CN113090255B - Method for extracting natural gas hydrate associated authigenic carbonate rock lattice sulfate - Google Patents
Method for extracting natural gas hydrate associated authigenic carbonate rock lattice sulfate Download PDFInfo
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- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 title claims abstract description 96
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 78
- 239000011435 rock Substances 0.000 title claims abstract description 75
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 85
- 239000003957 anion exchange resin Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 15
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- 239000002734 clay mineral Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 238000009616 inductively coupled plasma Methods 0.000 claims description 8
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- 238000012805 post-processing Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 28
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 13
- 239000011707 mineral Substances 0.000 abstract description 13
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- 239000011148 porous material Substances 0.000 abstract description 5
- 230000033558 biomineral tissue development Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 113
- 239000000523 sample Substances 0.000 description 80
- 235000011167 hydrochloric acid Nutrition 0.000 description 38
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 239000002245 particle Substances 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- 239000002689 soil Substances 0.000 description 8
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- 238000005406 washing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910001748 carbonate mineral Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910015853 MSO4 Inorganic materials 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000010419 fine particle Substances 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- -1 natural gas hydrates Chemical class 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- 241000534000 Berula erecta Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B49/00—Testing the nature of borehole walls; Formation testing; Methods or apparatus for obtaining samples of soil or well fluids, specially adapted to earth drilling or wells
- E21B49/001—Testing the nature of borehole walls; Formation testing; Methods or apparatus for obtaining samples of soil or well fluids, specially adapted to earth drilling or wells specially adapted for underwater installations
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
-
- 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
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Plasma & Fusion (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention provides a method for extracting natural gas hydrate associated authigenic carbonate rock lattice sulfate. The extraction method can extract the authigenic carbonate rock lattice sulfate in the authigenic carbonate rock sample accompanied by the natural gas hydrate, is simple to operate and high in extraction precision, and can be widely applied to various technical fields needing to extract the authigenic carbonate rock lattice sulfate from the natural gas hydrate authigenic carbonate rock sample. The sulfur isotope in the authigenic carbonate rock lattice sulfate extracted by the invention can be used for indicating the sulfur isotope of seawater sulfate in the hydrate formation period or the sulfur isotope of pore water in the mineralization period, so that the formation periods of different authigenic carbonate rock minerals can be divided, and the mineralization period of the natural gas hydrate can be judged.
Description
Technical Field
The invention relates to the field of oil and gas geochemistry, in particular to a method for extracting natural gas hydrate associated authigenic carbonate rock lattice sulfate.
Background
Natural gas hydrate is an ice-like non-stoichiometric clathrate crystal compound generated by hydrocarbon gas and/or small molecule gas and water molecules under low temperature and high pressure conditions, and is considered as an alternative energy source in the 21 st century.
According to two runs of hydrate pilot mining experience which has been successfully completed in China, the natural carbonate minerals associated with the natural gas hydrate can be formed in a natural gas hydrate reservoir layer due to the increase of the flux of hydrocarbon mining fluids such as methane and the like in the natural gas hydrate mining process, and the natural carbonate minerals and hydrate ore bodies are formed almost at the same time. During the formation of these Authigenic carbonate minerals associated with natural gas hydrates, very little sulfate present in seawater or sediment pore water replaces carbonate and enters the carbonate lattice, forming Authigenic carbonate lattice sulfate (ACAS). As the ACAS is associated with the hydrate and is formed almost simultaneously, the sulfur isotope of the ACAS can be used for indicating seawater sulfate or the sulfur isotope of pore water when the hydrate is formed into the ore, so that different authigenic carbonate rock minerals can be divided into formation stages according to the difference of the sulfur isotopes, and the formation stage of the natural gas hydrate can be further judged. The research on the ACAS can play an important role in future natural gas hydrate large-scale exploration.
