A roasting material and its application

Abstract

The present invention discloses a roasting material and its application, belonging to the field of metallurgy. The roasting material of the present invention is based on the technical bottleneck that the lithium conversion rate and comprehensive recovery rate of the existing roasting material need to be improved, and it is difficult to ensure stability under further leaching. By limiting the chemical composition and physical property parameters of the roasting material product, the lithium activation rate contained in the product can be high, and the lithium carbonate product can be uniformly and completely precipitated during the lithium extraction process. At the same time, the selectivity of the activated lithium precipitation is high, and the precipitation amount of impurity ions is small. When the product is subjected to industrial lithium extraction, not only the lithium extraction efficiency and the comprehensive lithium recovery rate are high, but also the stability of lithium extraction between batches can be guaranteed, which is conducive to quality monitoring and data statistics during factory-scale large-scale production.

Description

Technical Field

[0001] The present invention relates to the field of metallurgy, and in particular to a roasting material and application thereof. Background Art

[0002] Lepidolite ore and ore materials with similar compositions (such as spodumene and lithium-containing mining waste) are the main raw materials for industrial mineral lithium extraction. In the existing industry, there are various methods for extracting lithium from lepidolite and similar ore materials, including roasting and cooking. The roasting method is further subdivided into multiple roasting methods based on the differences in the addition of auxiliary materials and roasting conditions.

[0003] The most popular roasting method at present is the sulfate method, which uses sulfates such as sodium sulfate and potassium sulfate as roasting aids and roasts them together with lepidolite or similar materials to prepare roasting materials, thereby improving the lithium conversion rate and comprehensive recovery rate of the ore material.

[0004] However, due to the low lithium grade and complex composition of this type of ore material, the composition of the output ores varies greatly, and local melting and local hypoxia will occur during sulfate compound roasting (taking a rotary kiln as an example, as roasting proceeds, furnace agglomeration is generated in the kiln, and the oxygen content in the kiln decreases, which will cause oxygen deficiency in some roasted materials, directly affecting the lithium conversion rate of the product). The current lithium extraction efficiency of lepidolite and similar ore materials still needs to be improved. At the same time, even if the same additives and processing kilns are used to process the lepidolite ore, and the same leaching process is used for lithium extraction, the results of further lithium extraction from roasted materials prepared in different batches still vary greatly, making it difficult to control quality and statistics of finished products during the production process. As the production capacity of existing factories gradually increases, unlike laboratory lithium extraction, if this problem is not solved in a timely manner, it will inevitably affect the factory's production revenue and output expansion (large-scale roasted material production requires small-batch pre-production to evaluate the reagent consumption and revenue of the final product. If the lithium extraction of the roasted materials varies greatly, it is likely that the pre-production results will be significantly different from the final results). Summary of the Invention

[0005] Based on the defects of the prior art, the purpose of the present invention is to provide a roasted material, which has high lithium conversion rate and comprehensive recovery rate of ore raw materials as the results of lithium extraction by using the roasted material, and at the same time, the extraction results between batches are highly stable, and the quality control of the lithium extraction process and the difficulty of finished product statistics are significantly reduced.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] A roasting material for extracting lithium from lithium-containing raw ore materials, comprising the following components in percentage by mass:

[0008] Li 0.09-2.8%, K 1.5-8% and / or Na 1.5-10%, S 3.4-13.5% and at least one of Ca, Ba and Sr 1.5-10%;

[0009] The specific surface area of ​​the calcined material is 1 to 2 m 2 / g, average pore radius is 8-15nm, and bulk density is 0.2-0.8g / cm 3 .

[0010] Preferably, the roasting material for extracting lithium from lithium-containing raw ore materials comprises the following components in percentage by mass:

[0011] Li 0.09-2.8%, K 1.5-8%, Na 1.5-10%, S 3.4-13.5%, and at least one of Ca, Ba, and Sr 1.5-10%

[0012] At least one of Ca, Ba, and Sr is a sintering auxiliary element in the composition of the calcined material of the present invention.

[0013] It should be noted that the composition testing method of the roasting material described in the present invention can use elemental analysis methods to qualitatively and quantitatively analyze each element. Specifically, it can be carried out with reference to the method of YST 509.1-2008 "Chemical analysis method of spodumene and lepidolite concentrates - Determination of lithium oxide, sodium oxide and potassium oxide content - Flame atomic absorption spectrometry".

[0014] In the roasting material of the present invention, lithium element exists almost in the form of lithium sulfate. For the convenience of statistics, the mass percentage of Li in the roasting material can be calculated based on the main form of Li in the raw ore material, Li2O. Similarly, S mainly exists in the form of SO4 2- It exists in the form of SO4, so those skilled in the art can also 2- The mass percentage of S in the roasting material is calculated. For the roasting material product, in order to facilitate its application in industrial lithium extraction, it can also be directly expressed by the ratio of each element as described above. However, those skilled in the art should know that the actual ranges of the two measurement methods are consistent based on common knowledge.

[0015] In the existing technology, depending on the type of roasting kiln, the raw ore will be mixed with a lithium conversion agent and a roasting aid and prepared into a powder or prepared into a block for roasting to prepare the roasting material, but each roasting kiln will have certain defects during roasting: the rotary kiln can be used to feed the roasting material into the kiln in powder or spherical form, but due to the problem of local hypoxia in the kiln during the roasting process, the lithium conversion rate of the roasting material may be locally uneven or overall reduced; the tunnel kiln or roller kiln has more oxygen during roasting, so brick-shaped materials are generally used to feed the kiln, but most of the processes in this type of roasting kiln require manual operation, and it is difficult to accurately control the condition variables. Based on the above reasons, the lithium conversion rate and comprehensive recovery rate of the existing roasting material need to be improved, and it is difficult to ensure stability under further leaching. In the roasting material described in the present invention, the lithium contained therein is effectively activated. During further leaching and impurity removal, these activated lithiums can evenly precipitate lithium carbonate after adding lithium sodium carbonate. At the same time, the activated lithium precipitation is highly selective and the amount of impurity ions precipitated is small. Therefore, under the above-mentioned limitations, the yield and purity of the lithium extraction product will not be affected by the impurity ions. Ultimately, not only is the lithium extraction efficiency high and the comprehensive lithium recovery rate high, but the stability of lithium extraction between batches can also be guaranteed.

