CN116754588B - Method for predicting ion adsorption type rare earth deposit burial depth in weathered crust - Google Patents

Method for predicting ion adsorption type rare earth deposit burial depth in weathered crust Download PDF

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CN116754588B
CN116754588B CN202310559942.2A CN202310559942A CN116754588B CN 116754588 B CN116754588 B CN 116754588B CN 202310559942 A CN202310559942 A CN 202310559942A CN 116754588 B CN116754588 B CN 116754588B
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kaolinite
weathered
rare earth
crust
ray diffraction
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CN116754588A (en
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谭伟
罗莲英
秦效荣
陈可妍
韩梦麒
何宏平
梁晓亮
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Guangzhou Institute of Geochemistry of CAS
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3563Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/359Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light

Abstract

The invention discloses a method for predicting the burial depth of ion adsorption type rare earth ore deposit in weathered crust, which relates to the technical field of prospecting and comprises the following steps: analyzing and calculating the characteristic peak area of the kaolinite and halloysite mineral phases by using the clay mineral non-oriented powder crystal X-ray diffraction and oriented sheet X-ray diffraction analysis results through Jade 6.5 to obtain the content of the kaolinite-halloysite minerals in the weathered crust; in the X-ray diffraction spectrum of clay mineral powder crystals, the crystallinity of kaolinite in the weathered crust was calculated. According to the method, the position of the groundwater fluctuation zone is determined through the rapid change of the kaolinite-halloysite content and the kaolinite crystallization index, and the bottom of the groundwater fluctuation zone is determined at the enrichment layer of ion adsorption state rare earth in the weathering crust; the invention can combine the correlation between the specific parameters of visible light-near infrared reflection spectrum and the crystallinity of kaolinite, and rapidly and accurately delineate the weathered shell ion adsorption type rare earth ore body in the prospecting work.