Different from the traditional carbonate rock reservoir, the natural gas hydrate ore body in south China sea is generally distributed on the seabed by about 200 meters, the reservoir is not consolidated into rock, but has a certain compaction effect, the mechanical property is between that of seabed loose sediment and sedimentary rock, the minerals in the reservoir mostly exist in a particle form, and a large amount of calcium biogenetic fossil and clay minerals are contained. The lattice sulfate in the calcareous biogenetic fossil represents the sulfate signal of seawater in the ontogeny period of organisms, but not the sulfate signal of ACAS, and the clay mineral has strong adsorbability and small particle size and can adsorb and wrap the authigenic carbonate rock mineral. These factors can severely interfere with the extraction accuracy of ACAS. In addition, the ACAS content in the natural gas hydrate reservoir is extremely low (ppm level), so that the precision requirement on the extraction method and the experimental process is extremely high, and no method capable of extracting the natural gas hydrate associated ACAS exists at present.
Disclosure of Invention
The invention provides an extraction method of natural gas hydrate associated authigenic carbonate rock lattice sulfate, which can extract ACAS in a natural gas hydrate associated authigenic carbonate rock sample, wherein the extracted sulfur isotope of the ACAS can be used for indicating the sulfur isotope of seawater sulfate or the sulfur isotope of pore water in the hydrate formation period, and further can divide the formation period of authigenic carbonate rock minerals according to different sulfur isotope characteristics, thereby providing strong evidence for judging the formation period of the natural gas hydrate.
The embodiment of the invention provides a method for extracting natural gas hydrate associated authigenic carbonate rock lattice sulfate, which comprises the following steps:
1) adding a first super-grade pure hydrochloric acid solution into a natural gas hydrate associated authigenic carbonate rock sample to obtain a first solution;
2) injecting the first solution into a chromatographic column filled with Cl-type anion exchange resin for resin adsorption treatment to obtain a second solution;
3) and evaporating the second solution to dryness to obtain the natural gas hydrate associated authigenic carbonate crystal lattice sulfate.
The extraction method as described above, wherein the first guaranteed reagent hydrochloric acid solution has an equivalent concentration of 0.5N.
The extraction method as described above, wherein the mass-to-volume ratio of the natural gas hydrate associated authigenic carbonate rock sample to the first guaranteed hydrochloric acid solution is (1-10 mg): (0.5-5 mL).
The extraction method as described above, wherein step 2) is preceded by post-treating the first solution;
the post-processing comprises: drying the first solution and then adding a second superior pure hydrochloric acid solution;
the volume percentage of the second super-pure hydrochloric acid solution is 0.5-1%, and the volume of the second super-pure hydrochloric acid solution is 0.3-0.5 mL.
The extraction method as described above, wherein the eluent for the resin adsorption treatment is a nitric acid solution.
The extraction method as described above, wherein the equivalent concentration of the nitric acid solution is 0.5N.
The extraction method as described above, wherein the Cl-type anion exchange resin is AG 1-X8-Cl-type anion exchange resin.
The extraction method as described above, wherein the natural gas hydrate associated authigenic carbonate rock sample is obtained by removing calcareous biogenetic stones and clay minerals in the natural gas hydrate reservoir sample.
The extraction method as described above, wherein step 3) is followed by dissolving the natural gas hydrate associated with authigenic carbonate rock lattice sulfate in deionized water having a resistivity of 18.2M Ω to obtain a third solution, and testing the molar concentration of sulfate ions in the third solution using an ion chromatograph;
and determining the mass percentage of the natural gas hydrate associated authigenic carbonate rock lattice sulfate in the natural gas hydrate associated authigenic carbonate rock sample according to the molar concentration of the sulfate ions.
The extraction method as described above, wherein step 3) is followed by testing the sulfur isotope composition in the third solution using an inductively coupled plasma mass spectrometer.
