An on-line device and method for detecting elements in a resin adsorption process

Abstract

The application discloses a kind of on-line detection device and method for resin adsorption process element, device includes shell and from top to bottom sequentially arranged in the inside of shell neutron source system, shielding body module, gamma detector system and for controlling the work and detection result analysis of each component control system;The application generates continuous neutrons or pulsed neutrons by neutron source system, generates prompt gamma rays by the interaction of continuous neutrons and resin atomic nuclei, realizes the quantitative analysis of non-fissionable elements by analyzing the energy and intensity of gamma rays, and then generates prompt fission neutrons by pulsed neutrons to excite fissile nuclides, and the quantitative analysis of fissile nuclides is carried out by analyzing the intensity of prompt fission neutrons generated.The whole detection process is simple and convenient, and the detection will not damage the test sample, and in-situ measurement and on-line analysis can be realized.

Description

Technical Field

[0001] This invention belongs to the field of elemental detection technology, specifically a device and method for online elemental detection in resin adsorption processes. Background Technology

[0002] Hydrometallurgical processes are frequently used in the mining of rare mineral resources such as rare earth and uranium. In the resin adsorption stage of hydrometallurgical processes, timely acquisition of information on the content of each element in the solution and resin is of great significance for the intelligent control of hydrometallurgical processes. Currently, in practical industrial applications, the adsorption of elements in the resin is mainly judged by detecting changes in the element content in the tail liquid, which is difficult to accurately obtain the changes in the element content in the resin. Alternatively, resin sampling can be used to accurately analyze the adsorbed elements, but this has problems such as poor sample representativeness and complex and time-consuming sample preparation processes. Summary of the Invention

[0003] The purpose of this invention is to provide an online detection device and method for elements in resin adsorption processes, so as to solve the problems mentioned in the background art.

[0004] To achieve the above objectives, the present invention provides the following technical solution: an online detection device for elements in resin adsorption processes, comprising a housing and, from top to bottom, a neutron source term system, a shielding module, and a gamma detector system arranged inside the housing. The neutron source term system is used to generate and emit pulsed neutrons, and neutron detection systems for acquiring neutron time spectra under pulsed neutron operating conditions are arranged on both sides of the neutron source term system. The shielding module is used to slow down the absorption of neutrons and reduce the influence of fast neutrons on the gamma detector.

[0005] Preferably, the neutron source term system employs a DT neutron generator, and the neutron detection system includes a He-3 thermal neutron detector and a He-3 hyperthermal neutron detector, with the He-3 thermal neutron detector and the He-3 hyperthermal neutron detector respectively positioned on either side of the target location of the DT neutron generator. The gamma detector system includes a LaBr3 detector and a BGO detector, and the DT neutron generator, He-3 thermal neutron detector, He-3 hyperthermal neutron detector, LaBr3 detector, and BGO detector are all connected to the control system via circuitry.

[0006] Preferably, the housing is made of aluminum alloy.

[0007] Preferably, the shielding module is made of boron-containing polyethylene block.

[0008] A detection method for an online element detection device in resin adsorption process includes the following steps:

[0009] S1: Place the device in the resin, turn on the DT neutron generator through the control system, select the continuous neutron working mode of the DT neutron generator, and turn on the LaBr3 detector and BGO detector to collect and record the gamma energy spectrum respectively.

[0010] S2: Switch the DT neutron generator to pulse mode, set the pulse cycle according to the time it takes for thermal neutrons in the resin sample to completely decay, and select the narrowest pulse width while ensuring the number of pulse neutrons. Then, use the neutron detection system to collect the ultrathermal neutron time spectrum and the thermal neutron time spectrum respectively.

[0011] S3: The gamma spectrum acquired in step S1 is subjected to noise reduction, smoothing, peak stabilization, channel merging, and total count normalization. The processed LaBr3 detector energy spectrum (0-3MeV portion) is fused with the BGO detector energy spectrum (greater than 3MeV portion) to form a dual-detector fused energy spectrum, with the 0-3MeV energy region being the high-resolution LaBr3 detector energy spectrum and the greater than 3MeV energy region being the high-detection-efficiency BGO energy spectrum.