Description

Method for predicting ion adsorption type rare earth deposit burial depth in weathered crust
Technical Field
The invention relates to the technical field of prospecting and prospecting, in particular to a method for predicting the burial depth of an ion adsorption type rare earth deposit in a weathered crust.
Background
Rare earth elements are used as industrial vitamins and are widely applied to the fields of new energy technology, new materials, aerospace, national defense and military industry and the like. As global demand for rare earths, particularly heavy rare earths, has increased year by year, exploration and development of rare earth deposits has become particularly important. The ion adsorption type rare earth ore deposit is an dominant ore deposit resource in China, is mainly distributed in the weathered shell of granite rock in south China, has the characteristics of high medium-heavy rare earth content, complete distribution, low radioactivity, easy exploitation and the like, and provides more than 90% of heavy rare earth resources worldwide.
It is generally believed that clay minerals can adsorb rare earth ions released from rare earth-containing secondary minerals during weathering, thereby enriching the agglomerate in the fully weathered layer of the weathered crust, with kaolinite and halloysite being the primary carriers of ionic rare earths. The mineral composition and crystal structure property of clay mineral can reflect the adsorption capacity of the weathering crust to rare earth ions, when the exchangeable ionic rare earth content adsorbed by clay in the weathering crust reaches the boundary grade (more than 300 ppm) for exploitation, the mineral deposit can be formed.
The burial depth of weathered shell ion adsorption type rare earth ore bodies is generally 5-30m, and the utilization of geochemical exploration to outline ore bodies often leads to the omission of part of ore bodies. Therefore, the approximate position and distribution condition of the ore body are judged by using mineralogy indexes, effective support can be provided for the prospecting work of the weathered shell ion adsorption type rare earth ore deposit, the ore deposit evaluation accuracy is improved, and the purpose of efficiently utilizing rare earth resources is achieved.
Therefore, a method for predicting the burial depth of the ion adsorption type rare earth ore deposit in the weathered crust is provided to solve the difficulty existing in the prior art, and is a problem to be solved by the person skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a method for predicting the burial depth of an ion adsorption type rare earth mineral deposit in a weathered crust, which utilizes the means such as the relative content of kaolinite (Kln) -halloysite (Hly) in the weathered crust, the abrupt change of kaolinite crystallinity index R2 and SC11-int and the like to judge the fluctuation zone of the groundwater surface, and then mainly distributes the burial depth of a rare earth element rich mineral deposit in the Wenying crust below the diving surface, thereby further improving the definition of the burial horizon of the weathered crust ion adsorption type rare earth mineral deposit and the precision of evaluating the mineral deposit reserves, and meeting the purposes of the exploration work of the weathered crust ion adsorption type rare earth mineral deposit and the efficient utilization of rare earth resources.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for predicting the burial depth of ion adsorption type rare earth ore deposit in weathered crust comprises the following steps:
s1, taking a weathering crust sample, and carrying out powder crystal X-ray diffraction analysis on all rocks;
s2, clay minerals in the weathered crust sample are extracted;
s3, performing powder crystal X-ray diffraction and oriented sheet X-ray diffraction analysis on the extracted clay mineral;
s4, obtaining and calculating the characteristic peak area of the kaolinite-halloysite mineral phase by utilizing the powder crystal X-ray diffraction of all rocks and the X-ray diffraction analysis result of the clay mineral directional sheet, so as to obtain the content of the kaolinite-halloysite mineral in the weathered crust;
s5, calculating the crystallinity of the kaolinite in the weathered crust in the X-ray diffraction spectrum of the clay mineral powder crystal by the following formula;
R2=[1/2(K1+K2)-k]/[1/3(K1+K2+k)]
wherein K1 is the intensity value of the crystal face diffraction of the kaolinite (131) in the weathering crust, K2 is the intensity value of the crystal face diffraction of the kaolinite (1-31) in the weathering crust, and K is the height value of the peak valley between the crystal face diffraction of the kaolinite (1-31) and the crystal face diffraction of the kaolinite (131) in the weathering crust;
s6, judging a fluctuation zone of the groundwater surface through the change of the mineral content of kaolinite-halloysite and the crystallinity of kaolinite, and rapidly and efficiently predicting the occurrence level of the weathered shell ion adsorption type rare earth deposit by combining the correlation of specific parameters SC11-int of visible light-near infrared reflection spectrum and the crystallinity of kaolinite.
According to the method, optionally, clay minerals in the weathered crust sample are obtained by physical sedimentation according to Stokes' law in S2.
The method, optionally, the X-ray diffraction analysis and extraction of the oriented sheet in S3 specifically includes:
the clay mineral is firstly tested for natural orientation, then the clay mineral after natural orientation is subjected to heating treatment at 120 ℃ for 6 hours, and then the clay mineral after formamide saturation for 20 minutes is tested.
In the method, optionally, the characteristic peak area of the kaolinite-halloysite mineral phase is obtained and calculated in S4 through Jade 6.5.
In the above method, optionally, S6 further includes performing near infrared spectrum analysis on the extracted clay mineral.
The method can optionally use ViewSpecPro to conduct second order derivation on near infrared spectrum to obtain 4559.14-4561.54cm -1 And judging the position of a groundwater wave band according to the correlation between spectral parameters SC11-int and the crystallinity of kaolinite, and predicting the occurrence level of the ion adsorption type ore deposit.
Compared with the prior art, the invention provides a method for predicting the burial depth of ion adsorption type rare earth ore deposit in weathered crust,
(1) The invention relates to a method for searching a weathered crust rare earth rich mineral horizon by using clay minerals, which is characterized in that a groundwater level fluctuation zone is determined by the rapid change of kaolinite-halloysite content, kaolinite crystallization index R2 and SC11-int, and the rare earth rich horizon is determined to be positioned at the bottom of the groundwater level fluctuation zone.
