CN117074508A - In-situ characterization method for organic matter element distribution in coal-based stratum - Google Patents
In-situ characterization method for organic matter element distribution in coal-based stratum Download PDFInfo
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- 239000003245 coal Substances 0.000 title claims abstract description 47
- 238000012512 characterization method Methods 0.000 title claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 15
- 239000005416 organic matter Substances 0.000 title claims description 34
- 235000013619 trace mineral Nutrition 0.000 claims abstract description 72
- 239000011573 trace mineral Substances 0.000 claims abstract description 72
- 238000004458 analytical method Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000011435 rock Substances 0.000 claims abstract description 23
- 238000001514 detection method Methods 0.000 claims abstract description 7
- 238000005259 measurement Methods 0.000 claims abstract description 6
- 238000007781 pre-processing Methods 0.000 claims abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 44
- 235000010755 mineral Nutrition 0.000 claims description 44
- 239000011707 mineral Substances 0.000 claims description 42
- 239000000126 substance Substances 0.000 claims description 39
- 238000013507 mapping Methods 0.000 claims description 37
- 238000000095 laser ablation inductively coupled plasma mass spectrometry Methods 0.000 claims description 36
- 238000001819 mass spectrum Methods 0.000 claims description 34
- 150000002500 ions Chemical class 0.000 claims description 20
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 14
- 238000012937 correction Methods 0.000 claims description 12
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 claims description 9
- 238000002679 ablation Methods 0.000 claims description 8
- 229910052622 kaolinite Inorganic materials 0.000 claims description 8
- 239000002366 mineral element Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000010812 external standard method Methods 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 238000010813 internal standard method Methods 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 4
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 208000011117 substance-related disease Diseases 0.000 claims description 2
- 239000000523 sample Substances 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 9
- 238000011160 research Methods 0.000 description 4
- 238000007619 statistical method Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
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- 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
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- G01N27/626—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 using heat to ionise a gas
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- 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
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Abstract
The invention relates to the technical field of coal seam detection, in particular to a method for in-situ characterization of element distribution in organic matters in a coal-based stratum, which comprises the following steps: preparing a rock microscope observation sheet aiming at a coal-series stratum rock sample to be analyzed, and preprocessing the prepared rock microscope observation sheet to obtain a preprocessed observation sheet; determining an analysis area to which each analysis scanning device belongs according to a pre-processed observation sheet and the analysis scanning device and a selection area strategy of each analysis scanning device; measuring the respective analysis region by means of an analysis scanning device, obtaining a plurality of measurement signal values; and acquiring element distribution information in organic matters in the coal-based stratum for in-situ characterization according to the measured signal values and the predefined element distribution relation. The method can directly quantitatively characterize the trace elements in the organic matters in the coal sample and visually output the trace element distribution in different organic matters.
Description
Technical Field
The invention relates to the technical field of coal seam detection, in particular to an in-situ characterization method for organic matter element distribution in a coal measure stratum.
Background
The current determination of elements in coal includes two broad classes of methods: direct and indirect assays. The direct mineral element trace element characterization method such as spectrum analysis, energy spectrum analysis, raman analysis and the like can only measure the distribution of the main element, but cannot obtain the trace element distribution of the organic matters in the coal due to low concentration of the trace elements in the organic matters and various types of the organic matters, such as a mirror body, an idler body, a shell body and a lipoid body. At present, the research of obtaining the analysis of organic matter elements in the separated coal by an indirect method is more, and the research comprises statistical analysis, floating and sinking experiments and step-by-step chemical extraction. The statistical method is to carry out linear analysis on the trace element content in the simultaneous coal, including all the contents of minerals and organic matters and the contents of various organic matters counted under a microscope. The floating and sinking experiment is carried out by separating the density differences of various microscopic components, and further the trace elements in the coal are measured. The stepwise chemical extraction is based on stepwise corrosion and determination of different microcomponents by strong acids and strong bases. Although the three experiments are feasible in theory, the three experiments (1) cannot be directly captured or the result cannot be visually output; (2) All results have very large errors, and the statistical method has very strong artificial interference when measuring the content of microscopic components; the floating and sinking experiment can not strip different organic matter types with similar densities; the step-by-step extraction can not separate organic matters of similar chemical components one by one at the same time. Meanwhile, the sample preparation link of the experiment is very complex, and particularly, the step-by-step chemical extraction is limited in application range.
