CN112129744B - Chemical phase analysis method for lithium in ore - Google Patents
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Abstract
The invention discloses a chemical phase analysis method for lithium in ore, which comprises the following steps: step one, leaching lithium in the lepidolite in an ore sample by using hydrochloric acid as a leaching agent, and measuring the lithium content of the lepidolite by using an inductively coupled plasma emission spectrometry; step two, leaching the filter residue obtained in the step one by using 10% HCl-5% HF as a leaching agent, and measuring the lithium content of the filter residue by using an inductively coupled plasma emission spectrometry; and step three, calcining the filter residue obtained in the step two, adding concentrated hydrochloric acid, concentrated nitric acid, concentrated hydrofluoric acid and perchloric acid, and measuring the content of lithium in the liquid in the volumetric flask by using an inductively coupled plasma emission spectrometry. The chemical phase analysis method can accurately analyze the lithium content of various phases in the ore sample, and has low equipment cost.
Description
Technical Field
The invention relates to the technical field of chemical phase analysis of ores, in particular to a chemical phase analysis method of lithium in ores.
Background
Lithium is the most potential energy metal in the 21 st century, the rapid growth of new energy automobiles drives the comprehensive outbreak of the lithium battery industry chain, the quantity and price of the lithium ore at the upstream of the lithium automobile are more rise, the development and utilization of the lithium ore resources are trending, and the lithium ion battery is widely applied to the important fields of energy, aerospace, national defense industry and other national construction, and is an important new energy and new material.
The demand of lithium resources is increased rapidly, the comprehensive utilization of the lithium ore resources is driven, the occurrence state of lithium in the ore is found out, technical reference and basis are provided for the separation and metallurgy process of the lithium ore resources, and the phase analysis of the lithium in the ore is very important.
The lithium resources in China are rich, typical lithium minerals mainly comprise spodumene, lepidolite and lepidolite, and also comprise spodumene, eucryptite, amphibole and the like, but the three types of mineral resources are less. At present, reports related to chemical phase analysis of lithium are not seen, most existing lithium ore analysis is carried out on occurrence states of lithium through an X-ray diffractometer and a time-of-flight secondary ion mass spectrometer, the X-ray diffractometer is insufficient in quantitative accuracy, the time-of-flight secondary ion mass spectrometer is expensive, and due to the fact that the atomic weight of lithium is small, a conventional mineral parameter automatic quantitative analysis system (MLA) cannot carry out quantitative analysis on the lithium ore.
Disclosure of Invention
The main object of the present invention is to provide a chemical phase analysis method for lithium in an ore, which can accurately measure the lithium content of each phase in the ore and which is low in equipment cost.
In order to achieve the above object, the present invention provides a method for chemical phase analysis of lithium in an ore, comprising the steps of:
the method comprises the following steps: putting a mineral sample into a glass beaker, adding a hydrochloric acid solution with the volume fraction of 10% -50%, uniformly mixing, covering a watch glass, heating for 10-60 min on a boiling water bath, shaking at intervals of 5-20 min, taking down, cooling to room temperature, filtering with qualitative slow filter paper, collecting filtrate, washing the precipitate for 6-7 times with a dilute hydrochloric acid solution, washing the precipitate for 4-5 times with water, heating and concentrating the filtrate on a low-temperature furnace to be nearly dry, taking down, cooling, adding concentrated nitric acid, continuously heating and concentrating to be nearly dry, taking down, cooling, heating and dissolving salts on the low-temperature furnace, taking down, cooling, transferring into a volumetric flask, fixing the volume with water, uniformly mixing with lithium iron, standing for 10-30 min, and measuring the content of lithium in the liquid in the volumetric flask by using an inductively coupled plasma emission volumetric method, namely the content of lithium in mica;
step two: putting the filter residue filtered in the step one and filter paper into a polytetrafluoroethylene beaker, adding a mixed solution of 5-30% of HCl and 2-20% of HF by volume fraction, stirring to enable the filter residue on the filter paper to be in contact with the solution as much as possible, covering a watch glass, putting the polytetrafluoroethylene beaker on a boiling water bath, heating for 30-120 min, stirring at intervals of 5-20 min, taking down and cooling to room temperature, filtering with qualitative slow-speed filter paper, collecting filtrate in the polytetrafluoroethylene beaker, washing the precipitate for 6-7 times with a dilute hydrochloric acid solution, washing the precipitate for 4-5 times with water, heating and concentrating the filtrate on a low-temperature furnace to near dryness, taking down and cooling, adding concentrated nitric acid, continuing heating and concentrating to near dryness, taking down and cooling, heating and dissolving salts on the low-temperature furnace, taking down and cooling, transferring into a volumetric flask, fixing the volume with water, uniformly mixing, standing for 10-30 min, and measuring the content of lithium in the liquid in the volumetric flask by inductively coupled plasma emission spectrometry, namely the content of lithium in the lepidolite;
step three: and (3) putting the filter residue filtered in the step two and filter paper into a ceramic crucible, putting the ceramic crucible into a muffle furnace for carbonization, taking out the ceramic crucible, cooling to room temperature, completely transferring the residue in the ceramic crucible into a polytetrafluoroethylene beaker, adding concentrated hydrochloric acid, concentrated nitric acid and concentrated hydrofluoric acid, putting the polytetrafluoroethylene beaker on a low-temperature electric furnace for heating for 10-30 min, taking down, cooling, supplementing concentrated hydrofluoric acid, continuing to heat for 10-30 min, taking down, slightly cooling, adding perchloric acid, continuing to heat until dense white smoke is emitted, taking down, cooling to room temperature, heating and dissolving salts on the low-temperature furnace, taking down, cooling, transferring into a volumetric flask, fixing the volume with water, mixing uniformly, standing for 10-30 min, and measuring the content of lithium in the liquid of the volumetric flask by using an inductive coupling plasma emission spectrometry, namely the content of lithium in spodumene.