[0012] S4: Calculate the net count of hydrogen peaks in the fused energy spectrum of the dual detectors, use the hydrogen peak count as an internal standard to calculate the neutron self-shielding factor, and process the fused energy spectrum of the dual detectors using the weighted spectral library least squares method based on the neutron self-shielding effect correction model to obtain the elemental content of non-fissile nuclides.

[0013] S5: Under the pulse width determined in step S2, after the DT neutron generator emits neutrons in a uranium-free environment, the time points at which the hyperthermal neutrons and thermal neutrons in the resin sample completely decay are obtained. The hyperthermal neutron count and thermal neutron count in the neutron time spectrum obtained in step S2 are calculated in the time interval between the time points at which the hyperthermal neutrons and thermal neutrons completely decay. The ratio of the hyperthermal neutron count to the thermal neutron count, E / T, is calculated in this time interval, and a calibration curve is plotted. The elemental content of the fissile nuclide in the resin is obtained by comparing the E / T value with that of a known concentration of fissile nuclide solution.

[0014] Preferably, in step S4, the formula for calculating the neutron self-shielding factor is: In the formula, f is the neutron self-shielding factor of the fused energy spectrum of the two detectors to be analyzed, and H LaBr,j and H BGO,j The hydrogen peak counts for the LaBr3 detector and BGO detector energy spectra, respectively, are the fused energy spectra of the dual detectors to be analyzed. Labr,0 and H BGO,0 These are the hydrogen peak counts of the LaBr3 detector and BGO detector energy spectra measured when the resin did not adsorb any elements.

[0015] Preferably, in step S4, the calculation process for the elemental content of non-fissile nuclides is as follows: First, let... Xm =f m ·x m In the formula, a nm For the count of the nth channel of the response spectrum of the mth element, y n f is the count of the nth channel of the fused energy spectrum of the dual detectors to be analyzed; m Let x be the neutron self-shielding factor of the m-th element in the fused energy spectrum of the dual detectors to be analyzed. m Let m be the content of the m-th element in the resin to be tested; then introduce a weighting factor diagonal matrix. In the formula, b i For counting the i-th channel address of the fused energy spectrum of the dual detectors, the matrix expression of the weighted spectral library least squares method based on the neutron self-shield effect correction model is obtained as: WAX = WY; then, A T WAX = A T WY, solving for X, we get: X = (A T WA) -1 A T If WY, then the content of the m-th element in the resin to be tested is x. m =X m / f m .

[0016] Compared with the prior art, the beneficial effects of the present invention are:

[0017] This invention generates continuous or pulsed neutrons using a DT neutron generator. The continuous neutrons interact with the atomic nuclei of resin to produce transient gamma rays. The energy and intensity of the gamma rays are analyzed to achieve quantitative analysis of non-fissile elements. Then, pulsed neutrons excite fissile nuclides to produce transient fissile neutrons. The intensity of the transient fissile neutrons is analyzed to perform quantitative analysis of fissile nuclides. The entire detection process is simple and convenient, and the detection does not damage the sample. It can achieve in-situ measurement and online analysis. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the structure of the online detection device for resin adsorption process elements provided in an embodiment of the present invention;

[0019] Figure 2 This is a schematic diagram of the placement position of the online detection device for resin adsorption process elements provided in this embodiment of the invention.

[0020] Figure 3 This is a flowchart of the detection process of the online detection device for resin adsorption process elements provided in the embodiments of the present invention;

[0021] Figure 4 This is the dual-detector fused energy spectrum obtained by processing the energy spectra measured by the LaBr3 detector and the BGO detector during the resin detection process provided in this embodiment of the invention;

[0022] Figure 5 These are the time spectra of ultrathermal neutrons and thermal neutrons under different uranium concentration environments provided in the embodiments of the present invention;

[0023] Figure 6 This is a line graph showing the elemental composition analysis results of non-fissile nuclides provided in this embodiment of the invention.

