CN105510456A - Method for determining high-maturity condensate oil source - Google Patents
Method for determining high-maturity condensate oil source Download PDFInfo
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- CN105510456A CN105510456A CN201510849902.7A CN201510849902A CN105510456A CN 105510456 A CN105510456 A CN 105510456A CN 201510849902 A CN201510849902 A CN 201510849902A CN 105510456 A CN105510456 A CN 105510456A
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 28
- 239000011593 sulfur Substances 0.000 claims abstract description 28
- 238000012360 testing method Methods 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- -1 sulfo-adamantane compound Chemical class 0.000 claims description 73
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 34
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- 150000003568 thioethers Chemical class 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 229930192474 thiophene Natural products 0.000 claims description 21
- 150000003577 thiophenes Chemical class 0.000 claims description 20
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 19
- MVXVYAKCVDQRLW-UHFFFAOYSA-N 1h-pyrrolo[2,3-b]pyridine Chemical compound C1=CN=C2NC=CC2=C1 MVXVYAKCVDQRLW-UHFFFAOYSA-N 0.000 claims description 14
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- 238000004458 analytical method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 12
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 7
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 6
- 239000004519 grease Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 238000007069 methylation reaction Methods 0.000 claims description 5
- 238000001819 mass spectrum Methods 0.000 claims description 4
- 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 claims description 3
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229940045105 silver iodide Drugs 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000007445 Chromatographic isolation Methods 0.000 claims description 2
- 238000004252 FT/ICR mass spectrometry Methods 0.000 claims description 2
- 238000011097 chromatography purification Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000000717 retained effect Effects 0.000 claims description 2
- 239000003921 oil Substances 0.000 abstract description 81
- 239000010779 crude oil Substances 0.000 abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 3
- 239000011435 rock Substances 0.000 abstract 1
- QPHBUJJTFKRYHM-UHFFFAOYSA-N adamantane-1-sulfonic acid Chemical compound C1C(C2)CC3CC2CC1(S(=O)(=O)O)C3 QPHBUJJTFKRYHM-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 4
- 239000000090 biomarker Substances 0.000 description 3
- 230000017858 demethylation Effects 0.000 description 3
- 238000010520 demethylation reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000004648 ion cyclotron resonance mass spectroscopy Methods 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 230000001035 methylating effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012546 transfer Methods 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
- 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
-
- 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
- G01N30/14—Preparation by elimination of some components
-
- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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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)
Abstract
The invention provides a method for determining a high-maturity condensate oil source, which comprises the following steps: (1) analyzing and detecting the oil sample to determine whether the oil sample contains the thio-adamantane compound; (2) enriching the thioadamantane compounds in the oil sample containing the thioadamantane compounds; (3) and carrying out sulfur isotope test on the enriched thioadamantane compounds, and comparing the test result with the known sulfur isotope data of the sulfate of the crude oil layer, thereby determining the oil source of the oil sample. According to the method for determining the oil source of the high-maturity condensate, the oil source of the high-maturity condensate is determined by the method for determining the unique factors in the high-maturity condensate, the blank that the oil source of the high-maturity condensate cannot be determined in the current petroleum industry is filled, and by determining the oil source of the high-maturity condensate, the dominant hydrocarbon source rock can be truly and objectively found out, and the target layer system and the resource potential of the exploration heavy point can be determined.
Description
Technical field
The invention belongs to oil field prospecting field, be specifically related to a kind of high ripe white oil oil sources defining method.
Background technology
Deep Oil And Gas Exploration is the major domain of following global Oil Gas exploration.Deep layer temperature is high, pressure large, and organic-inorganic interacts strong, causes Deep Oil And Gas Exploration degree of ripeness high, standard biologic marker compounds information dropout, cannot sentence and know Deep Oil And Gas Exploration source, be international headache, constrain the evaluation of deep layer resource potential and oil-gas exploration.Particularly Tarim Basin, deep petroleum resource is very abundant, and current main force series of strata for exploration Ordovician Oil And Gas character is very complicated, and Oil-gas source exists dispute always, also lack effective ways and means to solve high stand oil and carry out source problem, constrain Deep Oil And Gas Exploration exploitation and evaluation.
Summary of the invention
For overcoming the problems referred to above, the object of this invention is to provide a kind of high ripe white oil oil sources defining method, the method chooses sulfo-adamantane compound as biomarker, and determines oil sources by the mensuration of separation and concentration and sulfur isotope.
For achieving the above object, the invention provides a kind of high ripe white oil oil sources defining method, the method comprises:
(1) carry out analysis to oil sample to detect, whether determine in oil sample containing sulfo-adamantane compound;
(2) oil sample containing sulfo-adamantane compound is carried out to the enrichment of sulfo-adamantane compound, the step of enrichment comprises: utilize methylation reaction to make the sulfocompound in oil sample change sulfonium salt into, after isolating sulfonium salt, substep, by thiophenes wherein and thio-ether type compounds removing, can obtain the sulfo-adamantane compound after enrichment;
(3) sulfur isotope test is carried out to the sulfo-adamantane compound after enrichment, the sulfur isotope data of test result and known source sequence sulfate are contrasted, thus determines the oil sources of oil sample.
In height ripe white oil oil sources defining method, first, need to choose the biomarker that the high stage of ripeness has thermal stability, finding after to substantial oil analysis, diamantane and sulfo-adamantane compound ubiquity in high maturated oil, and there is high thermal stability, be therefore elected to be the marker compounds of high maturated oil.Secondly, how by the enrichment of sulfo-diamantane, its requirement reaching isotope assay amount is made to be a difficult problem, the scheme that the application provides is based on methylating and the separation principle of demethylation, establish a kind of method being separated oil sample component, Selective Separation sulfo-adamantane series compound wherein enrichment, make monomer sulfocompound in mensuration crude oil
34s isotope becomes a reality.Again, the sulfo-adamantane compound of isotope mass spectrometer to enrichment is used to carry out the mensuration (sulfur isotope mass spectrum can measure the sulfo-adamantane monomer compound in sulfo-adamantane compound respectively) of sulfur isotope, because the sulphur in compound comes from the sulphur in source sequence sulfate, interacted by organic-inorganic and transfer in sulfo-diamantane.According to stable isotope fractionation principle, sulfur isotope in the sulfur isotope of sulfo-adamantane monomer compound and source sequence sulfate is close, then there is sibship, gap is larger, then there is not sibship, this provides the scientific information of molecular water sane level for exploring deep-seated oil gas field, can determine oil sources accordingly.
In above-mentioned height ripe white oil oil sources defining method, preferably, described sulfo-adamantane compound comprises sulfo-list adamantane compound, thiobis adamantane compound and sulfo-three Double diamantane hydrocarbons compounds.In the ripe white oil of height, can according to actual conditions, one or more choosing in sulfo-adamantane compound carry out analytical test.
In above-mentioned height ripe white oil oil sources defining method, preferably, when determining whether in step (1) containing sulfo-adamantane compound, comprehensive two dimensional gas chromatography-flight time mass spectrum (GC × GC-TOFMS) and/or comprehensive two dimensional gas chromatography-flame ionization ditector (GC × GC-FID) is used to carry out analyzing and compound test.Further preferably, carry out in analysis and compound test above-mentioned, choose m/z=168,182 and 192 as the characteristic ion peak of sulfo-list adamantane compound; Choose the characteristic ion peak of m/z=206 and 220 as thiobis adamantane compound; Choose the characteristic ion peak of m/z=258 and 272 as sulfo-three adamantane compound; Choose m/z=136,135,149,163,177 and 191 as the characteristic ion peak of single adamantane compound.
In above-mentioned height ripe white oil oil sources defining method, preferably, methylation reaction described in step (2) uses iodomethane and silver tetrafluoroborate to process; Further preferably, the step using iodomethane and silver tetrafluoroborate to carry out processing comprises: be dissolved in by oil sample in methylene chloride, add silver tetrafluoroborate and iodomethane reaction, after reaction terminates, cross the silver iodide precipitation filtered in reactant liquor, then remove methylene chloride and obtain grease; In grease, add normal hexane, through concussion cooling, be separated and obtain sulfonium salt precipitation.In above-mentioned methylation reaction, after grease adds normal hexane, the temperature of cooling is preferably 0 DEG C, can use Rotary Evaporators during removing methylene chloride.In addition, when being separated sulfonium salt precipitation, the most handy normal hexane repeatedly washs precipitation, makes in sulfonium salt not containing unreacted oil phase as far as possible.
In above-mentioned height ripe white oil oil sources defining method, preferably, wherein, in step (2) during removing thiophenes, be that isolated sulfonium salt and 7-azaindole are reacted, thus by the thiophenes removing in sulfonium salt;
Further preferably, isolated sulfonium salt and 7-azaindole are reacted, thus the step of the thiophenes removing in sulfonium salt is comprised: sulfonium salt is dissolved in acetonitrile, add the reaction of 7-azaindole, reaction terminates rear normal hexane and carries out extraction separatory, thiophenes in sulfonium salt is dissolved in normal hexane and is removed, and other sulfonium salts substances are retained in acetonitrile phase.
In above-mentioned height ripe white oil oil sources defining method, preferably, in step (2) during removing thio-ether type compounds, that other sulfonium salts substances and DMAP are reacted, thus removing thio-ether type compounds (is a demethylation, methyl on the sulfonium salt of sulfo-adamantane compound is divested, thus makes sulfo-adamantane compound and thio-ether type compounds realize being separated);
Further preferably, other sulfonium salt materials described and DMAP are reacted, thus the step of removing thio-ether type compounds comprises: by other sulfonium salt class substance dissolves in acetonitrile, add DMAP, react under counterflow condition, add watery hydrochloric acid after reaction terminates, then use n-hexane extraction separatory; Through extraction separatory, thio-ether type compounds is dissolved in normal hexane and is removed mutually, sulfo-adamantane compound remain in acetonitrile-water mutually in, by acetonitrile-water mutually in solvent removing namely obtain the sulfo-adamantane compound of enrichment.
In above-mentioned height ripe white oil oil sources defining method, preferably, the method also comprises the checking sulfo-adamantane compound whether successful step of separation and concentration, this step comprises: detect the sulfo-adamantane compound of isolated thiophenes and thio-ether type compounds, enrichment, to demonstrate the whether separation and concentration success of sulfo-adamantane compound.If the not firm alkyl compound of sulfur-bearing cash equivalent substantially in isolated thiophenes and thio-ether type compounds, and the sulfo-adamantane compound of enrichment obtains confirmation, then demonstrate sulfo-adamantane compound separation enrichment success.
In above-mentioned height ripe white oil oil sources defining method, preferably, in the successful step of checking sulfo-adamantane compound separation enrichment, sulphur Mass Spectrometer Method (GC-SCD) and/or gas chromatography mass spectrometry (GC-MS) analysis are carried out respectively to isolated thiophenes and thio-ether type compounds; The analysis of positive ionization electrospray-Fourier transform-Ion cyclotron Resonance Mass Spectrometry (ESIFT-ICRMS) is carried out to the sulfo-adamantane compound of enrichment.
In above-mentioned height ripe white oil oil sources defining method, preferably, in the successful step of checking sulfo-adamantane compound separation enrichment, also comprise the operation first isolated thiophenes and thio-ether type compounds being carried out to column chromatographic isolation and purification before analysis.
Height provided by the invention ripe white oil oil sources defining method, solves the difficult problems such as high stand oil OIL SOURCE CORRELATION, resource potential evaluation, can determine main hydrocarbon and exploration zone of interest.Scheme provided by the invention is by this method determining uniqueness factor in high stage of ripeness white oil, specify the oil sources of high stage of ripeness white oil, fill up the blank that current petroleum industry cannot determine high ripe white oil OIL SOURCE CORRELATION problem, by clear and definite high ripe white oil oil sources, thus can the finding out main hydrocarbon and determine exploration highest priority series of strata and resource potential of objective.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide a kind of method determining high ripe white oil oil sources, the method comprises the following steps:
Step one, choose In The Central Tarim Area height Matured oil sample (ZS1C crude oil), comprehensive two dimensional gas chromatography/flight time mass spectrum (GC × GC-TOFMS) and comprehensive two dimensional gas chromatography-flame ionization ditector (GC × GC-FID) carry out analyzing and compound test, be sulfo-list adamantane compound according to characteristic ion m/z=168,182,192, characteristic ion m/z=206,220 is thiobis adamantane compound, and Selective ion mode m/z136,135,149,163,177,191 is single adamantane series compound; After tested, feature biomarker is contained in oil sample: sulfo-list adamantane compound and thiobis adamantane compound.
The separation of step 2, sulfo-adamantane compound and enrichment (methylating and demethylation process)
Oil sample (0.5g) is dissolved in the methylene chloride of 5mL, add silver tetrafluoroborate and the 15mL iodomethane of 5mol equivalent successively, 24h reaction is carried out under room temperature lucifuge condition, after reaction terminates, cross the silver iodide precipitation filtered in reactant liquor, the methylene chloride in filtrate is removed by rotary distillation instrument; In residue grease, add 10mL normal hexane, be chilled to 0 DEG C after concussion, sulfonium salt is separated out under this condition, under centrifugal condition, sulfonium salt is gathered in bottle bottom, inclines to the normal hexane going out to be dissolved with unreacted oil, is separated the sulfonium salt obtaining polarity; Use n-hexane can ensure for 5 times in sulfonium salt not containing unreacted oil phase;
Sulfonium salt is dissolved in 5mL acetonitrile, adds the 7-azaindole of 10mol equivalent; Reaction, after stirring at room temperature carries out 48h, extracts and separatory with normal hexane (3 × 10mL); Be divided into the normal hexane phase and acetonitrile phase that are dissolved with thiophene compound; Normal hexane phase extract is merged concentrated rear silica gel chromatography (5g silica gel, eluent is 100mL normal hexane) of passing through and obtain thiophenes;
Be added to the DMAP of 10mol equivalent to above-mentioned acetonitrile, after reacting 12h under gained solution return condition, be cooled to room temperature; Add 5mL diluted hydrochloric acid aqueous solution (2mol/L) wherein, gained solution normal hexane (3 × 10mL) extraction also separatory, obtains the normal hexane phase and the acetonitrile-water phase that are dissolved with thio-ether type compounds; The normal hexane being dissolved with thio-ether type compounds is concentrated with rotary distillation instrument mutually, then uses silica gel chromatography (5g silica gel, eluent is 100mL normal hexane) to obtain thio-ether type compounds;
Above-mentioned acetonitrile-water, after rotary distillation instrument removing solvent acetonitrile and water, obtains enriched composition, enriched composition is again dissolved in acetonitrile, and the concentration being made into 0.005mg/mL is analyzed for positive ion ESIFT-ICRMS; To be separated the thiophenes that obtains and thio-ether type compounds carry out respectively GC-SCD and GC-MS analyze and and crude oil GC-SCD analyze and compare.Analytical test result shows: the not firm alkyl compound of sulfur-bearing cash equivalent substantially in thiophenes and thio-ether type compounds, and it is main containing sulfo-list adamantane compound and thiobis adamantane chemical combination in enriched composition, it can thus be appreciated that, sulfo-adamantane compound separation enrichment success.
The free sulfur isotope test of step 3, sulfo-adamantane compound and OIL SOURCE CORRELATION
Isotope mass spectrometer is used each sulfo-adamantane monomer compound in enriched composition to be carried out respectively to the mensuration of sulfur isotope, isotope test result shows: the sulfur isotope of sulfo-adamantane monomer compound sulfur isotope and Cambrian system sulfate is close, and very far away with Ordovician system sulfur isotope gap, thus determine that tower Crude Oil is Tarim Basin Cambrian system typical case end member oil.Wherein, the sulfur isotope of sulfo-adamantane monomer: 35-38 ‰, the sulfur isotope of Cambrian system sulfate: 31-37 ‰ in ZS1C crude oil, average: 34 ‰, the two relatively.Sulfo-diamantane is the compound that in diamantane molecule, C-2 carbon potential is replaced by sulphur atom, is the mark of TSR, is that the sulfide linkage in stratum is incorporated in organism, forms organic compounds containing sulfur.Therefore, the sulfur isotope of sulfo-diamantane represents the information of corresponding series of strata substantially.Thus, can determine that the sulphur in ZS1C crude oil in sulfo-adamantane comes from Cambrian system Sulfates.And the sulfur isotope of Ordovician, tarim Basin sulfate: 22-27 ‰, average: 25.8 ‰, obviously and the sulfur isotope (average 35 ‰) of ZS1C crude oil and the free sulfur isotope (35-38 ‰) of sulfo-adamantane far apart, there is not sibship.Therefore, the sulfur isotope of sulfo-adamantane monomer compound sulfur isotope and Cambrian system sulfate is close, and very far away with Ordovician system sulfur isotope gap, thus determines that ZS1C well crude oil is Tarim Basin Cambrian system typical case end member oil.
Claims (10)
1. a high ripe white oil oil sources defining method, the method comprises:
(1) carry out analysis to oil sample to detect, whether determine in oil sample containing sulfo-adamantane compound;
(2) oil sample containing sulfo-adamantane compound is carried out to the enrichment of sulfo-adamantane compound, the step of enrichment comprises: utilize methylation reaction to make the sulfocompound in oil sample change sulfonium salt into, after isolating sulfonium salt, substep, by thiophenes wherein and thio-ether type compounds removing, can obtain the sulfo-adamantane compound after enrichment;
(3) sulfur isotope test is carried out to the sulfo-adamantane compound after enrichment, the sulfur isotope data of test result and known source sequence sulfate are contrasted, thus determines the oil sources of oil sample.
2. height according to claim 1 ripe white oil oil sources defining method, wherein, described sulfo-adamantane compound comprises sulfo-list adamantane compound, thiobis adamantane compound and sulfo-three Double diamantane hydrocarbons compounds.
3. height according to claim 1 ripe white oil oil sources defining method, wherein, when determining whether in step (1) containing sulfo-adamantane compound, use comprehensive two dimensional gas chromatography-flight time mass spectrum and/or comprehensive two dimensional gas chromatography-flame ionization ditector to carry out analysis and detect.
4. height according to claim 3 ripe white oil oil sources defining method, wherein, carries out in analysis and compound test described, chooses m/z=168,182 and 192 as the characteristic ion peak of sulfo-list adamantane compound; Choose the characteristic ion peak of m/z=206 and 220 as thiobis adamantane compound; Choose the characteristic ion peak of m/z=258 and 272 as sulfo-three adamantane compound; Choose m/z=136,135,149,163,177 and 191 as the characteristic ion peak of single adamantane compound.
5. height according to claim 1 ripe white oil oil sources defining method, wherein, methylation reaction described in step (2) uses iodomethane and silver tetrafluoroborate to process;
Preferably, the step using iodomethane and silver tetrafluoroborate to carry out processing comprises:
Oil sample is dissolved in methylene chloride, adds silver tetrafluoroborate and iodomethane reaction, after reaction terminates, cross the silver iodide precipitation filtered in reactant liquor, then remove methylene chloride and obtain grease; In grease, add normal hexane, through concussion cooling, be separated and obtain sulfonium salt precipitation.
6. height according to claim 1 ripe white oil oil sources defining method wherein, in step (2) during removing thiophenes, is that isolated sulfonium salt and 7-azaindole are reacted, thus by the thiophenes removing in sulfonium salt;
Preferably, isolated sulfonium salt and 7-azaindole are reacted, thus the step of the thiophenes removing in sulfonium salt are comprised:
Be dissolved in by sulfonium salt in acetonitrile, add the reaction of 7-azaindole, reaction terminates rear normal hexane and carries out extraction separatory, and the thiophenes in sulfonium salt is dissolved in normal hexane and is removed, and other sulfonium salts substances are retained in acetonitrile phase.
7. height according to claim 6 ripe white oil oil sources defining method, wherein, in step (2) during removing thio-ether type compounds, is that other sulfonium salts substances described and DMAP are reacted, thus removing thio-ether type compounds;
Preferably, other sulfonium salt materials and DMAP are reacted, thus the step of removing thio-ether type compounds comprises:
By other sulfonium salt class substance dissolves in acetonitrile, add DMAP, react under counterflow condition, add watery hydrochloric acid after reaction terminates, then use n-hexane extraction separatory; Through extraction separatory, thio-ether type compounds is dissolved in normal hexane and is removed mutually, sulfo-adamantane compound remain in acetonitrile-water mutually in, by acetonitrile-water mutually in solvent removing namely obtain the sulfo-adamantane compound of enrichment.
8. height according to claim 1-7 any one ripe white oil oil sources defining method, wherein, the method also comprises the checking sulfo-adamantane compound whether successful step of separation and concentration, and this step comprises:
The sulfo-adamantane compound of isolated thiophenes and thio-ether type compounds, enrichment is detected, to demonstrate the whether separation and concentration success of sulfo-adamantane compound.
9. height according to claim 8 ripe white oil oil sources defining method, wherein, in the successful step of checking sulfo-adamantane compound separation enrichment,
Respectively sulphur Mass Spectrometer Method and/or Gc-ms are carried out to isolated thiophenes and thio-ether type compounds; Positive ionization electrospray-Fourier transform-Ion cyclotron Resonance Mass Spectrometry analysis is carried out to the sulfo-adamantane compound of enrichment.
10. height according to claim 8 ripe white oil oil sources defining method, wherein, in the successful step of checking sulfo-adamantane compound separation enrichment, also comprise the operation first isolated thiophenes and thio-ether type compounds being carried out to column chromatographic isolation and purification before analysis.
Priority Applications (1)
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