The method for analyzing the chemical phase of lithium in the ore comprises the steps of firstly, leaching an ore sample by using hydrochloric acid as a leaching agent, wherein the hydrochloric acid solution can selectively dissolve the lepidolite under the condition of heating, so that the lithium in the lepidolite is released into the solution, the lithium in other phases is remained in filter residues, and the measured lithium in the filtrate is the lithium content in the lepidolite; then, a mixed solution of hydrochloric acid and hydrofluoric acid solution is used as a leaching agent, the hydrochloric acid and the hydrofluoric acid solution can selectively dissolve the lepidolite, so that lithium in the lepidolite is released into the solution, lithium in other phases is left in filter residues, and the measured lithium in the filtrate is the lithium content in the lepidolite; for spodumene in an ore sample, which is insoluble aluminosilicate, can be dissolved by aqua regia and hydrofluoric acid, the invention adopts aqua regia and hydrofluoric acid to dissolve spodumene, so that lithium in the spodumene is released, and the content of lithium in the spodumene is measured. The chemical phase analysis method can accurately measure the lithium content of each phase in the ore, and has simple operation and low equipment cost.
Further, the method also comprises the following steps:
step four: and (3) putting an ore sample equal to the ore sample obtained in the first step into a polytetrafluoroethylene beaker, adding concentrated hydrochloric acid, concentrated nitric acid and hydrofluoric acid, putting the polytetrafluoroethylene beaker on a low-temperature electric furnace, heating for 10-30 min, taking down, cooling, supplementing the hydrofluoric acid, continuing to heat for 10-30 min, taking down, cooling slightly, adding perchloric acid, continuing to heat until dense white smoke is emitted, taking down, cooling to room temperature, heating on a low-temperature furnace to dissolve salts, taking down, cooling, transferring into a volumetric flask, fixing the volume with water, mixing uniformly, standing for 10-30 min, and measuring the content of lithium in the liquid of the volumetric flask by using an inductive coupling plasma emission spectrometry, namely the total amount of lithium in the ore.
The method is used for measuring the total lithium content in an ore sample with the same quantity, and the total lithium content is compared with the sum of the lithium components of each phase state measured step by step in the first step to the third step, so that whether the phase separation of the chemical phase analysis method is accurate or not can be judged.
Further, the content of lithium in the liquid in the volumetric flask is measured by inductively coupled plasma emission spectrometry, which specifically comprises the following steps:
measuring strength values of a plurality of groups of lithium solutions with known concentrations by using an inductively coupled plasma emission spectrometer, taking the lithium concentrations and the strength values as two coordinate axes of a two-dimensional coordinate system respectively, putting the lithium concentrations and the corresponding strength values of the plurality of groups of lithium solutions with known concentrations into the two-dimensional coordinate system to obtain a plurality of coordinate points, and drawing a standard curve of the lithium concentrations and the strength values;
measuring the intensity values of the liquid in the volumetric flask at the wavelengths of 610.362nm and 670.784nm by using an inductively coupled plasma emission spectrometer, and substituting the intensity values into a standard curve of proper lithium concentration and intensity values to obtain the lithium concentration in the liquid in the volumetric flask;
and (3) calculating the content of lithium in the sample according to the concentration of lithium in the liquid in the volumetric flask, the constant volume of the liquid in the volumetric flask, the dilution ratio of the liquid in the volumetric flask and the mass of the sample.
Further, the standard curve of lithium concentration versus intensity value includes the following two types:
the first one is: accurately transferring 0.00mL, 0.50mL, 1.00mL, 1.50mL, 2.00mL, 2.5mL and 3.00mL of lithium standard solution into a volumetric flask respectively, diluting the solution to a scale with water, uniformly mixing the solution, adjusting the solution to zero with water, measuring the strength value of lithium, and drawing a standard curve of the lithium by taking the concentration of the lithium as an abscissa and the strength value at the wavelength of 670.784nm as an ordinate;
the second method is as follows: accurately transferring 3.00mL, 5.00mL, 7.00mL, 10.00mL, 15.00mL and 20.00mL of lithium standard solution into a volumetric flask respectively, diluting the solution to a scale with water, uniformly mixing the solution, adjusting the solution to zero with water, measuring the lithium intensity value, and drawing a standard curve of the lithium by taking the lithium concentration as an abscissa and taking the intensity value at the wavelength of 610.362nm as an ordinate.
When the lithium is measured by an inductively coupled plasma emission spectrometry, a plurality of spectral lines can be selected, the linearity and the anti-interference capability at 610.362nm and 670.784nm are good, the sensitivity at 670.784nm is high, but when the standard solution exceeds 3mg/L, the standard solution is easy to saturate, so that the method is suitable for measuring low-concentration lithium under the spectral lines; the linear range of a spectral line at 610.362nm is 3-100 mg/L, and the method is suitable for measuring high-concentration lithium without dilution. The invention selects two standard curves to make the standard curves by segments, simultaneously measures the intensity values at 610.362nm and 670.784nm when a sample is measured, and selects a proper standard curve to calculate, thereby leading the measurement operation to be more convenient and the measurement result to be more accurate.
Further, when the content of lithium in the liquid in the volumetric flask was measured by inductively coupled plasma emission spectrometry, the intensity values of lithium at 610.362nm and 670.784nm were measured at the same time, and when the concentration of lithium was less than 3.00mg/L, the calculation was performed using the first standard curve, and when the concentration of lithium was greater than or equal to 3.00mg/L, the calculation was performed using the second standard curve.