(2) The invention gives out accurate mineralogy index, can avoid rare earth ore body ring leakage, can accurately evaluate rare earth mineral products and efficiently and reasonably utilize rare earth resources.
(3) The invention can meet the requirement of rapidly and accurately delineating the ore body for the sample by combining visible light-near infrared reflection spectrum and weathered shell ion adsorption type rare earth ore deposit prospecting work.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for predicting the depth of burial of ion-adsorbed rare earth deposits in weathered crust according to the present invention;
fig. 2 is a graph showing the relationship between the rapid change of the relative content of kaolinite and halloysite and the rapid change of the index of crystallinity of kaolinite, R2 and SC11-int, and the rare earth element enrichment horizon of the weathered crust sample.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to FIG. 1, the invention discloses a method for predicting the burial depth of ion adsorption type rare earth ore deposit in weathered crust, comprising the following steps:
s1, taking a weathering crust sample, and carrying out powder crystal X-ray diffraction analysis on all rocks;
s2, clay minerals in the weathered crust sample are extracted;
s3, performing powder crystal X-ray diffraction and oriented sheet X-ray diffraction analysis on the extracted clay mineral;
s4, obtaining and calculating the characteristic peak area of the kaolinite-halloysite mineral phase by utilizing the powder crystal X-ray diffraction of all rocks and the X-ray diffraction analysis result of the clay mineral directional sheet, so as to obtain the content of the kaolinite-halloysite mineral in the weathered crust;
s5, calculating the crystallinity of the kaolinite in the weathered crust in the X-ray diffraction spectrum of the clay mineral powder crystal by the following formula;
R2=[1/2(K1+K2)-k]/[1/3(K1+K2+k)]
wherein K1 is the intensity value of the crystal face diffraction of the kaolinite (131) in the weathering crust, K2 is the intensity value of the crystal face diffraction of the kaolinite (1-31) in the weathering crust, and K is the height value of the peak valley between the crystal face diffraction of the kaolinite (1-31) and the crystal face diffraction of the kaolinite (131) in the weathering crust;
s6, judging the fluctuation zone of the groundwater surface through the change of the kaolinite-halloysite mineral content and the kaolinite crystallinity, and predicting the occurrence position of the weathered shell ion adsorption type rare earth deposit.
Further, in S2, according to Stokes' law, clay minerals in the weathered crust sample are obtained by physical sedimentation.
Further, the X-ray diffraction analysis and extraction of the orientation sheet in S3 specifically includes:
the clay mineral is firstly tested for natural orientation, then the clay mineral after natural orientation is subjected to heating treatment at 120 ℃ for 6 hours, and then the clay mineral after formamide saturation for 20 minutes is tested.
Further, in S4, the peak area characteristic of the kaolinite-halloysite mineral phase was obtained and calculated by Jade 6.5.
Further, S6 further includes near infrared spectrum analysis of the extracted clay mineral.
Further, the ViewSpecPro is used for carrying out second order derivation on the near infrared spectrum to obtain 4559.14-4561.54cm -1 And judging the position of a groundwater wave band according to the correlation between spectral parameters SC11-int and the crystallinity of kaolinite, and predicting the occurrence level of the ion adsorption type ore deposit.
In one embodiment, the method for predicting the weathering crust ion-adsorbed rare earth deposit by clay mineral content and crystallinity is specifically implemented as follows:
a. carrying out full rock powder crystal X-ray diffraction (XRD) phase analysis on a weathered crust sample taken in the field;
b. according to Stokes' law, clay minerals in the sample are obtained through physical sedimentation, orientation sheet XRD analysis is carried out, and the sample after natural orientation, heat treatment (120 ℃ for 6 h) and formamide saturation for 20 minutes is respectively tested;
c. powder crystal XRD (X-ray diffraction) and near infrared spectrum (VNIR) analysis are respectively carried out on the extracted clay;
d. the powder crystal XRD and oriented sheet XRD analysis results of the whole rock are utilized to obtain the characteristic peak areas of each mineral phase through Jade 6.5, and the relative content of kaolinite-halloysite minerals in the weathered crust is obtained by calculating the areas;
e. in the XRD spectrum of clay powder crystal, the crystallinity of kaolinite in the weathered crust is calculated by the following formula;
R2=[1/2(K1+K2)-k]/[1/3(K1+K2+k)]
wherein K1 is the intensity value of the crystal face diffraction of the kaolinite (131) in the weathering crust, K2 is the intensity value of the crystal face diffraction of the kaolinite (1-31) in the weathering crust, and K is the height value of the peak valley between the crystal face diffraction of the kaolinite (1-31) and the crystal face diffraction of the kaolinite (131) in the weathering crust;
f. second order derivation of VNIR spectra using ViewSpecPro yields 4559.14-4561.54cm -1 Intensity values (SC 11-int) of spectral contribution centers in the range, and the crystallinity of kaolinite is judged in an auxiliary way through the SC 11-int;
g. judging the fluctuation zone of the groundwater surface through the relative content of kaolinite-halloysite minerals and the change of the crystallinity of kaolinite, and then combining the knowledge of the mineral rich layer of the weathered-crust ion-adsorbed rare earth mineral deposit below the diving surface to delineate the rare earth mineral bodies and evaluate the mineral deposit reserves.
The samples of the above examples were obtained from rock weathering crust of an ion-adsorbed rare earth deposit in the city of mezhou, guangdong, and in this example, as shown in table 1 below, by determination of the relative content of kaolinite Kln and halloysite Hly, the kaolinite crystallinity index R2, SC11-int, and the rare earth element REE, as shown in fig. 2, a groundwater level fluctuation band indicated by sharp changes in clay mineral content and crystallinity was obtained, indicating the location of REE enrichment in the weathering crust.
TABLE 1
Depth (m) Kln(%) Hly(%) R2 SC11-int(a.u.E-04) REE(μg/g)
2 74.3 5.6 1.02 1.26 607
3 64.1 5.2 1.03 1.42 -
4 53.7 12.0 0.97 1.74 315
5 57.5 9.7 0.98 1.45 -
6 56.1 17.7 0.86 1.33 537
7 35.9 39.0 0.85 0.44 -
8 51.2 20.8 0.87 0.98 354
9 48.2 18.7 0.85 0.61 -
10 22.5 47.5 0.84 -1.10 501
12 14.1 54.5 0.79 -1.42 1107
14 40.4 15.4 0.90 0.93 996
16 57.6 11.5 0.95 1.35 3343
18 27.5 31.2 0.87 0.22 1761
20 33.6 25.2 0.95 -0.14 1661
22 44.7 9.0 1.05 1.93 1143
24 22.5 27.1 0.98 0.95 1976
26 37.4 6.8 0.98 1.04 1420
28 33.4 16.4 0.99 1.16 817
30 38.5 2.1 0.99 1.40 918
32 40.2 3.9 0.94 0.72 966
34 45.8 3.9 1.00 1.09 660
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (4)

