Ion adsorption type rare earth content determination method, system, equipment and medium

Abstract

The invention relates to the technical field of rare earth resource exploration, in particular to an ion adsorption type rare earth content determination method, system, equipment and medium, and the method comprises the following steps: constructing a quantitative relation prediction model between normalized charge rate and total rare earth oxide mass fraction, arranging an impedance measurement system in a research area, and collecting impedance amplitude and phase; and obtaining a normalized charge rate based on the impedance amplitude and the phase, constructing a quantitative relation prediction model between the normalized charge rate and the total rare earth oxide mass fraction, and calculating to obtain the total rare earth oxide mass fraction based on the quantitative relation prediction model. According to the method, the surface electrical influence of the ion adsorption type rare earth ore sample is considered, the correlation between the spectrum induced polarization response and the chemical parameters is established, and the content of the rare earth oxide in the ion adsorption type rare earth sample is estimated by using the correlation.

Description

Technical Field

[0001] This invention relates to the field of rare earth resource exploration technology, and in particular to an ion adsorption method, system, equipment and medium for determining rare earth content. Background Technology

[0002] Rare earth elements are key components of many advanced technologies in defense, aerospace, and new energy fields. Ion adsorption rare earth resource exploration heavily relies on shallow wells, shallow drilling, and chemical analysis techniques. Traditional drilling methods suffer from limited depth, high cost, and low borehole coverage, while chemical analysis methods are costly, time-consuming, and destructive, making rapid surveys and real-time monitoring difficult.

[0003] Spectral induced polarization (SIP) method measures the complex resistivity spectrum of rocks and soils over a wide frequency band (typically mHz to kHz) to obtain electrical parameters related to the medium's pore structure, mineral composition, and ion concentration. According to the mineralization mechanism of ion-adsorption rare earth deposits, rare earth ions migrate and transport with acidic fluids, are adsorbed onto clay minerals, and enriched in the weathering layer, with light and heavy rare earth enrichment exhibiting stratification. The formation of a stable electrical bilayer at the clay-water interface helps to establish the relationship between surface adsorption and physical properties, while the ion concentration in the solution affects the conductivity of the underground medium. Based on the main electrical parameters—resistivity (conductivity), polarizability, and other physical properties—of samples at different depths in the weathering profile of ion-adsorption rare earth deposits, this study investigates the response relationship between rare earth oxide content and electrical parameters in weathering profile soil samples. This can provide a theoretical basis and technical support for the development and implementation of a comprehensive physical and chemical exploration technology system for ion-adsorption rare earth deposits.

[0004] While methods such as resistivity tomography and seismic refraction are helpful in guiding the location distribution of rare earth ore boreholes and characterizing weathered layers, current techniques often overlook the contribution of surface electrical properties to overall conductivity. Secondly, the complex conductivity of a sample reflects the superposition of polarization responses at different scales, such as low-frequency film polarization, mid-frequency Stern layer polarization and diffusion layer polarization, and high-frequency Maxwell-Wagner polarization. Ion-adsorbed rare earth ore exhibits a "lighter at the top, heavier at the bottom" stratified enrichment characteristic in weathered layers, and the two column packing methods for soil samples lead to different ionic states in the samples. Specifically, introducing water into a dry sample causes ions to concentrate in the electric bilayer at the clay-water interface, while pre-mixing the solution with the sample causes some ions to diffuse. Therefore, the polarization length distribution in water-bearing soil samples is complex and it is difficult to distinguish between different polarization mechanisms. Although the Cole-Cole model is widely used to explain the spectral induced electrical response of rocks and minerals, a single model cannot accurately describe the polarization caused by the electric double layer in ion-adsorbed rare earth mineral samples at different depths. Therefore, it is necessary to select an appropriate model for fitting based on the sample state and spectral characteristics, and then establish the response relationship between rare earth content and physical property parameters in ion-adsorbed rare earth minerals.

