Method for determining and analyzing lithium ore transformation rate and acidification rate

Abstract

The present invention proposes a method for measuring and analyzing the transformation rate and acidification rate of lithium ore. By preparing a lithium standard solution and using an inductively coupled plasma mass spectrometer to detect the total lithium and soluble lithium content of the roasted material produced in the transformation roasting process and the lithium element of the clinker and the soluble lithium content of the filter residue produced in the acidification roasting process, etc., the transformation rate and the acidification rate can be quickly and accurately determined. By regularly detecting the transformation roasting and acidification roasting effects, and based on the comparison results between the measured transformation rate and acidification rate and the threshold value / multiple consecutive measurement values, the lithium extraction effect of the production process is analyzed, and the process affecting the lithium extraction yield in the production is pointed out or the process that may cause the lithium extraction yield to decline is warned. Timely feedback of abnormalities or warnings enables technical personnel to make targeted adjustments and optimizations to the operation of the production process.

Description

Technical Field

[0001] The present invention relates to the field of lithium extraction yield measurement from ores, and in particular to a method for measuring and analyzing the transformation rate and acidification rate of lithium ore. Background Art

[0002] Currently, the performance of lithium ore extraction processes is primarily evaluated based on yield. This is achieved by comparing the lithium content of the raw lithium ore and the resulting lithium salts to determine the efficiency of the process in extracting lithium from the ore.

[0003] Patent CN201810554232.X discloses a hydrofluoric acid-resistant method for rapid analysis of lithium content in spodumene samples. This method involves digesting the spodumene sample by adding a certain ratio of HNO3 and HF to the sample. After diluting the sample to volume with ultrapure water, the lithium content in the sample is determined using an inline liquid cathode glow discharge spectrometer using the standard addition method. Xu Xiuping, Li Bo, and others published a paper titled "Determination of Lithium Oxide in Spodumene by Inductively Coupled Plasma Optical Emission Spectrometry," which describes digesting the spodumene sample with a mixed acid system, then dissolving and diluting the sample with hydrochloric acid and deionized water, and then determining the lithium oxide content in the sample using an inductively coupled plasma spectrometer. Similarly, patent CN202410650883.4 discloses a method for rapidly determining the lithium content in a lithium ore sample. The method first adds a certain amount of ammonium bifluoride and hydrofluoric acid to the lithium ore sample for heating and digestion, then adds aqua regia to dissolve it while hot, cools it to a constant volume and clarifies it, and then uses inductively coupled plasma emission spectroscopy or inductively coupled plasma emission spectroscopy to determine the lithium ion concentration to obtain the lithium content in the lithium ore sample.

[0004] The aforementioned patents and papers disclose methods for detecting lithium oxide content in lithium ore, but fail to provide further methods for determining the yield of lithium extraction processes or procedures, making it impossible to obtain yield data using these methods. Furthermore, the testing process involves digesting the ore using a mixture of multiple acid (salt) solutions, requiring consideration of the specific gravity of each solution. The mixing process also poses the risk of acid splashing. Some methods involve the addition of strong acid at high temperatures, making the testing methods complex, difficult, and dangerous. Furthermore, the storage requirements and procurement costs of the multiple acid solutions are very high.

[0005] Li Zhong, Li Huan and others published a paper entitled "Research on the Yield of Spodumene in the Roasting and Acidification Leaching Process", which explored the effects of parameters such as roasting time, roasting temperature, acidification time, acidification temperature, and material-acid ratio on the yield of spodumene, and gave the optimal value ranges for the above parameters. However, it did not give the measurement methods of the transformation rate and acidification rate, nor did it analyze the changes in the transformation rate and acidification rate indicators during the production process.

[0006] In addition, the operating conditions are evaluated by comparing the lithium content in the lithium ore raw materials and the final lithium salt products. There is a lack of regular monitoring of the lithium extraction yield during the production process, and thus it is impossible to provide timely feedback and effective early warning for working conditions where the yield is lower than the production requirements; and by comparing the lithium content in the spodumene raw materials and the final lithium salt products, it is impossible to provide the direct cause of the low lithium content in the product, and it is impossible to give targeted suggestions for optimizing the production process. Technical personnel can generally only find the problem by checking each process one by one, and the work efficiency is low.

[0007] In summary, the method for detecting lithium elements in lithium ore in the prior art is to use a variety of acid solutions for combined digestion, which has the problems of complex and difficult procedures, high risks, high costs, etc., and there is no complete standardized and normalized determination method for the transformation rate and acidification rate of lithium ore. It is impossible to achieve rapid determination of the transformation rate and acidification rate, and it is impossible to effectively analyze the changes in the transformation rate and acidification rate during the production process to prompt or warn of the process that causes low or reduced lithium extraction yield. Once a problem occurs, the maintenance efficiency is low. Summary of the Invention

[0008] In order to overcome the deficiencies in the prior art regarding the determination and analysis of lithium ore yield, the present invention provides a method for determining the lithium ore conversion rate, comprising the following steps:

[0009] Step A1, preparing a lithium standard solution and drawing a standard curve;

[0010] Step A2, detecting the total lithium content of the roasted material produced in the transition roasting process;

[0011] Step A3, detecting the soluble lithium content of the roasted material produced in the transition roasting process;

[0012] Step A4, measuring the transformation rate.

[0013] Furthermore, the specific process of preparing the lithium standard solution and drawing the standard curve in step A1 is as follows:

[0014] Take a certain amount of lithium carbonate sample and place it in a vacuum drying oven at 105°C for 2 hours;

[0015] After cooling for 30 minutes, weigh 2.4729g of lithium carbonate sample using an analytical balance, place it in a 100ml beaker, add 30ml of water, and then add 10ml of (1+1) sulfuric acid solution dropwise to dissolve the lithium carbonate sample;

[0016] Heat the dissolved sample to boiling in a multi-purpose electric furnace to eliminate CO2. After cooling for 30 minutes, transfer the solution in the beaker to a 1000ml volumetric flask and dilute it to the 1000ml volumetric flask mark with water to obtain a 1000μg / ml lithium standard solution (calculated as Li2O).

