CN116413326A - Method for determining crude oil source based on thioethyl noradamantane - Google Patents
Method for determining crude oil source based on thioethyl noradamantane Download PDFInfo
- Publication number
- CN116413326A CN116413326A CN202111675303.XA CN202111675303A CN116413326A CN 116413326 A CN116413326 A CN 116413326A CN 202111675303 A CN202111675303 A CN 202111675303A CN 116413326 A CN116413326 A CN 116413326A
- Authority
- CN
- China
- Prior art keywords
- thioethyl
- determining
- noradamantane
- crude oil
- atmospheric pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 thioethyl noradamantane Chemical compound 0.000 title claims abstract description 75
- 239000010779 crude oil Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 36
- 150000002500 ions Chemical class 0.000 claims abstract description 44
- 238000005040 ion trap Methods 0.000 claims abstract description 26
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 23
- 239000011435 rock Substances 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000003921 oil Substances 0.000 claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 17
- 150000001793 charged compounds Chemical class 0.000 claims abstract description 14
- 239000012634 fragment Substances 0.000 claims abstract description 12
- 238000004896 high resolution mass spectrometry Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 48
- 238000000065 atmospheric pressure chemical ionisation Methods 0.000 claims description 27
- 238000001819 mass spectrum Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 238000010494 dissociation reaction Methods 0.000 claims description 9
- 230000005593 dissociations Effects 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 7
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 238000012546 transfer Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 6
- 239000000523 sample Substances 0.000 description 17
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- 229910018503 SF6 Inorganic materials 0.000 description 10
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 4
- 239000000090 biomarker Substances 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 241000084490 Esenbeckia delta Species 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- PCFIPYFVXDCWBW-UHFFFAOYSA-N tricyclo[3.3.1.03,7]nonane Chemical compound C1C(C2)C3CC2CC1C3 PCFIPYFVXDCWBW-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth 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)
Abstract
The invention provides a method for determining a crude oil source based on thioethyl diamantane, which comprises the following steps: mixing crude oil with a solvent to prepare a solution to be tested; injecting the solution to be detected into an atmospheric pressure electrochemical ionization source, ionizing the solution into ions by the atmospheric pressure electrochemical ionization source, and performing high-resolution mass spectrometry by an ion trap to obtain mass spectrometry result data; determining element information and structure information of the thioethyl noradamantane according to the molecular ion mass number and the fragment ion mass number in the mass spectrometry analysis result data, and determining stable isotopes of the thioethyl noradamantane 32 S and 34 signal intensity of S; according to the formula delta = mill ×% 34 R sample / 34 R SF6 ) -1 determining the isotope ratio of the thioethyl noradamantane, and comparing the isotope ratio of the thioethyl noradamantane with isotope data of sulfate in known hydrocarbon source rock, thereby determining the oil source of the crude oil. The invention has the advantages of simple process, good repeatability, high efficiency and the like.
Description
Technical Field
The invention relates to the technical fields of oil and gas field exploration and development and paint geochemistry, in particular to a method for determining a crude oil source based on thioethyl diamantane.
Background
Deep hydrocarbon exploration is an important and realistic field of global hydrocarbon exploration. Deep oil and gas exploration faces the dilemma and problems of high reservoir temperature, high pressure, complex ground stress, strong inorganic-organic interaction and the like, so that the deep oil and gas exploration risk is extremely high, the sources of deep oil and gas exploration cannot be accurately locked by the traditional method, the cracking degree of crude oil cannot be easily judged, and the implementation of potential of deep resources and the evaluation of oil and gas exploration prospect are extremely limited. One of the main reasons for the above dilemma and problems is the ancient deep oil and gas age, complex sources, high maturity, and the failure of conventional biomarker compounds to obtain valuable information. Chinese patent document CN105510456a discloses a method for determining a high-maturity condensate oil source, comprising: (1) Analyzing and detecting the oil sample to determine whether the oil sample contains the thioadamantane compound; (2) Enrichment of the thioadamantane compounds is carried out on the oil sample containing the thioadamantane compounds, and the enrichment step comprises the following steps: converting the sulfur-containing compounds in the oil sample into sulfonium salts by methylation reaction, separating the sulfonium salts, and then removing the thiophene compounds and the thioether compounds in the sulfonium salts step by step to obtain enriched thioadamantane compounds; (3) The sulfur isotope test is carried out on the enriched thioadamantane compounds, and the test result is compared with the sulfur isotope data of the known crude oil layer sulfate, so that the oil source of the oil sample is determined.
