A method for rapidly detecting concentration of gallium in gallium-containing liquid in recovery of aluminum gallium oxide

Abstract

This invention discloses a rapid spectroscopic detection method for gallium concentration in gallium-containing liquid during gallium alumina recovery. The method includes: step one, sample processing; step two, establishment of a standard model for different operating conditions; step three, spectral acquisition of the sample to be tested; and step four, spectral correction and result output. This method is applicable to the rapid detection of gallium concentration in the desorption solution and subsequent process solutions in the Bayer process for gallium alumina recovery under different temperatures and acid / alkali conditions. It can achieve both offline batch detection and online real-time detection, used to determine resin desorption rate and precisely control acid / alkali dosage and desorption time. The method employs a preprocessing method for different operating conditions and a differentiated modeling detection scheme to achieve synergistic correction of multiple interfering factors. It effectively solves the problems of poor adaptability, weak anti-interference ability, and insufficient accuracy of traditional detection methods. It eliminates the need for complex digestion preprocessing and can simultaneously meet the needs of offline batch detection in laboratories and online real-time detection in industrial production lines.

Description

Technical Field

[0001] This invention relates to the field of rare metal gallium detection technology based on spectral analysis in the Bayer process of alumina production, and in particular to a rapid spectral detection method for gallium concentration in gallium-containing liquid during gallium recovery from alumina. Background Technology

[0002] Gallium is a strategic rare metal used in high-end fields such as semiconductors and new energy. Industrially, over 90% of gallium is recovered and extracted from the Bayer process of alumina production. In the Bayer process mother liquor, gallium mainly exists in the form of tetrahydroxygallate. Industrially, a resin adsorption-acid-base desorption process is commonly used to enrich and recover gallium. This involves using chelating resin to adsorb gallium from the mother liquor, followed by desorption of the loaded resin by an acidic liquid, thus concentrating and enriching the gallium.

[0003] In the Bayer process for gallium recovery from alumina, the gallium concentration in the gallium desorption solution and subsequent gallium-containing solutions is a core indicator for evaluating resin lifespan, optimizing desorption process parameters, improving overall gallium recovery rate, and controlling production and operating costs. The gallium concentration in the desorption solution and the desorption duration directly determine the gallium desorption efficiency; the gallium concentration in the mother liquor can be used to determine the resin adsorption saturation level, guiding resin switching and regeneration operations; and the gallium concentration in the gallium electrolysis feed solution can determine the electrolysis time, shortening the electrolysis cycle and reducing power consumption.

[0004] Currently, the mainstream industrial methods for gallium concentration detection are inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), spectrophotometry, and chemical titration. These methods have significant technical limitations: ICP-OES offers high accuracy but requires complex pretreatment processes such as acidification and digestion, dilution, and volume adjustment, resulting in expensive equipment, long detection times, and high maintenance costs, making it difficult to meet real-time detection requirements; spectrophotometry has weak resistance to matrix interference, and the high content of aluminum and sodium in the Bayer process mother liquor severely interferes with the gallium colorimetric reaction, with acid-base fluctuations further amplifying detection errors and resulting in poor repeatability; chemical titration is cumbersome to operate, prone to large human errors, and has low detection efficiency, making it suitable for rough detection but unable to meet the needs of precise production control.

[0005] Non-destructive rapid spectroscopic quantitative detection technology has been applied to some extent in the field of rapid detection of material components. However, existing spectroscopic detection schemes have not independently developed detection systems for various working conditions after desorption of Bayer process alumina mother liquor. They do not distinguish between acidic and alkaline matrices of the test solution, and it is difficult to eliminate the interference caused by different acid and alkaline environments, temperature differences, and coexisting metal ions on the characteristic spectral lines of the test target. They have defects such as large errors and poor applicability to working conditions, and cannot be directly applied to the accurate detection of gallium concentration under multiple working conditions in the alumina gallium recovery process.

[0006] To address the industry pain points of existing technologies being unable to adapt to alumina operating conditions, having weak anti-interference capabilities, lagging detection, and low efficiency, there is an urgent need to develop an online spectroscopic detection method for gallium concentration in solutions at each stage of the Bayer process for alumina gallium recovery that is adaptable to various operating conditions, accurate, fast, and low-cost. Summary of the Invention

[0007] The purpose of this invention is to provide a rapid spectral detection method for gallium concentration in gallium-containing liquid during gallium recovery from alumina, in order to solve the problems of existing methods being unsuitable for alumina conditions, having weak anti-interference capabilities, slow detection, and low efficiency.