[0017] Take 1000μg / ml lithium standard solution and prepare a series of lithium standard solutions with concentrations of 0μg / ml, 1μg / ml, 2μg / ml, 3μg / ml, 4μg / ml, 5μg / ml, and 6μg / ml by stepwise dilution method. Use inductively coupled plasma mass spectrometry to detect the series of lithium standard solutions, and draw a standard curve based on the relationship between the test results and concentrations.

[0018] Furthermore, the specific process of step A2 for detecting the total lithium content of the roasted material produced in the transition roasting process is as follows:

[0019] Step A2.1, prepare the roasted material full lithium solution:

[0020] A certain amount of roasted material produced in the transition roasting process of lithium extraction by sulfuric acid method using spodumene as raw material was taken as a sample, the sample was dried at 105-110°C for 2 hours, and after cooling, it was ground into 200 mesh;

[0021] Weigh 0.1500 g of the ground sample, place it in a polytetrafluoroethylene crucible, moisten it with a small amount of pure water, add 20 ml of hydrofluoric acid (density 1.15 g / ml), and gently shake the crucible to mix.

[0022] Place the crucible in a sand bath at 150-200°C and heat until the sample becomes wet salt.

[0023] After taking out the crucible and cooling it to room temperature, add 2ml (1+1) sulfuric acid, stir lightly with a glass rod, and then add 20ml pure water;

[0024] Place the crucible in a 150°C sand bath and heat until the sample is completely dissolved;

[0025] After the crucible is taken out and cooled to room temperature, the solution in the crucible is transferred to a 250ml volumetric flask, diluted to the 250ml volumetric flask mark with water, shaken, allowed to stand for 15 minutes, and filtered;

[0026] Take 10ml of the filtrate and put it into a 100ml volumetric flask, add 2ml of (1+1) sulfuric acid, dilute with water to the 100ml volumetric flask mark, shake well, and obtain a full lithium solution of the roasted material;

[0027] Step A2.2, measuring the concentration of the roasted material full lithium solution:

[0028] Prepare three full-lithium solutions of the same batch of roasted material samples according to step A2.1. Use inductively coupled plasma mass spectrometry to detect the three full-lithium solutions of the roasted material. According to the standard curve, the lithium concentrations of the solutions are T1Li2Oμg / ml, T2Li2Oμg / ml, and T3Li2Oμg / ml, respectively. Take the average value of the three concentrations, TLi2Oμg / ml, and record it as the full-lithium content of the roasted material. Save the data.

[0029] Furthermore, the specific process of step A3 for detecting the soluble lithium content of the roasted material produced in the transition roasting process is as follows:

[0030] Step A3.1, preparing a soluble lithium solution of the roasted material:

[0031] A certain amount of roasted material produced in the transition roasting process of lithium extraction by sulfuric acid method using spodumene as raw material was taken as a sample, the sample was dried at 105-110°C for 2 hours, and after cooling, it was ground into 200 mesh;

[0032] Weigh 0.1500 g of the ground sample into a ceramic crucible, add 3.5 ml of (4 + 1) sulfuric acid, and gently shake the crucible to mix.

[0033] The crucible was covered with a ceramic cover and placed in a muffle furnace, heated to 260°C and kept at this temperature for 30 minutes;

[0034] After the crucible is taken out and cooled to room temperature, the solution in the crucible is transferred to a 250ml volumetric flask, diluted to the 250ml volumetric flask mark with water, shaken, allowed to stand for 15 minutes, and filtered;

[0035] Take 10 ml of the filtrate and put it into a 100 ml volumetric flask, add 2 ml of (1+1) sulfuric acid, add water to the 100 ml volumetric flask mark, shake well, and obtain a soluble lithium solution of the roasted material;

[0036] Step A3.2, measuring the concentration of the soluble lithium solution of the roasted material:

[0037] Prepare three soluble lithium solutions from the same batch of roasted material samples according to step A3.1. Use inductively coupled plasma mass spectrometry to detect the three soluble lithium solutions. According to the standard curve, the lithium concentrations of the solutions are β1Li2Oμg / ml, β2Li2Oμg / ml, and β3Li2Oμg / ml, respectively. Take the average value of the three concentrations, βLi2Oμg / ml, and record it as the soluble lithium content of the roasted material. Save the data.

[0038] Furthermore, the specific process of determining the transformation rate in step A4 is as follows:

[0039] Substitute the total lithium content TLi2Oμg / ml of the baked material obtained in step A2 and the soluble lithium content βLi2Oμg / ml of the baked material obtained in step A3 into the transformation efficiency. , find the transformation rate and save the data.

[0040] The present invention also provides a method for determining the acidification rate of lithium ore, comprising the following steps:

[0041] Step B1, preparing a lithium standard solution and drawing a standard curve;

[0042] Step B2, detecting the lithium content of the clinker produced in the acidification and roasting process;

[0043] Step B3, detecting the soluble lithium content of the filter residue produced in step B2;

[0044] Step B4, measuring the acidification rate.

[0045] Furthermore, the specific process of preparing the lithium element standard solution and drawing the standard curve in step B1 of the lithium ore acidification rate determination method is the same as step B1 of the aforementioned lithium ore transformation rate determination method.