[0005] Therefore, it is necessary to provide an ion adsorption-based rare earth content determination method, system, equipment, and medium that can effectively fit the signal, accurately extract the electrical parameters related to rare earth content, and establish a reliable quantitative relationship to solve the above-mentioned technical problems. Summary of the Invention

[0006] The purpose of this invention is to provide an ion adsorption method, system, equipment, and medium for determining rare earth content. The specific technical solution is as follows: An ion adsorption-type rare earth content determination method involves setting up an impedance measurement system in the study area to collect impedance amplitude and phase, obtaining the normalized charge rate based on the impedance amplitude and phase, constructing a quantitative relationship prediction model between the normalized charge rate and the total rare earth oxide mass fraction, and calculating the total rare earth oxide mass fraction based on the quantitative relationship prediction model. The process of constructing a quantitative relationship prediction model includes: S1: Select the study area and collect weathering profile samples of ion adsorption type rare earth minerals according to the underground depth; S2: Pre-treatment of the collected samples by air drying, crushing and grinding; S3: Prepare the sample to be tested and perform spectral induced polarization measurements, as follows: S3.1 Prepare a soil column device with a bottom inlet and a top outlet, and install power supply electrodes at the bottom and top of the soil column device, and install measuring electrodes at symmetrical positions on the upper and lower sides of the side wall of the soil column device. S3.2. The sample after step S2 is filled into the sample cavity of the soil column device using both dry and wet methods, and an electrolyte solution is introduced through the bottom water inlet to form a soil column containing the sample that can be measured. S3.3 Connect the power supply electrode and the measuring electrode to the impedance analyzer, and use the four-electrode method to measure the complex resistivity spectrum of the soil column containing the sample within a preset frequency range to obtain the impedance amplitude and phase at multiple frequencies. S4: Based on the complex resistivity spectrum obtained in step S3, and combined with the measurement conditions of dry and wet methods, a preset Cole-Cole model is selected to fit the spectral data, and model parameters including at least charge rate and zero-frequency resistivity are obtained through inversion calculation. S5: Based on the model parameters obtained from step S4, calculate the normalized charge rate that characterizes the electrochemical polarization intensity of the sample. S6: Using calibrated samples with known rare earth oxide content, establish a quantitative relationship prediction model between the normalized charge rate and the total rare earth oxide mass fraction.

[0007] Specifically, in S1, select 3-5 typical ion-adsorption type rare earth mineral weathering profiles. When sampling, take several blocky humus layer, soil layer, fully weathered layer and semi-weathered layer samples from top to bottom of the weathering profile at the same interval.

[0008] Specifically, in S4, the process of fitting the spectral data is as follows: First, we compared and analyzed the measurement data of dry column packing and wet column packing, and then performed fitting in the following three cases; The first scenario involves the absolute phase values ​​measured by both dry and wet column packing methods. If the absolute phase value changes with increasing frequency at frequencies greater than 100 Hz, it indicates the presence of wideband Maxwell-Wagner polarization interference in the sample. A dual Cole-Cole model is then used to fit the data. The expression for the dual Cole-Cole model is as follows: ; in, For complex resistivity, The imaginary unit, The impedance amplitude, For phase, Angular frequency, To measure frequency, Resistivity at zero frequency , Indicates charge rate, , Represents the Cole-Cole exponent. , The subscripts 1 and 2 indicate the Cole-Cole relaxation time, and are used to distinguish the different polarization mechanisms in the double Cole-Cole model. The second method involves measuring data from samples taken from deeper formations. If the absolute phase value measured using either dry or wet column packing methods reaches its maximum or minimum value within the 100-1000 Hz frequency range, or if the change in absolute phase value decreases with increasing frequency, then the sample is considered to contain characteristic peaks of coupled polarization between the Stern layer and the diffuse layer, appearing within this range. Signals interfered with by high frequencies are discarded, and spectral data close to the characteristic peak frequency is extracted. A single Cole-Cole model is used to fit the data. The expression for the single Cole-Cole model is as follows: ; in, For charge rate, The Cole-Cole exponent. Cole-Cole relaxation time; The third case involves a characteristic peak frequency of less than 100Hz for the absolute value of the phase measured under dry column packing, while a steep rise occurs at high frequencies under wet column packing. The dry column packing data is fitted using a single Cole-Cole model, while the wet column packing data is fitted using a double Cole-Cole model. Substitute the spectral data into the model, and obtain the model parameters by nonlinear least squares inversion fitting method.