The implementation of the invention has at least the following advantages:
1. the extraction method of the natural gas hydrate associated ACAS can extract trace ACAS in authigenic carbonate rock minerals symbiotic with natural gas hydrate deposits, and is simple to operate and high in extraction precision;
2. the natural gas hydrate associated ACAS extracted by the invention can be used for indicating the sulfur isotope of seawater sulfate or the sulfur isotope of pore water in the hydrate formation period, and further can divide the formation periods of different authigenic carbonate rock minerals so as to judge the mineralization period of the natural gas hydrate;
3. the extraction method of the natural gas hydrate associated ACAS has simple operation, does not need large equipment and instrument assistance, has low execution cost, can be widely applied to various technical fields needing to extract the ACAS from the natural gas hydrate associated authigenic carbonate rock mineral, and has wide application prospect in future natural gas hydrate large-scale exploration.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for extracting natural gas hydrate associated authigenic carbonate rock lattice sulfate, which comprises the following steps:
1) adding a first super-grade pure hydrochloric acid solution into a natural gas hydrate associated authigenic carbonate rock sample to obtain a first solution;
2) injecting the first solution into a chromatographic column filled with Cl-type anion exchange resin for resin adsorption treatment to obtain a second solution;
3) and evaporating the second solution to dryness to obtain the natural gas hydrate associated with the authigenic carbonate crystal lattice sulfate (ACAS).
The natural gas hydrate associated monocarbonate sample in step 1) is typically from a natural gas hydrate reservoir. The superior pure hydrochloric acid solution is a hydrochloric acid solution with a common purity specification in the field, the superior pure hydrochloric acid solution can be used for improving the accuracy of the extraction process, and in a specific embodiment, the first superior pure hydrochloric acid can be produced by Emontol corporation of America
Ultra-high purity hydrochloric acid. Unless otherwise specified, all hydrochloric acids used in the present invention are those produced by Ementuou corporation
Ultra-high purity hydrochloric acid.
The Cl-type anion exchange resin in step 2) is a basic anion exchange resin, and when the aqueous solution passes through a chromatographic column containing the basic anion exchange resin, anions in the aqueous solution are adsorbed by the basic anion exchange resin. The Cl-type anion exchange resin selected by the invention can better adsorb sulfate ions in the aqueous solution.
In addition, since commercial ion exchange resins often contain small amounts of oligomers, unreacted monomers, and inorganic impurities such as iron, lead, and copper, when the solution to be treated comes into contact with the ion exchange resin, the substances are transferred into the solution, which affects the treatment effect of the ion exchange resin. Therefore, the ion exchange resin needs to be pretreated before the column is filled with the ion exchange resin. The pretreatment steps of the invention comprise: firstly, using nitric acid solution to perform infiltration treatment on Cl-type anion exchange resin for 2-5 times, and then using hydrochloric acid solution to perform infiltration treatment on the Cl-type anion exchange resin for 2-5 times.
Firstly, adding a first super-pure hydrochloric acid solution with a purity specification of super-pure into a natural gas hydrate associated authigenic carbonate rock sample, and dissolving the natural gas hydrate associated authigenic carbonate rock sample by using the first super-pure hydrochloric acid solution to obtain a first solution; then, injecting the first solution into a chromatographic column filled with Cl-type anion exchange resin, wherein sulfate ions in the first solution are adsorbed by the Cl-type anion exchange resin, and eluting the Cl-type anion exchange resin adsorbed with the sulfate ions to obtain an eluent containing the sulfate ions, wherein the eluent is a second solution; the second solution containing sulfate ions is evaporated to dryness to obtain the ACAS required by the present invention.
The step 3) may further include dissolving the obtained ACAS using ultrapure water for subsequent testing.
The extraction method can extract the ACAS in the natural gas hydrate associated authigenic carbonate rock sample, has the advantages of simplicity, high extraction precision which can reach ppb level, and can be widely applied to various technical fields needing to extract the ACAS from the natural gas hydrate associated authigenic carbonate rock sample.
In some embodiments of the invention, the first guaranteed hydrochloric acid solution has an equivalent concentration of 0.5N.
Normality refers to the number of gram equivalents of solute contained in one liter of solution, and one equivalent means the loss of one electron. The method comprises the following steps: the equivalent concentration of the hydrochloric acid solution is the molar concentration of the hydrochloric acid solution, and the equivalent concentration of the sulfuric acid solution is twice of the molar concentration of the sulfuric acid solution.