[0016] It should be noted that the specific surface area of ​​the calcined material of the present invention is determined by the multi-point BET method, which can be directly obtained by instrument detection. The specific surface area is a multi-point specific surface area; the average pore radius of the calcined material is also determined by this method. The average pore radius is the average radius of all pores of the calcined material under the saturated vapor pressure of the adsorbed gas during the test, that is, the single-point average pore radius. In the present invention, when testing the specific surface area and the average pore radius, the mesh size of the calcined material is -100 mesh, accounting for 80%. Specifically, the nitrogen adsorption and desorption method is used, the analytical instrument is (Autosorb iQ Station 1), the adsorbate is nitrogen, and the adsorbate is 4.353m 2 / mL, the sample was dried at 120℃ for 3h before testing, the test bath temperature was 77.35K, non-ideality: 6.58e-05 1 / Torr, cell type: 9mm w / o rod.

[0017] It should be noted that the bulk density of the calcined material of the present invention is determined using GB / T 1479.1-2011. In the present invention, when testing the bulk density, the mesh size of the calcined material is -100 mesh, accounting for 80%.

[0018] Preferably, the calcined material further comprises Al.

[0019] More preferably, the roasting material comprises the following components in percentage by mass:

[0020] Li 0.45-1.4%, K 4-8%, Na 1.5-9%, S 3.4-12.6%, Al 5.2-13%, and at least one of Ca, Ba, and Sr 2.5-9%.

[0021] More preferably, the roasting material comprises the following components in percentage by mass:

[0022] Li 0.45-1%, K 6-7%, Na 4-5%, S 8.2-10%, Al 5.2-11%, and at least one of Ca, Ba, and Sr 6-8%.

[0023] After screening, it was found that when the roasting material of the present invention is within the above-mentioned composition range, especially the Al content is within an appropriate range, and the roasting auxiliary elements such as Ca, Ba, and Sr and the sulfate content are controlled in an appropriate range ratio, the combination of feldspar, quartz and other components in the roasting material can achieve better lithium conversion rate and comprehensive recovery rate during lithium extraction, and the problem of incomplete leaching and low leaching efficiency caused by unstable lithium leaching rate or collapse of internal structure during lithium leaching will not occur.

[0024] More preferably, the mass content ratio of at least one of Ca, Ba, and Sr to S is 0.75 to 0.84.

[0025] The inventors found that since calcination aid elements such as Ca, Ba, Sr, Na and K have a great influence on the lithium leaching selectivity when the calcined material is used to extract lithium, when the composition of the calcined material is optimized, when the ratio of the calcination aid elements to the sulfate radicals matching at least one of Ca, Ba, Sr, Na and K in the calcined material is 0.75-0.84, the selectivity of the calcined material when extracting lithium is higher.

[0026] Preferably, the calcined material further comprises Si in an amount of 4.5 to 24% by mass.

[0027] More preferably, the calcined material further comprises 0.1-0.6% Mg, 0.15-0.75% Rb, 0.1-0.4% Cs, 0.01-0.5% Cl, 0.1-0.5% Fe and 0.15-6% F in mass percentage.

[0028] Preferably, the specific surface area of ​​the calcined material is 1 to 1.5 m 2 / g, average pore radius is 10-12nm, and bulk density is 0.5-0.7g / cm 3 .

[0029] Preferably, the single-point adsorption total pore volume of the calcined material is 0.005 to 0.009 cc / g.

[0030] More preferably, the single-point adsorption total pore volume of the calcined material is 0.007 to 0.008 cc / g.

[0031] The single-point total pore volume of the present invention is the total volume of all pores in the calcined material under the test conditions, that is, the single-point pore adsorption total pore volume, which can be directly detected by an instrument. When testing the single-point total pore volume, the mesh size of the calcined material is -100 mesh, accounting for 80%. Specifically, the BJH test is constructed using the nitrogen adsorption-desorption method to obtain the result. The nitrogen adsorption-desorption method is used, the analytical instrument is Autosorb iQ Station 1, the adsorbate is nitrogen, and the adsorbate is 4.353m 2 / mL, the sample was dried at 120℃ for 3h before testing, the bath temperature was 77.35K, non-ideality was 6.58e-05 1 / Torr, cell type was 9mm w / o rod, and the total pore volume was tested to below 200nm.

[0032] Preferably, the lithium extraction coefficient A of the calcined material satisfies the following relationship: 40≤A≤134, A=(M·B) / 3(b·p), wherein the mass content ratio of at least one of Ca, Ba, and Sr to S in the calcined material is M, and the specific surface area of ​​the calcined material is Bm 2 / g; the bulk density of the calcined material is bg / cm 3 ; The total pore volume of the calcined material by single-point adsorption is p cc / g.

[0033] The calcined material prepared by the sulfate process will contain residual Ca, Ba, and Sr ions from the added calcining aids. Compared with soluble Na or K, the removal of these ions requires the introduction of impurity removers, which in turn affects the efficiency and purity of lithium extraction and cannot maintain the stability of lithium extraction from the calcined material between batches. However, the content of these ions in the calcined material is too low, indicating that these ions are lost during the calcination process. Correspondingly, the degree of morphological modification of the original ore material during the calcination process will also be reduced, and the activation degree of the lithium contained therein will be insufficient. In particular, the introduction of the calcination aid will readjust the micropore structure of the original ore material itself, which will directly affect the specific surface area, pore volume, and bulk density of the calcined material. The inventors have found that when the lithium extraction coefficient A composed of these parameters is maintained at 40 to 134, on the one hand, the presence of the calcining aid elements can be avoided to affect the efficiency and purity of lithium leaching. On the other hand, the morphology of the calcined material can be effectively controlled so that the lithium element can be efficiently and stably leached under the most suitable pore structure, maintaining the lithium conversion rate deviation within 10% when the same batch of calcined materials is used.

[0034] More preferably, the lithium extraction coefficient A satisfies 52≤A≤119.

[0035] Among the roasting materials provided by the present invention, the roasting materials that further meet the lithium extraction coefficient A value of 52 to 119 have better lithium extraction efficiency and lithium extraction stability during leaching and lithium extraction.