[0009] Specifically, in S5, the calculation process for the normalized charge rate includes: In the double Cole-Cole model, the normalized charge rate is obtained by dividing the charge rate by the zero-frequency resistivity. , The normalized charge rate in the low-frequency Cole-Cole term with a longer relaxation time is used as a parameter to describe the magnitude of the electric double-layer polarization. In the single Cole-Cole model, the normalized charge rate is obtained by dividing the charge rate by the zero-frequency resistivity. ; in, The normalized charge rate is represented by the subscripts 1 and 2, which are used to distinguish the different polarization mechanisms in the double Cole-Cole model.

[0010] Specifically, in S6, the process of establishing a quantitative relationship prediction model includes: A quantitative relationship prediction model between charge rate and total rare earth oxide mass fraction was established by fitting measurement data obtained under wet and dry column packing methods. The expression is as follows: ; in, REO This represents the mass fraction of total rare earth oxides. The model parameters were obtained by performing linear regression on a set of calibration samples with known total rare earth oxide mass fractions. A quantitative predictive model for the relationship between normalized charge rate and total rare earth oxide mass fraction obtained by fitting measurement data under wet-filled column conditions was established, directly correlating rare earth oxide content and electrical parameters under fully saturated conditions. ; in, γ , δ The model parameters are obtained by performing linear regression on a set of calibration samples with known total rare earth oxide mass fractions.

[0011] Specifically, after establishing a quantitative relationship prediction model, it also includes: S7. Model reliability test: The model reliability test is performed in sequence by testing the model fitting index, cross-validation with leave-one-out method and comparison method. If all the above tests are passed, the model reliability test is passed. Model fit index verification: Calculate the relative root mean square error of the model fit. The relative root mean square error of the amplitude is less than 4.5% and the relative root mean square error of the phase is less than 15%. If the above indexes are not met, the model is refitted. Comparison method: Sample and use a quantitative relationship prediction model to predict the total rare earth oxide mass fraction. Compare the prediction results with the results of standard chemical analysis methods. If the average relative error is less than 15%, the model is considered to have passed the test; otherwise, the model is refitted.

[0012] In addition, the present invention also provides an ion adsorption type rare earth content determination system, including a soil column device, an electrode group and a full waveform impedance analyzer; The soil column device includes a sample chamber, a bottom water inlet, and a top water outlet, with the bottom water inlet and top water outlet respectively located at the top and bottom of the sample chamber. The electrode assembly includes a power supply electrode and a measuring electrode. The power supply electrode is disposed at the top and bottom of the sample chamber, and the measuring electrode is disposed on the side wall of the sample chamber. The full-waveform impedance analyzer is electrically connected to the electrode group and is used to measure the complex resistivity spectrum of the soil column containing the sample within a preset frequency range using the four-electrode method.

[0013] In addition, the present invention also provides a computer device, including a memory and a processor; The memory is used to store computer programs that can run on the processor; The processor is used to execute the computer program to implement the steps of the ion adsorption type rare earth content determination method as described above.

[0014] In addition, the present invention also provides a computer-readable storage medium storing a computer program, which, when executed by a processor, implements the steps of the ion adsorption type rare earth content determination method described above.

[0015] The application of the technical solution of the present invention has at least the following beneficial effects: This invention provides a method for determining the content of rare earth elements through ion adsorption. Considering the influence of the surface electrical properties of ion-adsorbed rare earth mineral samples, it establishes a correlation between the spectral induced polarization response and chemical parameters, and uses this correlation to estimate the content of rare earth oxides in the ion-adsorbed rare earth samples. This method can effectively extract electrical parameters directly related to rare earth content by selecting an appropriate model fitting scheme based on the sample state, depth, and spectral characteristics, and it also distinguishes strata with different physicochemical properties in weathered profiles.

[0016] Compared with traditional chemical methods for content determination, the method of this invention has the advantages of being fast, non-destructive, environmentally friendly, and low-cost. The method of this invention can be used to directly and preliminarily assess the content of rare earth oxides and the spatial distribution of rare earth mineralization in the ground in the field.