According to the invention, the equivalent concentration of the first super-pure hydrochloric acid solution is selected to be 0.5N, so that the natural gas hydrate associated with the authigenic carbonate rock sample can be fully dissolved, the extraction of ACAS is facilitated, the first super-pure hydrochloric acid solution is not wasted, and the extraction cost is saved.
In some embodiments of the present invention, the mass-to-volume ratio of the natural gas hydrate associated authigenic carbonate rock to the first guaranteed hydrochloric acid solution is (1-10 mg): (0.5-5 mL).
When the mass-to-volume ratio is too large, the first super-grade pure hydrochloric acid solution cannot fully dissolve the natural gas hydrate associated authigenic carbonate rock sample, so that ACAS in the natural gas hydrate associated authigenic carbonate rock sample is accurately quantified; when the mass-to-volume ratio is too small, the first high-grade pure hydrochloric acid solution is wasted, and the extraction cost is increased. The mass-volume ratio of the invention is (1-10 mg): (0.5-5mL), not only can make first superior pure hydrochloric acid solution fully dissolve natural gas hydrate associated with the authigenic carbonate rock sample, but also can not waste first superior pure hydrochloric acid solution.
In some embodiments of the present invention, step 2) is preceded by post-treating the first solution;
the post-treatment comprises the following steps: drying the first solution and then adding a second superior pure hydrochloric acid solution;
wherein, the volume percentage of the second superior pure hydrochloric acid solution is 0.5-1%, and the volume of the second superior pure hydrochloric acid solution is 0.3-0.5 mL.
The volume percentage of the second super-grade pure hydrochloric acid refers to the volume percentage of the second super-grade pure hydrochloric acid and deionized water. Since the natural gas hydrate associated with the authigenic carbonate rock sample has a low mass of about 10mg, the present invention performs the above-mentioned post-treatment on the first solution in order to avoid mass loss of the natural gas hydrate associated with the authigenic carbonate rock sample during the dissolution process.
In some embodiments of the present invention, in order to better elute sulfate ions adsorbed on the Cl type anion exchange resin, the eluent for the above resin adsorption treatment is a nitric acid solution; the equivalent concentration of the nitric acid solution was 0.5N.
In some embodiments of the invention, the Cl-type anion exchange resin is AG 1-X8-Cl-type anion exchange resin for more complete adsorption of sulfate ions in the first solution. Further, the mesh number of the Cl-type anion exchange resin is 50-100 meshes.
In some embodiments of the invention, the natural gas hydrate associated authigenic carbonate rock sample is obtained by removing calcareous biogenetic stones and clay minerals from a natural gas hydrate reservoir sample.
The calcareous biogenetic fossil refers to fossil formed by skeletons or biological remains containing calcium carbonate, such as poriferous insects, radial insects, ultramicro calcareous fossil, spicule spongiosa, fish teeth, fish bones and the like, and because natural gas hydrate associated with authigenic carbonate rock minerals, a large amount of calcareous biogenetic clay and minerals with strong adsorbability and small particle size are contained in a natural gas hydrate reservoir, lattice sulfate in the calcareous biogenetic fossil represents sulfate signals of seawater in the individual development period of organisms and can influence sulfate signals of ACAS, and the encapsulation of authigenic carbonate rock minerals by the clay minerals can also seriously interfere the extraction of ACAS. Therefore, the natural gas hydrate associated authigenic carbonate rock sample is obtained by removing the calcareous biogenetic fossil and the clay mineral in the natural gas hydrate reservoir sample, and the extraction precision of the ACAS can be improved.
