CN105510561B - Method for determining oil source by using sulfur isotope in crude oil monomer sulfur-containing compound - Google Patents
Method for determining oil source by using sulfur isotope in crude oil monomer sulfur-containing compound Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 68
- 239000011593 sulfur Substances 0.000 title claims abstract description 68
- 239000010779 crude oil Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003921 oil Substances 0.000 title claims abstract description 35
- 239000000178 monomer Substances 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 title claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 51
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 27
- -1 thiophene compound Chemical class 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011435 rock Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006900 dealkylation reaction Methods 0.000 claims abstract description 16
- 230000020335 dealkylation Effects 0.000 claims abstract description 15
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229930192474 thiophene Natural products 0.000 claims abstract description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000002152 alkylating effect Effects 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 16
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- MVXVYAKCVDQRLW-UHFFFAOYSA-N 1h-pyrrolo[2,3-b]pyridine Chemical class C1=CN=C2NC=CC2=C1 MVXVYAKCVDQRLW-UHFFFAOYSA-N 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000004519 grease Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 2
- 150000003568 thioethers Chemical class 0.000 abstract 2
- 229960001701 chloroform Drugs 0.000 abstract 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000002035 hexane extract Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000009671 shengli Substances 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000090 biomarker Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000012045 crude solution Substances 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- APTZNLHMIGJTEW-UHFFFAOYSA-N pyraflufen-ethyl Chemical compound C1=C(Cl)C(OCC(=O)OCC)=CC(C=2C(=C(OC(F)F)N(C)N=2)Cl)=C1F APTZNLHMIGJTEW-UHFFFAOYSA-N 0.000 description 1
- YALHCTUQSQRCSX-UHFFFAOYSA-N sulfane sulfuric acid Chemical compound S.OS(O)(=O)=O YALHCTUQSQRCSX-UHFFFAOYSA-N 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2823—Raw oil, drilling fluid or polyphasic mixtures
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01V—GEOPHYSICS; GRAVITATIONAL MEASUREMENTS; DETECTING MASSES OR OBJECTS; TAGS
- G01V9/00—Prospecting or detecting by methods not provided for in groups G01V1/00 - G01V8/00
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geophysics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention provides a method for determining an oil source by utilizing a sulfur isotope in a sulfur-containing compound in a crude oil monomer. The method comprises the following steps: dissolving crude oil in ethanol, dichloromethane or dichloroethane, adding an alkylating reagent, and reacting to obtain a filtrate; removing ethanol, dichloromethane or dichloroethane from the filtrate to obtain an oily substance; mixing the oily substance with alkane solvent of C5-C7, and separating precipitate; dissolving the precipitate in dichloromethane, trichloromethane or acetonitrile, adding a first dealkylation reagent, and reacting to obtain a solution A; extracting the mixture to obtain a thiophene compound and a solution B; adding a second dealkylation reagent into the solution B to carry out a second dealkylation reaction to obtain a solution C; extracting the mixture to obtain a thioether compound; measuring the distribution of the single sulfur isotopes in the thiophene compound and the thioether compound and the distribution of the sulfur isotopes in the sulfate salt in the crude oil rock stratum system; and comparing the sulfur isotope distribution of the two, wherein the stratum with the isotope distribution closest to the sulfur isotope distribution is an oil source layer.
Description
Technical field
The present invention relates to the method that the sulfur isotope in a kind of monomer sulfur-containing compound using crude oil determines oil sources, belongs to oil
Gas exploration technical field.
Background technology
OIL SOURCE CORRELATION is a key link in oil-gas exploration, and it is related to preferred, the resource of exploration play and dived
The evaluation of power, more and more deep, some high Matured oils or complicated phase stream more and more finer in particular with oil-gas exploration
Body, because biomarker is lost or more set series of strata biomarker is similar etc., OIL SOURCE CORRELATION is caused to have difficulties,
For example Tarim Basin marine oil and gas comes from Cambrian source rocks, or Ordovician Hydrocarbon Source Rocks, or mixed source etc. actually, always
In the presence of dispute；For another example, Sichuan Basin Zhong Ba gas fields, actually or thunderbolt ways condensate marine strata by Triassic system terrestrial facies hydrocarbon
Source rock generation etc., all more or less there are some OIL SOURCE CORRELATION problems in each oil-gas bearing basin, this brings tired for fine granularing scalability
Difficulty, therefore, it is quite necessary to start with from new idea and method, explore the channel for solving these key issues.Sulphur is deposition basin
A kind of important common elements in ground, always with deposition diagenesis and oil-gas generation, from sedimentary series to converting crude oil during
There is certain isotope fractionation, but the isotopic characteristic of parent is inherited substantially.Sulfur Compounds from Crude Oils enriches, and has
Belong to hydrocarbon source rock, some are then that organic-inorganic occurs with reservoir to react to each other, therefore the sulphur of crude oil is same
Position element is a mixed number, it is difficult to accurately determines source of parents.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide in a kind of monomer sulfur-containing compound using crude oil
The method that sulfur isotope determines oil sources.