Disclosure of Invention
The invention provides a method for determining crude oil source based on thioethyl diamantane, which has the advantages of simple process, good repeatability, high efficiency and the like, and can effectively overcome the defects existing in the prior art.
The invention provides a method for determining a crude oil source based on thioethyl diamantane, which comprises the following steps: mixing crude oil with a solvent to prepare a solution to be tested; injecting the solution to be measured into an atmospheric pressure electrochemical ionization source, ionizing the solution into ions by the atmospheric pressure electrochemical ionization source, and then ionizingCarrying out high-resolution mass spectrometry on the sub-wells to obtain mass spectrometry analysis result data; wherein the atmospheric pressure chemical ionization source comprises a gas containing SF 6 Is a secondary gas of (a); the mass numbers of molecular ion peaks extracted by the four-stage rod of the ion trap high-resolution mass spectrum are respectively 180+14n,232+14n,284+14n,336+14n,388+14n,440+14n,492+14n, n is 0 or a positive integer, and the mass numbers of the fragment ion peaks are respectively 91, 105, 79, 81, 119, 131, 145 and 159; element information and structure information of the thioethyl diamantane are determined according to the molecular ion mass number and the fragment ion mass number in the mass spectrometry result data, and stable isotopes of the thioethyl diamantane are determined according to the mass spectrometry result data 32 S and 34 signal intensity of S; according to the formula delta = mill ×% 34 R sample / 34 R SF6 ) -1 determining the isotope ratio of thioethyl noradamantane, wherein, 34 R sample as thioethyl noradamantane 34 S signal intensity 32 The ratio of the S signal strengths is set, 34 R SF6 for the SF 6 A kind of electronic device 34 S signal intensity 32 Ratio of S signal intensities; and comparing the isotope ratio of the thioethyl noradamantane with isotope data of sulfate in the known hydrocarbon source rock, and determining the oil source of the crude oil according to the comparison result.
Further, the method for determining a crude oil source based on the thioethyl noradamantane as described above, wherein the solution to be measured is injected into the atmospheric pressure chemical ionization source at a rate of 1 to 100. Mu.L/min.
Further, the method for determining the crude oil source based on the thioethyl noradamantane, which is described above, wherein the concentration of the solution to be detected is 0.01-2.0 mg/mL.
Further, the method for determining a crude oil source based on the thioethyl diamantane as described above, wherein the solvent comprises at least one of carbon disulfide, carbon tetrachloride, isooctane, and dimethyl sulfoxide.
Further, the method for determining a crude oil source based on the thioethyl diamantane comprises the following steps ofHelium, SF in the auxiliary gas 6 The volume content of (2) is 0.1-0.5%.
Further, the method for determining a crude oil source based on thioethyl noradamantane as described above, wherein the flow rate of the assist gas is 1 to 25Arb.
Further, the method for determining a crude oil source based on the thioethyl diamantane, wherein the atmospheric pressure chemical ionization source further comprises a sheath gas, the sheath gas comprises nitrogen and/or helium, and the flow rate of the sheath gas is 1-100 Arb.
Further, the method for determining a crude oil source based on thioethyl noradamantane as described above, wherein the atmospheric pressure electrochemical ionization source further comprises a back-blow gas comprising nitrogen (N 2 ) And/or helium (He), the flow rate of the back-blowing gas being 0.01-1.0 Arb.
Further, the method for determining a crude oil source based on thioethyl noradamantane as described above, wherein the conditions of the atmospheric pressure chemical ionization source are: the discharge current is set to 1-40 mu A, the temperature of the ion transfer capillary is set to 200-400 ℃, and the temperature of the evaporator is set to 200-400 ℃.
Further, the method for determining a crude oil source based on thioethyl diamantane as described above, wherein the ion trap high-resolution mass spectrum is set to a full scan of from 50.0 to 800.0m/z with a resolution of 100000 ～ 700000; the ion trap high-resolution mass spectrum conditions are as follows: the concentration of the implanted ions extracted by the four-stage rod satisfies the number of the implanted ions of (1-9) x 10 5 And the maximum injection duration is 10-1000 ms, the microscan number is 1-10, and the energy of high-energy collision dissociation is 5-50 eV.
According to the invention, the element analysis and the structure information analysis are carried out on the thioethyl diamantane in the crude oil through the atmospheric pressure chemical ionization source-ion trap high-resolution mass spectrum, and simultaneously the isotope information of the thioethyl diamantane is obtained, and the crude oil source is determined based on the analysis result of the thioethyl diamantane.