[0036] Another object of the present invention is to provide a method for preparing the calcined material, comprising the following steps:

[0037] The lithium-containing raw ore material is mixed with a roasting aid and a lithium conversion agent, placed in a roasting device for roasting, and crushed to -100 mesh accounting for 80%, thereby obtaining the roasted material;

[0038] The lithium-containing ore material is pre-crushed into a powder with a size of -100 mesh accounting for 80% before being mixed with the roasting aid and the lithium conversion agent.

[0039] Preferably, the roasting device is at least one of a rotary kiln, a tunnel kiln, a roller kiln, and a vertical kiln.

[0040] Preferably, the roasting material is a rotary kiln roasting material

[0041] More preferably, the rotary kiln roasting material is prepared according to the following method:

[0042] The lithium-containing ore material is mixed with a roasting aid and a lithium converter, and the resulting mixture is placed in a rotary kiln and calcined at 550-650° C. for 1.5-2.5 hours. During the calcination, fluorine is removed by exhausting. The mixture is then heated to 1100-1110° C. and calcined at a rotary kiln rotation speed of 2.5-3.5 r / min for 3.5-4.5 hours to obtain the rotary kiln roasted material.

[0043] More preferably, the mixed material is in powder or spherical form before being placed in the rotary kiln, and the diameter of the spherical mixed material is 5 to 20 mm.

[0044] More preferably, the heating rate during calcination is 3-3.5°C / min.

[0045] Preferably, the roasting material is a roasting material made in a roller kiln.

[0046] More preferably, the roller kiln roasting material is prepared according to the following method:

[0047] The lithium-containing ore material is mixed with a roasting aid and a lithium converter, and the resulting mixture is then pressed into blocks of designed size, placed in a roller kiln and calcined at 800-1100° C. for 5.5-6.5 hours to obtain the roller kiln roasted material.

[0048] More preferably, the mixed material is in block shape before being placed into the roller kiln, with a length of 450 to 550 mm, a width of 400 to 450 mm, and a thickness of 40 to 50 mm.

[0049] More preferably, the heating rate during calcination is 3-3.5°C / min.

[0050] Preferably, the roasting material is a roasting material made in a tunnel kiln.

[0051] More preferably, the tunnel kiln roasting material is prepared according to the following method:

[0052] The lithium-containing ore material is mixed with a roasting aid and a lithium converter, and the resulting mixture is then pressed into blocks of designed size, placed in a tunnel kiln and calcined at 800-1100° C. for 5.5-6.5 hours to obtain the tunnel kiln roasted material.

[0053] More preferably, the mixture is in block shape before being placed into the tunnel kiln, with a length of 200 to 300 mm, a width of 50 to 150 mm, and a thickness of 40 to 60 mm.

[0054] More preferably, the heating rate during calcination is 3-3.5°C / min.

[0055] Preferably, the roasting material is roasting material produced in a vertical kiln.

[0056] More preferably, the vertical kiln roasting material is prepared according to the following method:

[0057] The lithium-containing ore material is mixed with a roasting aid and a lithium converter, and the resulting mixture is then pressed into balls of designed size, placed in a tunnel kiln and calcined at 800-1100° C. for 5.5-6.5 hours to obtain the vertical kiln roasted material.

[0058] More preferably, the mixed material is in a spherical shape with a diameter of 30 to 35 mm before being placed in the vertical kiln.

[0059] More preferably, the heating rate during calcination is 3-3.5°C / min.

[0060] It should be noted that, in addition to the preparation method described above, the roasting material of the present invention can also be prepared by other methods, as long as the prepared product can meet the above standard range.

[0061] Preferably, the lithium-containing ore material is at least one of lepidolite, spodumene, and lithium-containing ore waste.

[0062] More preferably, the lepidolite is lepidolite ore powder obtained by flotation of lepidolite ore.

[0063] Preferably, the lithium oxide mass content of the lithium-containing ore material is 0.5 to 4.5 wt%.

[0064] Preferably, the lithium conversion agent is at least one of sodium sulfate and potassium sulfate, and the roasting aid is at least one of calcium sulfate or its precursor, barium sulfate or its precursor, and strontium sulfate or its precursor.

[0065] More preferably, the mass ratio of the raw ore material, lithium conversion agent and roasting aid is: (raw ore material): (lithium conversion agent): (roasting aid) = 100: (6-25): (8-35).

[0066] In the preparation process of the roasting material described in the present invention, since the lithium grade of most raw ore materials is not high, it is necessary to introduce specific additives during the calcination of the raw ore materials. The introduction of the lithium converter is to destroy the original structure of the raw ore materials so that the lithium in the raw ore materials can be effectively released. The introduction of the roasting additive can reduce the generation rate of the melt during the combined calcination of the raw ore materials and the lithium converter, thereby improving the final lithium conversion rate.

[0067] At the same time, the roasting aid of the present invention can be directly added in advance, or a precursor can be added first and converted during the calcination process. Specifically, taking calcium sulfate as an example, those skilled in the art can directly mix calcium sulfate and raw ore materials into the kiln, or a precursor of calcium sulfate, such as calcium carbonate, calcium oxide, calcium chloride, etc., can be pre-mixed with the raw ore materials, and then sulfuric acid is added. During the roasting process, the precursor of calcium sulfate reacts with sulfuric acid to generate calcium sulfate and reacts with the raw ore materials and the lithium conversion agent.

[0068] Another object of the present invention is to provide application of the calcined material in industrial lithium extraction.

[0069] Preferably, the industrial lithium extraction process includes the steps of crushing, lithium leaching, impurity removal, and concentrated precipitation of lithium carbonate.

[0070] More preferably, the steps of extracting lithium in the process are:

[0071] (1) adding the roasted material into a ball mill, adding an appropriate amount of lithium-containing washing water and grinding it into a slurry, then adjusting the slurry pH to 6.5-7.5 and controlling the slurry liquid-solid ratio to (2-1.5):1, after the lithium is completely leached, separating the solid and the liquid to obtain a lithium leachate;

[0072] (2) After the lithium leaching solution is impurity-removed, it is concentrated and sodium carbonate, a lithium precipitating agent, is added to precipitate lithium carbonate, thereby completing the industrial lithium extraction of the roasted material.