Further, the content of lithium in the liquid sample in the volumetric flask is determined from the concentration of lithium in the liquid in the volumetric flask, the constant volume of the liquid in the volumetric flask, the dilution factor of the liquid in the volumetric flask and the mass of the sample, and specifically:
the lithium content in the sample was calculated according to the following formula:
wherein, omega is the mass fraction,%, of lithium; c is the lithium concentration in the liquid of the volumetric flask, which is obtained by checking from a standard curve, and the unit is mug/mL; v is the constant volume of the liquid in the volumetric flask, and the unit is mL; f is the dilution multiple of the liquid in the volumetric flask; m is the mass of the sample in g.
Further, the density of concentrated hydrochloric acid used was 1.19g/mL, the density of concentrated nitric acid used was 1.42g/mL, the density of concentrated hydrofluoric acid used was 1.15g/mL, and the density of concentrated perchloric acid used was 1.67 g/mL.
Further, the ore sample was spodumene or mica-type lithium ore.
Compared with the prior art, the invention has the following beneficial effects:
according to the phase analysis method of lithium in ore, disclosed by the invention, the hydrochloric acid solution, the hydrochloric acid-hydrofluoric acid solution and the mixed acid of hydrochloric acid, nitric acid, hydrofluoric acid and perchloric acid are used for respectively leaching lithium in lepidolite, lepidolite and spodumene in the lithium ore, so that the content of lithium in various phases in an ore sample can be accurately analyzed, and the defects of instrumental methods, such as incapability of quantitative analysis of the lithium ore by an automatic quantitative analysis system (MLA) for mineral parameters, inaccurate quantification of an X-ray diffraction method, high price of a flight time-secondary ion mass spectrometry method and the like are overcome. The chemical phase analysis method is particularly suitable for phase analysis of lithium in spodumene or mica lithium ores, and phase separation is accurate.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Because the market has no standard sample of lithium phase, the pure mineral used in the invention is prepared by adopting natural mineral crystal ore dressing enrichment, under-mirror selection, chemical treatment and other purifications. Mica is easier to select under a mirror, so that pure minerals of the lepidolite and the lepidolite are obtained by selecting under the mirror, and spodumene is obtained by carrying out three-time ore dressing and flotation on concentrate by spodumene minerals. By adopting the step four of the invention, the content of lithium in the pure mineral lepidolite is measured to be 0.69 percent, the content of lithium in the lepidolite is measured to be 2.22 percent, and the content of lithium in the spodumene is measured to be 3.66 percent by the method for measuring the total amount of lithium in the ore.
In the following examples, the content of lithium in the liquid in the volumetric flask was measured by inductively coupled plasma emission spectrometry, which specifically comprises the following steps:
firstly, measuring strength values of a plurality of groups of lithium solutions with known concentrations by using an inductively coupled plasma emission spectrometer, taking the lithium concentrations and the strength values as two coordinate axes of a two-dimensional coordinate system respectively, putting the lithium concentrations and the corresponding strength values of the plurality of groups of lithium solutions with known concentrations into the two-dimensional coordinate system to obtain a plurality of coordinate points, and drawing a standard curve of the lithium concentrations and the strength values;
then, measuring the strength value of the liquid in the volumetric flask by using an inductively coupled plasma emission spectrometer, and substituting the strength value into a standard curve of lithium concentration and the strength value to obtain the lithium concentration in the liquid in the volumetric flask;
finally, the lithium content in the liquid in the volumetric flask is obtained according to the lithium concentration in the liquid in the volumetric flask, the constant volume of the liquid in the volumetric flask, the dilution factor of the liquid in the volumetric flask and the mass of the solution.
The standard curve of lithium concentration versus intensity values includes the following two:
the first one is: accurately transferring 0.00mL, 0.50mL, 1.00mL, 1.50mL, 2.00mL, 2.5mL and 3.00mL of lithium standard solution into a volumetric flask respectively, diluting the solution to a scale with water, uniformly mixing the solution, adjusting the solution to zero with water, measuring the strength value of lithium, and drawing a standard curve of the lithium by taking the concentration of the lithium as an abscissa and the strength value at the wavelength of 670.784nm as an ordinate;
the second method is as follows: accurately transferring 3.00mL, 5.00mL, 7.00mL, 10.00mL, 15.00mL and 20.00mL of lithium standard solution into a volumetric flask respectively, diluting the solution to a scale with water, uniformly mixing the solution, adjusting the solution to zero with water, measuring the lithium intensity value, and drawing a standard curve of the lithium by taking the lithium concentration as an abscissa and taking the intensity value at the wavelength of 610.362nm as an ordinate.
The preparation method of the lithium standard solution is as follows:
lithium standard stock solution: the concentration of a commercially available certified standard solution is 1000 mg/L;
lithium standard solution: 10mL of the above standard stock solution of lithium was transferred to a 100mL volumetric flask, diluted to the mark with water and mixed well, and 1mL of the solution contained 100. mu.g of lithium.
When the content of lithium in the liquid in the volumetric flask is measured by inductively coupled plasma emission spectrometry, the intensity values of lithium at 610.362nm and 670.784nm are simultaneously measured, and when the concentration of lithium is less than 3.00mg/L, the calculation is carried out by using the first standard curve, and when the concentration of lithium is greater than or equal to 3.00mg/L, the calculation is carried out by using the second standard curve.
Further, the content of lithium in the sample was calculated according to the following formula:
the lithium content in the sample was calculated according to the following formula:
wherein, omega is the mass fraction,%, of lithium; c is the lithium concentration in the liquid of the volumetric flask, which is obtained by checking from a standard curve, and the unit is mug/mL; v is the constant volume of the liquid in the volumetric flask, and the unit is mL; f is the dilution multiple of the liquid in the volumetric flask; m is the mass of the sample in g.
In the following examples, the density of concentrated hydrochloric acid used in each step was 1.19g/mL, the density of concentrated nitric acid used was 1.42g/mL, the density of concentrated hydrofluoric acid used was 1.15g/mL, and the density of concentrated perchloric acid used was 1.67 g/mL; the preparation method comprises the following steps: concentrated hydrochloric acid, concentrated hydrofluoric acid and water are mixed according to the volume ratio of 2: 1: 17, mixing to prepare a mixed solution.