[0046] Furthermore, the specific process of step B2 for detecting the lithium content of the clinker produced in the acidification and roasting process is as follows:

[0047] Step B2.1, prepare clinker solution:

[0048] Take a certain amount of clinker produced in the acidification and roasting process of lithium extraction using spodumene as raw material as a sample, weigh 0.2000g of the sample and place it in a 250ml beaker, and add 50ml of pure water;

[0049] Place a magnetic stirring bar in a beaker, cover with a glass slide, place the beaker in the middle of the stirrer, and stir for 20 minutes;

[0050] Add 5 ml (1+1) sulfuric acid, stir evenly, transfer to a 250 ml volumetric flask, add water to dilute to the 250 ml volumetric flask scale, shake well, let stand for 15 minutes, and filter to obtain the filtrate and residue;

[0051] Take 10 ml of the filtrate and put it into a 100 ml volumetric flask, add 2 ml of (1+1) sulfuric acid, dilute with water to the 100 ml volumetric flask mark, shake well, and let it stand for 15 minutes to obtain a clinker solution;

[0052] Step B2.2, measuring the concentration of the clinker solution:

[0053] Prepare three clinker solutions from the same batch of clinker samples according to step B2.1. Use inductively coupled plasma mass spectrometry to detect the three clinker solutions. According to the standard curve, the lithium concentrations of the solutions are S1Li2Oμg / ml, S2Li2Oμg / ml, and S3Li2Oμg / ml, respectively. Take the average value of the three concentrations, SLi2Oμg / ml, and record it as the lithium content of the clinker. Save the data.

[0054] Furthermore, the specific process of step B3 detecting the soluble lithium content of the filter residue produced in step B2 is as follows:

[0055] Step B3.1, preparing a residue-soluble lithium solution:

[0056] The filter residue produced in step B2 was dried at 105-110°C for 2 hours, and then ground to 200 mesh after cooling;

[0057] Weigh the ground filter residue and place it in a ceramic crucible. Add 3.5 ml (4 + 1) sulfuric acid and gently shake the crucible to mix.

[0058] The crucible was covered with a ceramic cover and placed in a muffle furnace, heated to 260°C and kept at this temperature for 30 minutes;

[0059] After the crucible is taken out and cooled to room temperature, the solution in the crucible is transferred to a 250ml volumetric flask, diluted to the 250ml volumetric flask mark with water, shaken, allowed to stand for 15 minutes, and filtered;

[0060] Take 10 ml of the filtrate and put it into a 100 ml volumetric flask, add 2 ml of (1+1) sulfuric acid, add water to the 100 ml volumetric flask mark, shake well to obtain a soluble lithium solution of the filter residue;

[0061] Step B3.2, measuring the concentration of the soluble lithium solution in the filter residue:

[0062] Three filter residues were produced in step B2. Soluble lithium solutions of the filter residue were prepared according to step B3.1. The soluble lithium solutions of the filter residue were detected using an inductively coupled plasma mass spectrometer. The lithium concentrations of the solutions were obtained according to the standard curve, namely ST1Li2Oμg / ml, ST2Li2Oμg / ml, and ST3Li2Oμg / ml, respectively. The average value of the three concentrations, STLi2Oμg / ml, was taken as the soluble lithium content of the filter residue, and the data was saved.

[0063] Furthermore, the specific process of determining the acidification rate in step B4 is as follows: the lithium content SLi20 μg / ml of the clinker obtained in step B2 and the soluble lithium content STLi20 μg / ml of the filter residue obtained in step B3 are substituted into the acidification rate , calculate the acidification rate and save the data.

[0064] In addition, the present invention also discloses a method for analyzing the transformation rate and acidification rate of lithium ore. By measuring and analyzing the transformation rate and acidification rate data, the operation status of the transformation roasting process and the acidification roasting process is judged. The method specifically includes the following steps:

[0065] Step S1, setting a transformation rate threshold and an acidification rate threshold that meet the production requirements of lithium extraction from ore by sulfuric acid method;

[0066] Step S2, regularly extracting the roasted material produced in the transformation roasting process as a measurement sample to determine the transformation rate;

[0067] Step S3, regularly extracting clinker produced in the acidification and roasting process as a measurement sample to determine the acidification rate;

[0068] Step S4: Compare the data and analyze whether an abnormality or warning is required:

[0069] Step S4.1: Compare the measured transformation rate and acidification rate data with the transformation rate threshold and acidification rate threshold to determine whether the transformation roasting process and the acidification roasting process are operating abnormally:

[0070] When the measured transformation rate is less than the transformation rate threshold, it indicates that the operation of the transformation roasting process cannot meet the actual production requirements, and the operation parameters and related equipment of the transformation roasting process need to be optimized, indicating that the transformation roasting process is operating abnormally;

[0071] When the measured acidification rate is less than the acidification rate threshold, it indicates that the operation of the acidification and roasting process cannot meet the actual production requirements, and the operating parameters and related equipment of the acidification and roasting process need to be optimized, indicating that the acidification and roasting process is operating abnormally.

[0072] Step S4.2, compare the continuously measured transformation rate and acidification rate data to determine whether to issue an early warning for the operation of the transformation roasting process and the acidification roasting process:

[0073] When the conversion rates α1 and α2 measured twice in a row drop by more than 1.0%, that is, α1-α2>1.0%, or the conversion rates α1, α2, α3, and α4 measured four times in a row all drop in comparison, that is, α1>α2>α3>α4, it indicates that the operation of the conversion roasting process continues to deteriorate and an early warning is issued;

[0074] When the acidification rates η1 and η2 measured twice in a row decrease by more than 1.0%, that is, η1-η2>1.0%, or the acidification rates η1, η2, η3, and η4 measured four times in a row all decrease in comparison, that is, η1>η2>η3>η4, it indicates that the operation of the acidification roasting process continues to deteriorate and an early warning is issued.