Specifically, the calcareous biogenetic stones and clay minerals in the gas hydrate reservoir sample can be removed by a method comprising the following steps: step a, placing a natural gas hydrate reservoir sample in pure water, wherein the mass volume ratio of the natural gas hydrate reservoir sample to the pure water is 1g-10 g: soaking for 5-10 minutes in 50-500 mL until the natural gas hydrate reservoir sample is in a loose state, pouring the natural gas hydrate reservoir sample into a first geotechnical sieve, washing the natural gas hydrate reservoir sample in the first geotechnical sieve with deionized water until water flowing out of the first geotechnical sieve is clear, collecting the sample passing through the first geotechnical sieve by using a beaker, standing the beaker until an upper-layer aqueous solution is clear, absorbing a supernatant, and retaining a solid-phase substance (the rest sample 1);
b, pouring the residual sample 1 into a second soil sieve, wherein the aperture of the second soil sieve is smaller than that of the first soil sieve, washing the residual sample 1 in the second soil sieve with deionized water, pressing the residual sample 1 in the second soil sieve to enable fine particles to smoothly pass through the second soil sieve, washing with the deionized water until water flowing out of the second soil sieve is clear, and collecting a sample which does not pass through the second soil sieve by using a beaker to obtain a residual sample 2;
c, according to a separation and purification method of clay minerals in the national standard GB/T12763.8-2007 for marine geological geophysical survey, removing clay mineral particles with the particle size of less than 2 mu m in the residual sample 2 according to the Stokes sedimentation law, and drying to obtain a residual sample 3;
d, uniformly paving the residual sample 3 on a glass slide in batches, and selecting authigenic carbonate rock mineral particles by using a dissecting needle under a binocular stereoscopic microscope to obtain a residual sample 4, wherein the residual sample 4 is the natural gas hydrate associated authigenic carbonate rock sample.
In some embodiments of the invention, step 1) is preceded by: removing soluble non-natural gas hydrate associated ACAS in the natural gas hydrate associated authigenic carbonate rock sample.
The method removes the soluble non-ACAS in the natural gas hydrate associated with the authigenic carbonate rock sample before the step 1), and can prevent sulfate ions in the non-ACAS from entering the first solution in the treatment process of the step 1) and interfering the sulfur signal in the finally obtained ACAS.
Specifically, a sodium chloride solution with the mass percentage of 10% is used for soaking the residual sample 4, ultrasonic cleaning is carried out for 2-4 hours, a microcentrifuge is used for centrifugation, the rotating speed of the microcentrifuge is 1500-; and (3) washing the rest sample by using deionized water, centrifuging, repeating for multiple times, extracting supernatant by using a liquid transfer gun, and dripping a barium chloride solution into the supernatant, wherein no precipitate exists in the supernatant, so that the non-ACAS is completely removed.
The sodium chloride solution is used for removing non-ACAS, the sodium chloride solution can adsorb non-ACAS sulfate ions in the natural gas hydrate associated with the authigenic carbonate rock sample solution to achieve the aim of removing the non-ACAS, and the sodium chloride solution is low in cost, easy to obtain and suitable for wide application.
In some embodiments of the present invention, before the resin adsorption treatment with a nitric acid solution, the method further comprises: the column containing the first solution was pretreated with deionized water having a resistivity of 18.2M Ω.
Deionized water having a resistivity of 18.2M Ω, which is known to those skilled in the art, is ultrapure water, and the present invention pretreats the column containing the first solution using ultrapure water, which washes impurities in the column and improves the purity of the extracted ACAS.
In some embodiments of the invention, step 3) is followed by dissolving natural gas hydrate associated with authigenic carbonate rock lattice sulfate in deionized water having a resistivity of 18.2M Ω to obtain a third solution, and testing the third solution for molar concentration of sulfate ions using an ion chromatograph;
and determining the mass percentage of the lattice sulfate of the natural gas hydrate associated authigenic carbonate rock in the natural gas hydrate associated authigenic carbonate rock sample according to the molar concentration of the sulfate ions.
According to the invention, deionized water with the resistivity of 18.2 MOmega is used for dissolving the natural gas hydrate associated authigenic carbonate rock lattice sulfate, so that trace natural gas hydrate associated authigenic carbonate rock lattice sulfate can be prevented from being lost. The sulfate in the third solution may be considered as sulfate of ACAS. The molar concentration of sulfate ions in the third solution was measured using an ion chromatograph, and the measured molar concentration of sulfate ions can represent the molar concentration of sulfate ions in the ACAS. According to the molar concentration of sulfate radicals in the obtained ACAS, the mass percentage of the ACAS in a natural gas hydrate associated authigenic carbonate rock sample can be determined.