[0073] When the roasted material of the present invention is leached under a neutral environment, lithium ions can be stably and completely converted and leached, and at the same time, they will not be converted to generate colloidal impurities such as aluminum hydroxide that clog the subsequent filtration device and affect the product purity. The solid-liquid separation effect is good. At the same time, under the condition of the low liquid-solid ratio, the concentration of lithium ions in the lithium leachate is higher, the lithium extraction efficiency is significantly improved, and the lithium extraction batch stability is good, and the amplitude error of the lithium conversion rate and the recovery rate can be effectively controlled within an ideal range.

[0074] Preferably, the method for extracting lithium from a calcined material according to the present invention comprises the following steps:

[0075] The calcined material is added to a lithium-containing washing solution and ground in a ball mill to form a lithium-containing slurry, which is then added to a mixing tank. The slurry is filtered to obtain a lithium-containing mixed solution with a pH of 6.5 to 7.5. The mixed solution is then concentrated after impurities are removed and a lithium precipitator, sodium carbonate, is added to obtain a lithium carbonate product. The lithium precipitator mother liquor is evaporated and concentrated in an evaporator to crystallize into a sulphur powder product. The lithium-containing mother liquor is then added with a lithium precipitator, sodium carbonate, to precipitate the lithium carbonate product.

[0076] Compared with traditional acid leaching, this method does not produce colloidal substances such as iron hydroxide that clog the filter layer, resulting in low product yield or reduced purity. It has better solid-liquid separation effect and can be implemented with a lower liquid-solid ratio, resulting in higher leaching efficiency.

[0077] Preferably, the liquid-to-solid ratio of the mixed liquid is (1-2):1.

[0078] The beneficial effect of the present invention is that the present invention provides a roasting material and its application, based on the technical bottleneck that the lithium conversion rate and comprehensive recovery rate of the existing roasting material need to be improved, and it is difficult to ensure stability under further leaching. In the roasting material provided by the present invention, the lithium contained therein is effectively activated, and these activated lithiums can evenly precipitate lithium carbonate during the lithium extraction process. At the same time, the activated lithium precipitation is highly selective, and the amount of impurity ions precipitated is small. When the product is used for industrial lithium extraction, not only is the lithium extraction efficiency high and the comprehensive lithium recovery rate high, but the stability of lithium extraction between batches can also be guaranteed. It is only necessary to take an advance batch for pre-extraction of lithium after the preparation is completed, and the lithium extraction cost and lithium extraction profit of the entire batch can be calculated based on the results, which is conducive to quality monitoring and data statistics during factory-scale large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0079] Figure 1 This is a scanning electron microscope image of the lepidolite described in Example 1 of the present invention.

[0080] Figure 2 This is a scanning electron microscope image of the calcined material described in Example 1 of the present invention.

[0081] Figure 3 This is the XRD pattern of the lepidolite described in Example 1 of the present invention.

[0082] Figure 4 This is the XRD pattern of the calcined material described in Example 1 of the present invention. DETAILED DESCRIPTION

[0083] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments and comparative examples. Its purpose is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without making creative work premise belong to the protection scope of the present invention. The experimental reagents, raw materials and instruments designed for the implementation of the present invention and the comparative examples are all conventional common reagents, raw materials and instruments unless otherwise specified.

[0084] It should be noted that the terms "include", "comprising" and "having" and any variations thereof in the specification and claims of the present invention and the above-mentioned drawings are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device that includes a series of steps or units is not limited to the listed steps or units, but may optionally include steps or units that are not listed, or may optionally include other steps or units that are inherent to these processes, methods, products or devices. In the claims, specifications and drawings of the present invention, relational terms such as "first" and "secondarily" are merely used to distinguish one entity / operation / object from another entity / operation / object, and do not necessarily require or imply any actual relationship or order between these entities / operations / objects. In particular, there is no order between the parallel samples involved in the various embodiments and comparative examples in the specific implementation method of the present invention. Those skilled in the art should know that for the sake of convenience of expression, numbering and adjusting the placement order of the various embodiments / comparative examples and their parallel samples will not affect the display of the technical effects.

[0085] In a specific embodiment of the present invention, the calcined material includes the following components in percentage by mass: Li 0.7-1%, K 4-8%, Na 1.5-9%, S 5-10%, Al 7.5-13%, at least one of Ca, Ba, and Sr 6-10%, and Si 11.5-16.5%.

[0086] In a specific embodiment of the present invention, the calcined material includes the following components in percentage by mass: Li 1-1.4%, K 5-10%, Na 1.5-2.5%, S 3.4-5%, Al 11-13%, at least one of Ca, Ba, and Sr 1.5-5%, and Si 21-24%.

[0087] In a specific embodiment of the present invention, the calcined material includes the following components in percentage by mass: Li 0.23-0.7%, K 4-6%, Na 5-10%, S 12-13.5%, Al 5.2-11%, at least one of Ca, Ba, and Sr 8-10%, and Si 16-19%.

[0088] In each embodiment and comparative example, in addition to the main components, some trace elements are actually present in lithium-containing raw ore materials such as lithium mica flotation ore powder and roasted materials. For example, in the raw ore materials and roasted materials, in addition to the listed components, the remaining mass is trace elements such as Pb, Cr, Cd, As, and P. Because the content of such trace elements is extremely low (the single mass content in the raw ore material is less than 0.001wt% at most, and the single mass content in the roasted material is less than 0.00005wt% at most), and the freeness is high relative to other components, it has basically no effect on the processing and performance of the roasted material of the present invention, and therefore they are not listed one by one in the specific embodiments below.

[0089] After the calcined materials are prepared, they are crushed to -100 meshes accounting for 80%, and then the components and physical properties are tested.

[0090] In this specific embodiment, the grinding process used for material mixing is performed using a commercial stirring mill at a normal speed of 30 r / min, and the ball milling is performed using a commercial vertical ball mill at 120 r / min for 1 hour.

[0091] Example 1

[0092] An embodiment of the roasting material of the present invention is prepared according to the following method:

[0093] (1) Lepidolite flotation ore powder from a mineral processing plant in Jiangxi Province was selected. The composition (wt%) of the lepidolite raw material is shown in Table 1 (some trace elements are not listed one by one).

[0094] Table 1

[0095]

[0096] (2) After the lepidolite flotation ore powder is crushed into a powder with a mesh size of -100 accounting for 80%, it is mixed with calcium sulfate and sodium sulfate in a mass ratio of lepidolite ore powder: calcium sulfate: sodium sulfate = 100:25:15, stirred and ground, and ball-milled uniformly. It is then pressed into a block material of 510 mm × 430 mm × 45 mm, placed in a roller kiln, calcined at 900 ° C for 6 hours, and crushed into a powder with a mesh size of -100 accounting for 80%, thereby obtaining the calcined material.

