pr does not exist.
Preferably, the diagnostic ratio combined by determining the type of the oil sample to be detected as the hydrogenated wax oil sample is: the value of Σchr/Σpah is not 0, the value of Σphens/Σfluos is smaller than 10.
Preferably, the diagnostic ratio for determining the type of the oil sample to be tested as the combination of the circulating oil sample is: the value of Σchr/Σpah is not 0, and the value of Σphens/Σpyr is greater than 0.8.
Preferably, the diagnostic ratio for determining the type of the oil sample to be tested as being bound to the slurry oil sample is: the value of Σchr/Σpah is not 0, and the value of Σphens/Σpyr is smaller than 0.8.
Any range recited in the present invention includes any numerical value between the end values and any sub-range formed by any numerical value between the end values or any numerical value between the end values unless specifically stated otherwise.
The advantageous effects of the present invention will be further described below with reference to examples.
Example 1
The embodiment provides a fingerprint tracing method for oil leakage in groundwater, which comprises the following steps:
step one, pretreatment of an oil sample to be tested:
taking a silica gel chromatographic column, wherein the specification of the silica gel chromatographic column is 30cm long, the outer diameter of the silica gel chromatographic column is 10.5cm, a polytetrafluoroethylene piston is arranged, a small amount of glass wool is added at the upper end of the piston, 3.0g of activated silica gel is added, and anhydrous sodium sulfate with the thickness of about 0.5cm is added at the upper end of the silica gel. Adding 200 μl of oil sample, eluting saturated hydrocarbon and aromatic hydrocarbon with 15ml of mixed solution of n-hexane, dichloromethane and n-hexane (volume ratio of 1:1), concentrating, and adding internal standard substance (n-alkane is C) 24 D 50 The aromatic hydrocarbon was deuterated terphenyl) and was sized to 1ml for GC-MS determination of chemical composition.
Step two, determining fingerprint characteristics of an oil sample to be detected by adopting gas chromatography-mass spectrometry to obtain a saturated hydrocarbon total ion flow chromatogram and an aromatic hydrocarbon total ion flow chromatogram, wherein the saturated hydrocarbon total ion flow chromatograms and the aromatic hydrocarbon total ion flow chromatograms are respectively shown in fig. 1 and fig. 2;
wherein, the gas chromatography mass spectrometry instrument conditions are: the carrier gas is high-purity helium with the flow rate of 1.0 mL min -1 The temperature of the sample inlet is 290 ℃, the temperature of the ion source is 230 ℃, the temperature of the interface is 280 ℃, and sample introduction is not split. Heating program: the initial temperature was 50℃and after 2min, it was raised to 300℃at a rate of 6℃per min and maintained for 16min. Scanning is performed in a full scan mode and in a selected ion detection (SIM) mode. The detector adopts a mass spectrum detector and a flame ion detector.
Based on gas chromatography mass spectrometry, carrying out data analysis by a complete quantitative method (adding an internal standard substance), calculating to obtain concentration distribution of normal alkane and polycyclic aromatic hydrocarbon according to formulas I and II, and drawing to obtain a concentration distribution of normal alkane and a concentration distribution of polycyclic aromatic hydrocarbon, wherein the calculation formulas are as follows, as shown in fig. 3 and 4:
complete quantification method:I；
II；
in the formulae I and II,
RRF represents the relative corresponding factor; a is that C0 Representing the peak area of the components in the standard; a is that I0 Representing the peak area of an internal standard in the standard; w (W) C0 The component amount in the standard is expressed in g; w (W) I0 The internal scalar in the standard is represented in g; c represents the concentration of components in the oil sample to be measured; a is that C1 Representing the peak area of components in the oil sample to be measured; a is that I1 Representing the area of an internal standard peak in the oil sample to be measured; w (W) I1 The internal scalar in the oil sample to be measured is represented, and the unit is g; w (W) S Indicating the amount of the standard.
Judging the type of the oil sample to be detected:
analyzing the saturated hydrocarbon total ion flow chromatogram, the aromatic hydrocarbon total ion flow chromatogram, the normal alkane concentration distribution map and the polycyclic aromatic hydrocarbon concentration distribution map to obtain the following figures:
chromatographic peak-to-peak type of saturated hydrocarbon total ion flow chromatogram is n-C 20 As the center, normal paraffins on two sides are uniformly distributed, and the saturated hydrocarbon and the aromatic hydrocarbon have UCM bulges;
the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 40 min;
and polycyclic aromatic hydrocarbons including benzene, phenanthrene, fluorene, chrysene, anthracene, pyrene, naphthalene, dibenzothiophene.