Drawings
FIG. 1 is a schematic representation of the chemical structure (formula) of thioethylnoradamantane;
fig. 2 is a mass spectrum (ordinate: relative abundance (Relative Abundance)) of fragment ions obtained by high-energy collision dissociation of 5-cage thioethyl diamantane determined in example 1.
Detailed Description
The present invention will be described in further detail below for the purpose of better understanding of the aspects of the present invention by those skilled in the art. The following detailed description is merely illustrative of the principles and features of the present invention, and examples are set forth for the purpose of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the examples of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a method for determining a crude oil source based on thioethyl noradamantane, which comprises the following steps: mixing crude oil with a solvent to prepare a solution to be tested; injecting the solution to be detected into an atmospheric pressure electrochemical ionization source, ionizing the solution into ions by the atmospheric pressure electrochemical ionization source, and performing high-resolution mass spectrometry by an ion trap to obtain mass spectrometry result data; wherein the atmospheric pressure chemical ionization source comprises a gas containing SF 6 Is a secondary gas of (a); the mass numbers of molecular ion peaks extracted by the four-stage rod of the ion trap high-resolution mass spectrum are respectively 180+14n,232+14n,284+14n,336+14n,388+14n,440+14n,492+14n, n is 0 or a positive integer, and the mass numbers of the fragment ion peaks are respectively 91, 105, 79, 81, 119, 131, 145 and 159; determining element information and structure information of the thioethyl diamantane according to the mass number of molecular ions and the mass number of fragment ions in mass spectrometry analysis result dataAnd determining stable isotope of thioethyl diamantane according to mass spectrometry analysis result data 32 S and 34 signal intensity of S; according to the formula delta = mill ×% 34 R sample / 34 R SF6 ) -1 determining the isotope ratio of thioethyl noradamantane, wherein, 34 R sample as thioethyl noradamantane 34 S signal intensity 32 The ratio of the S signal strengths is set, 34 R SF6 is SF 6 A kind of electronic device 34 S signal intensity 32 Ratio of S signal intensities; and comparing the isotope ratio of the thioethyl noradamantane with isotope data of sulfate in the known hydrocarbon source rock, and determining the oil source of the crude oil according to the comparison result.
In determining the oil source of crude oil, it is first required to find a biomarker which has high thermal stability and is not easy to be biodegraded, and the thioethyl noradamantane has extremely high thermodynamic stability and biostability due to a special chemical structure (figure 1), so that the biomarker can be selected as the biomarker for determining the oil source, however, how to analyze the thioethyl noradamantane in the crude oil and how to efficiently and accurately obtain the sulfur isotope for determining the thioethyl noradamantane is a pending problem. According to the invention, through the determination process, the element information (molecular formula) and the structure information (molecular structure) of the thioethyl diamantane in the crude oil can be determined, the signal intensity of the stable isotopes 32S and 34S of the thioethyl diamantane in the mass spectrometry result can be obtained according to the formula, and the isotope ratio is further obtained according to the formula, because sulfur in the sulfur-containing compound (including the thioethyl diamantane) in the crude oil comes from sulfate in the source rock and is transferred into the sulfur-containing compound through sulfate thermal reduction, the sulfur isotope of the crude oil thioethyl diamantane is close to the sulfur isotope of sulfate in the source rock corresponding to the crude oil, if the two are not close to each other, the crude oil is not from the source rock, and the larger the numerical difference is, the poorer the corresponding relation is. Thus, if the isotope ratio of the thioethyl noradamantane is close to the isotope data of the sulfate in a known source rock, the crude oil is derived from the known source rock, thereby determining the crude oil source.
Typically, there are a plurality of thioalkyldown adamantane species in crude oil, and the mass spectrometry data includes isotopes of the plurality of thioalkyldown adamantane species 32 S and 34 s signal intensity is shown as delta = mill × @ according to the formula 34 R sample / 34 R SF6 ) And 1, determining the isotope ratio of each thioalkyldiamantane, calculating the average value of the isotope ratios of the obtained multiple thioalkyldiamantanes, comparing the average value with isotope data of sulfate in known hydrocarbon source rocks, and determining the oil source of crude oil according to the comparison result. In particular, stable isotopes of thioethyl noradamantane 32 S and 34 s is the signal strength of each of the two 32 Mass spectrum peak intensity and band of S ion 34 The mass spectrum peak intensity of S ion, the isotope data of sulfate in known hydrocarbon source rock can be measured according to the measurement mode of sulfur isotope composition in DZ/T0184.15-1997 sulfate.