[0075] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0076] 1. The present invention proposes a method for determining the transformation rate and acidification rate of lithium ore. This method measures the transformation rate and acidification rate of lithium ore extracted by the sulfuric acid method by preparing a standard lithium solution and using an inductively coupled plasma mass spectrometer to detect the total lithium content and soluble lithium content of the roasted material produced in the transformation roasting process, as well as the lithium content of the clinker produced in the acidification roasting process and the soluble lithium content of the filter residue. The solution preparation and testing process are based on existing comprehensive experimental instrumentation, and the specific operational procedures of the method steps are clearly defined. The operational procedures are simple and standardized, and the results are highly reliable, achieving rapid and accurate determination of the transformation rate and acidification rate.

[0077] 2. The method for determining the transformation rate and acidification rate proposed in the present invention makes full use of the property that natural α-spodumene generally reacts only with hydrofluoric acid. By adding an appropriate amount of hydrofluoric acid, that is, using only hydrofluoric acid as the digestion acid of the roasted material, digestion is achieved. Compared with the prior art method of using a mixed solution composed of multiple acid solutions for digestion, the present invention does not involve the quantitative mixing of multiple acid solutions, is less likely to produce errors and is less likely to cause danger, is easy to achieve standardization, and has high safety.

[0078] 3. The present invention provides a method for analyzing the transformation rate and acidification rate of lithium ore. By adding regular testing of the transformation rate of transformation roasting and the acidification rate of acidification roasting in the process of lithium extraction using spodumene as raw material, the lithium extraction effect of the production process is analyzed based on the comparison results between the measured transformation rate and acidification rate and the threshold value / multiple continuous measurement values, and the process affecting the lithium extraction yield in the production is pointed out or the process that may cause the lithium extraction yield to decline is warned. Timely feedback of abnormalities or warnings allows technical personnel to make targeted adjustments and optimizations to the operation of the production process, solving the problem of lag in the existing method of evaluating the lithium extraction effect of lithium salt production by comparing the lithium content in the ore raw materials and the final lithium salt product. It also provides the specific process that affects the lithium extraction yield, clarifies the direction of adjustment and optimization, and helps to improve maintenance efficiency.

[0079] 4. The present invention also provides specific operations for judging the process affecting the lithium extraction yield and the steps for warning of a downward trend in the lithium extraction yield, as well as reference values for various working conditions, thereby realizing the standardization and standardization of operations for comparing data, analyzing and judging abnormalities or warning processes. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] Figure 1 The present invention is a flow chart of the method for determining the lithium ore transformation rate.

[0081] Figure 2 The present invention is a flow chart of the method for determining the acidification rate of lithium ore.

[0082] Figure 3 The present invention is a flow chart of the method for analyzing the transformation rate and acidification rate of lithium ore. DETAILED DESCRIPTION

[0083] To make the objectives, technical solutions, and advantages of the present invention more apparent, embodiments of the present invention will be further described below with reference to the accompanying drawings. The following describes a preferred embodiment of the present invention among multiple possible embodiments, which is intended to provide a basic understanding of the present invention, but is not intended to identify the key or decisive elements of the present invention or to limit the scope of protection.

[0084] In the description of the present invention, it should be noted that, unless otherwise expressly specified or limited, the terms "mounted" and "connected" should be understood in a broad sense. For example, they can refer to fixed connections, detachable connections, or integral connections; mechanical connections, electrical connections; direct connections, indirect connections through an intermediate medium, and internal connections between two components. Those skilled in the art will understand the specific meanings of the above terms in the present invention based on the specific circumstances.

[0085] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, but the embodiments of the present invention are not limited thereto.

[0086] Example 1:

[0087] This embodiment provides a method for measuring the conversion rate of lithium ore. Figure 1 As shown, the following steps are included:

[0088] Step A1: prepare lithium standard solution and draw standard curve;

[0089] Step A2: Detecting the total lithium content of the roasted material produced in the transition roasting process;

[0090] Step A3: detecting the soluble lithium content of the roasted material produced in the transition roasting process;

[0091] Step A4: Determine the transformation rate.

[0092] Example 2:

[0093] This example, based on Example 1, describes the specific operations of preparing a lithium standard solution and drawing a standard curve in step A1. The specific process is as follows:

[0094] Take 20g of lithium carbonate sample and place it in a vacuum drying oven at 105℃ for 2 hours;

[0095] After cooling for 30 minutes, weigh 2.4729g of lithium carbonate sample using an analytical balance, place it in a 100ml beaker, and add 30ml

[0096] water, then add 10ml (1+1) sulfuric acid solution to dissolve the lithium carbonate sample;

[0097] Heat the dissolved sample to boiling in a multi-purpose electric furnace to eliminate CO2. After cooling for 30 minutes, transfer the solution in the beaker to a 1000ml volumetric flask and dilute it to the 1000ml volumetric flask mark with water to obtain a 1000μg / ml lithium standard solution (calculated as Li2O).

[0098] Take 1000μg / ml lithium standard solution and prepare a series of lithium standard solutions with concentrations of 0μg / ml, 1μg / ml, 2μg / ml, 3μg / ml, 4μg / ml, 5μg / ml, and 6μg / ml by stepwise dilution method. Use inductively coupled plasma mass spectrometry to detect the series of lithium standard solutions, and draw a standard curve based on the relationship between the test results and concentrations.

[0099] The rest of this embodiment is the same as that of embodiment 1, so it will not be described again.