[0097] Five batches of roasted material products (ie, five blocks of block material, one block being counted as one batch) were prepared in parallel using this scheme, and were labeled as products of Example 1-1 to Example 1-5.

[0098] The properties of each product are shown in Table 2 (the mass content of some trace elements is not listed one by one):

[0099] Table 2

[0100]

[0101]

[0102] Example 2

[0103] An embodiment of the roasting material of the present invention is prepared according to the following method:

[0104] (1) Same as Example 1;

[0105] (2) After the lepidolite flotation ore powder is crushed into a powder with a mesh size of -100 accounting for 80%, it is mixed with calcium sulfate and sodium sulfate in a mass ratio of lepidolite ore powder: calcium sulfate: sodium sulfate = 100:25:15, stirred and ground, and ball-milled uniformly. Subsequently, it is pressed into a block material of 245 mm × 90 mm × 50 mm, placed in a tunnel kiln, calcined at 920° C. for 6 h, and crushed into a powder with a mesh size of -100 accounting for 80%, thereby obtaining the calcined material.

[0106] This scheme prepared five batches of roasted material products in parallel, which were labeled as Example 2-1 to Example 2-5.

[0107] The properties of each product are shown in Table 3 (the mass content of some trace elements is not listed one by one):

[0108] Table 3

[0109]

[0110]

[0111] Example 3

[0112] An embodiment of the roasting material of the present invention is prepared according to the following method:

[0113] (1) Lepidolite flotation ore powder from a ore dressing plant in Jiangxi Province was selected. The composition (wt%) of the lepidolite raw material is shown in Table 4 (some trace elements are not listed one by one).

[0114] Table 4

[0115]

[0116] (2) Same as Example 2.

[0117] Five batches of roasted material products were prepared in parallel using this scheme, which were labeled as Example 3-1 to Example 3-5.

[0118] The properties of each product are shown in Table 5 (the mass content of some trace elements is not listed one by one):

[0119] Table 5

[0120]

[0121]

[0122] Example 4

[0123] An embodiment of the roasting material of the present invention, the preparation method of the lepidolite flotation ore powder and the roasting material selected in this embodiment is the same as that in Example 1, the only difference being that the preparation batches are different, and the calcination condition is calcination at 890°C for 6h;

[0124] This scheme prepared five batches of roasted material products in parallel, which were labeled as Example 4-1 to Example 4-5 products.

[0125] The properties of each product are shown in Table 6 (the mass content of some trace elements is not listed one by one):

[0126] Table 6

[0127]

[0128]

[0129] Example 5

[0130] An embodiment of the roasting material of the present invention is prepared according to the following method:

[0131] (1) Same as Example 1;

[0132] (2) After the lepidolite flotation ore powder is crushed into a powder with a mesh size of -100 accounting for 80%, it is mixed with calcium sulfate and sodium sulfate in a mass ratio of lepidolite ore powder: calcium sulfate: sodium sulfate = 100:23:17, stirred, ground and ball-milled uniformly, and then pressed into a block material of 245mm×90mm×50mm, placed in a tunnel kiln, calcined at 920°C for 6h, and crushed into a powder with a mesh size of -100 accounting for 80%, thereby obtaining the calcined material.

[0133] This scheme prepared five batches of roasted material products in parallel, which were labeled as Example 5-1 to Example 5-5 products.

[0134] The properties of each product are shown in Table 7 (the mass content of some trace elements is not listed one by one):

[0135] Table 7

[0136]

[0137]

[0138] Example 5-A

[0139] An embodiment of the roasting material of the present invention is prepared according to the following method:

[0140] (1) Same as Example 1;

[0141] (2) After the lepidolite flotation ore powder is crushed into a powder with a mesh size of -100 accounting for 80%, it is mixed with calcium sulfate and sodium sulfate in a mass ratio of lepidolite ore powder: calcium sulfate: sodium sulfate = 100:23:17, ground and ball-milled uniformly, and then pressed into a block material of 245mm×90mm×50mm, placed in a roller kiln, calcined at 920°C for 6h, and crushed into a powder with a mesh size of -100 accounting for 80%, thereby obtaining the calcined material.

[0142] This scheme prepared five batches of roasted material products in parallel, which were labeled as Example 5-1 to Example 5-5 products.

[0143] The properties of each product are shown in Table 7-1 (the mass content of some trace elements is not listed one by one):

[0144] Table 7-1

[0145]

[0146]

[0147] Example 6

[0148] An embodiment of the roasting material of the present invention is prepared according to the following method:

[0149] (1) Same as Example 1;

[0150] (2) After the lepidolite flotation ore powder is crushed into a powder with a mesh size of -100 and a proportion of 80%, the powder is mixed with calcium sulfate and sodium sulfate in a mass ratio of lepidolite ore powder: calcium sulfate: sodium sulfate = 100:25:15, ground and ball-milled uniformly, and then pressed into a sphere with a diameter of 26 mm, placed in a rotary kiln and calcined at 500° C. for 2 h, during which fluorine is removed by exhaustion, and then heated to 1100° C. and calcined at a rotary kiln rotation speed of 3 r / min for 4 h to obtain the rotary kiln roasted material.

[0151] This scheme prepared five batches of roasted material products in parallel, which were labeled as Example 6-1 to Example 6-5.

[0152] The properties of each product are shown in Table 8 (the mass content of some trace elements is not listed one by one):

[0153] Table 8

[0154]

[0155]

[0156] Example 7

[0157] An embodiment of the roasting material of the present invention is prepared according to the following method:

[0158] (1) Same as Example 1;

[0159] (2) After the lepidolite flotation ore powder is crushed into a powder with a mesh size of -100 accounting for 80%, it is evenly mixed with calcium sulfate and sodium sulfate in a mass ratio of lepidolite ore powder: calcium sulfate: sodium sulfate = 100:24:16, and then pressed into a block material of 245mm×90mm×50mm, placed in a tunnel kiln, calcined at 1000°C for 6h, and crushed into a powder with a mesh size of -100 accounting for 80%, thereby obtaining the calcined material.