In some embodiments, the solution to be measured is injected into the atmospheric pressure chemical ionization source at a speed of 1-100 mu L/min, preferably at a speed of 5-50 mu L/min, and ions (such as molecular ions) are generated after high-energy collision dissociation in the atmospheric pressure chemical ionization source, and then high-resolution mass spectrometry is performed through an ion trap to obtain mass spectrometry result data.
In some embodiments, the concentration of the test solution is in the range of 0.01 to 2.0mg/mL, e.g., 0.01mg/mL, 0.05mg/mL, 0.1mg/mL, 0.5mg/mL, 0.8mg/mL, 1mg/mL, 1.2mg/mL, 1.5mg/mL, 1.8mg/mL, 2mg/mL, or any two thereof, and generally preferably in the range of 0.05 to 0.8mg/mL.
The solvent comprises at least one of carbon disulfide, carbon tetrachloride, isooctane and dimethyl sulfoxide, such as carbon disulfide or carbon tetrachloride or isooctane or dimethyl sulfoxide. In some preferred embodiments, the solvent comprises carbon disulfide and/or isooctane, and when a mixed solvent of carbon disulfide and isooctane, the volume ratio of carbon disulfide to isooctane can be in the range of (1:9) - (9:1), such as 1:8, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, or any two of these.
Auxiliary gas-assisted ionization of atmospheric pressure ionization source containing sulfur hexafluoride (SF 6 ) A gas, wherein the mass spectrum analysis result data comprises SF 6 A kind of electronic device 34 S signal intensity 32 S signal intensity, thus, delta= =% 34 R sample / 34 R SF6 ) -1 determining the isotope ratio of thioethyl noradamantane. In some embodiments, the assist gas of the atmospheric pressure chemical ionization source further comprises nitrogen (N 2 ) And/or helium (He), wherein SF is 6 The auxiliary gas is, for example, N, in a volume content of 0.1 to 0.5%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, or a range of any two thereof 2 With SF 6 Or He and SF 6 Is a mixed gas of (a) and (b). The flow rate of the assist gas of the atmospheric pressure chemical ionization source may be generally in the range of 1 to 25Arb, for example, 1Arb, 2Arb, 5Arb, 8Arb, 10Arb, 12Arb, 15Arb, 18Arb, 20Arb, 22Arb, 25Arb or any two of them.
In addition, the atmospheric pressure chemical ionization source also comprises a sheath gas, and the sheath gas comprises N 2 And/or helium He, the flow rate of the sheath gas is 1-100 Arb, for example, 1Arb, 5Arb, 10Arb, 20Arb, 30Arb, 40Arb, 50Arb, 60Arb, 70Arb, 80Arb, 90Arb, 100Arb or any two of them, and the sheath gas can play roles of atomization, desolvation and the like.
In addition, the atmospheric pressure chemical ionization source also comprises back blowing gas, and the back blowing gas comprises N 2 And/or He, the flow rate of the back-blowing gas is 0.01-1.0 Arb, for example, 0.01Arb, 0.05Arb, 0.1Arb, 0.2Arb, 0.3Arb, 0.5Arb, 0.8Arb, 1Arb or the range formed by any two of them, and the back-blowing gas can back-blow the solution to be tested entering the atmospheric pressure chemical ionization source so as to make the system more uniform and improve the measurement efficiency.
Specifically, after the solution to be measured enters an atmospheric pressure chemical ionization source, a solvent can be evaporated through an evaporator of the atmospheric pressure chemical ionization source, crude oil is dissociated into ions in the atmospheric pressure chemical ionization source, and the ions are transferred to an ion trap high-resolution mass spectrometry unit by an ion transfer capillary tube to carry out mass spectrometry, so that mass spectrometry analysis result data are obtained. According to the study of the invention, the conditions of the atmospheric pressure chemical ionization source are as follows: the discharge current is set to 1 to 40. Mu.A, for example, 1. Mu.A, 2. Mu.A, 5. Mu.A, 10. Mu.A, 15. Mu.A, 20. Mu.A, 25. Mu.A, 30. Mu.A, 35. Mu.A, 40. Mu.A or any two of them, the ion transfer capillary temperature is set to 200 to 400 ℃, for example, 200 ℃, 220 ℃, 250 ℃, 280 ℃, 300 ℃, 320 ℃, 350 ℃, 380 ℃, 400 ℃ or any two of them, and the evaporator temperature is set to 200 to 400 ℃, for example, 200 ℃, 220 ℃, 250 ℃, 280 ℃, 300 ℃, 320 ℃, 350 ℃, 380 ℃, 400 ℃ or any two of them, which is advantageous for further improvement of the measurement efficiency.