[0024] Figure 7 This is a comparison chart of the elemental analysis results of non-fissile nuclides and the detection results of PGNAA provided in the embodiments of the present invention;

[0025] Figure 8 This is a line graph showing the elemental content of fissile nuclides provided in an embodiment of the present invention;

[0026] Figure 9 This is a line graph showing the relationship between known uranium concentration and E / T value provided in an embodiment of the present invention;

[0027] In the diagram, 1-shell, 2-DT neutron generator, 3-thermal neutron detector, 4-ultrathermal neutron detector, 5-shielding module, 6-LaBr3 detector, 7-BGO detector, 8-control system, 9-resin tank, 10-resin. Detailed Implementation

[0028] 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 some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] Please see Figures 1-6This invention provides a technical solution: an online detection device for resin adsorption process elements, comprising a sealed aluminum alloy shell 1, a DT neutron generator 2, a shielding module 5, a LaBr3 detector 6, a BGO detector 7, a thermal neutron detector 3, and a hyperthermal neutron detector 4; wherein, the DT neutron generator 2, the shielding module 5, the LaBr3 detector 6, and the BGO detector 7 are sequentially fixedly connected inside the shell from top to bottom, the thermal neutron detector 3 and the hyperthermal neutron detector 4 are arranged on both sides of the target position of the DT neutron generator 2, and the DT neutron generator 2 is located at the central axis of the device. The system generates continuous or pulsed neutrons. Thermal neutron detector 3 and ultrathermal neutron detector 4 are used to collect the neutron time spectrum under pulsed neutron operating conditions. The shielding module 5 is a boron-containing polyethylene block located between DT neutron generator 2 and LaBr3 detector 6. It is used to slow down and absorb neutrons, reducing the influence of fast neutrons on gamma ray collection by LaBr3 detector 6 and BGO detector 7. DT neutron generator 2, thermal neutron detector 3, ultrathermal neutron detector 4, LaBr3 detector 6, and BGO detector 7 are connected to control system 8. Control system 8 supplies power to each component and controls the feedback operating status.

[0030] This invention is used for online detection of elements in resin adsorption processes, and the specific steps are as follows:

[0031] S1: Press the device as shown Figure 2 (a) or Figure 2 (b) is placed in resin tank 9, wherein, Figure 2 The application method shown in (a) can detect the change in the content of adsorbed elements in the bottom resin 10 of resin tank 9 and can be used to determine the state of adsorbed elements in resin 10. Figure 2 (b) The application method shown can detect the adsorption of elements in resin layers at different heights in resin tank 9 by moving the detection device up and down; then the DT neutron generator 2 is turned on by the control system 8 and the continuous neutron working mode of the DT neutron generator 2 is selected. The resin is excited by neutrons to generate transient gamma rays, and the LaBr3 detector 6 and BGO detector 7 are turned on to collect and record the gamma energy spectrum respectively.

[0032] S2: Switch the working mode of DT neutron generator 2 to pulse working mode. According to the experimental detection of resin sample, the thermal neutron duration is 1250μs. Therefore, the pulse working period of DT neutron generator 2 is set to 1250μs. In this experiment, the pulse width of DT neutron generator 2 is set to 130μs. Then, thermal neutron detector 3 and ultrathermal neutron detector 4 are turned on to collect thermal neutron time spectrum and ultrathermal neutron time spectrum, respectively.

[0033] S3: The gamma spectrum acquired in step S1 is subjected to noise reduction, smoothing, peak stabilization, channel merging, and total count normalization. The processed LaBr3 detector energy spectrum (0-3 MeV portion) is then fused with the BGO detector energy spectrum (greater than 3 MeV portion) to form a dual-detector fused energy spectrum. This spectrum consists of a high-resolution LaBr3 detector energy spectrum in the 0-3 MeV energy range and a high-detection-efficiency BGO energy spectrum in the greater than 3 MeV energy range. The dual-detector fused energy spectrum obtained in this embodiment is as follows: Figure 4 As shown.