1. A method for predicting the depth of burial of an ion-adsorbed rare earth deposit in a weathered crust, comprising the steps of:
s1, taking a weathering crust sample, and carrying out powder crystal X-ray diffraction analysis on all rocks;
s2, clay minerals in the weathered crust sample are extracted;
s3, performing powder crystal X-ray diffraction and oriented sheet X-ray diffraction analysis on the extracted clay mineral;
s4, obtaining and calculating the characteristic peak area of the kaolinite-halloysite mineral phase by utilizing the powder crystal X-ray diffraction of all rocks and the X-ray diffraction analysis result of the clay mineral directional sheet, so as to obtain the content of the kaolinite-halloysite mineral in the weathered crust;
s5, calculating the crystallinity of the kaolinite in the weathered crust in the X-ray diffraction spectrum of the clay mineral powder crystal by the following formula;
R2=[1/2(K1+K2)-k]/[1/3(K1+K2+k)]
wherein K1 is the intensity value of the crystal face diffraction of the kaolinite (131) in the weathering crust, K2 is the intensity value of the crystal face diffraction of the kaolinite (1-31) in the weathering crust, and K is the height value of the peak valley between the crystal face diffraction of the kaolinite (1-31) and the crystal face diffraction of the kaolinite (131) in the weathering crust;
s6, judging a groundwater wave zone according to the content of kaolinite-halloysite minerals and the change of the crystallinity of kaolinite, and predicting occurrence positions of weathered shell ion adsorption type rare earth mineral deposits;
s6, near infrared spectrum analysis is carried out on the extracted clay minerals;
second order derivation of near infrared spectrum using ViewSpecPro to obtain 4559.14-4561.54cm -1 And judging the position of a groundwater wave band according to the correlation between spectral parameters SC11-int and the crystallinity of kaolinite, and predicting the occurrence level of the ion adsorption type ore deposit.
2. The method for predicting the burial depth of an ion-adsorbed rare earth deposit in a weathered shell according to claim 1, characterized in that,
and S2, according to Stokes' law, physically settling to obtain clay minerals in the weathered crust sample.
3. The method for predicting the burial depth of an ion-adsorbed rare earth deposit in a weathered shell according to claim 1, characterized in that,
the X-ray diffraction analysis and extraction of the oriented sheet in the S3 specifically comprises the following steps:
the clay mineral is firstly tested for natural orientation, then the clay mineral after natural orientation is subjected to heating treatment at 120 ℃ for 6 hours, and then the clay mineral after formamide saturation for 20 minutes is tested.
4. The method for predicting the burial depth of an ion-adsorbed rare earth deposit in a weathered shell according to claim 1, characterized in that,
the peak areas characteristic of the kaolinite-halloysite mineral phases were obtained and calculated in S4 by means of Jade 6.5.
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