Typically, the ion trap high resolution mass spectrum may be set to a full scan of from 50.0 to 800.0m/z with a resolution of 100000 ～ 700000, preferably the ion trap high resolution mass spectrum is set to a full scan of from 60.0 to 600.0m/z with a resolution of 300000 ～ 600000.
Through further research, the conditions of ion trap high-resolution mass spectrum are as follows: the concentration of the implanted ions extracted by the four-stage rod of the ion trap high-resolution mass spectrum satisfies the requirement that the number of the implanted ions is (1-9) multiplied by 10 5 Preferably (3-8). Times.10 5 The maximum injection duration is 10-1000 ms, preferably 50-200 ms, the microscan number is 1-10, preferably 2-5, and the energy of high-energy collision dissociation is 5-50 eV, preferably 10-35 eV. Specifically, the number of the injected ions is generally the total number of molecular ions, the four-stage rod injects ions into the ion transmission multistage rod (the maximum time length is the maximum time length of the four-stage rod injecting ions into the ion transmission multistage rod of the ion trap high-resolution mass spectrum), high-energy collision dissociation is performed in the ion transmission multistage rod, and the "fragment ions" formed after collision and the "molecular ions" which are not collided are sent to a mass spectrometry unit together for mass spectrometry, so that mass spectrometry analysis result data are obtained.
The invention can determine the crude oil source by adopting a mass spectrometer according to the process, wherein the mass spectrometer comprises an atmospheric pressure chemical ionization source, an ion trap high-resolution mass spectrum and a panel for controlling the conditions of the atmospheric pressure chemical ionization source and the ion trap high-resolution mass spectrum. The mass spectrometer is, for example, an Orbitrap Fusion model mass spectrometer from the company sammer femto technology (Thermo Scientific), and the control software is Orbitrap Fusion 2.0Tune.
For the purpose of promoting an understanding of the principles of the invention, reference will now be made in detail to specific examples, some but not all of which are illustrated in the accompanying drawings. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. In the following examples, an Orbitrap Fusion model mass spectrometer from the company sameimer femto technology (Thermo Scientific) was used, the control software of which was Orbitrap Fusion 2.0Tune.
Example 1
The method for determining the crude oil source based on the thioethyl diamantane provided by the embodiment is carried out according to the following process:
dissolving the crude oil of the wheel probe 1 in carbon disulfide to prepare a solution with the concentration of 0.2mg/mL, and injecting the solution into an atmospheric pressure chemical ionization source at the speed of 20 mu L/min; ionization into ions by an atmospheric pressure electrochemical ionization source, and high-resolution mass spectrometry analysis by an ion trap to obtain mass spectrometry analysis result data;
wherein the sheath gas of the atmospheric pressure chemical ionization source is N 2 The flow rate was 20Arb; the auxiliary gas was SF containing 0.1vol% (volume content) 6 N2 of gas at a flow rate of 5Arb; the back blowing is N 2 The flow rate was 0.5Arb; the discharge current was set at 10 μA, the ion transfer capillary temperature was set at 350℃and the evaporator temperature was set at 400 ℃.
Ion trap high resolution mass spectrometry was set to a full scan of from 50.0 to 800.0m/z with a resolution of 500000;
the mass numbers of molecular ion peaks extracted by the four-stage rod of the ion trap high-resolution mass spectrum are (180+14n, 232+14n,284+14n,336+14n,388+14n,440+14n,492+14n, n is 0 and positive integer), respectively, and the extracted implanted ionsThe concentration is 5×10 of the number of implanted ions 5 The maximum injection duration is 200ms, the microscanning number is 5, and the energy of high-energy collision dissociation is 25eV;
the molecular formula (element information) and the molecular structure (structure information) of the thioethyl diamantane are jointly determined by the molecular ion mass numbers (180+14n, 232+14n,284+14n,336+14n,388+14n,440+14n,492+14n, n is 0 and a positive integer) and the fragment ion mass numbers (91, 105, 79, 81, 119, 131, 145, 159) in the mass spectrometry result data, wherein the determined structural formula of the 5-cage thioethyl diamantane and a fragment ion mass spectrum obtained by high-energy collision dissociation of the same are shown in fig. 2;
stable isotope of different thioethyl noradamantane 32 S and 34 signal strength and SF of S 6 The gas comparison obtains the isotope ratio (i.e. delta =% 34 R sample / 34 R SF6 ) -1 determining the isotope ratio of the thioethyl noradamantane), and calculating to obtain monomer delta = +36.5-39.6 of the thioethyl noradamantane compound in the crude oil of the wheel probe 1, wherein the average value is +37.6; the distribution range of the isotopes of the sulfate in the british hydrocarbon source rock of the basin where the crude oil is located is 33.5-38.0, the average value is +35.5, the distribution range of the isotopes of the sulfate in the otto hydrocarbon source rock of the basin where the crude oil is located is 21.1-24.6, and the average value is +23.6, and obviously, the monomer sulfur isotopes of the thioethyl diamantane compound in the round 1 crude oil are closer to the isotopes of the sulfate in the british hydrocarbon source rock.