Specifically, a natural gas hydrate associated authigenic carbonate rock sample is placed in a microcentrifuge tube with the mass of a g, the mass of the microcentrifuge tube containing the natural gas hydrate associated authigenic carbonate rock sample is weighed and marked as b g, and a first high-grade pure hydrochloric acid solution is added into the microcentrifuge tube to obtain a first solution;
injecting the first solution into a chromatographic column filled with Cl-type anion exchange resin for resin adsorption treatment to obtain a second solution;
evaporating the second solution to dryness to obtain ACAS, and dissolving the obtained ACAS in V mL deionized water with the resistivity of 18.2 MOmega to obtain a third solution;
the molar concentration of sulfate, denoted C, was measured using a chromatographACASmol/L; for example, DIONEX ICS-5000 produced by American Sammer fly is used+And (2) carrying out sulfate radical molar concentration measurement by using a type ion chromatograph, wherein an AS-18 type chromatographic column is selected AS the chromatographic column, and an eluent is NaOH solution, then:
the mass M of the natural gas hydrate associated with the authigenic carbonate rock sample is (b-a) g;
the molar amount of ACAS in the third solution is n ═ CACAS×V×10-3)mol；
Mass M of ACAS in natural gas hydrate associated authigenic carbonate rock sampleACAS＝MSO4 2-×n＝96n＝(96×10-3×CACAS×V)g；
The ACAS content of the natural gas hydrate associated with the authigenic carbonate rock sample is (M)ACAS/M)×100％＝0.096×V×CACAS/(b-a)×100％。
In some embodiments of the invention, step 3) is followed by testing the composition of the sulfur isotope in the third solution using an inductively coupled plasma mass spectrometer.
Specifically, the third solution was pipetted into a beaker, and a sodium chloride solution and a nitric acid solution were added to the beaker to obtain a fourth solution. The fourth solution was transferred into a headspace bottle with a pipette and the sulfur isotope composition in the fourth solution was tested using an inductively coupled plasma mass spectrometer. The sulfur isotope composition in the fourth solution can be tested, for example, using a Neptune model multi-receiver inductively coupled plasma mass spectrometer manufactured by Sammerfei USA.
The inductively coupled plasma emission spectrometer is externally connected with an atomizer ARIDUS II sample injection system, the temperature of a spray chamber is set to be 105-.
Hereinafter, the extraction method of the present invention will be described in detail by way of specific examples.
Examples
The extraction method of the embodiment comprises the following steps:
1) obtaining a natural gas hydrate associated authigenic carbonate rock sample
Step a, placing 10g of a natural gas hydrate reservoir sample in 500mL of pure water for soaking for 10 minutes until the natural gas reservoir sample is in a loose state, then pouring the natural gas hydrate reservoir sample into a first geotechnical sieve with the aperture of 63 mu m, washing the natural gas hydrate reservoir sample in the first geotechnical sieve with deionized water until water flowing out of the first geotechnical sieve is clear, collecting the sample passing through the first geotechnical sieve by using a beaker, standing the beaker until an upper-layer aqueous solution is clear, sucking and removing a supernatant, and keeping a solid-phase substance (the rest sample 1);
b, pouring the residual sample 1 into a second geotechnical sieve with the aperture of 10 mu m, washing the residual sample 1 in the second geotechnical sieve with deionized water, pressing the residual sample 1 in the second geotechnical sieve by a latex glove on the right hand to enable fine particles to smoothly pass through the second geotechnical sieve, washing with the deionized water until water flowing out of the second geotechnical sieve is clear, and collecting a sample which does not pass through the geotechnical sieve by using a beaker to obtain a residual sample 2;
c, according to a separation and purification method of clay minerals in the national standard GB/T12763.8-2007 for marine geological geophysical survey, removing clay mineral particles with the particle size of less than 2 mu m in the residual sample 2 according to the Stokes sedimentation law, and drying to obtain a residual sample 3;
d, uniformly paving the residual sample 3 on a glass slide in batches, and selecting authigenic carbonate rock mineral particles by using a dissecting needle under a binocular stereoscopic microscope to obtain a residual sample 4, wherein the residual sample 4 is the natural gas hydrate associated authigenic carbonate rock sample.