[0017] In addition to the objectives, features, and advantages described above, the present invention has other objectives, features, and advantages. The invention will now be described in further detail with reference to the figures. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0019] Figure 1 This is a flowchart of the steps of the ion adsorption type rare earth content determination method in a preferred embodiment of the present invention; Figure 2 This is a schematic diagram of the ion adsorption type rare earth content determination system in a preferred embodiment of the present invention; Wherein, 1-first sidewall insertion hole, 2-second sidewall insertion hole, 3-top power supply electrode, 4-bottom power supply electrode, 5-sample chamber, 6-bottom water inlet, 7-top water outlet. Detailed Implementation

[0020] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0021] Example: like Figure 1 As shown, this embodiment provides a method for determining rare earth content based on spectral induced polarization: An impedance measurement system was deployed in the study area to collect impedance amplitude and phase. Based on the impedance amplitude and phase, the normalized charge rate was obtained. A quantitative relationship prediction model between the normalized charge rate and the total rare earth oxide mass fraction was constructed. The total rare earth oxide mass fraction was calculated based on the quantitative relationship prediction model.

[0022] Furthermore, the process by which the impedance measurement system acquires the impedance amplitude and phase is as follows: Electrodes were laid out at equal intervals along the research area and connected to a multi-channel field impedance measurement system via cables. The impedance amplitude and phase of each unit at a preset frequency were collected using a pseudo-Weiner sequence. After removing outliers, the charge rate and normalized charge rate could be obtained by fitting the data.

[0023] The process of constructing a quantitative relationship prediction model includes (S1 to S7): S1: Select the study area and collect weathering profile samples of ion adsorption type rare earth minerals according to the underground depth.

[0024] In this embodiment, 3-5 typical ion-adsorption type rare earth mineral weathering profiles are selected. When sampling, several blocky humus layer, soil layer, fully weathered layer and semi-weathered layer samples are taken from top to bottom of the weathering profile at the same interval.

[0025] S2: Pre-treatment of the collected samples by air drying, crushing and grinding.

[0026] S3: Prepare the sample to be tested and perform spectral induced polarization measurements, as follows: S3.1 Prepare a soil column device with a bottom inlet and a top outlet, and install power supply electrodes at the bottom and top of the soil column device, and install measuring electrodes at symmetrical positions on the upper and lower sides of the side wall of the soil column device. S3.2. The sample after step S2 is filled into the sample cavity of the soil column device using both dry and wet methods, and an electrolyte solution is introduced through the bottom water inlet to form a soil column containing the sample that can be measured. S3.3 Connect the power supply electrode and the measuring electrode to the impedance analyzer, and use the four-electrode method to measure the complex resistivity spectrum of the soil column containing the sample within a preset frequency range to obtain the impedance amplitude and phase at multiple frequencies.

[0027] It should be noted that the preferred preset frequency range in this embodiment is 0.001-1000Hz. This range is based on the widest frequency setting range that the impedance analyzer can achieve. Secondly, this is an important frequency band where electrochemical polarization signals appear. Higher frequency signals may mask the low-frequency electrochemical polarization signals of interest, while lower frequency film polarization will also cause signal interference.

[0028] In S3.2, the soil column device is filled with samples using both dry and wet methods. The dry filling method involves first filling the sample cavity with the sample processed in step S2, then introducing an electrolyte solution into the soil column device through the bottom inlet and expelling the air from the soil column device through the top outlet until the liquid level reaches the top of the soil column device, ensuring that the electrolyte solution is in full contact with the electrodes. The wet filling method involves pre-mixing the sample processed in step S2 with the electrolyte solution and removing excess air by vacuuming, then filling the sample cavity with the mixture, and using the electrolyte solution to fill the excess space in the soil column, ensuring that the electrolyte solution is in full contact with the electrodes.

[0029] S4: Based on the complex resistivity spectrum obtained in step S3, and combined with the measurement conditions of dry and wet methods, a preset Cole-Cole model is selected to fit the spectral data, and model parameters including at least charge rate and zero-frequency resistivity are obtained through inversion calculation.

[0030] Specifically, in this embodiment, a copper electrode plate is used as power supply electrode A and power supply electrode B, and a non-polarized electrode is used as measurement electrode M and measurement electrode N. The copper electrode plate and the non-polarized electrode are connected to a full-waveform impedance analyzer, where AM=NB=5cm and MN=7cm. A laboratory SIP measurement system is used to measure the complex resistivity spectrum of the sample within the range of 0.001 to 1000Hz, obtaining the impedance amplitude at multiple frequencies. ) and the phase (rad) between the injected signal and the measured signal.