Example 1:
the method comprises the following steps: determination of lithium in iron lepidolite in ore
Weighing 0.1000g of a pure mineral lepidolite sample with the granularity of less than 0.075mm in a 250mL glass beaker, adding 50mL of a leaching agent (namely hydrochloric acid solution with the volume fraction of 30%), uniformly mixing, covering a watch glass, heating for 30min in a boiling water bath, shaking at intervals of 10min, taking down and cooling to room temperature, filtering with qualitative slow-speed filter paper, collecting filtrate in a 250mL glass beaker, washing the precipitate with hydrochloric acid solution with the volume fraction of 3% for 6-7 times, washing the precipitate with water for 4-5 times, heating and concentrating the filtrate on a low-temperature furnace to near dryness, taking down and cooling, flushing the wall of the beaker with a little water, adding 2mL of concentrated nitric acid, continuously heating and concentrating to near dryness, taking down and cooling, flushing the wall of the beaker with a little water, heating and dissolving salts on the low-temperature furnace, taking down and cooling, transferring into a 100mL volumetric flask, fixing the volume with water, uniformly mixing, standing for 30min, measuring the content of lithium in the liquid in the volumetric flask by an inductively coupled plasma emission spectrometry, namely the lithium content in the lepidolite.
Step two: determination of lithium in lepidolite in ore
Putting the filter residue filtered in the first step and filter paper into a 200mL polytetrafluoroethylene beaker, adding 50mL of mixed solution of 10% by volume of HCl and 5% by volume of HF, putting the mixture into a plastic rod, stirring to enable the filter residue on the filter paper to be in contact with the solution as much as possible, covering a watch glass, putting the polytetrafluoroethylene beaker on a boiling water bath, heating for 60min, stirring at intervals of 10min, taking down and cooling to room temperature, filtering with qualitative slow-speed filter paper, collecting the filtrate into a 200mL polytetrafluoroethylene beaker, washing the precipitate with 3% hydrochloric acid solution for 6-7 times, washing the precipitate with water for 4-5 times, heating and concentrating the filtrate on a low-temperature furnace to near dryness, taking down and cooling, washing the wall of the beaker with a little water, adding 2mL of concentrated nitric acid, continuing heating and concentrating to near dryness, taking down and cooling, washing the wall of the beaker with a little water, heating and dissolving salts on the low-temperature furnace, taking down and cooling, and transferring into a 50mL volumetric flask, fixing the volume with water, uniformly mixing, standing for 30min, and measuring the content of lithium in the liquid in the volumetric flask by using an inductively coupled plasma emission spectrometry, namely the content of lithium in the lepidolite.
Step three: determination of lithium in spodumene in ores
Putting the filter residue filtered in the step two and filter paper into a 50mL ceramic crucible, placing the ceramic crucible into a muffle furnace at 650 ℃, carbonizing the filter paper for 30min, taking out the ceramic crucible, cooling to room temperature, completely transferring the residue in the ceramic crucible into a 100mL polytetrafluoroethylene beaker, purging the wall of the beaker with a small amount of water, adding 9mL concentrated hydrochloric acid, 3mL concentrated nitric acid and 10mL concentrated hydrofluoric acid, placing the polytetrafluoroethylene beaker on a low-temperature electric furnace at 230 ℃, heating for 20min, taking down, cooling, purging the wall of the beaker with a small amount of water, supplementing 10mL concentrated hydrofluoric acid, continuing to heat for 20min, taking down slightly cold, adding 5mL perchloric acid, continuing to heat until dense white smoke appears, taking down, cooling to room temperature, purging the wall of the beaker with a small amount of water, heating and dissolving salts on the low-temperature furnace, taking down, cooling, transferring into a 50mL volumetric flask, fixing the volume with water, mixing uniformly, standing for 30min, measuring the content of lithium in the liquid in the volumetric flask by an inductively coupled plasma emission spectrometry, i.e. the content of lithium in the spodumene.
Step four: determination of total amount of lithium in pure mineral lepidolite
Weighing 0.1000g of a pure mineral lepidolite sample in a 100mL polytetrafluoroethylene beaker, purging the wall of the beaker by using a small amount of water, adding 9mL of concentrated hydrochloric acid, 3mL of concentrated nitric acid and 10mL of hydrofluoric acid, placing the polytetrafluoroethylene beaker on a low-temperature electric furnace at 230 ℃ for heating for 20min, taking down and cooling, purging the wall of the beaker by using a small amount of water, supplementing 10mL of hydrofluoric acid, continuing to heat for 20min, taking down and cooling slightly, adding 5mL of perchloric acid, continuing to heat until dense white smoke is emitted, taking down and cooling to room temperature, purging the wall of the beaker by using a small amount of water, heating and dissolving salts on a low-temperature furnace, taking down and cooling, transferring the beaker into a 100mL volumetric flask, fixing the volume by using water, uniformly mixing, standing for 30min, and measuring the content of lithium in the liquid of the volumetric flask by using an inductively coupled plasma emission volumetric spectrometry, namely the total amount of lithium in the ore.