Disclosure of Invention
First, the technical problem to be solved
In view of the defects and shortcomings of the prior art, the invention provides an in-situ characterization method for organic matter element distribution in a coal-based stratum, which solves the technical problems that quantitative characterization cannot be performed on trace elements in organic matters in a coal sample and visual output cannot be performed on trace element distribution in different organic matters.
(II) technical scheme
In order to achieve the above purpose, the main technical scheme adopted by the invention comprises the following steps:
in a first aspect, an embodiment of the present invention provides a method for in-situ characterization of an element distribution in an organic matter in a coal measure formation, including:
s1, preparing a rock microscope observation sheet aiming at a coal series stratum rock sample to be analyzed, and preprocessing the prepared rock microscope observation sheet to obtain a preprocessed observation sheet;
s2, determining an analysis area to which each analysis scanning device belongs according to a pre-processed observation sheet and the analysis scanning device and a selection area strategy of each analysis scanning device;
the analysis scanning apparatus includes: LA-ICP-MS mapping laser ablation inductively coupled plasma mass spectrometry scanning apparatus for analyzing microscopic components having a particle size greater than 10 μm, toF-SIMS mapping time-of-flight secondary ion mass spectrometry scanning apparatus for analyzing microscopic components having a particle size less than or equal to 10 μm;
s3, measuring the respective analysis areas by means of an analysis scanning device to obtain a plurality of measurement signal values;
s4, acquiring element distribution information in organic matters in the coal-based stratum for in-situ characterization according to the measured signal values and the predefined element distribution relation.
Optionally, the S1 includes:
the thickness of the rock microscope observation sheet is larger than the maximum diameter of the ablation laser beam of the analysis scanning device;
or the thickness of the rock microscope observation sheet is 2-4 times of the maximum diameter of the ablation laser beam of the analysis scanning device;
pre-treating the finished rock microscope viewing sheet, comprising:
and polishing the upper surface and the lower surface of the rock microscope observation sheet respectively.
Optionally, the S2 includes:
LA-ICP-MS mapping determines a first analysis area based on a first selection policy,
ToF-SIMS mapping determines a second analysis region based on a second selective area strategy,
the first selection policy includes: the first analysis area covers organic matter information in the pretreated observation sheet and contains internal standard minerals, and the length and the width of the first analysis area are 10-14 times longer than the length of the organic matter;
the second selection policy includes: the second analysis zone comprises the microscopic component to be determined.
Optionally, the S3 includes:
the LA-ICP-MSmapping adopts a continuous ablation scanning mode, and a combined mineral internal and external standard method and an organic matter signal correction method are used for quantitatively measuring trace elements in a first analysis area;
wherein, the auxiliary substances used by the mineral internal and external standard method comprise: an internal standard substance, an external standard substance, and a signal detection substance; the internal standard substance is the internal standard mineral, and the external standard substance uses a standard glass sample; selecting a standard glass sample from the signal detection substances;
ToF-SIMSmapping detects trace elements in organic matters in the second analysis area by means of a primary ion source-secondary ion extraction system;
LA-ICP-MSmapping confirms the type of element to be measured by ICP-MS mass spectrometry, and the measured signal values include: a mineral trace element mass spectrum signal value and an organic trace element mass spectrum signal value;
ToF-SIMSmaping identifies the element type based on the secondary ion mass to charge ratio; comprising the following steps: secondary ion mass spectrum signal values.
Optionally, the S4 includes:
obtaining the content of trace elements of the internal standard minerals according to the formula (1);
obtaining the content of trace elements in the organic matters according to a formula (2);
formula (1): trace element content of internal standard mineral = trace element mass spectrum signal value in mineral/trace element mass spectrum signal value of external standard substance x trace element content in external standard substance;
the mass spectrum signal value of the external standard substance element and the element content in the external standard substance are all known values;
formula (2): trace element content in organic matter = trace element mass spectrum signal value in organic matter/internal standard mineral mass spectrum signal value x internal standard mineral trace element content x correction coefficient;
equation (3): correction coefficient = mineral signal value in LA-ICP-MSmapping/LA-ICP-MS single mineral element signal value;
the mineral signal value in LA-ICP-MS mapping is obtained in the determination of trace elements in organic matters;
the LA-ICP-MS single mineral element signal values were obtained in the determination of internal standard minerals.