[0034] S4: Calculate the net count of hydrogen peaks in the fused energy spectrum of the dual detectors, use the hydrogen peak count as an internal standard to calculate the neutron self-shielding factor, and use the weighted spectral library least squares method based on the neutron self-shielding effect correction model to analyze the fused energy spectrum of the dual detectors and obtain the elemental content of non-fissile nuclides.

[0035] The formula for calculating the neutron self-shielding factor is as follows: In the formula, f is the neutron self-shielding factor of the fused energy spectrum of the two detectors to be analyzed, and H LaBr,j and H BGO,j The hydrogen peak counts for the LaBr3 detector and BGO detector energy spectra, respectively, are the fused energy spectra of the dual detectors to be analyzed. Labr,0 and H BGO,0 These are the hydrogen peak counts of the LaBr3 detector and BGO detector energy spectra measured when the resin did not adsorb any elements.

[0036] The calculation process for the elemental content of non-fissile nuclides is as follows: First, let, X m =f m ·x m In the formula, a nm For the count of the nth channel of the response spectrum of the mth element, y n f is the count of the nth channel of the fused energy spectrum of the dual detectors to be analyzed; m Let x be the neutron self-shielding factor of the m-th element in the fused energy spectrum of the dual detectors to be analyzed. m Let m be the content of the m-th element in the resin to be tested; then introduce a weighting factor diagonal matrix. In the formula, b i For counting the i-th channel address of the fused energy spectrum of the dual detectors, the matrix expression of the weighted spectral library least squares method based on the neutron self-shield effect correction model is obtained as: WAX = WY; then, A T WAX = A T WY, solving for X, we get: X = (A T WA) -1 A T If WY, then the content of the m-th element in the resin to be tested is x. m =Xm / f m The elemental composition of the non-fissile nuclides obtained from the final analysis is as follows: Figure 6 As shown, and in this embodiment, the element parsing results are verified using PGNAA detection, the verification results are as follows. Figure 7 As shown, the results indicate that the elemental content of non-fissile nuclides obtained by this analytical method is consistent with the actual content in the sample.

[0037] S5: As Figure 5 As shown, under different uranium concentrations, both the number of hyperthermal neutrons and thermal neutrons rapidly increases within the 0-130 μs time range. At a uranium concentration of 0, hyperthermal neutrons decay rapidly within approximately 215 μs, while thermal neutrons are further captured and absorbed by the uranium solution as they diffuse, lasting up to 1250 μs. Therefore, hyperthermal neutrons generated after 215 μs are considered to originate from uranium fission reactions. The hyperthermal neutron count at this point is only related to the uranium content in the uranium solution. Therefore, the uranium content in the sample can be estimated using the hyperthermal and thermal neutron counts. Specifically, the hyperthermal and thermal neutron counts within the 215-1250 μs time interval of the neutron time spectrum obtained in step S2 are used to calculate the ratio E / T of the hyperthermal and thermal neutron counts within this time interval, and a calibration curve is plotted. The elemental content of the fissile nuclide in the resin (e.g., [missing information]) is obtained by comparing the E / T value with that of a known concentration of fissile nuclide solution. Figure 8 ), Figure 9 This is a line graph showing the relationship between known uranium concentration and E / T value.