2) Removal of soluble non-ACAS
Step a, immersing 10mg of the rest sample 4 into a microcentrifuge tube filled with 1mL of NaCl solution with the mass fraction of 10%, ultrasonically cleaning for 4 hours to remove soluble non-ACAS, placing the microcentrifuge tube into a microcentrifuge, setting the rotating speed of the microcentrifuge to be 2000 r/min, centrifuging, sucking supernatant liquid by using a 500 mu L liquid-transferring gun after centrifuging, and retaining the cleaned rest sample 4 (solid phase 1) in the microcentrifuge tube;
b, adding ultrapure water with the resistivity of 18.2 MOmega into a microcentrifuge tube to clean the solid phase 1, placing the microcentrifuge tube into a microcentrifuge, setting the rotating speed of the microcentrifuge to 2000 r/min, centrifuging, sucking supernatant by using a 500 mu L liquid transfer gun after centrifuging, retaining the cleaned solid phase 1 in the microcentrifuge tube, and repeating the step for 5 times;
step c, collecting supernatant liquor of the 5 th time by using a micro-centrifugal tube, and dripping 30% of BaCl into the supernatant liquor at room temperature2Centrifuging the solution and observing whether precipitates are generated or not, if no precipitates are generated, indicating that all soluble non-ACAS are completely removed, and if precipitates are generated, continuing the step b until the precipitates disappear;
and d, drying the micro centrifugal tube filled with the cleaned solid phase 1 in a laminar flow drying oven at room temperature to obtain a residual sample 5.
3) Extraction of ACAS
Step a, filling the residueSample 5 was added to a microcentrifuge tube with 0.5mL of 0.5N equivalent hydrochloric acid solution
Ultra-pure hydrochloric acid, hereinafter unless otherwise specified, is produced by Ementuou corporation
Ultra-high purity hydrochloric acid. Drying, adding 0.5mL of 0.5% high-grade pure hydrochloric acid solution in percentage by volume, and standing for 1 hour to obtain a first solution;
step b, measuring 8mL Berle Life medicine company
The produced 50-100 mesh AG1-X8-Cl type anion exchange resin is prepared by using 8mL of HNO with volume fraction of 10%3Soaking resin for 2 times by using the solution, then soaking the resin for 3 times by using 8mL of hydrochloric acid solution with the volume fraction of 30%, placing the soaked resin on a vibration experiment table for at least 2 hours each time, then drying the resin subjected to acid treatment on a laminar flow drying table, and filling the resin subjected to acid treatment into a chromatographic column, wherein an EXL-1115-0502 type pressure chromatographic column produced by Emameux corporation is selected;
step c, injecting the first solution into the chromatographic column, injecting 8mL of ultrapure water with the resistivity of 18.2M omega to rinse the chromatographic column, repeating the rinsing process for 3 times, and then injecting 1.5mL of HNO with the equivalent concentration of 0.5N3Eluting the chromatographic column by the solution, and collecting the solution passing through the chromatographic column by a micro beaker if the solution can not successfully pass through the chromatographic column and can be blown off by nitrogen gas, thereby obtaining a second solution;
and d, heating the beaker containing the second solution on a heating table, steaming the solution in the beaker to obtain the ACAS, and dropwise adding 3mL of ultrapure water with the resistivity of 18.2 MOmega into the beaker to obtain a third solution, wherein the sulfur of the sulfate ions in the third solution is the sulfate ions in the ACAS.