Optionally, the S4 includes:
obtaining the content of trace elements in the organic matters according to a formula (4);
equation (4): trace element content in organic matter = secondary ion mass spectrum signal value/standard ion mass spectrum signal value x element content in standard substance;
the content of the element in the standard substance is a known value.
Optionally, the method further comprises:
and S5, fitting the calculated distribution information of the elements in the organic matters and a mass spectrogram of the sample, extracting and calibrating to obtain a step-by-step image of the microelements in the organic matters, and outputting the step-by-step image.
Optionally, the S2 includes:
and respectively selecting a wooden body with the grain size of 1mm in the germanium-enriched coal and a colloid chip body with the grain size of 7 mu m in the lithium-enriched coal as analysis areas aiming at the analysis areas of the rock microscope observation lens.
Optionally, characterized in that,
the second selection policy further includes: and fitting a standard mass spectrum and a sample spectrum in the second analysis region, extracting and calibrating a characteristic peak mass spectrum signal value, and measuring the content of elements in the organic matters.
Optionally, characterized in that,
LA-ICP-MS mapping selects kaolinite as an internal standard substance;
ToF-SIMS mapping selects Bi+ as the primary ion source.
(III) beneficial effects
The beneficial effects of the invention are as follows: compared with the prior art, the method can solve the technical problems that the prior art cannot quantitatively characterize the trace elements in the coal sample and visually output the trace element distribution in different organic matter types, and can directly capture the trace element distribution in the organic matter and visually output the trace elements in the organic matter.
Drawings
FIG. 1 is a flow chart of a method for visualizing and quantitatively outputting in-situ characterization of organic matter element distribution in a coal-based stratum;
FIG. 2 (A) is a diagram of a conventional single point denuded-plane scan pattern of the present invention;
FIG. 2 (B) is a schematic view of a continuous stripping surface sweep of the present invention;
FIG. 3 (A) is a diagram of a wood body of about 1mm particle size in a selected germanium-enriched coal according to the present invention;
FIG. 3 (B) is a 7 μm bulk plot of gum crumb in the lithium-enriched coal of the present invention;
FIG. 4 (A) is a graph of an experiment based on kaolinite as an internal standard mineral according to the invention;
FIG. 4 (B) is a plot of the harmonic curve or correction equation of the present invention;
FIG. 5 is a graph of distribution characteristics and abundance of trace elements in the body of the present invention;
fig. 6 is a graph showing the distribution and abundance of trace elements in the colloidal chip bodies in the lithium-rich coal of the invention.
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.
The method for quantitatively characterizing the trace element content and distribution in the organic matters by adopting a laser ablation inductively coupled plasma mass spectrometry scanning method, a time-of-flight secondary ion mass spectrometry scanning method and an established error correction formula solves the problems that the trace element in the organic matters in a coal sample cannot be quantitatively characterized by a direct method and the trace element distribution in different organic matters cannot be visually output by an indirect method, and the distribution characteristics of the trace elements in the organic matters can be directly captured.
In order that the above-described aspects may be better understood, exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present invention are shown in the drawings, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
As shown in fig. 1, the embodiment of the invention provides a method for in-situ characterization of element distribution in organic matters in a coal-based stratum, which comprises the following steps:
s1, preparing a rock microscope observation sheet aiming at a coal series stratum rock sample to be analyzed, and preprocessing the prepared rock microscope observation sheet to obtain a preprocessed observation sheet;
specifically, the pretreatment of the microscope viewing lens requires double-sided polishing, i.e., the surface is polished to a flat surface with a polisher. The implementation ensures that the artificial error is ensured during sample preparation, and the selected thickness is more than twice the diameter of the laser beam, namely more than 400 mu m.
S2, determining an analysis area to which each analysis scanning device belongs according to a pre-processed observation sheet and the analysis scanning device and a selection area strategy of each analysis scanning device;
the analysis scanning apparatus includes: LA-ICP-MS mapping laser ablation inductively coupled plasma mass spectrometry scanning apparatus for analyzing microscopic components having a particle size greater than 10 μm, toF-SIMS mapping time-of-flight secondary ion mass spectrometry scanning apparatus for analyzing microscopic components having a particle size less than or equal to 10 μm;
s3, measuring the respective analysis areas by means of an analysis scanning device to obtain a plurality of measurement signal values;
s4, acquiring element distribution information in organic matters in the coal-based stratum for in-situ characterization according to the measured signal values and the predefined element distribution relation.