[0008] The technical solution of this invention: A rapid spectroscopic detection method for gallium concentration in gallium-containing liquid during gallium oxide recovery, comprising the following steps:

[0009] Step 1, Sample processing: Collect two types of samples after desorption of Bayer process resin: acidic and alkaline. Filter the samples to remove impurities, and then perform static defoaming and constant temperature and pressure pretreatment to remove suspended matter, precipitates and bubbles, ensuring that the sample composition is uniform and stable. Detect the concentration of gallium and impurity ions in the collected samples.

[0010] Step 2: Establishing standard models for different operating conditions: First, configure multiple sets of gallium-containing neutral blank samples covering the process concentration range to perform blank calibration and baseline calibration on the spectrometer, which will serve as standard curves; then, configure multiple sets of acidic and alkaline gallium-containing standard samples corresponding to acid and alkaline concentration ranges, and use the spectrometer to collect the gallium element characteristic spectra of the two types of standard samples, and construct linear calibration models of spectral intensity-gallium concentration under acidic and alkaline operating conditions respectively; then, dissolve the sample solution into the impurity ion sample to make the content of other interfering elements the same as the field conditions, and then perform heating and cooling treatments to establish a temperature-impurity ion joint calibration model for the corresponding operating conditions; finally, complete the model fitting and error verification.

[0011] Step 3, Spectral acquisition of the sample to be tested: GaN characteristic spectra of the sample from Step 1 are acquired multiple times, and environmental peaks, instrument noise and matrix peaks are removed.

[0012] Step 4, Spectral Correction and Result Output: Take the average effective intensity of the gallium characteristic spectrum of the sample to be tested from multiple samplings, substitute it into the corresponding working condition calibration model, and perform impurity interference correction to eliminate the spectral superposition interference of coexisting metal elements, and output the final gallium concentration detection result.

[0013] Furthermore, in step one, the acid concentration range for acidic conditions is 0.1–3.0 mol / L; and the alkali concentration range for alkaline conditions is 0.1–15.0 mol / L.

[0014] Furthermore, the sample pretreatment in step one specifically involves filtering the alkaline sample to remove suspended impurities and colloidal precipitates; both alkaline and acidic samples are allowed to stand to completely eliminate air bubbles inside the liquid, and then placed in a constant temperature water bath and kept at a constant pressure under standard atmospheric pressure.

[0015] Furthermore, in step two, the gallium concentration of the standard samples covers the industrial detection range of 100–80,000 mg / L, and the number of acidic and alkaline standard samples is at least 10 sets.

[0016] Furthermore, in step two, acid and alkaline interference coefficients are obtained by calibrating samples under two different working conditions, thereby achieving differentiated correction of acid and alkaline environments. After fitting the calibration models for the two working conditions, the coefficient of determination R² ≥ 0.999.

[0017] Furthermore, the impurity ions in step two are aluminum, sodium, vanadium, and iron.

[0018] Furthermore, in steps two and three, the spectral detection selects characteristic spectral lines of gallium, and shields the overlapping interference of spectral lines of aluminum, sodium, vanadium, and iron, and eliminates the detection deviation caused by temperature based on the temperature change compensation curve.

[0019] Furthermore, in step three, each group of samples is tested repeatedly 3 to 5 times. After removing abnormal data, the average effective spectral intensity is taken and filtered to ensure the stability and effectiveness of the spectral signal.

[0020] Furthermore, in step three, the relative deviation of gallium concentration detection after acid-base and impurity correction is ≤5.0%, and the overall detection time for a single sample is ≤5 min.

[0021] The advantages of this invention compared to existing technologies are as follows: This method is applicable to the rapid detection of gallium concentration in the desorption solution and subsequent process solutions in the Bayer process for gallium alumina recovery under different temperatures and acid / alkali conditions. It can achieve offline batch detection and online real-time detection, and is used to determine the resin desorption rate and accurately control the amount of acid and alkali and the desorption time. A condition-specific pretreatment and differentiated modeling detection scheme is adopted: First, the acidic and alkaline gallium-containing desorption solutions generated from the Bayer process resin desorption are subjected to standardized pretreatment including filtration, defoaming, and constant temperature and pressure stabilization to unify the detection substrate. Then, wide-concentration gradient acid and alkali standard solutions are prepared to construct independent linear calibration models of "spectral intensity-gallium concentration" for acidic and alkaline conditions. Combined with the actual industrial temperature fluctuation range and coexisting impurity system, a temperature-impurity ion joint calibration model is established to achieve synergistic correction of multiple interference factors. Finally, after multiple spectral acquisitions, noise reduction, and impurity removal of the test sample, the data are input into the corresponding model for calculation, outputting accurate gallium concentration results. By employing differentiated modeling under acid-base conditions and joint correction for temperature and matrix impurities, this method effectively addresses the problems of poor adaptability, weak anti-interference ability, and insufficient accuracy of traditional detection methods. It eliminates the need for complex digestion pretreatment and can simultaneously meet the needs of offline batch testing in laboratories and online real-time testing in industrial production lines. It accurately reflects the resin desorption rate and gallium enrichment state, guiding precise control of process parameters such as acid-base dosage and adsorption time on-site, significantly improving the comprehensive gallium resource recovery rate in alumina production. It boasts strong process adaptability, high efficiency and accuracy in detection, and high industrial application value. This method effectively solves the problems of traditional detection methods being unable to adapt to acid-base conditions, complex pretreatment, detection lag, temperature and metal ion interference, and insufficient accuracy, filling the technological gap in the field of precise gallium detection using spectroscopic technology. It achieves rapid, non-destructive, and high-precision detection of gallium concentration, accurately guiding industrial gallium recycling production control and improving gallium resource recovery rates. Attached Figure Description

