CN109813665A - The method for quickly analyzing rock weathering shell content of rare earth using visible light-near-infrared spectral reflectance - Google Patents

The method for quickly analyzing rock weathering shell content of rare earth using visible light-near-infrared spectral reflectance Download PDF

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Publication number
CN109813665A
CN109813665A CN201910083918.XA CN201910083918A CN109813665A CN 109813665 A CN109813665 A CN 109813665A CN 201910083918 A CN201910083918 A CN 201910083918A CN 109813665 A CN109813665 A CN 109813665A
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China
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sample
rare earth
content
visible light
spectral reflectance
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谭伟
刘嘉成
何宏平
秦效荣
梁晓亮
马灵涯
黄健
黄玉凤
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Guangzhou Institute of Geochemistry of CAS
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Guangzhou Institute of Geochemistry of CAS
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Abstract

The invention discloses a kind of methods for the content of rare earth in rock weathering shell being tested and being analyzed using visible light-near-infrared spectral reflectance data, it is appeared using hand-held visible light-near-infrared spectral reflectance instrument to rock weathering shell, content of rare earth in topsoil and drilling sample is tested, and pass through specific sample pre-treatments and data processing means, eliminate water in sample, organic matter, it is interfered caused by the accuracy that the ingredients such as ferriferous oxide test content of rare earth, improve the accuracy and sensitivity of content of rare earth test in rock weathering shell, meets the needs of sample is quickly analyzed in the work of weathering crust ion-adsorbed REE deposit mineral exploration.