In this embodiment, for different types of organic matters in coal under different geological backgrounds, the included organic matter subgroups, i.e., microscopic component types, are also greatly different, and LA-ICP-MS mapping laser ablation inductively coupled plasma mass spectrometry scanning equipment and ToF-SIMS mapping time-of-flight secondary ion mass spectrometry scanning equipment are preferentially used.
To better illustrate the in-situ characterization method of the distribution of organic elements in the coal-based stratum in this embodiment, because LA-ICP-MS mapping laser ablation inductively coupled plasma mass spectrometry scanning equipment, the laser beam is larger, and is suitable for analysis of organic matters with larger particle size, for example, LA-ICP-MS analysis is adopted for microscopic components with particle size >10 μm, and three principles are followed with respect to LA-ICP-MS mapping selection area, including: the laser ablation area is to cover the main organic matter type in the coal sample, and the length and width of the selected area, which can be used as an internal standard mineral and is covered by the selected area, are more than ten times the length of the organic matter.
In this embodiment, since the LA-ICP-MS mapping selection area cannot calibrate the organic matters in the absence of the internal standard mineral, it is particularly important to include a rule capable of being used as the internal standard mineral in the selected area to be followed, and on the basis of the three selection area principles, the selection area can be calibrated on the microscope observation lens by the marker pen, so that the subsequent experiments can be facilitated.
Wherein the length of the ablated region and the thickness of the microcomponent are visually estimated by means of a microscope eyepiece.
Regarding the ToF-SIMS mapping time-of-flight secondary ion mass spectrometry equipment, because of the different working principles, no internal standard minerals are needed, and therefore, the principle of microscopic components of selected area coverage measurement is mainly followed.
In addition, the LA-ICP-MS combined mineral internal and external standard method and the organic matter signal correction method adopted in the embodiment are used for quantitatively measuring trace elements in organic matters in coal.
The mineral internal and external standard method comprises three elements, namely an internal standard substance, an external standard substance and a signal detection substance. The internal standard substance, namely the internal standard mineral and the external standard substance selected in the second step, is selected from a standard glass sample NIST610, a signal monitoring is performed to select a standard glass sample NIST612, and the type of the element to be detected is confirmed through ICP-MS mass spectrum.
In addition, the LA-ICP-MS mapping analysis adopted in the present embodiment is different from the conventional single-point ablation pulse type, and the present embodiment adopts a continuous ablation scanning mode, as shown in fig. 2 (a) and 2 (B), which has two advantages: the influence of element heterogeneity is small and the spatial resolution of the element is high.
The embodiment of the invention provides an in-situ characterization method for the distribution of elements in organic matters in a coal-based stratum, which further comprises the following steps:
and S5, fitting the calculated distribution information of the elements in the organic matters and a mass spectrogram of the sample, extracting and calibrating to obtain a step-by-step image of the microelements in the organic matters, and outputting the step-by-step image.
In this embodiment, since the laser beam of the LA-ICP-MS mapping laser ablation apparatus is 10 μm at the minimum, the trace element content in the organic matter with the particle size of less than or equal to 10 μm is measured by ToF-SIMS mapping, and the trace element content is firstly fitted to the mass spectrum of the standard substance and the mass spectrum of the sample, and then the signal value of the characteristic peak mass spectrum is extracted and calibrated, and finally the element content in the organic matter is measured.
The ToF-SIMS mapping adopted in the implementation measures trace elements in organic matters through a primary ion source-secondary ion extraction system, and confirms element types based on the secondary ion mass-to-charge ratio.
Of course, in order to better ensure the accuracy of the element distribution information in the organic matter, the trace elements in the selected internal standard mineral need to be measured, and the element distribution information in the organic matter is obtained through the calculation of the trace element content of the internal standard mineral and the calculation of the trace element content in the organic matter.
Example two
The method of the present invention will be described in detail in this example.