Preliminarily judging the oil sample to be detected as a hydrogenated wax oil sample according to the characteristics;
from the two sets of diagnostic ratios in Table 1, ΣChr/ΣPAH is 0.017, not 0; sigma Phens/Sigma Fluos is 3.040, less than 10, so the oil sample to be measured can be determined to be the hydrogenated wax oil sample.
Table 1 example two sets of diagnostic ratios for oil samples to be tested
TABLE 2 ranges of 7 diagnostic ratios in 12 oil sample experiments with atmospheric and vacuum unit and catalytic cracker
Note that: the diagnostic ratios are determined in the order Σchr/Σpah, Σfluos/Σpah, LMW/HMW (smaller than Σc21/larger than Σc21), C17/Pr, (c21+c22)/(c28+c29), Σphens/Σfluos, Σphens/Σpyr.
Description: the analysis process for identifying the oil sample is based on comprehensive measurement of the original fingerprint of the oil product, the wind change of the oil product with different degrees, soil adsorption and the fingerprint characteristics of the oil product after column experiments. The specific experimental process is as follows:
(1) Original fingerprint: taking a silica gel chromatographic column, wherein the specification of the silica gel chromatographic column is 30cm long, the outer diameter of the silica gel chromatographic column is 10.5cm, a polytetrafluoroethylene piston is arranged, a small amount of glass wool is added at the upper end of the piston, 3.0g of activated silica gel is added, and anhydrous sodium sulfate with the thickness of about 0.5cm is added at the upper end of the silica gel. Adding 200 μl of oil sample, eluting saturated hydrocarbon and aromatic hydrocarbon with 15ml of mixed solution of n-hexane, dichloromethane and n-hexane (volume ratio of 1:1), concentrating, and adding internal standard substances (n-alkane is C) 24 D 50 The aromatic hydrocarbon was deuterated terphenyl) and the volume was set to 1ml for the GC-MS determination of fingerprint characteristics.
(2) And (3) weathering experiment: the glass petri dishes were taken, labeled and weighed. 3.0g of oil was added to the dish to keep the liquid level evenly immersed over the surface of the dish. Placing the culture dish in a natural ventilation place, weighing light oil every 2 hours, weighing heavy oil every 24 hours, and calculating the weathering loss rate. The sample is operated in the step 1, and the sample is separated into saturated hydrocarbon and aromatic hydrocarbon by a silica gel chromatographic column so as to prepare GC-MS for measuring fingerprint characteristics.
(3) Soil adsorption experiment: 1.0g of soil was taken out in a 100ml conical flask, 50ml of water and 1.0g of oil were added, and the mixture was shaken in a constant temperature shaker for 4 hours, taken out and allowed to stand for 24 hours. The surface organic phase is extracted by using 20ml of dichloromethane, the organic phase is concentrated, the sample is operated in the step 1, and the sample is separated into saturated hydrocarbon and aromatic hydrocarbon by a silica gel chromatographic column so as to prepare the GC-MS fingerprint feature.
(4) Earth pillar simulation experiment: the length of the soil column is 10cm, and the inner diameter is 3cm. The sample injection bottle, the peristaltic pump, the soil column (horizontally placed) and the sample receiving bottle are sequentially connected from left to right. The sample injection bottle is filled with uncontaminated groundwater, the peristaltic pump is used for controlling constant inflow velocity (2.5 m/d), the soil column filled with soil is horizontally placed to simulate groundwater flow in the horizontal direction, and the sample receiving bottle is used for collecting aqueous solution. After the soil column is saturated with water, the soil column is placed vertically, and 5.0g of oil sample is added into the soil column. And after the oil sample completely enters the soil, connecting the devices in sequence. The soil column is supplied with water, and the water is sampled from the water outlet every 1 hour. Transferring 20ml of the respectively collected solution to a separating funnel, adding 10ml of dichloromethane for extraction, concentrating an organic phase, performing operation of step 1 on the sample, and separating the sample into saturated hydrocarbon and aromatic hydrocarbon by using a silica gel chromatographic column to prepare GC-MS for measuring fingerprint characteristics.