Description

Rock weathering shell content of rare earth is quickly analyzed using visible light-near-infrared spectral reflectance Method
Technical field:
The present invention relates to analysis fields, and in particular to a kind of quickly to analyze rock using visible light-near-infrared spectral reflectance The method of weathering crust content of rare earth.
Background technique:
Rare earth element in numerous areas such as defence and military, aerospace, special material, metallurgy, the energy and agriculturals due to having It is widely used, referred to as " industrial vitamin ".In recent years, fast due to fields such as aerospace, new energy and new materials Speed development is so that rare earth becomes a kind of crucial strategic resource.Demand due to western developed country to rare earth increases year by year, leads Rare earth (especially heavy rare earth) price on international market is caused persistently to rise.It is driven by the market demand and economic benefit, the world The exploration and development and utilization of rare earth mineral deposit are all attached great importance in recent years in various countries.Southern region of China (Guangdong, Guangxi, Fujian, Jiangxi Etc. ground province) weathering crust ion-adsorbed REE deposit be important one of the rare earth resources type in China, provide the whole world and exceed four / tri- heavy rare earth product.
Weathering crust ion-adsorbed REE deposit is largely developed in the rock weathering shell based on granite.These areas Atmospheric disintegration of rocks shell thickness reaches 10-30 meters, provides advantage for the formation and preservation of such rare earth mineral deposit.In rock weathering shell Rare earth element be the basement rock (granite, volcanic rock) rich in rare earth by after strong slacking, decompose with mineral and It is precipitated, is adsorbed on the secondary mineral of weathering crust.If the content of rare earth in rock weathering shell can reach the side for exploitation Boundary's grade (300ppm or more) can form mineral deposit.In planning ore prospect area, delineation ore body range and assessment ore deposit reserve etc. In mineral exploration practice, need to divide the content of rare earth in the appearing of rock weathering shell, topsoil and drilling sample Analysis.
At present for the detection of Geological Samples for Rare Earth content rely primarily on inductivity coupled plasma mass spectrometry (ICP-MS), The analysis means such as x-ray fluorescence analyzer (XRF), inductively coupled plasma emission spectrum (ICP-ES).These analysis means are although inspection Rising limit is lower (be better than 1ppm), but requires indoors to pre-process sample, experimental period it is long and expensive (50~ 200RMB/ sample).Since weathering crust ion-adsorbed REE deposit has the characteristics that distributed areas are wide, in mineral exploration practice It generally requires that a large amount of samples in some region are sampled and analyzed.Therefore, mineralising side can be reached in analysis detection limit Under the premise of boundary's grade (300ppm or more), a kind of cheap and convenient and fast analytical technology is needed to realize to natural rock weathering shell Content of rare earth in sample carries out quickly, or even instant analysis in situ, to provide effective branch for the work of relevant mineral exploration Support.
Summary of the invention:
The rare earth in rock weathering shell is contained using visible light-near-infrared spectral reflectance the object of the present invention is to provide a kind of The method for being tested and being analyzed data is measured, using hand-held visible light-near-infrared spectral reflectance instrument to rock weathering shell Appear, topsoil and drilling sample in content of rare earth tested, and by specific sample pre-treatments and data at Reason means are interfered caused by eliminating the accuracy that ingredients such as water, organic matter, ferriferous oxide in sample test content of rare earth, are mentioned The accuracy and sensitivity that content of rare earth is tested in high rock weathering shell, meet weathering crust ion-adsorbed REE deposit and mine are looked for survey Look into the demand that sample is quickly analyzed in work.
The present invention is achieved by the following technical programs:
It is a kind of that the content of rare earth in rock weathering shell is tested and analyzed using visible light-near-infrared spectral reflectance Method, method includes the following steps:
A, by surface do clean rock weathering shell sample put into depth greater than 0.5cm, diameter greater than 1.5cm vessel in, benefit Surface is flattened with sheet glass;
B, reflective spectral measure, spectral region are carried out to the sample in vessel using visible light-near-infrared spectral reflectance instrument It is set as 350-1000nm, is rectified an instrument using standard reflection panel;It takes multiple measurements from different directions, records primary light Modal data;
C, the original spectral data for repeatedly measuring sample is weighted and averaged the spectroscopic data as the sample, to eliminate Sample inhomogeneities bring random error, draws sample spectra curve, this step can using the softwares such as ViewSpecpro into Row;
D, smoothly and continuously system removal is carried out to sample spectra curve and handles to obtain treated sample spectra curve, this step Suddenly it is carried out using softwares such as SpecWin.
E, to the curve of spectrum 743nm wavelength absorption intensity of the step d sample spectra curve sample that obtains that treated into Row second order derivation processing, show that its second order leads value;
F, the second order that step e is obtained is led into value as x value substitution following formula and obtains the content of rare earth y in rock weathering shell;
Y=58500x3+7200x2+2260x+520。
It is described to take multiple measurements from different directions in step b, powder sample is surveyed from the different directions for being spaced 90 ° Amount 2 times then measures 6 times rock block sample from the different directions for being spaced 30 °, records original spectral data.
Beneficial effects of the present invention are as follows:
1, the present invention is that one kind is quick, lossless, contains without the rare earth in cumbersome sample pre-processing analysis rock weathering shell Amount can realize instant analysis in situ by handheld device, also can to relevant remote sensing technology connected applications, meet weathering crust from The demand that sub- absorbent-type rare earth Ore Deposits preliminry basic research quickly analyzes sample.
2, the analysis methods such as ICP-MS, ICP-ES and XRF of the present invention are compared, and have biggish cost advantage, the present invention Analysis cost be about 2-5RMB/ sample.
3, the present invention can be effectively reduced water, organic matter and ferriferous oxide in soil to the shadow of rare earth elemental analysis It rings, accuracy with higher and lower detection limit.
4, analysis method editable according to the present invention is program, is implanted into existing spectral analysis software in the market, makes Its product and equipment have the function of quantitative analysis content of rare earth.
Detailed description of the invention:
Fig. 1 is that the Spectroscopic analysis results of weathering crust sample content of rare earth and ICP-MS analyze result Partial Least Squares Regression mould It is quasi-
Schematic diagram.
Specific embodiment:
It is to further explanation of the invention, rather than limiting the invention below.
Embodiment 1:
Rock weathering shell of the sample from Ganzhou City, Jiangxi Province ion adsorption rare-earth deposit, in this example, I Using Analytical Spectral Devices (ASD) FieldSpec-3 spectrometer carry out reflective spectral measure, and will The Spectroscopic analysis results of weathering crust sample content of rare earth are compared with ICP-MS analysis result.
Steps are as follows:
1, sample chooses about 10g and puts the vessel that 0.5cm is deep, diameter is 1.5cm into after laboratory condition natural air drying In, surface is flattened using sheet glass.
2, reflectance spectrum survey is carried out using Analytical Spectral Devices (ASD) FieldSpec-3 spectrometer Amount, wherein spectral region is 350-1000nm.Spectrometer first carries out preheating 30min in measurement process, utilizes standard white plate later Carry out spectrum correction.
3,2 samples are measured from the different directions for being spaced 90 °, records original spectral data.Utilize ViewSpecpro software Original spectrum curve is pre-processed, takes the averaged spectrum of each sample as the reflectance spectrum of the sample;Then SpecWin is utilized Continuum removal processing is carried out to the curve of spectrum.
4, the curve of spectrum 743nm wavelength absorption intensity of the sample obtained to step 3 carries out second order derivation processing, obtains it Second order leads value 743_2nd, empirical equation y=18045x is substituted into as x value3+2233.5x2+696.5x+80.6(R2>0.8), The y value obtained, as content of rare earth.
Data precision of the present invention and apply efficiency assessment: by same sample carry out ICP-MS analysis total amount of rare earth (reference Document: Shi Yihua;Qiu Li;Tang Biyu;Yang Zhongping;Song Cian;Gu Hanggan inductively coupled plasma mass spectrometry measures ionic Rare Earth Mine intermediate ion phase total amount of rare earth and component [J];Metallurgical analysis;9th phase in 2014), test result is compared such as 1 institute of table Show.Although certain data have relatively large deviation (result is referring to table 1), the data that two kinds of analysis methods obtain are after over-fitting Show stronger correlativity y=1.03x (R2=0.73), wherein y value is total with the rare earth of ICP-MS method analysis acquisition Content, the rare earth total content (such as Fig. 1) that x refers to be obtained with present invention analysis.In mineral exploration practice, by utilizing the present invention In technical method a large amount of samples in this region are sampled and are analyzed, planning can be met according to the distribution trend of data Ore prospect area, delineation ore body range and the requirement for assessing ore deposit reserve.
Table 1