[0022] Figure 1 This is a flowchart of the sample collection and preprocessing process in this invention;

[0023] Figure 2 This is a flowchart of the overall process for rapid spectral detection of gallium concentration in the Bayer process gallium alumina recovery process of the present invention.

[0024] Figure 3 This is a linear calibration curve of the model intensity after correction of the gallium concentration spectral characteristic lines of this invention. Detailed Implementation

[0025] 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.

[0026] It should be noted that all directional indications (such as up, down, left, right, front, back, etc.) in the embodiments of the present invention are only used to explain the relative positional relationship and movement of each component in a certain specific posture (as shown in the figure). If the specific posture changes, the directional indication will also change accordingly.

[0027] Furthermore, the use of terms such as "first" and "second" in this invention is for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" or "second" may explicitly or implicitly include at least one of that feature. Additionally, the technical solutions of the various embodiments can be combined with each other, but only on the basis of being achievable by those skilled in the art. When the combination of technical solutions is contradictory or impossible to implement, such a combination of technical solutions should be considered non-existent and not within the scope of protection claimed by this invention.

[0028] See Figure 1-3 This invention discloses a rapid spectroscopic detection method for gallium concentration in gallium-containing liquid during gallium alumina recovery. This method is applicable to the rapid detection of gallium concentration in the desorption solution and subsequent process solutions under different temperatures and acid / alkali conditions in the Bayer process for gallium alumina recovery. The method includes the following steps:

[0029] Step 1, Sample Preparation: Two types of samples were collected after desorption from the Bayer process resin: acidic and alkaline samples. The acid concentration range for the acidic sample was 0.1–3.0 mol / L, and the alkaline concentration range for the alkaline sample was 0.1–15.0 mol / L. These two types of samples covered important measurement points in the gallium extraction section of the Bayer process mother liquor. The samples were filtered to remove suspended impurities and colloidal precipitates. Both types of samples were allowed to stand to completely eliminate air bubbles, then placed in a constant-temperature water bath and stabilized at standard atmospheric pressure to ensure uniform and stable sample composition. All collected samples were sent to a testing institution to analyze the concentrations of gallium and impurity ions.

[0030] Step 2: Establishing Standard Models for Different Operating Conditions: First, configure multiple sets of gallium-containing neutral blank samples covering the process concentration range to perform blank and baseline calibration on the spectrometer, which will serve as standard curves. Then, configure multiple sets of acidic and alkaline gallium-containing standard samples corresponding to acid and alkaline concentration ranges. Use a spectrometer to collect the gallium element characteristic spectra of the two types of standard samples, and construct linear calibration models of spectral intensity-gallium concentration under acidic and alkaline conditions, respectively. Prepare a neutral solution, and dissolve the sample solution into impurity ion samples to make the content of other interfering elements the same as the field conditions. The impurity ions are aluminum, sodium, vanadium, and iron impurity ions that match the content in the industrial field, simulating the real production matrix environment. Collect spectral data every 5°C to establish a temperature-impurity ion joint calibration model. Fit and optimize all models and verify errors. At the same time, through blank matrix sample calibration, obtain the acid interference coefficient, alkaline interference coefficient, temperature and impurity ion interference coefficient, respectively, to achieve differentiated correction for various operating conditions. Finally, complete the model fitting and error verification.