[0038] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An online detection device for elements in resin adsorption processes, characterized in that: The device includes a housing and, from top to bottom, a neutron source term system, a shielding module, and a gamma detector system arranged inside the housing. The neutron source term system is used to generate and emit pulsed neutrons, and neutron detection systems are arranged on both sides of the neutron source term system to collect the neutron time spectrum under pulsed neutron operating conditions. The shielding module is used to slow down and absorb neutrons, reducing the impact of fast neutrons on the gamma detector. The neutron source term system uses a DT neutron generator. The neutron detection system includes a He-3 thermal neutron detector and a He-3 hyperthermal neutron detector, which are respectively arranged on both sides of the target position of the DT neutron generator. The gamma detector system includes a LaBr3 detector and a BGO detector. The DT neutron generator, He-3 thermal neutron detector, He-3 hyperthermal neutron detector, LaBr3 detector, and BGO detector are all connected to the control system via circuitry. The detection method for an online element detection device used in resin adsorption processes includes the following steps: S1: Place the device in the resin, turn on the DT neutron generator through the control system, select the continuous neutron working mode of the DT neutron generator, and turn on the LaBr3 detector and BGO detector to collect and record the gamma energy spectrum respectively. S2: Switch the DT neutron generator to pulse mode, set the pulse cycle according to the time it takes for thermal neutrons in the resin sample to completely decay, and select the narrowest pulse width while ensuring the number of pulse neutrons. Then, use the neutron detection system to collect the ultrathermal neutron time spectrum and the thermal neutron time spectrum respectively. S3: The gamma spectrum acquired in step S1 is subjected to noise reduction, smoothing, peak stabilization, channel merging, and total count normalization. The 0-3MeV portion of the processed LaBr3 detector energy spectrum is fused with the greater than 3MeV portion of the BGO detector energy spectrum to form a dual detector fused energy spectrum with a high-resolution LaBr3 detector energy spectrum in the 0-3MeV energy region and a high-detection-efficiency BGO energy spectrum in the greater than 3MeV energy region. S4: Calculate the net hydrogen peak count in the fused energy spectrum of the dual detectors. Use the hydrogen peak count as an internal standard to calculate the neutron self-shielding factor. Process the fused energy spectrum of the dual detectors using the weighted spectral library least squares method based on the neutron self-shielding effect correction model to obtain the elemental content of non-fissile nuclides in the resin. The formula for calculating the neutron self-shielding factor is as follows: In the formula, f is the neutron self-shielding factor of the fused energy spectrum of the two detectors to be analyzed, and H LaBr,j and H BGO,j The hydrogen peak counts for the LaBr3 detector and BGO detector energy spectra, respectively, are the fused energy spectra of the dual detectors to be analyzed. Labr,0 and H BGO,0 These are the hydrogen peak counts from the energy spectra of the LaBr3 detector and the BGO detector when the resin has not adsorbed any elements, respectively; the calculation process for the elemental content of non-fissile nuclides is as follows: First, let, X m =f m ·x m In the formula, a nm For the count of the nth channel of the response spectrum of the mth element, y n f is the count of the nth channel of the fused energy spectrum of the dual detectors to be analyzed; m Let x be the neutron self-shielding factor of the m-th element in the fused energy spectrum of the dual detectors to be analyzed. m Let m be the content of the m-th element in the resin to be tested; then introduce a weighting factor diagonal matrix. In the formula, b i For counting the i-th channel address of the fused energy spectrum of the dual detectors, the matrix expression of the weighted spectral library least squares method based on the neutron self-shield effect correction model is obtained as: WAX = WY; then, A T WAX = A T WY, solving for X, we get: X = (A T WA) -1 A T If WY, then the content of the m-th element in the resin to be tested is x. m =X m / f m ; S5: Under the pulse width determined in step S2, after the DT neutron generator emits neutrons in a uranium-free environment test, obtain the time points at which the hyperthermal neutrons and thermal neutrons in the resin sample completely decay. Calculate the hyperthermal neutron count and thermal neutron count in the time interval between the time points when the hyperthermal neutrons and thermal neutrons completely decay, as obtained in step S2. Calculate the ratio E / T of the hyperthermal neutron count to the thermal neutron count in this time interval, and plot a calibration curve. Based on the calibration curve and the E / T value of a known concentration of fissile nuclide solution, obtain the elemental content of fissile nuclides in the resin.

2. The online detection device for resin adsorption process elements according to claim 1, characterized in that: The shell is made of aluminum alloy.

3. The online detection device for resin adsorption process elements according to claim 1, characterized in that: The shielding module is made of boron-containing polyethylene.

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