Example 2
The method for determining the crude oil source based on the thioethyl diamantane provided by the embodiment is carried out according to the following process:
dissolving high probe 1 crude oil in dimethyl sulfoxide to prepare a solution with the concentration of 2.0mg/mL, and injecting the solution into an atmospheric pressure chemical ionization source at the speed of 100 mu L/min; ionization into ions by an atmospheric pressure electrochemical ionization source, and high-resolution mass spectrometry analysis by an ion trap to obtain mass spectrometry analysis result data;
wherein, the sheath gas of the atmospheric pressure chemical ionization source is He, and the flow rate is 95Arb; the assist gas was He containing 0.5vol% SF6 gas at a flow rate of 24Arb; the back blowing gas is He, and the flow rate is 1.0Arb; the discharge current was set at 36 μa, the ion transfer capillary temperature was set at 400 ℃, and the evaporator temperature was set at 400 ℃;
the ion trap high-resolution mass spectrum is set to be a full scan from 50.0 to 800.0m/z, and the resolution is 680000;
the mass numbers of molecular ion peaks extracted by four-level rods of the ion trap high-resolution mass spectrum are (180+14n, 232+14n,284+14n,336+14n,388+14n,440+14n,492+14n, n is 0 and positive integer), and the concentration of the extracted injection ions is that the number of the injection ions is 9 multiplied by 10 5 The maximum injection time is 1000ms, the microscan number is 10, and the energy of high-energy collision dissociation is 20eV;
the molecular formula (element information) and the molecular structure (structure information) of the thiothioethyl noradamantane are determined together by the molecular ion mass numbers (180+14n, 232+14n,284+14n,336+14n,388+14n,440+14n,492+14n, n being 0 and positive integers) and the fragment ion mass numbers (91, 105, 79, 81, 119, 131, 145, 159) in the mass spectrometry result data;
stable isotope of different thioethyl noradamantane 32 S and 34 signal strength and SF of S 6 The gas comparison obtains the isotope ratio (i.e. delta =% 34 R sample / 34 R SF6 ) -1 determining the isotope ratio of the thioethyl noradamantane), and calculating to obtain monomer delta = +26.0-29.9 of the thioethyl noradamantane compound in the high probe 1 crude oil, wherein the average value is +27.0; the isotope distribution range of sulfate in dwarf hydrocarbon source rock of the basin where the crude oil is positioned is 23.3-27.1, the average value is +25.4, and the isotope distribution range of sulfate in trisodium hydrocarbon source rock of the basin is positionedThe surrounding is 31.2-33.9, the average value is +32.5, the isotope distribution range of sulfate in the binary hydrocarbon source rock of the basin is 35.0-38.8, the average value is +36.6, it is obvious that the monomer sulfur isotope of the thioethyl diamantane compound in the high-grade 1 crude oil is closer to the isotope of sulfate in the dwarf hydrocarbon source rock, and because the thioethyl diamantane compound is formed by the thermal cracking of the ethyl diamantane compound and the sulfate in the hydrocarbon source rock, the monomer sulfur isotope information of the thioethyl diamantane compound indicates the original information of the hydrocarbon source rock, and the thioethyl diamantane compound has a cage-shaped structure with stable physicochemical property and cannot be interfered by other secondary actions, so that the dwarf hydrocarbon source rock of the basin can be judged from the high-grade 1 crude oil.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. 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 (10)