Test example 1
In this test example, one of the original oil sample, the weathered oil sample, the soil adsorption test oil sample and the earth pillar simulation test oil sample was randomly selected, and the first and second steps were performed according to the method provided in example 1, and the obtained saturated hydrocarbon total ion flow chromatograms and aromatic hydrocarbon total ion flow chromatograms are shown in fig. 5 and 6, respectively, and the obtained normal alkane concentration profile and polycyclic aromatic hydrocarbon concentration profile are shown in fig. 7 and 8, respectively.
Analyzing the saturated hydrocarbon total ion flow chromatogram, the aromatic hydrocarbon total ion flow chromatogram, the normal alkane concentration distribution map and the polycyclic aromatic hydrocarbon concentration distribution map according to the third step to obtain the following figures:
saturated and aromatic hydrocarbons have UCM bulges;
the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 30 min;
and polycyclic aromatic hydrocarbons including benzene, naphthalene, phenanthrene, fluorene, chrysene, anthracene, pyrene, dibenzothiophene.
Preliminarily judging the oil sample to be detected as a circulating oil sample according to the characteristics;
from the two sets of diagnostic ratios in Table 3, ΣChr/ΣPAH is 0.029, not 0; sigma Phens/Sigma Pyr is 1.488 and is larger than 0.8, so that the oil sample to be measured can be determined to be the circulating oil sample.
Table 3 two sets of diagnostic ratios for test samples of oil to be tested
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the invention fully plays the advantages of high speed and high sensitivity of the gas chromatography-mass spectrometry technology, and obtains the oil component information faster, and has strong practicability and good reproducibility. The influence of underground water and aqueous medium on the fingerprint characteristics of the oil samples is taken into the factors to be examined, 7 groups of diagnosis ratios are established, the accurate identification of the oil samples in the atmospheric and vacuum devices and the catalytic cracking device is realized, and an identification method is provided for tracing the leakage of the atmospheric and vacuum devices and the catalytic cracking device of the oil refinery.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The method for tracing the leakage of the underground water oil product is characterized by comprising the following steps of:
1) Measuring fingerprint characteristics of an oil sample to be measured by gas chromatography-mass spectrometry to obtain a saturated hydrocarbon total ion flow chromatogram and an aromatic hydrocarbon total ion flow chromatogram, respectively drawing an n-alkane concentration distribution map and a polycyclic aromatic hydrocarbon concentration distribution map, and calculating to obtain a diagnosis ratio;
2) Judging the type of the oil sample to be detected according to the saturated hydrocarbon total ion flow chromatogram, the aromatic hydrocarbon total ion flow chromatogram, the normal alkane concentration distribution map and the polycyclic aromatic hydrocarbon concentration distribution map and by combining the diagnosis ratio;
the diagnostic ratios include, in order, Σchr/Σpah, Σfluos/Σpah, LMW/HMW, C17/Pr, (c21+c22)/(c28+c29), Σphens/Σfluos, and Σphens/Σpyr, wherein LMW/HMW is less than Σc21/greater than Σc21; wherein Σchr/Σpah represents chrysene and the ratio of the total sum of the alkylated series/the total polycyclic aromatic hydrocarbon measured; ΣFluos/ΣPAH represents the ratio of fluorene to its alkylated series sum/total polycyclic aromatic hydrocarbon measured; ΣPhens/ΣFluos represents phenanthrene and its alkylated series sum/fluorene and its alkylated series sum, ΣPhens/Σpyr represents phenanthrene and its alkylated series sum/pyrene and its alkylated series sum;
the step 2) specifically comprises the following steps:
obtaining a peak type of a chromatographic peak, a retention time of the chromatographic spectrum and a type of polycyclic aromatic hydrocarbon according to the saturated hydrocarbon total ion flow chromatogram, the aromatic hydrocarbon total ion flow chromatogram, the normal alkane concentration distribution map and the polycyclic aromatic hydrocarbon concentration distribution map, so as to preliminarily judge the type of the oil sample to be detected;
determining the type of the oil sample to be detected by combining the data ranges of the diagnostic ratios of sigma Chu/sigma PAH, sigma Fluos/sigma PAH, LMW/HMW, C17/Pr, (C21+C22)/(C28+C29), sigma Phens/sigma Fluos and sigma Phens/sigma Pyr;