To reach above-mentioned purpose, the invention provides a kind of determination of the sulfur isotope in monomer sulfur-containing compound using crude oil
The method of oil sources, this method comprise the following steps：
Step 1：Crude oil is dissolved in ethanol, dichloromethane or dichloroethanes, alkylating reagent is then added and carries out alkane
Glycosylation reaction, it is filtered after reaction terminates, obtain filtrate；Ethanol, dichloromethane or the dichloroethanes in filtrate are removed, is obtained
Grease；
Step 2：The grease is mixed with C5-C7 alkane solvent, then obtained precipitation is separated；
Step 3：The precipitation that step 2 is obtained is dissolved in dichloromethane, chloroform or acetonitrile, then adds first
De- alkyl reagent carries out first time dealkylation, obtains solution A；
Step 4：The solution A is extracted using C5-C7 alkane solvent, obtains the thiophene compound in crude oil
And solution B；
Step 5：The second de- alkyl reagent is added into solution B and carries out second of dealkylation, obtains solution C；
Step 6：The solution C is extracted using C5-C7 alkane solvent, obtains the sulfide compound in crude oil；
Step 7：Determine free sulfur IP in the thiophene compound and sulfide compound；
Step 8：Determine the sulfur isotope distribution of sulfate in oil source rock series of strata；
Step 9：The free sulfur IP and the sulfur isotope distribution of sulfate in oil source rock series of strata are compared
Compared with the immediate stratum of IP, as oil source zone.
According to method of the present invention, it is preferable that ethanol described in step 1, dichloromethane or dichloroethanes and crude oil
Volume ratio be 1-20:1.
According to method of the present invention, it is preferable that the reaction temperature of alkylated reaction described in step 1 is 0-80 DEG C,
Reaction time is 12-48h.
According to method of the present invention, it is preferable that the alkylating reagent includes silver nitrate, silver tetrafluoroborate, iodine first
One or more of combinations in alkane and bromoethane；
The ratio between mole of total sulfur is 5-50 in more preferably described alkylating reagent and crude oil:1；More preferably 5-
30:1。
According to method of the present invention, it is preferable that the alkane solvent of the C5-C7 described in step 2 include pentane,
N-hexane or normal heptane；More preferably n-hexane；
More preferably described C5-C7 alkane solvent and the volume ratio of crude oil are 20-500:1.
According to method of the present invention, it is preferable that the reaction temperature of first time dealkylation described in step 3 is 0-
80 DEG C, reaction time 12-48h.
According to method of the present invention, it is preferable that the first de- alkyl reagent described in step 3 includes pyridine, 4- bis-
Methylamino pyridine or 7- azaindoles；
The ratio between mole of total sulfur is 5-20 in more preferably described first de- alkyl reagent and crude oil:1.
According to method of the present invention, it is preferable that dichloromethane described in step 3, chloroform or acetonitrile and crude oil
Volume ratio be 1-20:1.
According to method of the present invention, it is preferable that the alkane solvent of the C5-C7 described in step 4 include pentane,
N-hexane or normal heptane；More preferably n-hexane；
More preferably described C5-C7 alkane solvent and the volume ratio of crude oil are 10-50:1；More preferably 20-40:1；
In very particularly preferred embodiment of the invention, the alkane solvent of the C5-C7 and the volume ratio of crude oil are 30:1.
According to method of the present invention, it is preferable that the reaction temperature of second of dealkylation is described in step 5
60-120 DEG C, reaction time 12-48h；
More preferably described reaction temperature is 80-100 DEG C.
According to method of the present invention, it is preferable that the second de- alkyl reagent described in step 5 includes pyridine, 4- bis-
Methylamino pyridine or 7- azaindoles；
The ratio between mole of total sulfur is 5-20 in more preferably described second de- alkyl reagent and crude oil:1.