In order to verify the present invention, the present example takes the bi-basin chalk-based germanium-rich coal and the Erdos basin lithium-rich coal as examples, step 1, the original coal-based stratum rock sample was fabricated into a microscope observation piece suitable for LA-ICP-MS mapping and ToF-SIMS, with a thickness of 400 μm, and the upper and lower surfaces were polished.
And 2, observing organic matters in the coal under a microscope, identifying the types of microscopic components, respectively selecting wood bodies with the particle size of about 1mm in the germanium-rich coal as shown in fig. 3 (A) and colloid fragments with the particle size of 7 mu m in the lithium-rich coal as research objects, as shown in fig. 3 (B), and delineating the region where the microscopic components to be detected are located.
And 3, determining microelements in the selected microscopic components based on LA-ICP-MS mapping and ToF-SIMS, and selecting widely developed kaolinite as an internal standard mineral in the LA-ICP-MS mapping experiment and Bi+ as a primary ion source in the ToF-SIMS mapping according to mineralogy characteristics of a research area.
And step 4, respectively performing electronic probes on the internal surface minerals-kaolinite to obtain principal elements of the internal standard minerals. Based on the formula (1), the trace element content of the internal standard mineral=the trace element mass spectrum signal value in the mineral/the trace element mass spectrum signal value of the external standard substance×the trace element content in the external standard substance, and the main element result, the trace element of kaolinite is measured, and table 1 shows the main trace element composition of the internal standard mineral-kaolinite, the external standard substance-NIST 610 and the monitoring substance-NIST 612.
Further, based on the formula (2) in the method, the trace element content in the organic matter=trace element mass spectrum signal value/internal standard mineral mass spectrum signal value×internal standard mineral trace element content×correction coefficient, in the formula (3), the correction coefficient=mineral signal value in LA-ICP-MS mapping/LA-ICP-MS single mineral element signal value, and the trace element in the microscopic component with the particle size larger than 10 microns is measured. As shown in fig. 4 (a) and 4 (B), a correction curve established based on the kaolinite signal value is shown. Based on the formula (4), the trace element content in the organic matter=the secondary ion mass spectrum signal value/the standard ion mass spectrum signal value×the element content in the standard substance, the trace element in the micro component with the particle size smaller than 10 microns is measured.
Finally, the measurement results are output, and fig. 5 and 6 respectively represent the distribution and abundance of microelements in the wood body with the grain diameter of about 1mm in the germanium-enriched coal and the colloid chip body with the grain diameter of 7 mu m in the lithium-enriched coal.
Therefore, the embodiment can directly capture the distribution characteristics of the trace elements in the organic matters based on the calibration method for determining the trace elements in the organic matters by LA-ICP-MS mapping.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium; may be a communication between two elements or an interaction between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature is "on" or "under" a second feature, which may be in direct contact with the first and second features, or in indirect contact with the first and second features via an intervening medium. Moreover, a first feature "above," "over" and "on" a second feature may be a first feature directly above or obliquely above the second feature, or simply indicate that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is level lower than the second feature.
In the description of the present specification, the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., refer to particular features, structures, materials, or characteristics described in connection with the embodiment or example as being included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that alterations, modifications, substitutions and variations may be made in the above embodiments by those skilled in the art within the scope of the invention.
Claims (10)
1. The in-situ characterization method for the distribution of the elements in the organic matters in the coal-based stratum is characterized by comprising the following steps of:
s1, preparing a rock microscope observation sheet aiming at a coal series stratum rock sample to be analyzed, and preprocessing the prepared rock microscope observation sheet to obtain a preprocessed observation sheet;
s2, determining an analysis area to which each analysis scanning device belongs according to a pre-processed observation sheet and the analysis scanning device and a selection area strategy of each analysis scanning device;
the analysis scanning apparatus includes: LA-ICP-MS mapping laser ablation inductively coupled plasma mass spectrometry scanning apparatus for analyzing microscopic components having a particle size greater than 10 μm, toF-SIMS mapping time-of-flight secondary ion mass spectrometry scanning apparatus for analyzing microscopic components having a particle size less than or equal to 10 μm;
s3, measuring the respective analysis areas by means of an analysis scanning device to obtain a plurality of measurement signal values;
s4, acquiring element distribution information in organic matters in the coal-based stratum for in-situ characterization according to the measured signal values and the predefined element distribution relation.