leakage sources are primarily classified into two categories depending on whether chrysene material is present: (1) Hydrogenated wax oil, cycle oil and slurry oil containing chrysene substances; (2) Normal first-line oil, normal second-line oil, normal third-line oil, first-line oil reduced, second-line oil reduced, third-line oil reduced, crude oil, gasoline and diesel oil which do not contain chrysene substances;
the preliminary judgment that the type of the oil sample to be detected is a normal first line oil sample is as follows:
the peak form of the chromatographic peak is n-C 11 The normal paraffins at the two sides are symmetrically distributed;
the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 25 min;
and the polycyclic aromatic hydrocarbon species include benzene and naphthalene, and optionally dibenzothiophene;
the judgment standard for preliminarily judging the type of the oil sample to be detected as the normal second line oil sample is as follows:
from n-C in the saturated hydrocarbons of the peaks of the chromatogram 12 ~n-C 17 The aromatic hydrocarbon has UCM bulge;
the saturated hydrocarbon total ion stream chromatogram and the aromatic hydrocarbon total ion stream chromatogram have a retention time within 30 minutes;
and the polycyclic aromatic hydrocarbon species include benzene, naphthalene and dibenzothiophene;
the judgment standard for preliminarily judging the type of the oil sample to be detected as the normal three-line oil sample is as follows:
from n-C in the saturated hydrocarbons of the peaks of the chromatogram 14 ~n-C 29 The aromatic hydrocarbon has UCM bulge;
the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 45 min;
the polycyclic aromatic hydrocarbon is necessarily benzene, naphthalene, phenanthrene, dibenzothiophene and fluorene;
the preliminary judgment that the type of the oil sample to be detected is the first line subtracting oil sample is as follows:
from n-C in the saturated hydrocarbons of the peaks of the chromatogram 11 ~n-C 20 The aromatic hydrocarbon has UCM bulge;
the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 25 min;
and the polycyclic aromatic hydrocarbon comprises benzene, naphthalene, dibenzothiophene and fluorene, and optionally comprises phenanthrene;
the preliminary judgment that the type of the oil sample to be detected is the two-line oil sample is as follows:
from n-C in the saturated hydrocarbons of the peaks of the chromatogram 15 ~n-C 33 The aromatic hydrocarbon has UCM bulge;
the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 30 min;
and the polycyclic aromatic hydrocarbon includes benzene, naphthalene, phenanthrene, dibenzothiophene and fluorene;
the preliminary judgment that the type of the oil sample to be detected is the three-line subtracting oil sample is as follows:
from n-C in the saturated hydrocarbons of the peaks of the chromatogram 22 ~n-C 36 The aromatic hydrocarbon has UCM bulge;
the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 36 min;
and the polycyclic aromatic hydrocarbon comprises phenanthrene and dibenzothiophene, and optionally naphthalene;
the preliminary judgment that the type of the oil sample to be detected is crude oil is as follows:
the chromatographic peak has a peak value from n-C 8 To n-C 32 The peak heights of the (C) are gradually reduced, and the saturated hydrocarbon and the aromatic hydrocarbon have no UCM bulge;
the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 35 min;
and the polycyclic aromatic hydrocarbon includes benzene, naphthalene, phenanthrene, dibenzothiophene and fluorene;
the judgment standard for preliminarily judging that the type of the oil sample to be detected is a gasoline oil sample is as follows:
the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 15 min;
and the polycyclic aromatic hydrocarbon comprises benzene and naphthalene;
the judgment standard for preliminarily judging the type of the oil sample to be detected as the diesel oil sample is as follows:
the chromatographic peak-to-peak of the saturated hydrocarbon total ion flow chromatogram is n-C 14 Is distributed on the right side with the center;
the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 25 min;
and the polycyclic aromatic hydrocarbon includes benzene, naphthalene, phenanthrene, dibenzothiophene, fluorene, anthracene and pyrene;
the judgment standard for preliminarily judging the type of the oil sample to be detected as the hydrogenated wax oil sample is as follows:
the saturated hydrocarbon total ion flow chromatographyThe chromatographic peak-to-peak pattern is shown as n-C 20 As the center, normal paraffins on two sides are uniformly distributed, and the saturated hydrocarbon and the aromatic hydrocarbon have UCM bulges;
the retention time of the saturated hydrocarbon total ion flow chromatogram and the aromatic hydrocarbon total ion flow chromatogram is within 40 min;
and the polycyclic aromatic hydrocarbon comprises benzene, phenanthrene, fluorene, chrysene, anthracene and pyrene, and optionally naphthalene and dibenzothiophene;