[0031] Furthermore, based on the sample's state, depth location, and spectral characteristics, the data were analyzed and a model fitting scheme was selected. First, the measurement data of dry column packing and wet column packing were compared and analyzed, and the fitting was performed in the following three cases. The first scenario involves the absolute phase values ​​measured by both dry and wet column packing methods. If the absolute phase value changes with increasing frequency at frequencies greater than 100 Hz, it indicates the presence of wideband Maxwell-Wagner polarization interference in the sample. A dual Cole-Cole model is then used to fit the data. The expression for the dual Cole-Cole model is as follows: ; in, For complex resistivity, The imaginary unit, The impedance amplitude, For phase, Angular frequency, To measure frequency, Resistivity at zero frequency , Indicates charge rate, , Represents the Cole-Cole exponent. , The subscripts 1 and 2 indicate the Cole-Cole relaxation time, and are used to distinguish the different polarization mechanisms in the double Cole-Cole model. The second method involves measuring data from samples taken from deeper formations. If the absolute phase value measured using either dry or wet column packing methods reaches its maximum or minimum value within the 100-1000 Hz frequency range, or if the change in absolute phase value decreases with increasing frequency, then the sample is considered to contain characteristic peaks of coupled polarization between the Stern layer and the diffuse layer, appearing within this range. Signals interfered with by high frequencies are discarded, and spectral data close to the characteristic peak frequency is extracted. A single Cole-Cole model is used to fit the data. The expression for the single Cole-Cole model is as follows: ; in, For charge rate, The Cole-Cole exponent. Cole-Cole relaxation time; The third case involves a characteristic peak frequency of less than 100Hz for the absolute value of the phase measured under dry column packing, while a steep rise occurs at high frequencies under wet column packing. The dry column packing data is fitted using a single Cole-Cole model, while the wet column packing data is fitted using a double Cole-Cole model. Substitute the spectral data into the model, and obtain the model parameters by nonlinear least squares inversion fitting method.

[0032] S5: Based on the model parameters obtained from step S4, calculate the normalized charge rate that characterizes the electrochemical polarization intensity of the sample.

[0033] In this embodiment, the calculation process of the normalized charge rate includes: In the double Cole-Cole model, the normalized charge rate is obtained by dividing the charge rate by the zero-frequency resistivity. , The normalized charge rate in the low-frequency Cole-Cole term with a longer relaxation time is used as a parameter to describe the magnitude of the electric double-layer polarization. In the single Cole-Cole model, the normalized charge rate is obtained by dividing the charge rate by the zero-frequency resistivity. ; in, The normalized charge rate is represented by the subscripts 1 and 2, which are used to distinguish the different polarization mechanisms in the double Cole-Cole model.

[0034] S6: Using calibrated samples with known rare earth oxide content, establish a quantitative relationship prediction model between the normalized charge rate and the total rare earth oxide mass fraction.

[0035] In this embodiment, the process of establishing the quantitative relationship prediction model includes: A quantitative relationship prediction model between charge rate and total rare earth oxide mass fraction was established by fitting measurement data obtained under wet and dry column packing methods. The expression is as follows: ; in, REO This represents the mass fraction of total rare earth oxides. The model parameters were obtained by performing linear regression on a set of calibration samples with known total rare earth oxide mass fractions. A quantitative predictive model for the relationship between normalized charge rate and total rare earth oxide mass fraction obtained by fitting measurement data under wet-filled column conditions was established, directly correlating rare earth oxide content and electrical parameters under fully saturated conditions. ; in, γ , δ The model parameters are obtained by performing linear regression on a set of calibration samples with known total rare earth oxide mass fractions.

[0036] S7. Model reliability test: The model reliability test is performed in sequence by testing the model fitting index, cross-validation with leave-one-out method and comparison method. If all the above tests are passed, the model reliability test is passed. Model fit index verification: Calculate the relative root mean square error of the model fit. The relative root mean square error of the amplitude is less than 4.5% and the relative root mean square error of the phase is less than 15%. If the above indexes are not met, the model is refitted. Comparison method: Sample and use a quantitative relationship prediction model to predict the total rare earth oxide mass fraction. Compare the prediction results with the results of standard chemical analysis methods (such as ICP-MS). If the average relative error is less than 15%, the model is considered to have passed the test; otherwise, the model is refitted.