[0100] Example 3:

[0101] Based on Example 1, this example describes the specific operation of detecting the total lithium content of the roasted material produced in the transition roasting process in step A2. The specific process is:

[0102] Step A2.1, prepare the roasted material full lithium solution:

[0103] Take 10g of the roasted material produced by the transition roasting step in the production process of lithium extraction using spodumene as raw material as a sample, dry the sample at 105°C-110°C for 2 hours, and grind it to 200 mesh after cooling;

[0104] Weigh 0.1500 g of the ground sample, place it in a polytetrafluoroethylene crucible, moisten it with a small amount of pure water, add 20 ml of hydrofluoric acid (density 1.15 g / ml), and gently shake the crucible to mix.

[0105] Place the crucible in a sand bath at 150-200°C and heat until the sample becomes wet salt.

[0106] After taking out the crucible and cooling it to room temperature, add 2ml (1+1) sulfuric acid, stir lightly with a glass rod, and then add 20ml pure water;

[0107] Place the crucible in a 150°C sand bath and heat until the sample is completely dissolved;

[0108] After the crucible is taken out and cooled to room temperature, the solution in the crucible is transferred to a 250ml volumetric flask, diluted to the 250ml volumetric flask mark with water, shaken, allowed to stand for 15 minutes, and filtered;

[0109] Take 10ml of the filtrate and put it into a 100ml volumetric flask, add 2ml of (1+1) sulfuric acid, dilute with water to the 100ml volumetric flask mark, shake well, and obtain a full lithium solution of the roasted material;

[0110] Step A2.2, measuring the concentration of the roasted material full lithium solution:

[0111] Three full-lithium solutions of the same batch of roasted material samples were prepared according to step A2.1. The three full-lithium solutions were detected using an inductively coupled plasma mass spectrometer. According to the standard curve, the lithium concentrations of the solutions were 3.602 μg / ml, 3.605 μg / ml, and 3.599 μg / ml, respectively. The average of the three concentrations, 3.602 μg / ml, was taken as the full-lithium content of the roasted material, and the data was saved.

[0112] The rest of this embodiment is the same as that of embodiment 1, so it will not be described again.

[0113] Example 4:

[0114] This example, based on Example 1, describes the specific operation of step A3 for detecting the soluble lithium content of the roasted material produced in the transition roasting process. The specific process is:

[0115] Step A3.1, preparing a soluble lithium solution of the roasted material:

[0116] Take 10g of the roasted material produced by the transition roasting step in the production process of lithium extraction using spodumene as raw material as a sample, dry the sample at 105℃-110℃ for 2 hours, and grind it to 200 mesh after cooling;

[0117] Weigh 0.1500 g of the ground sample into a ceramic crucible, add 3.5 ml of (4 + 1) sulfuric acid, and gently shake the crucible to mix.

[0118] The crucible was covered with a ceramic cover and placed in a muffle furnace, heated to 260°C and kept at this temperature for 30 minutes;

[0119] After the crucible is taken out and cooled to room temperature, the solution in the crucible is transferred to a 250ml volumetric flask, diluted to the 250ml volumetric flask mark with water, shaken, allowed to stand for 15 minutes, and filtered;

[0120] Take 10 ml of the filtrate and put it into a 100 ml volumetric flask, add 2 ml of (1+1) sulfuric acid, add water to the 100 ml volumetric flask mark, shake well, and obtain a soluble lithium solution of the roasted material;

[0121] Step A3.2, measuring the concentration of the soluble lithium solution of the roasted material:

[0122] From the same batch of roasted material samples, three roasted material soluble lithium solutions were prepared according to step A3.1. The three roasted material soluble lithium solutions were detected using an inductively coupled plasma mass spectrometer. According to the standard curve, the lithium concentrations of the solutions were 3.5047 μg / ml, 3.5149 μg / ml, and 3.5155 μg / ml, respectively. The average of the three concentrations, 3.5117 μg / ml, was taken as the roasted material soluble lithium content, and the data was saved.

[0123] The rest of this embodiment is the same as that of embodiment 1, so it will not be described again.

[0124] Example 5:

[0125] This example describes the specific operation of determining the transformation rate in step A4 based on Examples 3 and 4. The specific process is as follows:

[0126] Substitute the total lithium content of the baked material obtained in Example 3 (3.602 μg / ml) and the soluble lithium content of the baked material obtained in Example 4 (3.5117 μg / ml) into the transformation efficiency. , the transformation rate α=97.49% is obtained, and the data is saved.

[0127] The rest of this embodiment is the same as that of embodiment 1, so it will not be described again.

[0128] Example 6:

[0129] This embodiment provides a method for measuring the acidification rate of lithium ore, such as Figure 2 As shown, the following steps are included:

[0130] Step B1: prepare a lithium standard solution and draw a standard curve;

[0131] Step B2: Detecting the lithium content of the clinker produced in the acidification and roasting process;

[0132] Step B3: detecting the soluble lithium content of the filter residue produced in step B2;

[0133] Step B4: Determine the acidification rate.

[0134] Example 7:

[0135] This embodiment, based on the embodiment 6, describes the specific operation of detecting the lithium content of the clinker produced in the acidification roasting process in step B2. The specific process is:

[0136] Step B2.1, prepare clinker sample solution:

[0137] Take 10g of clinker produced by the acidification and roasting process in the production process of lithium extraction using spodumene as raw material as a sample, weigh 0.2000g of the sample and place it in a 250ml beaker, and add 50ml of pure water;

[0138] Place a magnetic stirring bar in a beaker, cover with a glass slide, place the beaker in the middle of the stirrer, and stir for 20 minutes;

[0139] Add 5 ml (1+1) sulfuric acid, stir evenly, transfer to a 250 ml volumetric flask, add water to dilute to the 250 ml volumetric flask scale, shake well, let stand for 15 minutes, and filter to obtain the filtrate and residue;

[0140] Take 10 ml of the filtrate and put it into a 100 ml volumetric flask, add 2 ml of (1+1) sulfuric acid, dilute with water to the 100 ml volumetric flask mark, shake well, and let it stand for 15 minutes to obtain a clinker solution;

[0141] Step B2.2, measuring the concentration of the clinker solution:

[0142] Three clinker solutions were prepared from the same batch of clinker samples according to step B2.1. The three clinker solutions were tested using an inductively coupled plasma mass spectrometer. The lithium concentrations of the solutions were 3.4276 μg / ml, 3.4346 μg / ml, and 3.4270 μg / ml according to the standard curve. The average value of the three concentrations, 3.4297 μg / ml, was taken as the lithium content of the clinker and the data was saved.