According to method of the present invention, it is preferable that the alkane solvent of C5-C7 described in step 6 includes pentane, just
Hexane or normal heptane；More preferably n-hexane；
More preferably described C5-C7 alkane solvent and the volume ratio of crude oil are 10-50:1；More preferably 20-40:1；
In very particularly preferred embodiment of the invention, the alkane solvent of the C5-C7 and the volume ratio of crude oil are 30:1.
According to method of the present invention, monomer sulfur isotope in thiophene compound described in step 7 and sulfide compound
The measure of distribution using gas-chromatography icp mses carry out, using gas-chromatography inductive etc. from
It is this area conventional technology that daughter mass spectrograph, which determines free sulfur IP in thiophene compound and sulfide compound,
Those skilled in the art can need to select suitable operation to be measured according to field operation.
According to method of the present invention, the survey of the sulfur isotope distribution of sulfate in oil source rock series of strata described in step 8
Surely can be carried out according to step in detail below：Sulphur in sulfate sample in corresponding oil source rock series of strata is converted into SO2, using moral
The model Delta S of Finnigan MAT companies of state production isotope mass spectrometer is to SO2Mass spectral analysis is carried out, obtains oil generation
The sulfur isotope distribution of sulfate in the system of rock stratum.
According to method of the present invention, it is preferable that the crude oil includes condensate or heavy crude.
According to method of the present invention, it is preferable that the total sulfur content of the crude oil is 0.1wt%-5.0wt%.
Sulfur isotope in the monomer sulfur-containing compound provided by the present invention using crude oil determines to be related in the method for oil sources
Separation Sulfur Compounds from Crude Oils (thiophene compound, sulfide compound) method can realize sulfur-containing compound and hydro carbons and
Other heteroatomic compounds are kept completely separate.
Sulfur isotope in the monomer sulfur-containing compound provided by the present invention using crude oil determines that the method for oil sources can be accurate
Really measure crude oil monomer sulfur-containing compound sulfur isotope (34S/32S), and for OIL SOURCE CORRELATION to determine Oil-gas source, follow the trail of
Oil migration path, and then instruct New Discoveries During Hydrocarbon Exploration.
Sulfur isotope in the monomer sulfur-containing compound provided by the invention using crude oil determines that the method for oil sources uses methyl
Change the monomer sulphur compound in the separation method Selective Separation crude oil with demethylation, so as to realize crude oil sulfur-containing compound
Free sulfur isotope assay, new method is provided for OIL SOURCE CORRELATION, solve the problems, such as complex area OIL SOURCE CORRELATION difficulty.
Embodiment
In order to which technical characteristic, purpose and its advantage of the present invention is more clearly understood, now to the present invention's
Technical scheme carry out it is described further below, but can not be understood as to the present invention can practical range specific restriction.
Embodiment 1
The method that the sulfur isotope in a kind of monomer sulfur-containing compound using crude oil determines oil sources is present embodiments provided, its
In, this method comprises the following steps that：
Step 1：The crude oil that 500 milligrams of total sulfur contents are 2.06wt% (is derived from Tarim Basin ZS1C wells, at 20 DEG C
Density is 0.791 grams per milliliter) and 5 milliliters of dichloromethane be added in 25 milliliters of eggplant type bottle, then add 0.45 gram of tetrafluoro boron
Sour silver, after adding 0.45 milliliter of iodomethane with syringe under vigorous stirring, stirring reaction 12 is small under lucifuge and room temperature condition
Shi Hou, repeat the above steps once.After reaction terminates, the silver iodide precipitation generated in reaction solution is filtered to remove, by filtrate
Dichloromethane is removed by rotary distillation instrument；
Step 2：20 milliliters of n-hexanes are added into remaining grease, acutely 0 DEG C is cooled to after concussion, there is Precipitation,
Supernatant inclines to rear, acquirement sediment fraction；
Step 3：Gained precipitation is dissolved in 5 milliliters of acetonitriles, adds 400 milligrams of 7- azaindoles, and it is small to stir 24 at room temperature
Shi Jinhang first time dealkylations, obtain solution A；
Step 4：10 milliliters of n-hexane extractions and liquid separation are added into solution A, is repeated 2 times acquirement after the step just
Hexane extract merges.N-hexane extract is washed with 10 milliliters 2 moles every liter of dilute hydrochloric acid solution and liquid separation, takes organic phase dense
5 milliliters are reduced to, the thiophene compound referred to as separated from crude oil；Solution B is stand-by；
Step 5：To adding 400 milligrams of DMAPs in remaining acetonitrile solution (solution B), resulting solution in