2. The method of claim 1, wherein S1 comprises:
the thickness of the rock microscope observation sheet is larger than the maximum diameter of the ablation laser beam of the analysis scanning device;
or the thickness of the rock microscope observation sheet is 2-4 times of the maximum diameter of the ablation laser beam of the analysis scanning device;
pre-treating the finished rock microscope viewing sheet, comprising:
and polishing the upper surface and the lower surface of the rock microscope observation sheet respectively.
3. The method according to claim 2, wherein said S2 comprises:
LA-ICP-MS mapping determines a first analysis area based on a first selection policy;
ToF-SIMS mapping determines a second analysis region based on a second selection policy;
the first selection policy includes: the first analysis area covers organic matter information in the pretreated observation sheet and contains internal standard minerals, and the length and the width of the first analysis area are 10-14 times longer than the length of the organic matter;
the second selection policy includes: the second analysis zone comprises the microscopic component to be determined.
4. A method according to claim 3, wherein said S3 comprises:
the LA-ICP-MS mapping adopts a continuous ablation scanning mode, and a combined mineral internal and external standard method and an organic matter signal correction method are used for quantitatively measuring trace elements in a first analysis area;
wherein, the auxiliary substances used by the mineral internal and external standard method comprise: an internal standard substance, an external standard substance, and a signal detection substance; the internal standard substance is the internal standard mineral, and the external standard substance uses a standard glass sample; selecting a standard glass sample from the signal detection substances;
the ToF-SIMS mapping detects trace elements in the organic matters in the second analysis area by means of a primary ion source-secondary ion extraction system;
LA-ICP-MS mapping confirms the type of element to be measured by ICP-MS mass spectrometry, and the measured signal values include: a mineral trace element mass spectrum signal value and an organic trace element mass spectrum signal value;
ToF-SIMS mapping identifies the element type based on the secondary ion mass to charge ratio; comprising the following steps: secondary ion mass spectrum signal values.
5. The method of claim 4, wherein S4 comprises:
obtaining the content of trace elements of the internal standard minerals according to the formula (1);
obtaining the content of trace elements in the organic matters according to a formula (2);
formula (1): trace element content of internal standard mineral = trace element mass spectrum signal value in mineral/trace element mass spectrum signal value of external standard substance x trace element content in external standard substance;
the mass spectrum signal value of the external standard substance element and the element content in the external standard substance are all known values;
formula (2): trace element content in organic matter = trace element mass spectrum signal value in organic matter/internal standard mineral mass spectrum signal value x internal standard mineral trace element content x correction coefficient;
equation (3): correction coefficient = mineral signal value in LA-ICP-MS mapping/LA-ICP-MS single mineral element signal value;
the mineral signal value in LA-ICP-MS mapping is obtained in the determination of trace elements in organic matters;
the LA-ICP-MS single mineral element signal values were obtained in the determination of internal standard minerals.
6. The method of claim 4, wherein S4 comprises:
obtaining the content of trace elements in the organic matters according to a formula (4);
equation (4): trace element content in organic matter = secondary ion mass spectrum signal value/standard ion mass spectrum signal value x element content in standard substance;
the content of the element in the standard substance is a known value.
7. The method according to claim 2, wherein the method further comprises:
and S5, fitting the calculated distribution information of the elements in the organic matters and a mass spectrogram of the sample, extracting and calibrating to obtain a step-by-step image of the microelements in the organic matters, and outputting the step-by-step image.
8. The method of claim 7, wherein S2 comprises:
and respectively selecting a wooden body with the grain size of 1mm in the germanium-enriched coal and a colloid chip body with the grain size of 7 mu m in the lithium-enriched coal as analysis areas aiming at the analysis areas of the rock microscope observation lens.
9. The method of claim 3, wherein the step of,
the second selection policy further includes: and fitting a standard mass spectrum and a sample spectrum in the second analysis region, extracting and calibrating a characteristic peak mass spectrum signal value, and measuring the content of elements in the organic matters.
10. The method of claim 4, wherein the step of determining the position of the first electrode is performed,
LA-ICP-MS mapping selects kaolinite as an internal standard substance;
ToF-SIMS mapping selects Bi+ as the primary ion source.
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