TABLE 1 data and results of example 1
Example 2:
the method comprises the following steps: determination of lithium in iron lepidolite in ore
Weighing 0.1000g of pure mineral lepidolite sample with the granularity of less than 0.075mm in a 250mL glass beaker, adding 50mL of leaching agent (namely hydrochloric acid solution with the volume fraction of 30%), uniformly mixing, covering a watch glass, heating for 30min in a boiling water bath, shaking at intervals of 10min, taking down and cooling to room temperature, filtering with qualitative slow-speed filter paper, collecting filtrate in a 250mL glass beaker, washing the precipitate with 3% hydrochloric acid solution for 6-7 times, washing the precipitate with water for 4-5 times, heating and concentrating the filtrate on a low-temperature furnace to be nearly dry, taking down and cooling, flushing the wall of the beaker with a little water, adding 2mL of concentrated nitric acid, continuously heating and concentrating to be nearly dry, taking down and cooling, flushing the wall of the beaker with a little water, heating and dissolving salts on the low-temperature furnace, taking down and cooling, transferring into a 50mL volumetric flask, fixing the volume with water, uniformly mixing, standing for 30min, measuring the content of lithium in the liquid of the volumetric flask by inductive coupling plasma emission spectrometry, namely the lithium content in the lepidolite.
Step two: determination of lithium in lepidolite in ore
Putting the filter residue filtered in the first step and filter paper into a 200mL polytetrafluoroethylene beaker, adding 50mL of mixed solution of 10% by volume of HCl and 5% by volume of HF, putting the mixture into a plastic rod, stirring to enable the filter residue on the filter paper to be in contact with the solution as much as possible, covering a watch glass, putting the polytetrafluoroethylene beaker on a boiling water bath, heating for 60min, stirring at intervals of 10min, taking down and cooling to room temperature, filtering with qualitative slow-speed filter paper, collecting the filtrate into a 200mL polytetrafluoroethylene beaker, washing the precipitate with 3% hydrochloric acid solution for 6-7 times, washing the precipitate with water for 4-5 times, heating and concentrating the filtrate on a low-temperature furnace to near dryness, taking down and cooling, washing the wall of the beaker with a little water, adding 2mL of concentrated nitric acid, continuing heating and concentrating to near dryness, taking down and cooling, washing the wall of the beaker with a little water, heating and dissolving salts on the low-temperature furnace, taking down and cooling, transferring into a 100mL volumetric flask, fixing the volume with water, mixing uniformly, dividing 10mL into 50mL volumetric flasks, fixing the volume with water, mixing uniformly, and measuring the content of lithium in the liquid in the volumetric flask by using an inductively coupled plasma emission spectrometry, namely the content of lithium in the lepidolite.
Step three: determination of lithium in spodumene in ores
Putting the filter residue filtered in the step two and filter paper into a 50mL ceramic crucible, placing the ceramic crucible into a muffle furnace at 650 ℃, carbonizing the filter paper for 30min, taking out the ceramic crucible, cooling to room temperature, completely transferring the residue in the ceramic crucible into a 100mL polytetrafluoroethylene beaker, purging the wall of the beaker with a small amount of water, adding 9mL concentrated hydrochloric acid, 3mL concentrated nitric acid and 10mL concentrated hydrofluoric acid, placing the polytetrafluoroethylene beaker on a low-temperature electric furnace at 230 ℃, heating for 20min, taking down, cooling, purging the wall of the beaker with a small amount of water, supplementing 10mL concentrated hydrofluoric acid, continuing to heat for 20min, taking down slightly cold, adding 5mL perchloric acid, continuing to heat until dense white smoke appears, taking down, cooling to room temperature, purging the wall of the beaker with a small amount of water, heating and dissolving salts on the low-temperature furnace, taking down, cooling, transferring into a 50mL volumetric flask, fixing the volume with water, mixing uniformly, standing for 30min, measuring the content of lithium in the liquid in the volumetric flask by an inductively coupled plasma emission spectrometry, i.e. the content of lithium in the spodumene.
Step four: determination of total lithium content in ores
Weighing 0.1000g of a pure mineral lepidolite sample in a 100mL polytetrafluoroethylene beaker, purging the wall of the beaker by using a small amount of water, adding 9mL of concentrated hydrochloric acid, 3mL of concentrated nitric acid and 10mL of hydrofluoric acid, placing the polytetrafluoroethylene beaker on a low-temperature electric furnace at 230 ℃ for heating for 20min, taking down and cooling, purging the wall of the beaker by using a small amount of water, supplementing 10mL of hydrofluoric acid, continuing to heat for 20min, taking down and cooling slightly, adding 5mL of perchloric acid, continuing to heat until dense white smoke is emitted, taking down and cooling to room temperature, purging the wall of the beaker by using a small amount of water, heating and dissolving salts on a low-temperature furnace, taking down and cooling, transferring the cooled beaker into a 100mL volumetric flask, fixing the volume by using water, uniformly mixing, dividing 10mL into a 50mL volumetric flask, fixing the volume by using water, uniformly mixing, and measuring the content of lithium in the liquid in the volumetric flask by using inductive coupling plasma emission spectrometry, namely the total amount of lithium in the ore.
Table 2 data and results of example 2
Example 3:
the method comprises the following steps: determination of lithium in iron lepidolite in ore
Weighing 0.1000g of a pure mineral spodumene sample with the granularity of less than 0.075mm in a 250mL glass beaker, adding 50mL of a leaching agent (namely a hydrochloric acid solution with the volume fraction of 30%), uniformly mixing, covering a watch glass, heating for 30min in a boiling water bath, shaking at intervals of 10min, taking down, cooling to room temperature, filtering with qualitative slow-speed filter paper, collecting filtrate in a 250mL glass beaker, washing the precipitate with a 3% hydrochloric acid solution for 6-7 times, washing the precipitate with water for 4-5 times, heating and concentrating the filtrate on a low-temperature furnace to near dryness, taking down for cooling, flushing the wall of the beaker with a little water, adding 2mL of concentrated nitric acid, continuously heating and concentrating to near dryness, taking down for cooling, flushing the wall of the beaker with a little water, heating and dissolving salts on a low-temperature furnace, taking down for cooling, transferring into a 50mL volumetric flask, fixing the volume with water, uniformly mixing, standing for 30min, measuring the content of lithium in the liquid in the volumetric flask by an inductively coupled plasma emission spectrometry, namely the lithium content in the lepidolite.