[0160] This scheme prepared five batches of roasted material products in parallel, which were labeled as Example 7-1 to Example 7-5.

[0161] The properties of each product are shown in Table 9 (the mass content of some trace elements is not listed one by one):

[0162] Table 9

[0163]

[0164]

[0165] Example 8

[0166] An embodiment of the roasting material of the present invention is prepared according to the following method:

[0167] (1) Same as Example 3;

[0168] (2) After the lepidolite flotation ore powder is crushed into a powder with a mesh size of -100 accounting for 80%, it is evenly mixed with calcium sulfate and sodium sulfate in a mass ratio of lepidolite ore powder: calcium sulfate: sodium sulfate = 100:27:13, and then pressed into a block material of 510mm×430mm×45mm, placed in a roller kiln, calcined at 850°C for 6h, and crushed into a powder with a mesh size of -100 accounting for 80%, thereby obtaining the calcined material.

[0169] Five batches of roasted material products were prepared in parallel using this scheme, which were labeled as Example 8-1 to Example 8-5.

[0170] The properties of each product are shown in Table 10 (the mass content of some trace elements is not listed one by one):

[0171] Table 10

[0172]

[0173]

[0174] Example 9

[0175] An embodiment of the roasting material of the present invention is prepared according to the following method:

[0176] (1) A raw ore material of spodumene ore mixed with lithium-containing ore waste was collected from a mine in Jiangxi Province and crushed into a -100 mesh powder accounting for 80%. The composition (wt%) of the raw ore material is shown in Table 11 (some trace elements are not listed one by one).

[0177] Table 11

[0178] <![CDATA[Li2O]]> K Na Ca Mg Rb, Cs, Fe <![CDATA[Cl - ]]> <![CDATA[SO4 2- ]]> <![CDATA[SiO2]]> F <![CDATA[Al2O3]]> 2.30 9.05 0.25 1.35 0.56 2.2 0.00045 0.05 48.5 9.21 25.15

[0179] (2) Same as Example 2.

[0180] This scheme prepared five batches of roasted material products in parallel, which were labeled as Example 9-1 to Example 9-5.

[0181] The properties of each product are shown in Table 12 (the mass content of some trace elements is not listed one by one):

[0182] Table 12

[0183]

[0184]

[0185] Example 10

[0186] An embodiment of the roasting material of the present invention is prepared according to the following method:

[0187] (1) Lepidolite flotation ore powder from a mineral processing plant in Jiangxi Province was selected. The composition (wt%) of the lepidolite flotation ore powder is shown in Table 13 (some trace elements are not listed one by one).

[0188] Table 13

[0189] <![CDATA[Li2O]]> K Na Ca Mg Rb, Cs, Fe <![CDATA[Cl - ]]> <![CDATA[SO4 2- ]]> <![CDATA[SiO2]]> F <![CDATA[Al2O3]]> 2.5 9.08 0.25 1.38 0.35 0.75 0.0003 0.05 47.5 2.21 35.15

[0190] (2) After the lepidolite flotation ore powder is crushed into a powder with a size of -100 mesh accounting for 80%, it is mixed with calcium sulfate and sodium sulfate in a mass ratio of lepidolite ore powder: calcium sulfate: barium sulfate: sodium sulfate = 100:15:10:15, ground and ball-milled uniformly, and then pressed into pellets with a diameter of 30 mm, placed in a vertical kiln, and calcined at 1050° C. for 6 hours, and crushed into a powder with a size of -100 mesh accounting for 80%, thereby obtaining the roasted material.

[0191] Five batches of roasted material products (one block is counted as one batch) were prepared in parallel using this scheme and were labeled as Example 10-1 to Example 10-5.

[0192] The properties of each product are shown in Table 14 (the mass content of some trace elements is not listed one by one):

[0193]

[0194] Example 11

[0195] An embodiment of the roasting material of the present invention is prepared according to the following method:

[0196] (1) Same as Example 1;

[0197] (2) After the lepidolite flotation ore powder is crushed into a powder with a mesh size of -100 accounting for 80%, it is evenly mixed with calcium sulfate and sodium sulfate in a mass ratio of lepidolite ore powder: calcium sulfate: sodium sulfate = 100:25:15, and then pressed into a block material of 245mm×90mm×50mm, placed in a tunnel kiln, calcined at 900℃ for 6.5h, and crushed into a powder with a mesh size of -100 accounting for 80%, thereby obtaining the calcined material.

[0198] Five batches of roasted material products were prepared in parallel using this scheme, which were labeled as Example 11-1 to Example 11-5.

[0199] The properties of each product are shown in Table 15 (the mass content of some trace elements is not listed one by one):

[0200] Table 15

[0201]

[0202]

[0203] Comparative Example 1

[0204] A roasting material, wherein the roasting material is prepared according to the following method:

[0205] (1) Same as Example 1;

[0206] (2) After the lepidolite flotation ore powder is crushed into a powder with a mesh size of -100 accounting for 80%, it is mixed with calcium sulfate and sodium sulfate in a mass ratio of lepidolite ore powder: calcium sulfate: sodium sulfate = 100:30:10, ground and ball-milled uniformly, and then pressed into a block material of 245mm×90mm×50mm, placed in a tunnel kiln, calcined at 1050°C for 6.5h, and crushed into a powder with a mesh size of -100 accounting for 80%, thereby obtaining the calcined material.

[0207] Five batches of roasted material products were prepared in parallel using this scheme, which were labeled as Comparative Example 1-1 to Comparative Example 1-5 products.

[0208] The properties of each product are shown in Table 16 (the mass content of some trace elements is not listed one by one):

[0209] Table 16

[0210]

[0211]

[0212] Comparative Example 2

[0213] A roasting material, wherein the roasting material is prepared according to the following method:

[0214] (1) Same as Example 1

[0215] (2) After the lepidolite flotation ore powder is crushed into a powder with a mesh size of -100 accounting for 80%, it is mixed with calcium sulfate and sodium sulfate in a mass ratio of lepidolite ore powder: calcium sulfate: sodium sulfate = 100:22:18, ground and ball-milled uniformly, and then pressed into a block material of 510mm×430mm×45mm, placed in a roller kiln, calcined at 820°C for 6h, and crushed into a powder with a mesh size of -100 accounting for 80%, thereby obtaining the calcined material.