1. A method for determining a crude oil source based on thioethyl noradamantane, comprising:
mixing crude oil with a solvent to prepare a solution to be tested;
injecting the solution to be detected into an atmospheric pressure electrochemical ionization source, ionizing the solution into ions by the atmospheric pressure electrochemical ionization source, and performing high-resolution mass spectrometry by an ion trap to obtain mass spectrometry result data; wherein,,
the atmospheric pressure chemical ionization source comprises SF 6 Is a secondary gas of (a);
the mass numbers of molecular ion peaks extracted by the four-stage rod of the ion trap high-resolution mass spectrum are respectively 180+14n,232+14n,284+14n,336+14n,388+14n,440+14n,492+14n, n is 0 or a positive integer, and the mass numbers of the fragment ion peaks are respectively 91, 105, 79, 81, 119, 131, 145 and 159;
determining the thioethyl diamantane according to the molecular ion mass number and the fragment ion mass number in the mass spectrometry result dataElement information and structure information, and determining stable isotope of thioethyl diamantane according to mass spectrometry analysis result data 32 S and 34 signal intensity of S;
according to the formula delta = mill ×% 34 R sample / 34 R SF6 ) -1 determining the isotope ratio of thioethyl noradamantane, wherein, 34 R sample as thioethyl noradamantane 34 S signal intensity 32 The ratio of the S signal strengths is set, 34 R SF6 for the SF 6 A kind of electronic device 34 S signal intensity 32 Ratio of S signal intensities;
and comparing the isotope ratio of the thioethyl noradamantane with isotope data of sulfate in the known hydrocarbon source rock, and determining the oil source of the crude oil according to the comparison result.
2. The method for determining a crude oil source based on thioethyl noradamantane of claim 1 wherein the solution to be tested is injected into the atmospheric pressure chemical ionization source at a rate of 1 to 100 μl/min.
3. The method for determining a crude oil source based on thioethyl noradamantane of claim 1 or 2, wherein the concentration of the solution to be measured is 0.01-2.0 mg/mL.
4. The method for determining a crude oil source based on thioethyl noradamantane of claim 1 or 2 wherein the solvent comprises at least one of carbon disulfide, carbon tetrachloride, isooctane, dimethyl sulfoxide.
5. The method for determining a crude oil source based on thioethylnoradamantane of claim 1 wherein the assist gas of the atmospheric pressure ionization source further comprises nitrogen and/or helium, SF in the assist gas 6 The volume content of (2) is 0.1-0.5%.
6. The method for determining a crude oil source based on thioethyl noradamantane of claim 1 or 5 wherein the flow rate of the assist gas is from 1 to 25Arb.
7. The method for determining a crude oil source based on thioethyl noradamantane of claim 1 wherein the atmospheric pressure chemical ionization source further comprises a sheath gas comprising nitrogen and/or helium, the sheath gas having a flow rate of 1 to 100Arb.
8. The method for determining a crude oil source based on thioethyl noradamantane of claim 1 wherein the atmospheric pressure electrochemical ionization source further comprises a back-blow gas comprising nitrogen (N 2 ) And/or helium (He), the flow rate of the back-blowing gas being 0.01-1.0 Arb.
9. The method for determining a crude oil source based on thioethyl noradamantane of claim 1 or 5 wherein the conditions of the atmospheric pressure chemical ionization source are: the discharge current is set to 1-40 mu A, the temperature of the ion transfer capillary is set to 200-400 ℃, and the temperature of the evaporator is set to 200-400 ℃.