[0037] Furthermore, in the model fitting index test, the index is considered qualified if the relative root mean square error of the amplitude is less than 4.5% and the relative root mean square error of the phase is less than 15%. In some strict scenarios, the index can also be considered excellent if the relative root mean square error of the amplitude is less than 1.5% and the relative root mean square error of the phase is less than 5%.

[0038] This embodiment provides a method for determining the content of rare earth elements through ion adsorption. By considering the influence of the surface electrical properties of ion-adsorbed rare earth mineral samples, a correlation is established between the spectral induced polarization response and chemical parameters. This correlation is then used to estimate the content of rare earth oxides in ion-adsorbed rare earth samples, enabling rapid measurement of rare earth oxide content. This method can effectively extract electrical parameters directly related to rare earth content by selecting an appropriate model fitting scheme based on sample state, depth, and spectral characteristics, and it also distinguishes strata with different physicochemical properties in weathered profiles.

[0039] In addition, such as Figure 2 As shown, this embodiment also provides an ion adsorption type rare earth content determination system, including a soil column device, an electrode group and a full waveform impedance analyzer; The soil column device includes a sample chamber 5, a bottom water inlet 6, and a top water outlet 7, with the bottom water inlet 6 and the top water outlet 7 respectively located at the top and bottom of the sample chamber 5. The electrode assembly includes a power supply electrode and a measuring electrode, wherein the power supply electrode is disposed at the top and bottom of the sample chamber (e.g., ...). Figure 2 The top power supply electrode 3 and the bottom power supply electrode 4 shown are used to measure the electrode, which is disposed on the side wall of the sample chamber. The full-waveform impedance analyzer is electrically connected to the electrode group and is used to measure the complex resistivity spectrum of the soil column containing the sample within a preset frequency range using the four-electrode method.

[0040] Specifically, the soil column device in this embodiment is made of acrylic material, is 17cm high, has an inner diameter of 4cm for the sample chamber, a threaded cap on the top, and insertion holes (such as...) are provided on the side walls of the soil column device. Figure 2 The first sidewall socket 1 and the second sidewall socket 2 shown are used to install measuring electrodes.

[0041] Furthermore, in this embodiment, the power supply electrode is a copper electrode plate, and the measurement electrode is a non-polarized electrode.

[0042] In this embodiment, the full-waveform impedance analyzer obtains the impedance amplitude and the phase (rad) between the injected signal and the measured signal by injecting a sinusoidal current into two power supply electrodes and acquiring the measured potential difference between the two measuring electrodes at multiple frequencies (mHz to kHz). The full-waveform impedance analyzer is also connected to a computer device to transmit the obtained impedance amplitude and phase data to the computer device for analysis and processing.

[0043] In addition, this embodiment also provides a computer device, including a memory and a processor; The memory is used to store computer programs that can run on the processor; The processor is used to execute the computer program to implement the steps of the ion adsorption type rare earth content determination method as described above.

[0044] It should be noted that computer program code for performing the operations of this application can be written in one or more programming languages ​​or a combination thereof. These programming languages ​​include object-oriented programming languages—such as Java, Smalltalk, and C++—as well as conventional procedural programming languages—such as the "C" language or similar programming languages. The program code can be executed entirely on the user's computer, partially on the user's computer, as a standalone software package, partially on the user's computer and partially on a remote computer, or entirely on a remote computer or server. In cases involving remote computers, the remote computer can be connected to the user's computer via any type of network—including a Local Area Network (LAN) or a Wide Area Network (WAN)—or can be connected to an external computer (e.g., via the Internet using an Internet service provider).

[0045] The flowcharts and block diagrams in the accompanying drawings illustrate the architecture, functionality, and operation of possible implementations of systems, methods, and computer program products according to various embodiments of this application. In this regard, each block in a flowchart or block diagram may represent a module, segment, or portion of code containing one or more executable instructions for implementing a specified logical function. It should also be noted that in some alternative implementations, the functions indicated in the blocks may occur in a different order than those indicated in the drawings. For example, two consecutively indicated blocks may actually be executed substantially in parallel, and they may sometimes be executed in reverse order, depending on the functions involved. It should also be noted that each block in the block diagrams and / or flowcharts, and combinations of blocks in the block diagrams and / or flowcharts, can be implemented using a dedicated hardware-based system that performs the specified function or operation, or using a combination of dedicated hardware and computer instructions.