the preliminary judgment that the type of the oil sample to be detected is the circulating oil sample is as follows:
the saturated hydrocarbon and the aromatic hydrocarbon have UCM bulge;
the saturated hydrocarbon total ion stream chromatogram and the aromatic hydrocarbon total ion stream chromatogram have a retention time within 30 minutes;
and the polycyclic aromatic hydrocarbon comprises benzene, naphthalene, phenanthrene, fluorene, chrysene, anthracene and pyrene, and optionally dibenzothiophene;
the preliminary judgment that the type of the oil sample to be detected is the oil slurry oil sample is as follows:
the saturated hydrocarbons are less abundant than the aromatic hydrocarbons and both contain UCM bulges;
the saturated hydrocarbon total ion stream chromatogram and the aromatic hydrocarbon total ion stream chromatogram have a retention time within 35 minutes;
and the polycyclic aromatic hydrocarbon includes benzene, naphthalene, phenanthrene, dibenzothiophene, fluorene, chrysene, anthracene and pyrene;
the diagnosis ratio of the type of the oil sample to be detected combined with the normal line oil sample is determined as follows: the value of Σchr/Σpah is 0, the value of Σfluos/Σpah is 0, the value of LMW/HMW is absent, the value of C17/Pr is absent;
the diagnosis ratio of the normal two-line oil sample is determined as follows: the value of Σchr/Σpah is 0, the value of Σfluos/Σpah is 0, the value of LMW/HMW is absent, the value of C17/Pr is present;
the diagnosis ratio of the type of the oil sample to be detected combined with the normal three-line oil sample is determined as follows: the value of Σchr/Σpah is 0, and the value of (c21+c22)/(c28+c29) is greater than 10;
determining the type of the oil sample to be detected as the diagnosis ratio combined by the first-line subtracting oil sample as follows: the values of Σchr/Σpah are 0, Σfluos/Σpah are not 0, C17/Pr are not 0, and the value (c21+c22)/(c28+c29) is absent;
determining the type of the oil sample to be detected as the diagnosis ratio combined by the two-line oil sample is as follows: the values of Σchr/Σpah are 0, Σfluos/Σpah are not 0, C17/Pr are not 0, (c21+c22)/(c28+c29) are not 0, LMW/HMW are less than 1;
determining the type of the oil sample to be detected as the diagnosis ratio combined by the three-line subtracting oil sample as follows: the value of Σ Chur/ΣPAH is 0, the value of Σ Fluos/ΣPAH is 0, the value of LMW/HMW is smaller than 1;
the diagnostic ratio of the type of the oil sample to be detected combined with the crude oil sample is determined as follows: the values of Σchr/Σpah are 0, Σfluos/Σpah are not 0, C17/Pr are not 0, (c21+c22)/(c28+c29) are not 0, LMW/HMW are greater than 1;
the diagnosis ratio of the type of the oil sample to be detected combined with the gasoline oil sample is determined as follows: the value of Σ Chur/ΣPAH is 0, the value of Σ Fluos/ΣPAH is 0, the value of LMW/HMW is greater than 1;
the diagnosis ratio of the type of the oil sample to be detected combined with the diesel oil sample is determined as follows: the values of Σchr/Σpah are 0, Σfluos/Σpah are not 0, the value of C17/Pr is not present;
determining that the type of the oil sample to be detected is the diagnosis ratio combined by the hydrogenated wax oil sample is as follows: the value of Σ Chr/Σ PAH is not 0, the value of Σ Phens/Σ Fluos is less than 10;
determining that the type of the oil sample to be detected is the diagnosis ratio combined by the circulating oil sample is as follows: the value of Σ cr/Σ PAH is not 0, and the value of Σ Phens/Σ Pyr is greater than 0.8;
the diagnosis ratio for determining that the type of the oil sample to be detected is the combination of the oil slurry oil sample is as follows: the value of Σchr/Σpah is not 0, and the value of Σphens/Σpyr is smaller than 0.8.
2. The method according to claim 1, wherein in step 1), the gas chromatography-mass spectrometry further comprises pre-treating the oil sample to be measured before measuring the oil sample to be measured, and separating the oil sample to be measured into saturated hydrocarbons and aromatic hydrocarbons.
3. The method according to claim 2, characterized in that the pre-treatment specifically comprises:
when the oil sample to be detected is a pure oil sample, directly separating the oil sample to be detected into saturated hydrocarbon and aromatic hydrocarbon by using a chromatographic column;
when the oil sample to be detected contains moisture, extracting the oil sample to be detected by using an organic solvent, and separating the concentrated oil sample to be detected into saturated hydrocarbon and aromatic hydrocarbon by using a chromatographic column.
4. A process according to claim 3, wherein the organic solvent is methylene chloride.
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