Step two: determination of lithium in lepidolite in ore
Putting the filter residue filtered in the first step and filter paper into a 200mL polytetrafluoroethylene beaker, adding 50mL of mixed solution of 10% by volume of HCl and 5% by volume of HF, putting the filter residue into a plastic rod, stirring to enable the filter residue on the filter paper to be in contact with the solution as much as possible, covering a watch glass, putting the polytetrafluoroethylene beaker on a boiling water bath, heating for 60min, stirring at intervals of 10min, taking down, cooling to room temperature, filtering with qualitative slow-speed filter paper, collecting filtrate into a 200mL polytetrafluoroethylene beaker, washing the precipitate with 3% hydrochloric acid solution for 6-7 times, washing the precipitate with water for 4-5 times, heating and concentrating the filtrate on a low-temperature furnace to near dryness, taking down, cooling, washing the wall of the beaker with a little water, adding 2mL of concentrated nitric acid, continuing heating and concentrating to near dryness, taking down, cooling, washing the wall of the beaker with a little water, heating and dissolving salts on the low-temperature furnace, taking down, cooling, and transferring into a 100mL volumetric flask, fixing the volume with water, uniformly mixing, standing for 30min, and measuring the content of lithium in the liquid in the volumetric flask by using an inductively coupled plasma emission spectrometry, namely the content of lithium in the lepidolite.
Step three: determination of lithium in spodumene in ores
Putting the filter residue filtered in the step two and filter paper into a 50mL ceramic crucible, placing the ceramic crucible into a muffle furnace at 650 ℃, carbonizing the filter paper for 30min, taking out the ceramic crucible, cooling to room temperature, completely transferring the residue in the ceramic crucible into a 100mL polytetrafluoroethylene beaker, purging the wall of the beaker with a small amount of water, adding 9mL concentrated hydrochloric acid, 3mL concentrated nitric acid and 10mL concentrated hydrofluoric acid, placing the polytetrafluoroethylene beaker on a low-temperature electric furnace at 230 ℃, heating for 20min, taking down, cooling, purging the wall of the beaker with a small amount of water, supplementing 10mL concentrated hydrofluoric acid, continuing to heat for 20min, taking down slightly cold, adding 5mL perchloric acid, continuing to heat until dense white smoke appears, taking down, cooling to room temperature, purging the wall of the beaker with a small amount of water, heating and dissolving salts in the low-temperature furnace, taking down, cooling, transferring into a 100mL volumetric flask, fixing the volume with water, mixing uniformly, taking down 10mL into a 50mL volumetric flask, fixing the volume with water, mixing uniformly, and measuring the content of lithium in the liquid in the volumetric flask by using an inductively coupled plasma emission spectrometry, namely the content of lithium in the spodumene.
Step four: determination of total lithium content in ores
Weighing 0.1000g of a pure mineral spodumene sample in a 100mL polytetrafluoroethylene beaker, purging the wall of the beaker by using a small amount of water, adding 9mL of concentrated hydrochloric acid, 3mL of concentrated nitric acid and 10mL of hydrofluoric acid, placing the polytetrafluoroethylene beaker on a low-temperature electric furnace at 230 ℃ for heating for 20min, taking down and cooling, purging the wall of the beaker by using a small amount of water, supplementing 10mL of hydrofluoric acid, continuing to heat for 20min, taking down and cooling slightly, adding 5mL of perchloric acid, continuing to heat until dense white smoke is emitted, taking down and cooling to room temperature, purging the wall of the beaker by using a small amount of water, heating and dissolving salts on a low-temperature furnace, taking down and cooling, transferring into a 100mL flask, fixing the volume by using water, mixing uniformly, dividing 10mL into a 50mL flask, fixing the volume by using water, mixing uniformly, and measuring the content of lithium in the liquid in the flask by using inductive coupling plasma emission volumetric spectrometry, namely the total amount of lithium in the ore.
Table 3 data and results of example 3
Example 4:
the method comprises the following steps: determination of lithium in iron lepidolite in ore
0.1000g of the synthesized sample is weighed into a 250mL glass beaker, 50mL of leaching agent (i.e., hydrochloric acid solution with a volume fraction of 30%) is added and mixed uniformly, covering the surface dish, heating in boiling water bath for 30min, shaking at an interval of 10min, taking down, cooling to room temperature, filtering with qualitative slow speed filter paper, collecting the filtrate in a 250mL glass beaker, washing the precipitate for 6-7 times by using a 3% hydrochloric acid solution, washing the precipitate for 4-5 times by using water, heating and concentrating the filtrate on a low-temperature furnace until the filtrate is nearly dry, taking down and cooling, flushing the wall of the beaker by using a little water, adding 2mL of concentrated nitric acid, continuously heating and concentrating until the filtrate is nearly dry, taking down and cooling, flushing the wall of the beaker by using a little water, heating and dissolving salts on the low-temperature furnace, taking down and cooling, transferring to a 50mL volumetric flask, and (3) fixing the volume with water, uniformly mixing, standing for 30min, and measuring the content of lithium in the liquid in the volumetric flask by using an inductively coupled plasma emission spectrometry, namely the content of lithium in the lepidolite.
Step two: determination of lithium in lepidolite in ore
Putting the filter residue filtered in the first step and filter paper into a 200mL polytetrafluoroethylene beaker, adding 50mL of a 10% volume fraction HCl solution and a 5% volume fraction HF solution, putting the filter residue into a plastic rod, stirring to enable the filter residue on the filter paper to be in contact with the solution as much as possible, covering a watch glass, putting the polytetrafluoroethylene beaker on a boiling water bath, heating for 60min, stirring at an interval of 10min, taking down and cooling to room temperature, filtering with qualitative slow-speed filter paper, collecting the filtrate into a 200mL polytetrafluoroethylene beaker, washing the precipitate with a 3% hydrochloric acid solution for 6-7 times, washing the precipitate with water for 4-5 times, heating and concentrating the filtrate on a low-temperature furnace to near dryness, taking down and cooling, washing the wall of the beaker with a little water, adding 2mL of concentrated nitric acid, continuing heating and concentrating to near dryness, taking down and cooling, washing the wall of the beaker with a little water, heating and dissolving salts on the low-temperature furnace, taking down and cooling, transferring to a 100mL volumetric flask, and (3) fixing the volume with water, uniformly mixing, standing for 30min, and measuring the content of lithium in the liquid in the volumetric flask by using an inductively coupled plasma emission spectrometry, namely the content of lithium in the lepidolite.