[0143] The rest of this embodiment is the same as that of embodiment 6, so it will not be described again.

[0144] Example 8:

[0145] Based on Example 6, this example describes the specific operation of detecting the soluble lithium content of the filter residue produced in Step B2 in Step B3. The specific process is as follows:

[0146] Step B3.1, preparing a residue-soluble lithium solution:

[0147] The filter residue produced in step B2 was dried at 105-110°C for 2 hours, and then ground to 200 mesh after cooling;

[0148] Weigh the ground filter residue and place it in a ceramic crucible. Add 3.5 ml (4 + 1) sulfuric acid and gently shake the crucible to mix.

[0149] The crucible was covered with a ceramic cover and placed in a muffle furnace, heated to 260°C and kept at this temperature for 30 minutes;

[0150] After the crucible is taken out and cooled to room temperature, the solution in the crucible is transferred to a 250ml volumetric flask, diluted to the 250ml volumetric flask mark with water, shaken, allowed to stand for 15 minutes, and filtered;

[0151] Take 10 ml of the filtrate and put it into a 100 ml volumetric flask, add 2 ml of (1+1) sulfuric acid, add water to the 100 ml volumetric flask mark, shake well to obtain a soluble lithium solution of the filter residue;

[0152] Step B3.2, measuring the concentration of the soluble lithium solution in the filter residue:

[0153] Three filter residues were produced in step B2. Soluble lithium solutions of the filter residue were prepared according to step B3.1. The soluble lithium solutions of the filter residue were detected using an inductively coupled plasma mass spectrometer. The lithium concentrations of the solutions were 0.1014 μg / ml, 0.0998 μg / ml, and 0.1025 μg / ml according to the standard curve. The average value of the three concentrations, 0.1012 μg / ml, was taken as the soluble lithium content of the filter residue, and the data was saved.

[0154] The rest of this embodiment is the same as that of embodiment 6, so it will not be described again.

[0155] Example 9:

[0156] This example describes the specific operation of determining the acidification rate in step B4 based on Examples 7 and 8. The specific process is as follows:

[0157] Substitute the lithium content of the clinker obtained in Example 7 (3.4297 μg / ml) and the soluble lithium content of the filter residue obtained in Example 8 (0.1012 μg / ml) into the acidification rate. , the acidification rate η=97.13% is obtained, and the data is saved.

[0158] The rest of this embodiment is the same as that of Embodiment 7 and Embodiment 8, and therefore will not be described in detail.

[0159] Example 10:

[0160] This embodiment provides a method for analyzing the transformation rate and acidification rate of lithium ore. By measuring the transformation rate and acidification rate data, the operation status of the transformation roasting process and the acidification roasting process is analyzed and judged. Figure 3 As shown, the following steps are included:

[0161] Step S1: setting a transformation rate threshold and an acidification rate threshold that meet the production requirements of lithium extraction from ore by sulfuric acid method;

[0162] Step S2: Periodically extracting the roasted material produced in the transformation roasting process as a measurement sample to determine the transformation rate;

[0163] Step S3: periodically extracting clinker produced in the acidification and roasting process as a measurement sample to determine the acidification rate;

[0164] Step S4: Compare the data and analyze to determine whether an abnormality or warning is required.

[0165] In this embodiment, the transformation rate threshold α is set TH =96.5%, set the acidification rate threshold η TH =96.5%; at the same time, measurement samples are taken every 6 calendar days to determine the transformation rate and acidification rate:

[0166] Table 1 Transformation rate and acidification rate measured four times

[0167]

[0168] As shown in Table 1, on July 6, July 12, July 18, and July 24, the measured transformation rates were 97.45%, 97.25%, 97.13%, and 97.15%, respectively; and the measured acidification rates were 97.13%, 97.08%, 97.11%, and 97.10%.

[0169] Step S4 specifically includes step S4.1 and step S4.2;

[0170] Step S4.1, respectively comparing the measured transformation rate and acidification rate with the transformation rate threshold and acidification rate threshold to determine whether the transformation roasting process and the acidification roasting process are operating abnormally:

[0171] On July 6, July 12, July 18, and July 24, the measured transformation rate and acidification rate were all greater than the set transformation rate threshold α TH , acidification rate threshold η TH , indicating that the operation of the transformation roasting process and the acidification roasting process during this period can meet the actual production requirements and there is no abnormality;

[0172] Step S4.2, compare the continuously measured transformation rate and acidification rate data to determine whether to issue an early warning for the operation of the transformation roasting process and the acidification roasting process:

[0173] There was no decrease of more than 1.0% in any two consecutive measurement results on July 6, July 12, July 18 and July 24, and the results of the four consecutive measurements did not show a continuous decrease, indicating that there was no continuous deterioration trend in the operation of the transformation roasting process and the acidification roasting process during this period, and no warning was needed.

[0174] In this embodiment, the transformation rate is determined in step S2 by preferably using one of the methods for determining the transformation rate of lithium ore in embodiments 1-5; and the acidification rate is determined in step S3 by preferably using one of the methods for determining the acidification rate of lithium ore in embodiments 6-9.