4) Obtaining the mass percentage content of the ACAS natural gas hydrate associated authigenic carbonate rock sample
0.5mL of the third solution was pipetted into a headspace bottle using a 1mL pipette using DIONEX ICS-5000 manufactured by Samier fly, USA+Measuring the concentration of sulfate radical by an ion chromatograph, wherein the AS-18 chromatographic column is selected AS the chromatographic column, the solution is eluted into NaOH solution with the concentration of 23.5mM, and the molar concentration of the obtained sulfate radical is recorded AS CACASmol/L, then:
the molar amount of ACAS in the third solution is n ═ CACAS×3×10-3)mol；
Mass M of ACAS in natural gas hydrate associated authigenic carbonate rock sampleACAS＝MSO4 2-×n＝96n＝(0.288×10-3×CACAS)g；
The ACAS content of the natural gas hydrate associated with the authigenic carbonate rock sample is (M)ACAS/M)×100％＝28.8×CACAS×100％。
5) Testing of sulphur isotope composition in ACAS
And (3) sucking the third solution into a micro beaker by using a 1mL pipette, and adding 0.1mL of a 10 mass percent sodium chloride solution and 0.1mL of a 5 mass percent nitric acid solution into the micro beaker to obtain a fourth solution. The fourth solution was transferred into a headspace bottle with a pipette and tested for sulfur isotope composition using a Neptune model multi-receiver inductively coupled plasma mass spectrometer manufactured by Sammerfei USA.
The inductively coupled plasma emission spectrometer is externally connected with an atomizer ARIDUS II sample injection system, the temperature of a spray chamber is set to be 110 ℃, the sample injection speed is set to be 60 mu L/min, the total sample injection amount is controlled to be 270 mu L, the desolventizing temperature is set to be 160 ℃, the gas inlet speed of purge gas Ar is controlled to be about 4L/min, the gas inlet speed of carrier gas nitrogen is controlled to be about 0.02L/min, an entrance slit is set to be 15 mu m, the absorption time is 60s, and integration is started from a curve of 4.194 s.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (1)
1. The method for extracting the natural gas hydrate associated authigenic carbonate rock lattice sulfate is characterized by comprising the following steps of:
1) adding a first super-grade pure hydrochloric acid solution into a natural gas hydrate associated authigenic carbonate rock sample to obtain a first solution;
2) injecting the first solution into a chromatographic column filled with Cl-type anion exchange resin for resin adsorption treatment to obtain a second solution containing sulfate ions;
3) evaporating the second solution to dryness to obtain natural gas hydrate associated authigenic carbonate rock lattice sulfate;
the equivalent concentration of the first superior pure hydrochloric acid solution is 0.5N;
the mass-volume ratio of the natural gas hydrate associated authigenic carbonate rock sample to the first superior pure hydrochloric acid solution is (1-10 mg): (0.5-5 mL);
before the step 2), post-treating the first solution;
the post-processing comprises: drying the first solution and then adding a second superior pure hydrochloric acid solution;
wherein, the volume percentage of the second superior pure hydrochloric acid solution is 0.5-1%, and the volume is 0.3-0.5 mL;
the eluent for the resin adsorption treatment is a nitric acid solution;
the equivalent concentration of the nitric acid solution is 0.5N;
the Cl-type anion exchange resin is AG 1-X8-Cl-type anion exchange resin;
the natural gas hydrate associated authigenic carbonate rock sample is obtained by removing calcareous biogenetic stones and clay minerals in a natural gas hydrate reservoir sample;
step 3) is followed by dissolving the natural gas hydrate associated authigenic carbonate rock lattice sulfate in deionized water having a resistivity of 18.2 Μ Ω to obtain a third solution, and testing the molar concentration of sulfate ions in the third solution using an ion chromatograph;
determining the mass percentage of the natural gas hydrate associated authigenic carbonate rock lattice sulfate in the natural gas hydrate associated authigenic carbonate rock sample according to the molar concentration of the sulfate ions;
step 3) is followed by testing the composition of the sulfur isotope in the third solution using an inductively coupled plasma mass spectrometer.
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