Step three: determination of lithium in spodumene in ores
Putting the filter residue filtered in the step two and filter paper into a 50mL ceramic crucible, placing the ceramic crucible into a muffle furnace at 650 ℃, carbonizing the filter paper for 30min, taking out the ceramic crucible, cooling to room temperature, completely transferring the residue in the ceramic crucible into a 100mL polytetrafluoroethylene beaker, purging the wall of the beaker with a small amount of water, adding 9mL concentrated hydrochloric acid, 3mL concentrated nitric acid and 10mL concentrated hydrofluoric acid, placing the polytetrafluoroethylene beaker on a low-temperature electric furnace at 230 ℃, heating for 20min, taking down, cooling, purging the wall of the beaker with a small amount of water, supplementing 10mL concentrated hydrofluoric acid, continuing to heat for 20min, taking down slightly cold, adding 5mL perchloric acid, continuing to heat until dense white smoke appears, taking down, cooling to room temperature, purging the wall of the beaker with a small amount of water, heating and dissolving salts in the low-temperature furnace, taking down, cooling, transferring into a 100mL volumetric flask, fixing the volume with water, mixing uniformly, standing for 30min, measuring the content of lithium in the liquid in the volumetric flask by an inductively coupled plasma emission spectrometry, i.e. the content of lithium in the spodumene.
Step four: determination of the Total amount of lithium in the synthetic samples
Weighing 0.1000g of a synthetic sample in a 100mL polytetrafluoroethylene beaker, purging the wall of the beaker by using a small amount of water, adding 9mL of concentrated hydrochloric acid, 3mL of concentrated nitric acid and 10mL of hydrofluoric acid, placing the polytetrafluoroethylene beaker on a low-temperature electric furnace at 230 ℃ for heating for 20min, taking down and cooling, purging the wall of the beaker by using a small amount of water, supplementing 10mL of hydrofluoric acid, continuing to heat for 20min, taking down and cooling slightly, adding 5mL of perchloric acid, continuing to heat until dense white smoke appears, taking down and cooling to room temperature, purging the wall of the beaker by using a small amount of water, heating and dissolving salts on a low-temperature furnace, taking down and cooling, transferring the cooled beaker into a 100mL volumetric flask, fixing the volume by using water, mixing uniformly, taking out a 10mL volumetric flask to 50mL volumetric flask, fixing the volume by using water, mixing uniformly, and measuring the content of lithium in the volumetric flask by using an inductively coupled plasma emission spectrometry, namely the total amount of lithium in the ore.
Table 4 data and results of example 4
Wherein, the calculation formula of the standard value of lithium in the synthesized sample is as follows:
wherein: omega is the mass fraction,%, of lithium;
ωithe content of lithium in the pure mineral is used for preparing a synthetic sample;
miweighing the mass of the pure mineral in g when preparing a synthetic sample;
mgeneral assemblyThe total mass in g is the total mass at the time of making the synthetic sample.
It can be seen from the above examples that the difference obtained by the chemical phase analysis method of the present invention is small as compared with the standard value, indicating that the chemical phase analysis method of lithium of the present invention is reliable.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for chemical phase analysis of lithium in an ore, comprising the steps of:
the method comprises the following steps: putting an ore sample into a glass beaker, adding a hydrochloric acid solution with the volume fraction of 10-50%, uniformly mixing, covering a watch glass, heating for 10-60 min on a boiling water bath, shaking at intervals of 5-20 min, taking down, cooling to room temperature, filtering with qualitative slow filter paper, collecting filtrate, washing the precipitate for 6-7 times with a dilute hydrochloric acid solution, washing the precipitate for 4-5 times with water, heating and concentrating the filtrate on a low-temperature furnace to near dryness, taking down, cooling, adding concentrated nitric acid, continuing to heat and concentrate to near dryness, taking down, cooling, heating and dissolving salts on the low-temperature furnace, taking down, cooling, transferring into a volumetric flask, fixing the volume with water, uniformly mixing, standing for 10-30 min, and measuring the content of lithium in the liquid in the volumetric flask by using an inductively coupled plasma emission volumetric spectrometry, namely the content of lithium in the lithium iron mica;
step two: putting the filter residue filtered in the step one and filter paper into a polytetrafluoroethylene beaker, adding a mixed solution of 5-30% by volume of HCl and 2-20% by volume of HF, stirring to enable the filter residue on the filter paper to be in contact with the solution as much as possible, covering a watch glass, putting the polytetrafluoroethylene beaker on a boiling water bath, heating for 30-120 min, stirring at intervals of 5-20 min, taking down and cooling to room temperature, filtering with qualitative slow-speed filter paper, collecting filtrate in the polytetrafluoroethylene beaker, washing the precipitate for 6-7 times with a dilute hydrochloric acid solution, washing the precipitate for 4-5 times with water, heating and concentrating the filtrate on a low-temperature furnace to near dryness, taking down and cooling, adding concentrated nitric acid, continuing heating and concentrating to near dryness, taking down and cooling, heating and dissolving salts on the low-temperature furnace, taking down and cooling, transferring into a volumetric flask, fixing the volume with water, uniformly mixing, standing for 10-30 min, and measuring the content of lithium in the volumetric flask liquid by inductively coupled plasma emission spectrometry, namely the content of lithium in the lepidolite;
step three: and (3) putting the filter residue filtered in the step two and filter paper into a ceramic crucible, putting the ceramic crucible into a muffle furnace for carbonization, taking out the ceramic crucible, cooling to room temperature, completely transferring the residue in the ceramic crucible into a polytetrafluoroethylene beaker, adding concentrated hydrochloric acid, concentrated nitric acid and concentrated hydrofluoric acid, putting the polytetrafluoroethylene beaker on a low-temperature electric furnace for heating for 10-30 min, taking down, cooling, supplementing concentrated hydrofluoric acid, continuing to heat for 10-30 min, taking down, slightly cooling, adding perchloric acid, continuing to heat until dense white smoke is emitted, taking down, cooling to room temperature, heating and dissolving salts on the low-temperature furnace, taking down, cooling, transferring into a volumetric flask, fixing the volume with water, mixing uniformly, standing for 10-30 min, and measuring the content of lithium in the liquid of the volumetric flask by using an inductive coupling plasma emission spectrometry, namely the content of lithium in spodumene.