Second of dealkylation is carried out under counterflow condition, reaction is cooled to room temperature after 12 hours, obtains solution C；
Step 6：The diluted hydrochloric acid aqueous solution and 10 milliliters of n-hexanes that 10 milliliters 2 moles every liter is added into solution C shake simultaneously
Liquid separation, organic phase is taken to be concentrated into 5 milliliters, the sulfide compound referred to as separated from crude oil；
Step 7：Gas phase color is carried out respectively to the thiophene compound in the ZS1C well crude oil of Tarim Basin and sulfide compound
Icp mses analysis is composed, what analysis measured monomer sulfur isotope after terminating is distributed as 35 ‰ -45 ‰；
Step 8：By the sulphur in Tarim Basin Cambrian system sulfate sample and Ordovician, tarim Basin sulfate sample
It is converted into SO2, then use the model Delta S of German Finnigan MAT companies production isotope mass spectrometer right respectively
Obtained SO2Mass spectral analysis is carried out, the sulfur isotope for obtaining Tarim Basin Cambrian system sulfate is distributed as 32-45 ‰, Austria's pottery
It is that the sulfur isotope of sulfate is distributed as 21-25 ‰；
Step 9：By the free sulfur IP obtained in step 7 respectively with Tarim Basin Cambrian source rock
The sulfur isotope distribution of sulfate is compared, it is seen then that the free sulfur IP obtained in step 7 and Tarim Basin
The sulfur isotope of Cambrian system sulfate is distributed more closely, so Tarim Basin ZS1C well crude oil comes from Cambrian system.
Embodiment 2
The method that the sulfur isotope in a kind of monomer sulfur-containing compound using crude oil determines oil sources is present embodiments provided, its
In, this method comprises the following steps that：
Step 1：The crude oil that 200 milligrams of total sulfur contents are 4.86wt% (is derived from Shengli Oil Field Luojia area, at 20 DEG C
Density is 0.981 grams per milliliter) and 2 milliliters of dichloromethane be added in 10 milliliters of eggplant type bottle, then add 0.43 gram of tetrafluoro boron
Sour silver, after adding 0.43 milliliter of iodomethane with syringe under vigorous stirring, stirring reaction 12 is small under lucifuge and room temperature condition
Shi Hou, repeat the above steps once.After reaction terminates, the silver iodide precipitation generated in reaction solution is filtered to remove, by filtrate
Dichloromethane is removed by rotary distillation instrument；
Step 2：8 milliliters of normal heptanes are added into remaining grease, acutely 0 DEG C is cooled to after concussion, there is Precipitation,
Supernatant inclines to rear, acquirement sediment fraction；
Step 3：Gained precipitation is dissolved in 2 milliliters of acetonitriles, adds 370 milligrams of 7- azaindoles, and it is small to stir 24 at room temperature
Shi Jinhang first time dealkylations, obtain solution A；
Step 4：4 milliliters of n-hexane extractions and liquid separation are added into solution A, be repeated 2 times after the step by acquirement just oneself
Alkane extract merges.N-hexane extract is washed with 10 milliliters 2 moles every liter of dilute hydrochloric acid solution and liquid separation, takes organic phase to concentrate
To 2 milliliters, the thiophene compound referred to as separated from crude oil；Solution B is stand-by；
Step 5：To adding 370 milligrams of DMAPs in remaining acetonitrile solution (solution B), resulting solution in
Second of dealkylation is carried out under counterflow condition, reaction is cooled to room temperature after 12 hours, obtains solution C；
Step 6：The diluted hydrochloric acid aqueous solution and 10 milliliters of n-hexanes that 10 milliliters 2 moles every liter is added into solution C shake simultaneously
Liquid separation, organic phase is taken to be concentrated into 2 milliliters, the sulfide compound referred to as separated from crude oil；
Step 7：Gas phase is carried out respectively to the thiophene compound in the crude oil of Shengli Oil Field Luojia area and sulfide compound
Chromatogram icp mses are analyzed, and what analysis measured monomer sulfur isotope after terminating is distributed as 26-28 ‰；
Step 8：Sulphur in sulfate sample in the hydrocarbon source rock on SHAHEJIE FORMATION s_4 formation stratum is converted into SO2, then
Using the model Delta S of the German Finnigan MAT companies production isotope mass spectrometer SO to obtaining respectively2Carry out
Mass spectral analysis, the sulfur isotope for obtaining the sulfate in the hydrocarbon source rock on SHAHEJIE FORMATION s_4 formation stratum are distributed as 28-34 ‰；
Step 9：By in the hydrocarbon source rock on the free sulfur IP obtained in step 7 and SHAHEJIE FORMATION s_4 formation stratum
Sulfate sulfur isotope distribution be compared, it is seen then that the free sulfur IP and SHAHEJIE FORMATION obtained in step 7
The sulfur isotope distribution of sulfate in the hydrocarbon source rock on s_4 formation stratum is closer to, so Shengli Oil Field Luojia area crude oil comes
From in the hydrocarbon source rock of SHAHEJIE FORMATION s_4 formation.