[0046] In addition, this embodiment also provides a computer-readable storage medium storing a computer program, which, when executed by a processor, implements the steps of the ion adsorption type rare earth content determination method described above.

[0047] The readable storage medium provided in this application is a computer-readable storage medium, which stores computer-readable program instructions (i.e., a computer program) for executing the above-described ion adsorption type rare earth content determination method. Compared with the prior art, the beneficial effects of the computer-readable storage medium provided in this application are the same as the beneficial effects of the ion adsorption type rare earth content determination method provided in the above embodiments, and will not be repeated here.

[0048] The above description is only a preferred embodiment of the present invention and does not limit the scope of the present invention. All equivalent structural transformations made under the inventive concept of the present invention using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are included within the protection scope of the present invention.

Claims

1. A method for determining the content of ion adsorption type rare earth elements, characterized in that, An impedance measurement system is arranged in a study area, impedance amplitude and phase are collected, a normalized chargeability and total rare earth oxide mass fraction quantitative relationship prediction model is established based on the normalized chargeability and phase, and the total rare earth oxide mass fraction is calculated based on the quantitative relationship prediction model; The process of establishing the quantitative relationship prediction model includes: S1: selecting a study area and collecting weathering profile samples of ion-adsorption type rare earth ore according to underground depth; S2: pretreating the collected samples by air drying, crushing and grinding; S3: preparing the sample to be measured and performing frequency spectrum induced polarization measurement, the process is as follows: S3.1, preparing a soil column device with a bottom water inlet and a top water outlet, and installing power supply electrodes at the bottom and top of the soil column device, and installing measuring electrodes symmetrically at the upper and lower positions of the side wall of the soil column device; S3.2, respectively filling the samples treated in step S2 into the sample cavity of the soil column device by dry method and wet method, and passing electrolyte solution through the bottom water inlet to form a sample-containing soil column for measurement; S3.3, connecting the power supply electrodes and the measuring electrodes to an impedance analyzer, and measuring the complex resistivity spectrum of the sample-containing soil column in a preset frequency range by a four-electrode method to obtain impedance amplitude and phase at multiple frequencies; S4: based on the complex resistivity spectrum obtained in step S3, combining the measurement conditions of the dry method and the wet method, selecting a preset Cole-Cole model to fit the frequency spectrum data, and obtaining model parameters including at least chargeability and zero-frequency resistivity by inversion calculation; S5: calculating the normalized chargeability representing the electrochemical polarization intensity of the sample according to the model parameters fitted in step S4; S6: using calibration samples with known rare earth oxide content to establish a quantitative relationship prediction model between the normalized chargeability and the total rare earth oxide mass fraction.

2. The method for determining the content of ion-adsorbed rare earths according to claim 1, characterized in that, In S1, 3-5 typical ion-adsorption type rare earth ore weathering profiles are selected, and when sampling, a number of block humus layer, soil layer, fully weathered layer and semi-weathered layer samples are taken in the same interval from top to bottom of the weathering profile.

3. The method for determining the content of ion-adsorbed rare earths according to claim 2, characterized in that, In S4, the process of fitting the frequency spectrum data is as follows: First, compare and analyze the measurement data of the dry column and the wet column, and fit the data in the following three cases; First, the absolute values of the phases measured by the dry column and the wet column both increase with the increase of the frequency when the frequency is greater than 100 Hz, then it is determined that the sample has a wide frequency Maxwell-Wagner polarization interference, and a double Cole-Cole model is used to fit the data, and the expression of the double Cole-Cole model is as follows: ； wherein is the complex resistivity, is the imaginary unit, is the impedance amplitude, is the phase, is the angular frequency, is the measurement frequency, is the resistivity at zero frequency, , denotes the chargeability, , denotes the Cole-Cole exponent, , denotes the Cole-Cole relaxation time, the indices 1 and 2 are used to distinguish between different polarization mechanisms in the double Cole-Cole model; Second, the absolute value of the phase measured in any one of the dry column and wet column filling column appears the maximum value at the frequency of 100-1000 Hz or the phase absolute value changes decrease with the increase of frequency and the measurement data taken from the deeper stratum sample, then it is determined that the sample contains the characteristic peak of Stern layer and diffusion layer coupling polarization appearing at the frequency of 100-1000 Hz, the signal disturbed by high frequency is discarded and the frequency spectrum data is intercepted to the frequency close to the characteristic peak, and the single Cole-Cole model is used to fit the data, and the expression of the single Cole-Cole model is as follows: ； wherein, is the charge rate, is the Cole-Cole exponent, is the Cole-Cole relaxation time; Third, the characteristic peak frequency of the absolute value of the phase measured under the dry column filling column is less than 100 Hz, while the steep rise appears at high frequency under the wet column filling column, the data of the dry column filling column is fitted by using the single Cole-Cole model, and the data of the wet column filling column is fitted by using the double Cole-Cole model; The frequency spectrum data is substituted into the model, and each model parameter is obtained by solving through the nonlinear least square inversion fitting method.