Claims (4)

  1. Using visible light-near-infrared spectral reflectance the content of rare earth in rock weathering shell is tested and analyzed 1. a kind of Method, which is characterized in that method includes the following steps:
    A, clean rock weathering shell sample is done on surface and puts depth into greater than in the vessel of 0.5cm, diameter greater than 1.5cm, utilize glass Glass piece flattens surface;
    B, reflective spectral measure, spectral region setting are carried out to the sample in vessel using visible light-near-infrared spectral reflectance instrument For 350-1000nm, rectified an instrument using standard reflection panel;It takes multiple measurements from different directions, records original spectrum number According to;
    C, the original spectral data for repeatedly measuring sample is weighted and averaged the spectroscopic data as the sample, draws sample light Spectral curve;
    D, smoothly and continuously system removal is carried out to sample spectra curve and handles to obtain treated sample spectra curve;
    E, second order derivation processing is carried out to the curve of spectrum 743nm wavelength absorption intensity of the step d sample that obtains that treated, obtained Its second order leads value out;
    F, the second order that step e is obtained is led into value as x value substitution following formula and obtains the content of rare earth y in rock weathering shell;
    Y=58500x3+7200x2+2260x+520。
  2. 2. being carried out according to claim 1 using visible light-near-infrared spectral reflectance to the content of rare earth in rock weathering shell The method of test and analysis, which is characterized in that it is described to take multiple measurements from different directions in step b, for powder sample From interval, 90 ° of different directions are measured 2 times, and rock block sample is then measured 6 times from the different directions for being spaced 30 °.
  3. 3. it is according to claim 1 or claim 2 using visible light-near-infrared spectral reflectance to the content of rare earth in rock weathering shell into The method of row test and analysis, which is characterized in that step c is carried out using ViewSpecpro software.
  4. 4. it is according to claim 1 or claim 2 using visible light-near-infrared spectral reflectance to the content of rare earth in rock weathering shell into The method of row test and analysis, which is characterized in that step d is carried out using SpecWin software.
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Cited By (5)

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CN111678882A (en) * 2020-06-08 2020-09-18 中国科学院广州地球化学研究所 Method for predicting weathering crust ion adsorption type rare earth deposit horizon through ancient diving space
CN113125374A (en) * 2021-04-16 2021-07-16 自然资源实物地质资料中心 Method, device and equipment for detecting REE content in carbonate type rare earth deposit sample
CN113252600A (en) * 2021-05-24 2021-08-13 中国科学院广州地球化学研究所 Method for analyzing ion adsorption state rare earth content of weathering crust sample by reflection spectrum
CN113433152A (en) * 2021-06-23 2021-09-24 自然资源实物地质资料中心 Method for identifying carbonate type REE ore deposit mineralization zone based on V-NIR and XRF
CN114002410A (en) * 2021-11-04 2022-02-01 中国有色桂林矿产地质研究院有限公司 Method for rapidly delineating heavy rare earth ore exploration target area in weathered shell type based on geological body rare earth distribution

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111678882A (en) * 2020-06-08 2020-09-18 中国科学院广州地球化学研究所 Method for predicting weathering crust ion adsorption type rare earth deposit horizon through ancient diving space
CN111678882B (en) * 2020-06-08 2021-06-04 中国科学院广州地球化学研究所 Method for predicting weathering crust ion adsorption type rare earth deposit horizon through ancient diving space
CN113125374A (en) * 2021-04-16 2021-07-16 自然资源实物地质资料中心 Method, device and equipment for detecting REE content in carbonate type rare earth deposit sample
CN113252600A (en) * 2021-05-24 2021-08-13 中国科学院广州地球化学研究所 Method for analyzing ion adsorption state rare earth content of weathering crust sample by reflection spectrum
CN113433152A (en) * 2021-06-23 2021-09-24 自然资源实物地质资料中心 Method for identifying carbonate type REE ore deposit mineralization zone based on V-NIR and XRF
CN113433152B (en) * 2021-06-23 2023-03-07 自然资源实物地质资料中心 Carbonic acid identification based on V-NIR and XRF method for mineralizing zone of rock-type REE deposit
CN114002410A (en) * 2021-11-04 2022-02-01 中国有色桂林矿产地质研究院有限公司 Method for rapidly delineating heavy rare earth ore exploration target area in weathered shell type based on geological body rare earth distribution
CN114002410B (en) * 2021-11-04 2024-01-09 中国有色桂林矿产地质研究院有限公司 Method for rapidly delineating target area of heavy rare earth mine in weathered crust based on geologic body rare earth distribution

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Application publication date: 20190528