[0216] Five batches of roasted material products (one block is counted as one batch) were prepared in parallel using this scheme, and were labeled as Comparative Example 2-1 to Comparative Example 2-5 products.

[0217] The properties of each product are shown in Table 17 (the mass content of some trace elements is not listed one by one):

[0218] Table 17

[0219]

[0220]

[0221] Effect Example 1

[0222] In order to explore the properties of the calcined material of the present invention, the calcined material obtained in Example 1 and its raw material lepidolite were subjected to XRD detection and scanning electron microscopy observation respectively. The results are as follows: Figures 1-2 as well as Figures 3-4 As shown, from Figures 1 to 4 It can be seen that the lithium mica ore powder before calcination mainly presents a regular flake structure, and its main component is lithium mica, accompanied by some quartz and calcite. After calcination, the prepared roasted material is converted into a loose block structure, indicating that the introduction of lithium conversion agent and roasting aid has caused a major change in the structure of lithium mica. After testing, it can be seen that the main components of the product are converted into a composite mineral phase containing aluminum, silicon and calcium, mainly feldspar, quartz and gypsum, and there is no obvious agglomeration phenomenon.

[0223] Furthermore, the parallel batches of roasted materials prepared in each embodiment and comparative example were used for industrial lithium extraction. Since the mass of the roasted materials in each parallel batch was large, the crushed powder was further divided into 5 parts and processed in the following steps. The processing results of the 5 parts of powder were finally counted and recorded in Table 18:

[0224] (1) adding the crushed powder of the roasted material to deionized water to prepare a slurry, then controlling the pH of the slurry to 7 with sulfuric acid and lime powder, at which point the liquid-to-solid ratio of the slurry is 1.5:1, stirring and reacting for 2 hours, and after the lithium is completely leached, filtering the mixture to obtain a lithium leachate;

[0225] (2) The lithium leachate is removed from the impurities, then heated to 60°C and further stabilized at a pH of 7, and the lithium leachate is concentrated. When the solution is concentrated to only 3 / 4 of the initial concentration, it is heated to 95°C and sodium carbonate is added as a lithium precipitant to obtain lithium carbonate precipitate, which is then washed with water and dried at 150°C in air for 4 hours to obtain lithium carbonate fine product;

[0226] The impurity removal step includes: adding sodium hydroxide to the lithium leaching solution to adjust the solution pH to 12, then adding an impurity remover (5wt% sodium carbonate solution), heating to 95°C and keeping the temperature for 30 minutes, and filtering to obtain an impurity-removed solution after testing for qualified impurities.

[0227] The statistics of Tables 18 to 30 are calculated according to a statistical method similar to that of the inventor's prior patent CN106745097B. This table only shows the Li2O leaching rate of the leachate calculated after each statistical calculation (measured as the ratio of the lithium content in the leachate to the Li2O in the raw ore material), the total direct recovery of Li2O in the lithium precipitation process (measured as the ratio of the precipitated lithium in the lithium precipitation process to the lithium content in the leachate), the product purity and the total lithium recovery rate, and the lithium conversion rate (measured as the ratio of the final recovered lithium to the Li2O in the raw ore material). Among them, the indicators of each Li2O are converted based on the detection indicators of the target product lithium carbonate, and the variation range of the total direct recovery of Li2O and the total lithium recovery rate is the difference between the maximum and minimum values ​​of the test sample results.

[0228] Table 18

[0229]

[0230]

[0231] Table 19

[0232]

[0233]

[0234] Table 20

[0235]

[0236]

[0237] Table 21

[0238]

[0239]

[0240] Table 22

[0241]

[0242]

[0243] Table 22-1

[0244]

[0245] Table 23

[0246]

[0247] Table 24

[0248]

[0249]

[0250] Table 25

[0251]

[0252]

[0253] Table 26

[0254]

[0255]

[0256] Table 27

[0257]

[0258]

[0259] Table 28

[0260]

[0261]

[0262] Table 29

[0263]

[0264]

[0265] Table 30

[0266]

[0267]