4. The method for determining the content of ion-adsorbed rare earths according to claim 3, characterized in that, In S5, the calculation process of the normalized charge rate includes: The normalized charge rate is obtained by dividing the charge rate by the zero-frequency resistivity in the double Cole-Cole model , , the normalized charge rate in the low-frequency Cole-Cole term with a longer relaxation time is taken as a parameter for describing the polarization size of the electric double layer; The normalized chargeability is obtained by dividing the chargeability by the zero-frequency resistivity in the single Cole-Cole model ; where, denotes the normalized chargeability, the indices 1 and 2 are used to distinguish between different polarization mechanisms in the double Cole-Cole model.

5. The method for determining the content of ion-adsorbed rare earths according to claim 4, characterized in that, In S6, the establishment process of the quantitative relationship prediction model includes: The quantitative relationship prediction model of the charge rate and the total rare earth oxide mass fraction obtained by fitting the measurement data under the wet column filling and the dry column filling is established, and the expression is as follows: ； wherein, REO is the total rare earth oxide mass fraction, is a model parameter, obtained by linear regression on a set of calibration samples of known total rare earth oxide mass fraction; The quantitative relationship prediction model of the normalized charge rate and the total rare earth oxide mass fraction obtained by fitting the measurement data under the wet column filling is established, and the rare earth oxide content and the electrical parameter are directly related under the condition of sufficient saturation: ； wherein, γ , δ are model parameters, obtained by linear regression on a set of calibration samples of known total rare earth oxide mass fraction.

6. The method for determining the content of ion-adsorbed rare earths according to claim 5, characterized in that, After the quantitative relationship prediction model is established, it further includes: S7, model reliability test: sequentially perform model fitting index test, leave-one-out cross-validation and comparative method to test the reliability of the model, and the model reliability test passes if all the tests pass; Model fitting index test: calculate the relative root mean square error of the model fitting, the relative root mean square error of the amplitude is less than 4.5% and the relative root mean square error of the phase is less than 15%, and if the above indexes are not satisfied, the model is re-fitted; Comparative method: take samples and predict the total rare earth oxide mass fraction by using the quantitative relationship prediction model, compare the prediction results with the results of the standard chemical analysis method, and if the average relative error is less than 15%, the model test passes, otherwise the model is re-fitted.

7. An ion adsorption type rare earth content determination system, characterized in that, The system for realizing the ion adsorption type rare earth content determination method according to any one of claims 1-6 comprises a soil column device, an electrode group and a full-wave impedance analyzer; The soil column device comprises a sample cavity, a bottom water inlet and a top water outlet, and the bottom water inlet and the top water outlet are arranged at the top and bottom of the sample cavity, respectively; The electrode group comprises a power supply electrode and a measurement electrode, and the power supply electrode is arranged at the top and bottom of the sample cavity, and the measurement electrode is arranged on the side wall of the sample cavity; The full-wave impedance analyzer is electrically connected to the electrode group, and is used to measure the complex resistivity spectrum of the soil column device in a preset frequency range by using the four-electrode method.

8. A computer device, comprising: It comprises a memory and a processor; The memory is used to store a computer program executable on the processor; The processor implements the steps of the ion adsorption type rare earth content determination method as claimed in any one of claims 1 to 6 when executing the computer program.

9. A computer-readable storage medium, characterized in that, The computer readable storage medium stores a computer program, and the computer program is executed by the processor to implement the steps of the ion adsorption type rare earth content determination method as claimed in any one of claims 1 to 6.

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