10. The method of determining a crude oil source based on thioethyl noradamantane of claim 1 or 2 wherein the ion trap high resolution mass spectrometry is set to a full scan of from 50.0 to 800.0m/z with a resolution of 100000 ～ 700000; the ion trap high-resolution mass spectrum conditions are as follows: the concentration of the implanted ions extracted by the four-stage rod satisfies the number of the implanted ions of (1-9) x 10 5 And the maximum injection duration is 10-1000 ms, the microscan number is 1-10, and the energy of high-energy collision dissociation is 5-50 eV.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111675303.XA CN116413326A (en) | 2021-12-31 | 2021-12-31 | Method for determining crude oil source based on thioethyl noradamantane |
| PCT/CN2022/135855 WO2023124748A1 (en) | 2021-12-31 | 2022-12-01 | Method for determining crude oil source based on thioethyl noradamantane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111675303.XA CN116413326A (en) | 2021-12-31 | 2021-12-31 | Method for determining crude oil source based on thioethyl noradamantane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116413326A true CN116413326A (en) | 2023-07-11 |
Family
ID=86997572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111675303.XA Pending CN116413326A (en) | 2021-12-31 | 2021-12-31 | Method for determining crude oil source based on thioethyl noradamantane |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN116413326A (en) |
| WO (1) | WO2023124748A1 (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001116723A (en) * | 1999-10-19 | 2001-04-27 | Ebara Corp | Gc/ms/ms method using ion trap mass spectrometer |
| JP4800048B2 (en) * | 2006-01-31 | 2011-10-26 | 株式会社住化分析センター | Method for measuring isotope content |
| CN104792856A (en) * | 2015-04-21 | 2015-07-22 | 苏州大学 | Ion sample introduction method and multi-channel array ion trap mass spectrum system |
| CN105510561B (en) * | 2015-12-01 | 2017-11-10 | 中国石油天然气股份有限公司 | The method for determining oil sources using the sulfur isotope in crude oil monomer sulfur-containing compound |
| GB201701986D0 (en) * | 2017-02-07 | 2017-03-22 | Thermo Fisher Scient (Bremen) Gmbh | n |
| CN109752438A (en) * | 2017-11-06 | 2019-05-14 | 中国科学院大连化学物理研究所 | A kind of tetrahydrocannabinol fast qualitative analysis utilizing method in hemp plant |
| CN111595959A (en) * | 2020-04-29 | 2020-08-28 | 中国石油天然气股份有限公司 | Method and apparatus for analyzing sulfur isotopes of multiple single sulfur-containing compounds in crude oil |
| CN111595928B (en) * | 2020-04-29 | 2023-05-26 | 中国石油天然气股份有限公司 | Method for judging thermal cracking degree of crude oil |
-
2021
- 2021-12-31 CN CN202111675303.XA patent/CN116413326A/en active Pending
-
2022
- 2022-12-01 WO PCT/CN2022/135855 patent/WO2023124748A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023124748A1 (en) | 2023-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gross et al. | Triple analyzer mass spectrometry for high resolution MS/MS studies | |
| US6581013B1 (en) | Method for identifying compounds in a chemical mixture | |
| Lundqvist et al. | Novel time of flight instrument for doppler free kinetic energy release spectroscopy | |
| US20090114809A1 (en) | Isotope ratio mass spectrometer and methods for determining isotope ratios | |
| Dawson et al. | The use of triple quadrupoles for sequential mass spectrometry: 2—A detailed case study | |
| Hansel et al. | Improved detection limit of the proton‐transfer reaction mass spectrometer: on‐line monitoring of volatile organic compounds at mixing ratios of a few pptv | |
| Russ et al. | Osmium isotopic ratio measurements by inductively coupled plasma source mass spectrometry | |
| US20090194679A1 (en) | Methods and apparatus for reducing noise in mass spectrometry | |
| Eland | A new two-parameter mass spectrometry | |
| US20120211651A1 (en) | Mass Spectrometer and Method for Direct Measurement of Isotope Ratios | |
| US20210104391A1 (en) | Inorganic mass spectrometer | |
| Dubois et al. | Positive ion chemistry in an N2-CH4 plasma discharge: Key precursors to the growth of Titan tholins | |
| CN116413326A (en) | Method for determining crude oil source based on thioethyl noradamantane | |
| Guilhaus et al. | Advantages of a second electric sector on a double-focusing mass spectrometer of reversed configuration | |
| CN113156032B (en) | Mass spectrum system and method for simultaneously measuring isotope abundance and impurity content | |
| WO2021240710A1 (en) | Chromatography–mass spectrometry data processing method, chromatography–mass spectrometry device, and chromatography–mass spectrometry data processing program | |
| Lovestead et al. | Gas Chromatography-Mass Spectrometry (GC− MS) | |
| Kenttämaa et al. | Scanning a triple quadrupole mass spectrometer for doubly charged ions | |
| Cooks et al. | Metastable ions and ion kinetic energy spectrometry: the development of a new research area | |
| Cody | Accurate mass measurements on daughter ions from collisional activation in Fourier transform mass spectrometry | |
| Beynon et al. | Ion kinetic energy spectrometry | |
| Grayson | The mass spectrometer as a detector for gas chromatography | |
| CN115586237A (en) | Method for analyzing sulphaguanidine compounds in crude oil and determining oil source | |
| Safvan et al. | On the determination of the lifetime of metastable doubly charged molecules by ion translational energy spectrometry: CO2+ | |
| Rauth et al. | Production and identification of saturated hydrocarbon cluster dications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |