CN105510561A - 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 60
- 239000010779 crude oil Substances 0.000 title claims abstract description 59
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 56
- 239000011593 sulfur Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003921 oil Substances 0.000 title claims abstract description 37
- 239000000178 monomer Substances 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 title abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 thiophene compound Chemical class 0.000 claims abstract description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 21
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 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 15
- 230000020335 dealkylation Effects 0.000 claims abstract description 14
- 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
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 230000002152 alkylating effect Effects 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- MVXVYAKCVDQRLW-UHFFFAOYSA-N 1h-pyrrolo[2,3-b]pyridine Chemical compound C1=CN=C2NC=CC2=C1 MVXVYAKCVDQRLW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- 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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004519 grease Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001494 silver tetrafluoroborate Inorganic materials 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
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- 239000012045 crude solution Substances 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 abstract 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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract 1
- 229960001701 chloroform Drugs 0.000 abstract 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000002035 hexane extract Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000000155 isotopic effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000009671 shengli Substances 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- 150000003464 sulfur compounds Chemical class 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
- 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
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000090 biomarker Substances 0.000 description 2
- 230000009514 concussion 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
- 239000000376 reactant Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012071 phase Substances 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
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
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Analytical Chemistry (AREA)
- Pathology (AREA)
- Immunology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Food Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geophysics (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 a kind of method of the sulfur isotope determination oil sources utilized in crude oil monomer sulfocompound, belong to oil-gas exploration technical field.
Background technology
OIL SOURCE CORRELATION is a key link in oil-gas exploration, it is related to the evaluation of preferred, the resource potential of exploration play, particularly along with oil-gas exploration is more and more meticulousr, more and more deep, some high Matured oils or complicated phase fluid, due to biomarker lose or many cover series of strata biomarkers similar etc., OIL SOURCE CORRELATION is caused to have difficulties, such as, Tarim Basin marine oil and gas is actually from Cambrian source rocks, or Ordovician Hydrocarbon Source Rocks, or mixed source etc., there is dispute always; For another example, Zhong Ba gas field, the Sichuan Basin, actually or thunderbolt ways white oil marine strata is generated etc. by Triassic system nonmarine source rock, all more or less there are some OIL SOURCE CORRELATION difficult problems in each petroliferous basin, this brings difficulty for fine granularing scalability, therefore, be extremely necessary to start with from new thinking and countermeasure, explore the channel solving these key issues.Sulphur is a kind of important common elements in sedimentary basin, always along with deposition diagenesis and oil-gas generation, there is certain isotope fractionation, but substantially inherit the isotopic characteristic of parent from sedimentary series to converting crude oil process.Sulfur Compounds from Crude Oils enriches, and some belongs to hydrocarbon source rock, and some is then react to each other with reservoir generation organic-inorganic, and therefore the sulfur isotope of crude oil is a mixed number, is difficult to accurately determine source of parents.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of method of the sulfur isotope determination oil sources utilized in crude oil monomer sulfocompound.
For achieving the above object, the invention provides a kind of method of the sulfur isotope determination oil sources utilized in crude oil monomer sulfocompound, the method comprises the following steps:
Step one: be dissolved in by crude oil in ethanol, methylene chloride or ethylene dichloride, then adds alkylating reagent and carries out alkylated reaction, after reaction terminates, after filtration, obtains filtrate; Ethanol, methylene chloride or ethylene dichloride in removing filtrate, obtain grease;
Step 2: described grease is mixed with the alkane solvent of C5-C7, then the precipitation obtained is separated;
Step 3: precipitation step 2 obtained is dissolved in methylene chloride, methenyl choloride or acetonitrile, then adds the first de-alkyl reagent and carries out first time dealkylation, obtain solution A;
Step 4: use the alkane solvent of C5-C7 to extract described solution A, obtain the thiophene compound in crude oil and solution B;
Step 5: add the second de-alkyl reagent and carry out second time dealkylation in solution B, obtain solution C;
Step 6: use the alkane solvent of C5-C7 to extract described solution C, obtain the sulfide compound in crude oil;
Step 7: measure free sulfur isotope distribution in described thiophene compound and sulfide compound;
Step 8: the sulfur isotope distribution measuring sulfate in oil source rock series of strata;
Step 9: the distribution of described free sulfur isotope distributed with the sulfur isotope of sulfate in oil source rock series of strata and compare, isotope distributes immediate stratum, is oil source zone.
According to method of the present invention, preferably, the volume ratio of ethanol described in step one, methylene chloride or ethylene dichloride and crude oil is 1-20:1.
According to method of the present invention, preferably, the temperature of reaction of alkylated reaction described in step one is 0-80 DEG C, and the reaction time is 12-48h.
According to method of the present invention, preferably, described alkylating reagent comprises the combination of one or more in silver nitrate, silver tetrafluoroborate, iodomethane and bromoethane;
More preferably described alkylating reagent is 5-50:1 with the ratio of the molar weight of total sulfur in crude oil; More preferably 5-30:1.
According to method of the present invention, preferably, the alkane solvent of the C5-C7 described in step 2 comprises n-pentane, normal hexane or normal heptane; Be more preferably normal hexane;
More preferably the alkane solvent of described C5-C7 and the volume ratio of crude oil are 20-500:1.
According to method of the present invention, preferably, described in step 3, the temperature of reaction of dealkylation is 0-80 DEG C for the first time, and the reaction time is 12-48h.
According to method of the present invention, preferably, the de-alkyl reagent of first described in step 3 comprises pyridine, DMAP or 7-azaindole;
More preferably the described first de-alkyl reagent is 5-20:1 with the ratio of the molar weight of total sulfur in crude oil.
According to method of the present invention, preferably, the volume ratio of methylene chloride described in step 3, methenyl choloride or acetonitrile and crude oil is 1-20:1.
According to method of the present invention, preferably, the alkane solvent of the C5-C7 described in step 4 comprises n-pentane, normal hexane or normal heptane; Be more preferably normal hexane;
More preferably the alkane solvent of described C5-C7 and the volume ratio of crude oil are 10-50:1; More preferably 20-40:1; In the most preferred embodiment of the present invention, the alkane solvent of described C5-C7 and the volume ratio of crude oil are 30:1.
According to method of the present invention, preferably, the temperature of reaction of the dealkylation of second time described in step 5 is 60-120 DEG C, and the reaction time is 12-48h;
More preferably described temperature of reaction is 80-100 DEG C.
According to method of the present invention, preferably, the de-alkyl reagent of second described in step 5 comprises pyridine, DMAP or 7-azaindole;
More preferably the described second de-alkyl reagent is 5-20:1 with the ratio of the molar weight of total sulfur in crude oil.
According to method of the present invention, preferably, the alkane solvent of C5-C7 described in step 6 comprises n-pentane, normal hexane or normal heptane; Be more preferably normal hexane;
More preferably the alkane solvent of described C5-C7 and the volume ratio of crude oil are 10-50:1; More preferably 20-40:1; In the most preferred embodiment of the present invention, the alkane solvent of described C5-C7 and the volume ratio of crude oil are 30:1.
According to method of the present invention, in thiophene compound described in step 7 and sulfide compound, the mensuration of free sulfur isotope distribution adopts gas chromatography icp ms to carry out, adopt gas chromatography icp ms to measure free sulfur isotope in thiophene compound and sulfide compound and be distributed as the technological means of this area routine, those skilled in the art can need to select suitable operation to measure according to site work.
According to method of the present invention, in the series of strata of oil source rock described in step 8, the mensuration of the sulfur isotope distribution of sulfate can be carried out according to following concrete steps: the sulphur in sulfate sample in corresponding oil source rock series of strata is converted into SO
2, the model adopting German FinniganMAT company to produce is that the isotope mass spectrometer of DeltaS is to SO
2carry out mass spectrophotometry, obtain the sulfur isotope distribution of sulfate in oil source rock series of strata.
According to method of the present invention, preferably, described crude oil comprises white oil or heavy crude.
According to method of the present invention, preferably, the total sulfur content of described crude oil is 0.1wt%-5.0wt%.
The method of the separation Sulfur Compounds from Crude Oils (thiophene compound, sulfide compound) related in the method for the sulfur isotope determination oil sources utilized in crude oil monomer sulfocompound provided by the present invention can realize being separated completely of sulfocompound and hydro carbons and other heteroatomic compounds.
The method of the sulfur isotope determination oil sources utilized in crude oil monomer sulfocompound provided by the present invention can Accurate Determining crude oil monomer sulfocompound 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.
The method of the sulfur isotope determination oil sources utilized in crude oil monomer sulfocompound provided by the invention adopts the free sulfur compound methylated with in the separation method Selective Separation crude oil of demethylation, thus realize the free sulfur isotope assay of crude oil sulfocompound, for OIL SOURCE CORRELATION provides new method, solve the problem of complex area OIL SOURCE CORRELATION difficulty.
Embodiment
Clearly understanding to have technical characteristic of the present invention, object and beneficial effect thereof, existing following detailed description being carried out to technical scheme of the present invention, but can not be understood as to of the present invention can the concrete restriction of practical range.
Embodiment 1
Present embodiments provide a kind of method of the sulfur isotope determination oil sources utilized in crude oil monomer sulfocompound, wherein, the concrete steps of the method are as follows:
Step one: be that the crude oil of 2.06wt% (is derived from Tarim Basin ZS1C well by 500 milligrams of total sulfur contents, 20 DEG C of lower densities are 0.791 grams per milliliter) and 5 milliliters of methylene chloride join in the eggplant type bottle of 25 milliliters, add 0.45 gram of silver tetrafluoroborate subsequently, after adding 0.45 milliliter of iodomethane with syringe under vigorous stirring, under lucifuge and room temperature condition, stirring reaction is after 12 hours, repeats above-mentioned steps once.After reaction terminates, cross the silver iodide precipitation filtering and generate in reactant liquor, the methylene chloride in filtrate is removed by rotary distillation instrument;
Step 2: add 20 ml n-hexanes in residue grease, be cooled to 0 DEG C after concuss, have Precipitation, supernatant inclines to rear, obtains sediment fraction;
Step 3: gained precipitation is dissolved in 5 milliliters of acetonitriles, adds 400 milligrams of 7-azaindoles, carries out first time dealkylation in 24 hours, obtain solution A in stirred at ambient temperature;
Step 4: add 10 ml n-hexane extractions and separatory in solution A, after repeating 2 these steps, the n-hexane extract obtained is merged.The n-hexane extract dilute hydrochloric acid solution washing also separatory of 10 milliliters 2 moles often liter, gets organic phase and is concentrated into 5 milliliters, be called the thiophene compound be separated from crude oil; Solution B is stand-by;
Step 5: add 400 milligrams of DMAPs in remaining acetonitrile solution (solution B), gained solution carries out second time dealkylation under counterflow condition, reacts and is cooled to room temperature after 12 hours, obtain solution C;
Step 6: the diluted hydrochloric acid aqueous solution and the 10 ml n-hexanes concussion also separatory that add 10 milliliters 2 moles often liter in solution C, gets organic phase and is concentrated into 5 milliliters, be called the sulfide compound be separated from crude oil;
Step 7: carry out the analysis of gas chromatography icp ms respectively to the thiophene compound in the ZS1C well crude oil of Tarim Basin and sulfide compound, analyzes after terminating and records that free sulfur is isotopic is distributed as 35 ‰-45 ‰;
Step 8: the sulphur in Tarim Basin Cambrian system sulfate sample and Ordovician, tarim Basin sulfate sample is converted into SO
2, the model then adopting German FinniganMAT company to produce is that the isotope mass spectrometer of DeltaS is respectively to the SO obtained
2carry out mass spectrophotometry, the sulfur isotope obtaining Tarim Basin Cambrian system sulfate is distributed as 32-45 ‰, and the sulfur isotope of Ordovician system sulfate is distributed as 21-25 ‰;
Step 9: the free sulfur isotope obtained in step 7 distribution is distributed with the sulfur isotope of Tarim Basin Cambrian source rock sulfate respectively and compares, visible, the free sulfur isotope distribution obtained in step 7 distributes more close, so Tarim Basin ZS1C well crude oil comes from Cambrian system with the sulfur isotope of Tarim Basin Cambrian system sulfate.
Embodiment 2
Present embodiments provide a kind of method of the sulfur isotope determination oil sources utilized in crude oil monomer sulfocompound, wherein, the concrete steps of the method are as follows:
Step one: the crude oil being 4.86wt% by 200 milligrams of total sulfur contents (is derived from Shengli Oil Field Luojia area, 20 DEG C of lower densities are 0.981 grams per milliliter) and 2 milliliters of methylene chloride join in the eggplant type bottle of 10 milliliters, add 0.43 gram of silver tetrafluoroborate subsequently, after adding 0.43 milliliter of iodomethane with syringe under vigorous stirring, under lucifuge and room temperature condition, stirring reaction is after 12 hours, repeats above-mentioned steps once.After reaction terminates, cross the silver iodide precipitation filtering and generate in reactant liquor, the methylene chloride in filtrate is removed by rotary distillation instrument;
Step 2: add 8 milliliters of normal heptanes in residue grease, be cooled to 0 DEG C after concuss, have Precipitation, supernatant inclines to rear, obtains sediment fraction;
Step 3: gained precipitation is dissolved in 2 milliliters of acetonitriles, adds 370 milligrams of 7-azaindoles, carries out first time dealkylation in 24 hours, obtain solution A in stirred at ambient temperature;
Step 4: add 4 ml n-hexane extractions and separatory in solution A, after repeating 2 these steps, the n-hexane extract obtained is merged.The n-hexane extract dilute hydrochloric acid solution washing also separatory of 10 milliliters 2 moles often liter, gets organic phase and is concentrated into 2 milliliters, be called the thiophene compound be separated from crude oil; Solution B is stand-by;
Step 5: add 370 milligrams of DMAPs in remaining acetonitrile solution (solution B), gained solution carries out second time dealkylation under counterflow condition, reacts and is cooled to room temperature after 12 hours, obtain solution C;
Step 6: the diluted hydrochloric acid aqueous solution and the 10 ml n-hexanes concussion also separatory that add 10 milliliters 2 moles often liter in solution C, gets organic phase and is concentrated into 2 milliliters, be called the sulfide compound be separated from crude oil;
Step 7: carry out the analysis of gas chromatography icp ms respectively to the thiophene compound in the crude oil of Shengli Oil Field Luojia area and sulfide compound, analyzes after terminating and records that free sulfur is isotopic is distributed as 26-28 ‰;
Step 8: the sulphur in the sulfate sample in the hydrocarbon source rock on SHAHEJIE FORMATION s_4 formation stratum is converted into SO
2, the model then adopting German FinniganMAT company to produce is that the isotope mass spectrometer of DeltaS is respectively to the SO obtained
2carry out mass spectrophotometry, the sulfur isotope obtaining the sulfate in the hydrocarbon source rock on SHAHEJIE FORMATION s_4 formation stratum is distributed as 28-34 ‰;
Step 9: the free sulfur isotope obtained in step 7 distribution is distributed with the sulfur isotope of the sulfate in the hydrocarbon source rock on SHAHEJIE FORMATION s_4 formation stratum and compares, visible, the free sulfur isotope distribution obtained in step 7 distributes comparatively close, so Shengli Oil Field Luojia area crude oil comes from the hydrocarbon source rock of SHAHEJIE FORMATION s_4 formation with the sulfur isotope of the sulfate in the hydrocarbon source rock on SHAHEJIE FORMATION s_4 formation stratum.
Claims (10)
1. utilize a method for the sulfur isotope determination oil sources in crude oil monomer sulfocompound, wherein, the method comprises the following steps:
Step one: be dissolved in by crude oil in ethanol, methylene chloride or ethylene dichloride, then adds alkylating reagent and carries out alkylated reaction, after reaction terminates, after filtration, obtains filtrate, and ethanol, methylene chloride or ethylene dichloride in removing filtrate, obtain grease;
The volume ratio of preferred described ethanol, methylene chloride or ethylene dichloride and crude oil is 1-20:1;
Step 2: described grease is mixed with the alkane solvent of C5-C7, then the precipitation obtained is separated;
Step 3: precipitation step 2 obtained is dissolved in methylene chloride, methenyl choloride or acetonitrile, then adds the first de-alkyl reagent and carries out first time dealkylation, obtain solution A;
The volume ratio of preferred described methylene chloride, methenyl choloride or acetonitrile and crude oil is 1-20:1;
Step 4: use the alkane solvent of C5-C7 to extract described solution A, obtain the thiophene compound in crude oil and solution B;
Step 5: add the second de-alkyl reagent and carry out second time dealkylation in solution B, obtain solution C;
Step 6: use the alkane solvent of C5-C7 to extract described solution C, obtain the sulfide compound in crude oil; The alkane solvent of preferred described C5-C7 comprises n-pentane, normal hexane or normal heptane;
More preferably the alkane solvent of described C5-C7 and the volume ratio of crude oil are 10-50:1; More preferably 20-40:1;
Step 7: measure free sulfur isotope distribution in described thiophene compound and sulfide compound;
Step 8: the sulfur isotope distribution measuring sulfate in oil source rock series of strata;
Step 9: the distribution of described free sulfur isotope distributed with the sulfur isotope of sulfate in oil source rock series of strata and compare, isotope distributes immediate stratum, is oil source zone.
2. method according to claim 1, wherein, the temperature of reaction of alkylated reaction described in step one is 0-80 DEG C, and the reaction time is 12-48h.
3. method according to claim 1, wherein, alkylating reagent described in step one comprises the combination of one or more in silver nitrate, silver tetrafluoroborate, iodomethane and bromoethane;
Preferred described alkylating reagent is 5-50:1 with the ratio of the molar weight of total sulfur in crude oil; Be more preferably 5-30:1.
4. method according to claim 1, wherein, the alkane solvent of the C5-C7 described in step 2 comprises n-pentane, normal hexane or normal heptane;
The alkane solvent of preferred described C5-C7 and the volume ratio of crude oil are 20-500:1.
5. method according to claim 1, wherein, described in step 3, the temperature of reaction of dealkylation is 0-80 DEG C for the first time, and the reaction time is 12-48h.
6. method according to claim 1, wherein, the de-alkyl reagent of first described in step 3 comprises pyridine, DMAP or 7-azaindole;
Preferably the described first de-alkyl reagent is 5-20:1 with the ratio of the molar weight of total sulfur in crude oil.
7. method according to claim 1, wherein, the alkane solvent of the C5-C7 described in step 4 comprises n-pentane, normal hexane or normal heptane;
The alkane solvent of preferred described C5-C7 and the volume ratio of crude oil are 10-50:1; Be more preferably 20-40:1; More preferably 30:1.
8. method according to claim 1, wherein, the temperature of reaction of the dealkylation of second time described in step 5 is 60-120 DEG C, and the reaction time is 12-48h;
Preferred described temperature of reaction is 80-100 DEG C.
9. method according to claim 1, wherein, the de-alkyl reagent of second described in step 5 comprises pyridine, DMAP or 7-azaindole;
Preferably the described second de-alkyl reagent is 5-20:1 with the ratio of the molar weight of total sulfur in crude oil.
10. the method according to any one of claim 1-9, wherein, described crude oil comprises white oil or heavy crude;
The total sulfur content of preferred described crude oil is 0.1wt%-5.0wt%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107702953A (en) * | 2016-08-09 | 2018-02-16 | 中国石油化工股份有限公司 | Separation of Rhenium and/or the method for osmium element from crude oil |
| CN110320340A (en) * | 2018-03-29 | 2019-10-11 | 中国石油化工股份有限公司 | The method that evaporite rock and the comparison of petroleum sulfur isotope judge the petroleum hydrocarbon source rock epoch |
| CN111423900A (en) * | 2020-04-07 | 2020-07-17 | 中国石油大学(北京) | Method for derivatization and separation of sulfur-containing compound alkyl in petroleum component |
| 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 |
| WO2023124748A1 (en) * | 2021-12-31 | 2023-07-06 | 中国石油天然气股份有限公司 | Method for determining crude oil source based on thioethyl noradamantane |
-
2015
- 2015-12-01 CN CN201510861006.2A patent/CN105510561B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| MENG WANG 等: "Approach for Selective Separation of Thiophenic and Sulfidic SulfurCompounds from Petroleum by Methylation/Demethylation", 《ANALYTICAL CHEMISTRY》 * |
| MENG WANG 等: "Separation and Characterization of Sulfur Compounds in Ultra-deep Formation Crude Oils from Tarim Basin", 《ENERGY & FUELS》 * |
| 卢鸿 等: "傅里叶变换离子回旋共振质谱对中国高硫原油的分子组成表征", 《中国科学：地球科学》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107702953A (en) * | 2016-08-09 | 2018-02-16 | 中国石油化工股份有限公司 | Separation of Rhenium and/or the method for osmium element from crude oil |
| CN110320340A (en) * | 2018-03-29 | 2019-10-11 | 中国石油化工股份有限公司 | The method that evaporite rock and the comparison of petroleum sulfur isotope judge the petroleum hydrocarbon source rock epoch |
| CN110320340B (en) * | 2018-03-29 | 2021-11-09 | 中国石油化工股份有限公司 | Method for judging petroleum hydrocarbon source rock age by comparing evaporite and petroleum sulfur isotope |
| CN111423900A (en) * | 2020-04-07 | 2020-07-17 | 中国石油大学(北京) | Method for derivatization and separation of sulfur-containing compound alkyl in petroleum component |
| CN111423900B (en) * | 2020-04-07 | 2021-03-30 | 中国石油大学(北京) | Method for derivatization and separation of sulfur-containing compound alkyl in petroleum component |
| 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 |
| WO2023124748A1 (en) * | 2021-12-31 | 2023-07-06 | 中国石油天然气股份有限公司 | Method for determining crude oil source based on thioethyl noradamantane |
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