Claims (8)
1. the method that the sulfur isotope in a kind of monomer sulfur-containing compound using crude oil determines oil sources, wherein, this method include with
Lower step：
Step 1：Crude oil is dissolved in ethanol, dichloromethane or dichloroethanes, alkylating reagent is then added and is alkylated
Reaction, it is filtered after reaction terminates, filtrate is obtained, ethanol, dichloromethane or dichloroethanes in filtrate is removed, obtains oily
Thing；
The volume ratio of the ethanol, dichloromethane or dichloroethanes and crude oil is 1-20:1；
The reaction temperature of alkylated reaction described in step 1 is 0-80 DEG C, reaction time 12-48h；
Alkylating reagent described in step 1 includes the one or more in silver nitrate, silver tetrafluoroborate, iodomethane and bromoethane
Combination；
The ratio between mole of total sulfur is 5-50 in the alkylating reagent and crude oil:1；
Step 2：The grease is mixed with C5-C7 alkane solvent, then obtained precipitation is separated；
The alkane solvent of C5-C7 described in step 2 includes pentane, n-hexane or normal heptane；
The alkane solvent of the C5-C7 and the volume ratio of crude oil are 20-500:1；
Step 3：The precipitation that step 2 is obtained is dissolved in dichloromethane, chloroform or acetonitrile, then adds the first de- alkane
Base reagent carries out first time dealkylation, obtains solution A；
The volume ratio of the dichloromethane, chloroform or acetonitrile and crude oil is 1-20:1；
The reaction temperature of first time dealkylation described in step 3 is 0-80 DEG C, reaction time 12-48h；
The first de- alkyl reagent described in step 3 includes pyridine, DMAP or 7- azaindoles；
The ratio between mole of total sulfur is 5-20 in described first de- alkyl reagent and crude oil:1；
Step 4：The solution A is extracted using C5-C7 alkane solvent, obtains thiophene compound in crude oil and molten
Liquid B；
The alkane solvent of C5-C7 described in step 4 includes pentane, n-hexane or normal heptane；
The alkane solvent of the C5-C7 and the volume ratio of crude oil are 10-50:1；
Step 5：The second de- alkyl reagent is added into solution B and carries out second of dealkylation, obtains solution C；
The reaction temperature of second of dealkylation described in step 5 is 60-120 DEG C, reaction time 12-48h；
The second de- alkyl reagent described in step 5 includes pyridine, DMAP or 7- azaindoles；
The ratio between mole of total sulfur is 5-20 in described second de- alkyl reagent and crude oil:1；
Step 6：The solution C is extracted using C5-C7 alkane solvent, obtains the sulfide compound in crude oil；
The alkane solvent of C5-C7 described in step 6 includes pentane, n-hexane or normal heptane；
The alkane solvent of the C5-C7 and the volume ratio of crude oil are 10-50:1；
Step 7：Determine free sulfur IP in the thiophene compound and sulfide compound；
Step 8：Determine the sulfur isotope distribution of sulfate in oil source rock series of strata；
Step 9：By the free sulfur IP compared with the sulfur isotope distribution of sulfate in oil source rock series of strata,
The immediate stratum of IP, as oil source zone.
2. the method according to claim 11, wherein, the mole of alkylating reagent described in step 1 and total sulfur in crude oil
The ratio between be 5-30:1.
3. the method according to claim 11, wherein, the alkane solvent of C5-C7 described in step 4 and the volume ratio of crude oil
For 20-40:1.
4. the method according to claim 11, wherein, the alkane solvent of C5-C7 described in step 4 and the volume ratio of crude oil
For 30:1.
5. according to the method for claim 1, wherein, the reaction temperature of second of dealkylation is described in step 5
80-100℃。
6. the method according to claim 11, wherein, the alkane solvent of C5-C7 described in step 6 and the volume ratio of crude oil
For 20-40:1.
7. according to the method described in claim any one of 1-6, wherein, the crude oil includes condensate or heavy crude.
8. according to the method for claim 7, wherein, the total sulfur content of the crude oil is 0.1wt%-5.0wt%.
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