[0031] Linear calibration model of "spectral line intensity - gallium concentration" under acidic and alkaline conditions:

[0032] A series of experiments were conducted with a fixed gallium concentration and varying acid and alkaline concentrations. The slopes at different acid and alkaline levels were measured, and α1 and α2, i.e., acid interference coefficients and alkaline interference coefficients, were fitted. During detection, the operating conditions were first determined, and the corresponding set of coefficients was used to reconstruct the true slope at that acid or alkaline level. Then, the slopes were substituted into a linear model to calculate the gallium concentration.

[0033] Temperature-Impurity Ion Joint Calibration Model:

[0034] A set of experiments was conducted with fixed gallium concentration and impurity composition, but varying only the temperature. Spectra were collected every 5°C within the industrial temperature range, with one cycle of heating and one cycle of cooling. The relative intensity at each temperature was measured, and a1 and a2, i.e., temperature compensation coefficients, were fitted. Another set of experiments was conducted with fixed gallium concentration and temperature, but varying only the aluminum, sodium, vanadium, and iron contents. Multiple sets of simulated matrix samples were prepared using uniform or orthogonal designs, and the intensity shifts under different impurity contents were measured. α_Al, α_Na, α_V, and α_Fe, i.e., impurity ion interference coefficients, were fitted. The two sets of coefficients were combined and written into a single joint calibration model, i.e., the temperature-impurity ion joint calibration model.

[0035] During testing, the sample temperature and impurity content are first read in real time. The measured intensity is then normalized to a reference temperature of 25℃ using a temperature compensation coefficient. Next, the matrix absorption correction factor is calculated using an impurity interference coefficient to reconstruct the true intensity under the given temperature and matrix conditions. Finally, the gallium concentration is calculated by substituting the data into a linear model for the corresponding acid / alkali conditions. (See also...) Figure 3 In this study, a standard curve of blank sample gradient standard solution is combined with a temperature-impurity ion joint calibration model to participate in curve fitting. The curve range can fully cover the concentration range of the entire production process in the workshop, taking into account the needs of low-concentration trace detection and high-concentration sample analysis.

[0036] Step 3, Spectral Acquisition of Samples to be Tested: The samples are divided into two types: acidic and alkaline samples after desorption of Bayer resin in Step 1. By taking the pretreated samples, the characteristic spectra of gallium elements are collected multiple times for each group of samples. During the acquisition process, the sample temperature is monitored in real time. Through instrument filtering and interference shielding algorithms, environmental peaks, instrument noise and matrix peak interference are removed, abnormal spectral data are eliminated, and stable and effective original spectral signals are retained.

[0037] Step 4, Spectral Correction and Result Output: The average effective intensity of multiple gallium characteristic spectrum samples of the test sample is taken and substituted into the corresponding operating condition calibration model. Impurity interference correction is performed to eliminate spectral superposition interference from coexisting metal elements, and the final gallium concentration detection result is output. The average light intensity of multiple effective spectral samples of the test sample is calculated. Based on the acid / alkali operating condition type of the test sample, the corresponding operating condition linear calibration model is substituted. Combined with the temperature-impurity ion joint calibration model and acid / alkali interference coefficient, temperature deviation compensation, correction for spectral superposition interference from coexisting metal elements, and correction for acid / alkali matrix differences are completed to reduce various detection interference factors, ultimately outputting an accurate gallium concentration detection result. After correction, the relative deviation of gallium concentration detection using this method is ≤5.0%, and the overall detection time for a single sample is ≤5 minutes.

[0038] Specifically, the sample pretreatment in step one involves filtering the alkaline sample. The alkaline sample will crystallize if there is too much alkali, so filtration is necessary to remove suspended impurities and colloidal precipitates. Both alkaline and acidic samples are allowed to stand to completely eliminate air bubbles inside the liquid, and then placed in a constant temperature water bath and kept at a constant pressure under standard atmospheric pressure.

[0039] Specifically, in step two, the gallium concentration of the standard samples covers the industrial detection range of 100–80,000 mg / L, and the number of acidic and alkaline standard samples is at least 10 sets.

[0040] Specifically, in step two, the acid and alkaline interference coefficients are obtained by calibrating the samples under the two working conditions, respectively, so as to realize the differential correction of the acid and alkaline environment; after fitting the calibration models of the two working conditions, the coefficient of determination R²≥0.999.

[0041] Specifically, in steps two and three, the spectral detection selects the characteristic spectral lines of gallium, and shields the overlapping interference of spectral lines of aluminum, sodium, vanadium, and iron, and eliminates the detection deviation caused by temperature based on the temperature change compensation curve.

[0042] Specifically, in step three, each group of samples is tested 3 to 5 times. After removing abnormal data, the average effective spectral intensity is taken and filtered to ensure the stability and effectiveness of the spectral signal.

