CN114295664A - Method for detecting rare earth elements in minerals by using cathodoluminescence - Google Patents
Method for detecting rare earth elements in minerals by using cathodoluminescence Download PDFInfo
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- CN114295664A CN114295664A CN202111544988.4A CN202111544988A CN114295664A CN 114295664 A CN114295664 A CN 114295664A CN 202111544988 A CN202111544988 A CN 202111544988A CN 114295664 A CN114295664 A CN 114295664A
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- rare earth
- apatite
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- earth element
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 44
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 30
- 239000011707 mineral Substances 0.000 title claims abstract description 30
- 238000005136 cathodoluminescence Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 14
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 238000003384 imaging method Methods 0.000 claims abstract description 6
- 229910052586 apatite Inorganic materials 0.000 claims description 55
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 55
- 239000000523 sample Substances 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 238000004445 quantitative analysis Methods 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 abstract description 12
- 238000004458 analytical method Methods 0.000 description 11
- 238000009826 distribution Methods 0.000 description 6
- 238000004627 transmission electron microscopy Methods 0.000 description 6
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 4
- 229910052590 monazite Inorganic materials 0.000 description 4
- 238000002524 electron diffraction data Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
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Abstract
The invention belongs to the field of rare earth resource exploration, and particularly relates to a method for detecting rare earth elements in minerals by using cathodoluminescence. The detection method comprises the steps of analyzing minerals by using a cathodoluminescence imaging technology; and if the ring belt structure exists in the image, judging that the mineral contains the rare earth element.
Description
Technical Field
The invention belongs to the field of rare earth resource exploration, and particularly relates to a method for detecting rare earth elements in minerals by using cathodoluminescence.
Background
Rare earth is known as industrial vitamin and is an important strategic resource for the development of new material industry, modern high-tech industry and national defense industry in the world. The light rare earth is a general term for seven rare earth elements of lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium. They have a lower atomic number and a smaller mass. The content of light rare earth is high, the application range is wide, and the application of the rare earth plays a significant role. Apatite is a side mineral widely existing in various rocks and ores, can well record the experienced geological process, and is an ideal mineral for thermal chronology and isotope tracing research. The apatite may contain abundant rare earth elements, and the apatite containing the rare earth elements is a potential rare earth resource.
Cathodoluminescence imaging (CL) techniques can reveal the internal structural features of mineral crystals, reflecting the specific causative environment at that time, and therefore cathodoluminescence is widely used in mineralogy.
Because the occurrence state and the structure of the phosphorite containing the rare earth are complex, the comprehensive recovery of the rare earth in industrial production is restricted, and how to quickly and accurately judge whether the mineral contains the rare earth element is always a technical problem for the technicians in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for detecting rare earth elements in minerals by using cathodoluminescence, which comprises the steps of analyzing the minerals by using cathodoluminescence imaging technology; and if the ring belt structure exists in the image, judging that the mineral contains the rare earth element.
Preferably, the mineral is apatite; the rare earth elements are light rare earth elements, and most preferably the rare earth elements are lanthanum and/or cerium.
Further, after the rare earth elements in the minerals are judged to be contained, a scanning electron microscope and an electronic probe are adopted to carry out quantitative analysis on the constituent elements of the minerals; and/or the presence of a gas in the gas,
and (4) analyzing the microstructure and the internal element change of the mineral by adopting a transmission electron microscope after the rare earth element is judged to be contained in the mineral.
As a preferred embodiment of the present invention, the detection method comprises:
(1) analyzing the apatite by using a cathodoluminescence imaging technology; if the image has an annulus structure, the light rare earth element lanthanum and/or cerium is distributed in the core part of the apatite, and the light rare earth element is not arranged at the edge of the apatite;
(2) after the minerals are judged to contain light rare earth elements, a scanning electron microscope and an electronic probe are adopted to carry out quantitative analysis on the constituent elements of the apatite; and analyzing the microstructure and the internal element change of the apatite by adopting a transmission electron microscope.
The detection method can quickly and accurately detect the rare earth elements in the minerals; in addition, the method has important revelation significance on rare earth prospecting clues of the regions where the ores are located.
Drawings
FIG. 1 is a cathodoluminescence image of an apatite having an endless structure.
FIG. 2 is a log elemental surface scan of apatite electron probe data.
FIG. 3 is a schematic diagram of the backscattering image (BSE) and the cathodoluminescence image (CL) of the annular apatite and the position of the linear analysis.