2. The method of chemical phase analysis of lithium in an ore according to claim 1, further comprising the steps of:
step four: and (3) putting an ore sample equal to the ore sample obtained in the first step into a polytetrafluoroethylene beaker, adding concentrated hydrochloric acid, concentrated nitric acid and hydrofluoric acid, putting the polytetrafluoroethylene beaker on a low-temperature electric furnace, heating for 10-30 min, taking down, cooling, supplementing the hydrofluoric acid, continuing to heat for 10-30 min, taking down, cooling slightly, adding perchloric acid, continuing to heat until dense white smoke is emitted, taking down, cooling to room temperature, heating on a low-temperature furnace to dissolve salts, taking down, cooling, transferring into a volumetric flask, fixing the volume with water, mixing uniformly, standing for 10-30 min, and measuring the content of lithium in the liquid of the volumetric flask by using an inductive coupling plasma emission spectrometry, namely the total amount of lithium in the ore.
3. The method for chemical phase analysis of lithium in ores according to claim 1 or 2, wherein the content of lithium in the liquid in the volumetric flask is determined by inductively coupled plasma emission spectrometry, specifically:
measuring strength values of a plurality of groups of lithium solutions with known concentrations by using an inductively coupled plasma emission spectrometer, taking the lithium concentrations and the strength values as two coordinate axes of a two-dimensional coordinate system respectively, putting the lithium concentrations and the corresponding strength values of the plurality of groups of lithium solutions with known concentrations into the two-dimensional coordinate system to obtain a plurality of coordinate points, and drawing a standard curve of the lithium concentrations and the strength values;
measuring the intensity values of the liquid in the volumetric flask at the wavelengths of 610.362nm and 670.784nm by using an inductively coupled plasma emission spectrometer, and substituting the intensity values into a standard curve of lithium concentration and intensity values to obtain the lithium concentration in the liquid in the volumetric flask;
and (4) obtaining the content of lithium in the sample according to the concentration of lithium in the liquid in the volumetric flask, the constant volume of the liquid in the volumetric flask, the dilution ratio of the liquid in the volumetric flask and the mass of the sample.
4. The method of claim 3, wherein the standard curve of lithium concentration versus intensity values comprises the following two types:
the first one is: accurately transferring 0.00mL, 0.50mL, 1.00mL, 1.50mL, 2.00mL, 2.5mL and 3.00mL of lithium standard solution into a volumetric flask respectively, diluting the solution to a scale with water, uniformly mixing the solution, adjusting the solution to zero with water, measuring the strength value of lithium, and drawing a standard curve of the lithium by taking the concentration of the lithium as an abscissa and the strength value at the wavelength of 670.784nm as an ordinate;
the second method is as follows: accurately transferring 3.00mL, 5.00mL, 7.00mL, 10.00mL, 15.00mL and 20.00mL of lithium standard solution into a volumetric flask respectively, diluting the solution to a scale with water, uniformly mixing the solution, adjusting the solution to zero with water, measuring the lithium intensity value, and drawing a standard curve of the lithium by taking the lithium concentration as an abscissa and taking the intensity value at the wavelength of 610.362nm as an ordinate.
5. The method of claim 4, wherein the method comprises measuring the content of lithium in the liquid in the volumetric flask by inductively coupled plasma emission spectrometry, and simultaneously measuring the intensity values of lithium at 610.362nm and 670.784nm, wherein the method comprises calculating using the first standard curve when the concentration of lithium is less than 3.00mg/L, and calculating using the second standard curve when the concentration of lithium is greater than or equal to 3.00 mg/L.
6. The method for chemical phase analysis of lithium in ore according to claim 3, wherein the content of lithium in the sample is determined from the concentration of lithium in the liquid in the volumetric flask, the constant volume of the liquid in the volumetric flask, the dilution factor of the liquid in the volumetric flask, and the mass of the sample, and specifically:
the lithium content of the liquid sample in the volumetric flask was calculated according to the following formula:
wherein the content of the first and second substances,
mass fraction of lithium,%; c is the lithium concentration in the liquid of the volumetric flask, which is obtained by checking from a standard curve, and the unit is mug/mL; v is the constant volume of the liquid in the volumetric flask, and the unit is mL; f is the dilution multiple of the liquid in the volumetric flask; m is the mass of the sample in g.
7. The method according to claim 1 or 2, wherein the density of the concentrated hydrochloric acid used is 1.19g/mL, the density of the concentrated nitric acid used is 1.42g/mL, the density of the concentrated hydrofluoric acid used is 1.15g/mL, and the density of the concentrated perchloric acid used is 1.67 g/mL.
8. The method of claim 1 or 2, wherein the ore sample is a spodumene or mica-type lithium ore.
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