[0175] In the absence of conflict, the above embodiments and features in the embodiments may be combined with each other.

[0176] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for determining the acidification rate of lithium ore, characterized in that: The following steps are involved: Step B1, preparing a lithium standard solution and drawing a standard curve; Step B2, detecting the lithium content of the clinker produced in the acidification and roasting process, specifically comprising steps B2.1 and B2.2; Step B2.1, prepare clinker solution: Take 10g of clinker produced by the acidification and roasting process in the production process of lithium extraction using spodumene as raw material as the clinker sample, weigh 0.2000g of the clinker sample and place it in a 250ml beaker, and add 50ml of pure water; Place a magnetic stirring bar in a beaker, cover with a glass slide, place the beaker in the middle of the stirrer, and stir for 20 minutes; Add 5 ml (1+1) sulfuric acid, stir evenly, transfer to a 250 ml volumetric flask, add water to dilute to the 250 ml volumetric flask scale, shake well, let stand for 15 minutes, and filter to obtain the filtrate and residue; Take 10 ml of the filtrate and put it into a 100 ml volumetric flask, add 2 ml of (1+1) sulfuric acid, dilute with water to the 100 ml volumetric flask mark, shake well, and let it stand for 15 minutes to obtain a clinker solution; Step B2.2, measuring the concentration of the clinker solution: Prepare three clinker solutions from the same batch of clinker samples according to step B2.

1. Analyze the three clinker solutions using an inductively coupled plasma mass spectrometer. According to the standard curve, the lithium concentrations of the solutions are S1Li2Oμg / ml, S2Li2Oμg / ml, and S3Li2Oμg / ml, respectively. Take the average of the three concentrations, SLi2Oμg / ml, and record it as the clinker lithium content. Save the data. Step B3, detecting the soluble lithium content of the filter residue produced in step B2: Step B3.1, preparing a residue-soluble lithium solution: The filter residue produced in step B2 was dried at 105-110°C for 2 hours, and then ground to 200 mesh after cooling; Weigh the ground filter residue and place it in a ceramic crucible. Add 3.5 ml (4 + 1) sulfuric acid and gently shake the crucible to mix. The crucible was covered with a ceramic cover and placed in a muffle furnace, heated to 260°C and kept at this temperature for 30 minutes; After the crucible is taken out and cooled to room temperature, the solution in the crucible is transferred to a 250ml volumetric flask, diluted to the 250ml volumetric flask mark with water, shaken, allowed to stand for 15 minutes, and filtered; Take 10 ml of the filtrate and put it into a 100 ml volumetric flask, add 2 ml of (1+1) sulfuric acid, add water to the 100 ml volumetric flask mark, shake well to obtain a soluble lithium solution of the filter residue; Step B3.2, measuring the concentration of the soluble lithium solution in the filter residue: Three filter residues are produced in step B2. Soluble lithium solutions of the filter residues are prepared in accordance with step B3.

1. The soluble lithium solutions of the filter residues are detected using an inductively coupled plasma mass spectrometer. The lithium concentrations of the solutions (ST1Li2Oμg / ml, ST2Li2Oμg / ml, and ST3Li2Oμg / ml) are determined according to a standard curve. The average of the three concentrations (STLi2Oμg / ml) is taken as the soluble lithium content of the clinker, and the data is saved. Step B4, measuring the acidification rate.

2. The method for determining the acidification rate of lithium ore according to claim 1, wherein: The specific process of determining the acidification rate in step B4 is as follows: the lithium content of the clinker obtained in step B2 (SLi20 μg / ml) and the soluble lithium content of the clinker obtained in step B3 (STLi20 μg / ml) are substituted into the acidification rate. , calculate the acidification rate η and save the data.

3. A method for analyzing the conversion rate and acidification rate of lithium ore, characterized by: By measuring and analyzing the transformation rate and acidification rate data, the operation status of the transformation roasting process and the acidification roasting process is judged, including the following steps: Step S1, setting a transformation rate threshold and an acidification rate threshold that meet the production requirements of lithium extraction from ore by sulfuric acid method; Step S2, regularly extracting roasted materials produced in the transformation roasting process as roasted material samples, and measuring the transformation rate; Step S3, regularly extracting clinker produced in the acidification and roasting process as clinker samples, and measuring the acidification rate; Step S4: Compare the data and analyze to determine whether an abnormality and / or warning is required; In step S2, the method for determining the transformation rate comprises the following steps: Step A1, preparing a lithium standard solution and drawing a standard curve; Step A2, detecting the total lithium content of the roasted material produced in the transition roasting process, specifically including steps A2.1 and A2.2; Step A2.1, prepare the roasted material full lithium solution: Take 10g of the roasted material produced by the transition roasting step in the production process of lithium extraction by sulfuric acid method using spodumene as raw material as the roasted material sample, dry the roasted material sample at 105℃-110℃ for 2 hours, and grind it into 200 mesh after cooling; Weigh 0.1500 g of the ground roasted sample, place it in a polytetrafluoroethylene crucible, moisten it with pure water, add 20 ml of hydrofluoric acid, and gently shake the crucible to mix; Place the crucible in a sand bath at 150-200°C and heat until the roasted sample becomes wet salt. After taking out the crucible and cooling it to room temperature, add 2ml (1+1) sulfuric acid, stir lightly with a glass rod, and then add 20ml pure water; Place the crucible in a 150°C sand bath and heat until the roasted sample is completely dissolved; After the crucible is taken out and cooled to room temperature, the solution in the crucible is transferred to a 250ml volumetric flask, diluted to the 250ml volumetric flask mark with water, shaken, allowed to stand for 15 minutes, and filtered; Take 10ml of the filtrate and put it into a 100ml volumetric flask, add 2ml of (1+1) sulfuric acid, dilute with water to the 100ml volumetric flask mark, shake well, and obtain a full lithium solution of the roasted material; Step A2.2: Measure the concentration of the baked material full lithium solution: Prepare three full-lithium solutions of the same batch of roasted material samples according to step A2.