FIG. 4 is a diagram showing the distribution of elements in a linear analysis (from edge-nucleus-edge) of a cyclic apatite.
FIG. 5 is a transmission electron microscopy chemical element distribution diagram of apatite.
FIG. 6 is an electron diffraction pattern of apatite.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. In the specific implementation process, if not specifically stated, the adopted technical method can be realized by the conventional technical method and the method provided by the literature by the technical personnel in the field; the materials and equipment used are commercially available.
As a preferred embodiment of the present invention, the method comprises the following steps:
(1) samples are collected, slices are manufactured, and the structural characteristics of the apatite are described in detail through observation and identification under a microscope. By analyzing the cathodoluminescence characteristics, the internal ring band structure and morphological characteristics of the apatite revealed by the cathodoluminescence image and the crystal orientation characteristics of the apatite in the sheet are observed.
(2) Apatite component test. The method comprises the steps of carrying out quantitative analysis on the constituent elements of the apatite by using a scanning electron microscope and an electronic probe, and researching the relevance of the element composition in the apatite to judge the possible coupling substitution relation. The distribution characteristics of elements in the core and the border of apatite having a typical annular structure were analyzed in combination with the annular structure of a cathodoluminescence image.
(3) Transmission electron microscopy analysis of apatite.Transmission Electron Microscopy (TEM) is from the nanometer (10)-9) The grade of (2) is used for research of earth science, as apatite has an obvious annular structure under cathodoluminescence, a monazite inclusion can appear in the apatite, and the apatite has an interaction with the monazite, in order to investigate whether the structure of the type of apatite changes and whether chemical components in the apatite change, the technology of transmission electron microscopy is adopted to analyze the microstructure of the apatite and the change of internal elements.
Example 1 apatite cathodoluminescence image containing rare earth element
As can be seen from the attached figure 1, the apatite in the strip ore is in a ring belt shape under the cathodoluminescence, which is mainly characterized in that the core part is brighter and the edge is darker, and is closely related to the enrichment of rare earth minerals.
EXAMPLE 2 Electron Probe analysis
In order to explore the distribution rule of elements in apatite, element analysis is carried out by using an electron probe.
Apatite electron probe surface scan shows: the content of La, Ce, Nd and Si in the apatite is low, the element data distribution diagram of the electron probe is not obvious, and the element surface distribution diagram is made by taking logarithm of all the element content (figure 2). The analysis result shows that the core part of La, Ce, Cl and Si is obviously higher than the edge, and apatite and rare earth mineral have mutual reaction and conversion process.
Example 3 scanning Electron microscopy analysis
In order to further analyze the elemental part of the core and the edge of the cyclic apatite (fig. 3), TESCAN VEGA3 scanning electron microscope was used for linear analysis, voltage 20KV, current 16nA, data processing software Oxford Instruments Aztec 3.0, chalcopyrite was used as a standard sample, and the corresponding analysis results are shown in fig. 4.
Example 4 Transmission Electron microscopy analysis
Since the apatite contains monazite particles, the apatite has an obvious annular zone structure in CL, and the intercrossed monazite can be eroded in the apatite, and in order to investigate whether the structure of the type of apatite is changed or not and whether the chemical composition in the apatite is changed or not, the change of the microstructure and the internal elements of the apatite is analyzed by adopting the technology of a transmission electron microscope.
The transmission electron microscope analysis of the apatite shows that: white spots were observed in the HAADF image of apatite (fig. 5), and it was found by elemental analysis that they were mainly caused by Nd, Ce, Y, and Si, that is, the relatively bright portions inside the apatite having the band-shaped structure were mainly caused by the enrichment of rare earth elements such as Nd, Ce, and Y. An electron diffraction pattern (fig. 6) of apatite was obtained by transmission electron microscopy, and analyzed to obtain electron diffraction data of apatite. The apatite is rich in rare earth elements such as Nd, Ce, Y and the like, but the atomic structure of the apatite itself is not changed.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of this invention as claimed.
Claims (7)
1. A detection method, characterized in that the detection method comprises: analyzing the minerals by using a cathodoluminescence imaging technology; and if the ring belt structure exists in the image, judging that the mineral contains the rare earth element.