[0043] Specifically, in step three, the relative deviation of gallium concentration detection after acid-base and impurity correction is ≤5.0%, and the overall detection time for a single sample is ≤5 minutes.

[0044] In addition to the preferred embodiments described above, the present invention has other embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection claimed by the present invention.

Claims

1. A rapid spectroscopic detection method for gallium concentration in gallium-containing liquid alumina during gallium oxide recovery, characterized in that, Includes the following steps: Step 1, Sample processing: Collect two types of samples after desorption of Bayer process resin: acidic and alkaline. Filter the samples to remove impurities, and then perform static defoaming and constant temperature and pressure pretreatment to remove suspended matter, precipitates and bubbles, ensuring that the sample composition is uniform and stable. Detect the concentration of gallium and impurity ions in the collected samples. Step 2: Establishing standard models for different operating conditions: First, configure multiple sets of gallium-containing neutral blank samples covering the process concentration range to perform blank calibration and baseline calibration on the spectrometer, which will serve as standard curves; then, configure multiple sets of acidic and alkaline gallium-containing standard samples corresponding to acid and alkaline concentration ranges, and use the spectrometer to collect the gallium element characteristic spectra of the two types of standard samples, and construct linear calibration models of spectral intensity-gallium concentration under acidic and alkaline operating conditions respectively; then, dissolve the sample solution into the impurity ion sample to make the content of other interfering elements the same as the field conditions, and then perform heating and cooling treatments to establish a temperature-impurity ion joint calibration model for the corresponding operating conditions; finally, complete the model fitting and error verification. Step 3, Spectral acquisition of the sample to be tested: GaN characteristic spectra of the sample from Step 1 are acquired multiple times, and environmental peaks, instrument noise and matrix peaks are removed. Step 4, Spectral Correction and Result Output: Take the average effective intensity of the gallium characteristic spectrum of the sample to be tested from multiple samplings, substitute it into the corresponding working condition calibration model, and perform impurity interference correction to eliminate the spectral superposition interference of coexisting metal elements, and output the final gallium concentration detection result.

2. The rapid spectroscopic detection method for gallium concentration in gallium-containing liquid alumina recovery according to claim 1, characterized in that, In step one, the acid concentration range for acidic conditions is 0.1–3.0 mol / L; and the alkali concentration range for alkaline conditions is 0.1–15.0 mol / L.

3. The rapid spectroscopic detection method for gallium concentration in gallium-containing liquid alumina recovery according to claim 1, characterized in that, The sample pretreatment in step one specifically involves filtering alkaline samples to remove suspended impurities and colloidal precipitates; both alkaline and acidic samples are allowed to stand to completely eliminate air bubbles inside the liquid, and then placed in a constant temperature water bath and kept at a constant pressure under standard atmospheric pressure.

4. The rapid spectroscopic detection method for gallium concentration in gallium-containing liquid during gallium alumina recovery according to claim 1, characterized in that, In step two, the gallium concentration of the standard samples covers the industrial detection range of 100–80,000 mg / L, and the number of acidic and alkaline standard samples is at least 10 sets.

5. The rapid spectroscopic detection method for gallium concentration in gallium-containing liquid alumina recovery according to claim 1, characterized in that, In step two, the acid interference coefficient and the alkaline interference coefficient are obtained by calibrating the samples under acid and alkaline conditions, respectively, so as to realize the differential correction of acid and alkaline environments; after fitting the calibration models of the two types of conditions, the coefficient of determination R²≥0.

999.

6. The rapid spectroscopic detection method for gallium concentration in gallium-containing liquid alumina recovery according to claim 1, characterized in that, The impurity ions in step two are aluminum, sodium, vanadium, and iron.

7. The rapid spectroscopic detection method for gallium concentration in gallium-containing liquid alumina recovery according to claim 6, characterized in that, In steps two and three, the spectral detection selects characteristic spectral lines of gallium and shields against the overlapping interference of spectral lines of aluminum, sodium, vanadium, and iron. The detection deviation caused by temperature is eliminated based on the temperature change compensation curve.

8. The rapid spectroscopic detection method for gallium concentration in gallium-containing liquid alumina recovery according to claim 1, characterized in that, In step three, each group of samples is tested repeatedly 3 to 5 times. After removing abnormal data, the average effective spectral intensity is taken and filtered to ensure the stability and effectiveness of the spectral signal.

9. The rapid spectroscopic detection method for gallium concentration in gallium-containing liquid alumina recovery according to claim 1, characterized in that, In step four, the relative deviation of gallium concentration detection after acid-base and impurity correction is ≤5.0%, and the overall detection time for a single sample is ≤5 minutes.

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