1. Analyze the three full-lithium solutions using an inductively coupled plasma mass spectrometer. According to the standard curve, the lithium concentrations of the solutions are T1Li2Oμg / ml, T2Li2Oμg / ml, and T3Li2Oμg / ml, respectively. Take the average value of the three concentrations, TLi2Oμg / ml, and record it as the full-lithium content of the roasted material. Save the data. Step A3, detecting the soluble lithium content of the roasted material produced in the transition roasting process; Step A4, determining the transformation rate; In step S3, the acidification rate is measured using the method for measuring the acidification rate of lithium ore according to claim 1 or 2.

4. The method for analyzing lithium ore transformation rate and acidification rate according to claim 3, characterized in that: The step S4 specifically refers to comparing the measured transformation rate with the transformation rate threshold, comparing the measured acidification rate with the acidification rate threshold, and analyzing and judging whether the transformation roasting process and the acidification roasting process are operating abnormally: When the measured transformation rate is less than the transformation rate threshold, it indicates that the transformation roasting process is operating abnormally; When the measured acidification rate is less than the acidification rate threshold, it indicates that the acidification roasting process is operating abnormally.

5. The method for analyzing lithium ore transformation rate and acidification rate according to claim 3, characterized in that: The step S4 specifically refers to comparing the continuously measured transformation rate and the continuously measured acidification rate data to determine whether to issue an early warning for the operation of the transformation roasting process and the acidification roasting process: When the transformation rate measured twice in a row drops by more than 1.0%, or the transformation rate measured four times in a row drops, an early warning is issued; When the acidification rate measured twice in a row drops by more than 1.0%, or the acidification rate measured four times in a row drops, an early warning will be issued.

6. The method for analyzing lithium ore transformation rate and acidification rate according to claim 3, characterized in that: The frequency of regularly extracting measurement samples in steps S2 and S3 is once every six calendar days.

7. The method for analyzing lithium ore transformation rate and acidification rate according to claim 3, characterized in that: The specific process of preparing the lithium standard solution and drawing the standard curve in step A1 is as follows: Take 20g lithium carbonate sample and place it in a vacuum drying oven at 105℃ for 2 hours; After cooling for 30 minutes, weigh 2.4729g of lithium carbonate sample using an analytical balance, place it in a 100ml beaker, add 30ml of water, and then add 10ml of (1+1) sulfuric acid solution dropwise to dissolve the lithium carbonate sample; Heat the dissolved lithium carbonate sample to boiling in a multi-purpose electric furnace to eliminate CO2. After cooling for 30 minutes, transfer the solution in the beaker to a 1000ml volumetric flask and dilute it to the 1000ml mark with water to obtain a 1000μg / ml lithium standard solution. The lithium standard solution is calculated as Li2O. Take 1000μg / ml lithium standard solution and prepare a series of lithium standard solutions by serial dilution method: the concentrations are 0μg / ml, 1μg / ml, 2μg / ml, 3μg / ml, 4μg / ml, 5μg / ml and 6μg / ml. Use inductively coupled plasma mass spectrometry to detect the series of lithium standard solutions, and draw a standard curve based on the relationship between the test results and the concentrations.

8. The method for analyzing lithium ore transformation rate and acidification rate according to claim 3, characterized in that: The specific process of step A3 for detecting the soluble lithium content of the roasted material produced in the transition roasting process includes steps A3.1 and A3.2: Step A3.1, preparing a soluble lithium solution of the roasted material: Take 10g of the roasted material produced by the transition roasting step in the production process of lithium extraction by sulfuric acid method using spodumene as raw material as the roasted material sample, dry the roasted material sample at 105℃-110℃ for 2 hours, and grind it into 200 mesh after cooling; Weigh 0.1500 g of the ground roasted sample into a ceramic crucible, add 3.5 ml of (4 + 1) sulfuric acid, and gently shake the crucible to mix. The crucible was covered with a ceramic cover and placed in a muffle furnace, heated to 260°C and kept at this temperature for 30 minutes; After the crucible is taken out and cooled to room temperature, the solution in the crucible is transferred to a 250ml volumetric flask, diluted to the 250ml volumetric flask mark with water, shaken, allowed to stand for 15 minutes, and filtered; Take 10 ml of the filtrate and put it into a 100 ml volumetric flask, add 2 ml of (1+1) sulfuric acid, add water to the 100 ml volumetric flask mark, shake well, and obtain a soluble lithium solution of the roasted material; Step A3.2, measuring the concentration of the soluble lithium solution of the roasted material: Prepare three soluble lithium solutions from the same batch of roasted material samples according to step A3.

1. Use inductively coupled plasma mass spectrometry to detect the three soluble lithium solutions. According to the standard curve, the lithium concentrations of the solutions are β1Li2Oμg / ml, β2Li2Oμg / ml, and β3Li2Oμg / ml, respectively. Take the average value of the three concentrations, βLi2Oμg / ml, and record it as the soluble lithium content of the roasted material. Save the data.

9. The method for analyzing lithium ore transformation rate and acidification rate according to claim 8, characterized in that: The specific process of determining the transformation rate in step A4 is as follows: the total lithium content TLi20 μg / ml of the roasted material obtained in step A2 and the soluble lithium content βLi20 μg / ml of the roasted material obtained in step A3 are substituted into the transformation rate , find the transformation rate α and save the data.

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