2. The detection method according to claim 1, wherein the mineral is apatite.
3. The detection method according to claim 1, wherein the rare earth element is a light rare earth element.
4. The detection method according to claim 3, wherein the light rare earth element is lanthanum and/or cerium.
5. The detection method according to any one of claims 1 to 4, wherein after determining that the mineral contains a rare earth element, the detection method further comprises: and (3) carrying out quantitative analysis on the constituent elements of the minerals by adopting a scanning electron microscope and an electronic probe.
6. The detection method according to any one of claims 1 to 4, wherein after determining that the mineral contains a rare earth element, the detection method further comprises: and analyzing the microstructure and the internal element change of the mineral by adopting a transmission electron microscope.
7. The detection method according to any one of claims 1 to 4, characterized in that the detection method comprises:
(1) analyzing the apatite by using a cathodoluminescence imaging technology; if the image has an annulus structure, the light rare earth element lanthanum and/or cerium is distributed in the core part of the apatite, and the light rare earth element is not arranged at the edge of the apatite;
(2) after the minerals are judged to contain light rare earth elements, a scanning electron microscope and an electronic probe are adopted to carry out quantitative analysis on the constituent elements of the apatite; and analyzing the microstructure and the internal element change of the apatite by adopting a transmission electron microscope.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5267274A (en) * | 1992-05-29 | 1993-11-30 | Donelick Raymond A | Method of fission track analysis utilizing bulk chemical etching of apatite |
| JP2003158008A (en) * | 2001-11-21 | 2003-05-30 | Sumitomo Special Metals Co Ltd | Rare-earth bonded magnet and its manufacturing method |
| WO2014017544A1 (en) * | 2012-07-25 | 2014-01-30 | 国立大学法人京都大学 | Element analyzing device |
| CN107727677A (en) * | 2017-09-22 | 2018-02-23 | 中国科学院地质与地球物理研究所 | The cathodoluminescence imaging method of monazite |
| CN110530961A (en) * | 2019-08-02 | 2019-12-03 | 中国石油天然气股份有限公司 | The determination method and device of carbonate mineral cathodoluminescence strength control factor |
| CN112986529A (en) * | 2021-04-28 | 2021-06-18 | 中国煤炭地质总局勘查研究总院 | Coal-series mineral resource evaluation method |
| CN113109114A (en) * | 2021-04-14 | 2021-07-13 | 中山大学 | Pretreatment method for analyzing rare earth elements in apatite and detection method thereof |
| WO2021187492A1 (en) * | 2020-03-17 | 2021-09-23 | 株式会社オハラ | Complex between silicate-based substrate and rare earth element compound, light-emitting nano particles, cell detection method, animal treatment method, medical device, and method for producing complex between silicate-based substrate and rare earth element compound |
-
2021
- 2021-12-16 CN CN202111544988.4A patent/CN114295664A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5267274A (en) * | 1992-05-29 | 1993-11-30 | Donelick Raymond A | Method of fission track analysis utilizing bulk chemical etching of apatite |
| JP2003158008A (en) * | 2001-11-21 | 2003-05-30 | Sumitomo Special Metals Co Ltd | Rare-earth bonded magnet and its manufacturing method |
| WO2014017544A1 (en) * | 2012-07-25 | 2014-01-30 | 国立大学法人京都大学 | Element analyzing device |
| CN107727677A (en) * | 2017-09-22 | 2018-02-23 | 中国科学院地质与地球物理研究所 | The cathodoluminescence imaging method of monazite |
| CN110530961A (en) * | 2019-08-02 | 2019-12-03 | 中国石油天然气股份有限公司 | The determination method and device of carbonate mineral cathodoluminescence strength control factor |
| WO2021187492A1 (en) * | 2020-03-17 | 2021-09-23 | 株式会社オハラ | Complex between silicate-based substrate and rare earth element compound, light-emitting nano particles, cell detection method, animal treatment method, medical device, and method for producing complex between silicate-based substrate and rare earth element compound |
| CN113109114A (en) * | 2021-04-14 | 2021-07-13 | 中山大学 | Pretreatment method for analyzing rare earth elements in apatite and detection method thereof |
| CN112986529A (en) * | 2021-04-28 | 2021-06-18 | 中国煤炭地质总局勘查研究总院 | Coal-series mineral resource evaluation method |
Non-Patent Citations (2)
| Title |
|---|
| 刘晓东,华仁民: "福建碧田Au-Ag-Cu矿床含金石英脉中磷灰石的阴极发光研究" * |
| 朱利岗: ""云南武定地区铁-铜-金-铀-稀土矿成矿作用与成矿动力学"" * |
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Application publication date: 20220408 |