[0268] The statistical results are shown in Tables 18 to 30. The lithium conversion rate and the comprehensive lithium recovery rate of the calcined materials prepared in each embodiment are maintained at a high level during the industrial lithium extraction process. The average total direct recovery rate of Li2O in the lithium precipitation process of the products of each embodiment prepared by the roller kiln and the tunnel kiln can reach more than 92%, and the average total lithium recovery rate can reach 80%. At the same time, the total direct recovery rate of Li2O and the total lithium recovery rate in the industrial lithium precipitation process can be maintained within 15%. A statistical comparison of the calcined materials obtained in Example 1 and Example 2 shows that the total direct recovery rate of Li2O and the total lithium recovery rate of the five parallel products in Example 1 in the industrial lithium precipitation process can be maintained within 10%. While the physical properties such as specific surface area and apparent density of the product of Example 2 are similar to those of Example 1, its component composition can be controlled within the range of Li 0.45-1%, K 6-7%, Na 4-5%, S 8.2-10%, Al In the range of 5.2-11% and 6-8% of at least one of Ca, Ba, and Sr, the total direct recovery rate of Li2O and the total lithium recovery rate in the industrial lithium precipitation process can be maintained within 5%, indicating that within this range, under the same lithium extraction process, the leaching rate of Li2O in the roasted material is more stable, the leaching degree is more complete, the component uniformity of the roasted material is higher, and even if the leaching is carried out in batches, the leaching effect of each batch can be guaranteed to be almost the same. In large-scale industrial production, the product with high lithium recovery rate and high lithium extraction stability is more helpful for manufacturers to control quality and statistics of finished products, and avoid economic losses due to excessive fluctuations in batch production capacity; at the same time, when the five parallel products of Examples 2-1 to 2-5 were crushed into multiple powders for industrial lithium extraction, the total direct recovery rate of Li2O all reached more than 92%, and the total lithium recovery rate all reached more than 80%, which is the best among all the embodiments. As can be seen from Example 3, when different lepidolites are selected for the preparation of tunnel kiln calcined materials, when the composition and physical properties of the products are still within the specified range of the present invention, they can still achieve similar effects as in Examples 1 and 2 during industrial lithium extraction. Under the same preparation process, due to the large differences in the local uniformity of the composition of the lepidolite itself, and the presence of many random factors affecting the final composition of the product when mixed with various calcination aids and calcined in the kiln, the composition of the five parallel products prepared has certain differences, and the stability during industrial lithium extraction is also different. Compared with Examples 3-1 to 3-4, the composition of the product of Example 3-5 meets the preferred range combination of Li 0.45-1.4%, K 4-8%, Na 1.5-9%, S 3.4-12.6%, Al 5.2-13% and at least one of Ca, Ba, and Sr 2.5-9% of the present invention. Therefore, the total direct recovery rate of Li2O and the total recovery rate of lithium in the industrial lithium precipitation process can be maintained within 10%.There are certain differences in the composition of the five parallel samples in Example 4, among which the products of Example 4-4 and Example 4-5 meet the preferred composition range, and the stability during industrial lithium extraction is better than that of Example 4-1 to Example 4-3, and the total direct yield of Li2O and the total recovery rate of lithium are both maintained within 5%. In Example 5, the composition of the five parallel products is relatively similar, and all meet the further preferred composition range of the present invention. The difference between the parallel products lies in the difference in physical parameters such as the specific surface area, average pore radius, and bulk density of the products. The inventors have found through experiments that the difference in these physical parameters will further affect the direct yield of Li2O during lithium extraction and the extraction efficiency of the non-lithium components precipitated simultaneously. When the prepared roasted material product is further preferably prepared with a specific surface area of ​​1 to 1.5 m2. 2 / g, average pore radius is 10-12nm, and bulk density is 0.5-0.7g / cm 3 When the range is within the range, the corresponding Example 5-5 product has better lithium extraction stability than the products of Example 5-1 to Example 5-4, and the total lithium recovery rate is also higher. As can be seen from Example 6, when roasting in different kilns under the same conditions, there are also differences in physical parameters and element ratios compared with Example 5. This is mainly because the roasting method of the rotary kiln is different from that of other kilns during roasting, but the lithium extraction effect and rules of the product are also similar to those of Example 5. When the physical parameters meet the preferred range, the lithium extraction performance of the product is better. In addition, it can be seen from Example 9 that the raw materials for the preparation of the product of the present invention are not limited to lithium mica, and the same effect can be achieved by using materials such as spodumene, lithium-containing mine waste and mixtures thereof as raw ore materials. The product described in Example 10 uses a vertical kiln in the preparation process, and the calcination environment is more stable, so the quality of the roasted material is better and the lithium extraction effect is better.

[0269] From the lithium extraction effects of the products in Examples 1 to 3, it can be seen that when the components of the roasting materials are similar, the roasting auxiliary elements and SO4 2- When the mass content ratio is 0.75-0.84, the total lithium recovery rate of the product is higher. At the same time, this gap is more obvious when the product composition is preferably Li 0.45-1.4%, K 4-8%, Na 1.5-9%, S 3.4-12.6%, Al 5.2-13%. It can be seen from the 10 samples in Example 2 and Example 11 that the product has similar component compositions due to similar preparation processes and raw materials, but the difference between the calcination auxiliary elements and SO4 2- The average total lithium recovery rate of products with a mass content ratio of 0.75 to 0.84 is about 3% higher than that of other products.

[0270] On the other hand, the inventors found that when the prepared roasted material products are relatively close in component composition and physical property parameters, the change of lithium extraction coefficient A will also have a certain impact on the stability of the product during industrial lithium extraction. From the lithium extraction results of the products of Examples 7-1 to 7-5 and 8-1 to 8-5, it can be seen that even if the preferred Li0.45-1.4%, K 4-8%, Na 1.5-9%, S 3.4-12.6%, Al The range of the direct recovery rate of Li2O and the total recovery rate of lithium in the product is 5.2-13% and 2.5-9% of at least one of Ca, Ba, and Sr. However, if the lithium extraction coefficient A satisfies 40≤A≤134, the variation range of the direct recovery rate of Li2O and the total recovery rate of lithium in the product during lithium extraction can also be maintained within 10%. When the lithium extraction coefficient A of the product is in the further preferred range of 52-119, the stability of the product during lithium extraction is better, the variation range of the direct recovery rate of Li2O and the total recovery rate of lithium can be maintained within 5%, and the lower limits of the direct recovery rate of Li2O and the total recovery rate of lithium in a single batch of samples are higher. At the same time, the product performance of Examples 7-4 and 7-4 that meet the element ratio is better.

[0271] From the comparison of the results of lithium extraction between the examples and the comparative examples, it can be seen that even if parallel products are prepared using the same preparation process, if the component composition and physical properties of the products cannot be guaranteed to be within the range defined by the present invention, it will not only be difficult to ensure the lithium extraction stability of the products, but may even lead to a lower limit of the direct recovery rate of Li2O or the total recovery rate of lithium for some parallel products (i.e., the activation lithium precipitation efficiency is low, or the precipitation efficiency of the impurity components is too high, and the overall lithium selectivity is low). At this time, it will affect the quality control of the products during large-scale production and the accuracy of the finished product statistics. As shown in Comparative Example 1, some component compositions or physical properties of the products of Comparative Examples 1-1 to 1-4 do not conform to the range defined by the present invention, and are not It is only difficult to control the Li2O direct yield or total lithium recovery rate of each parallel sample within 15%. At the same time, the Li2O direct yield or total lithium recovery rate of some individual samples is low, resulting in a decrease in the overall average value compared with the example products. The products of Comparative Examples 1-5 prepared under the same process are in line with the limited range of the present invention and have performance similar to that of the example products. It can be seen that the lithium extraction stability of the roasting material cannot be judged simply based on the raw material formula for the preparation of the roasting material and the adjustment of the roasting device. This also corresponds to the problems existing in the existing process. The limitation of the roasting material described in the present invention can be separated from the preparation method and preparation formula of the roasting material, and excellent lithium extraction stability can be achieved only by relying on the property limitations of the product itself.

[0272] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A roasting material for extracting lithium from lithium-containing raw ore, characterized in that: Ingredients: Li, S, Na, K, Al, Si, and one, two or three of Ca, Ba and Sr, The mass percentages of Li, S, Na, K, Al and Si in the calcined material satisfy the following requirements: 0.45%≤Li≤1%, 8.2%≤S≤10%, 4%≤Na≤5%, 6%≤K≤7%, 5.2%≤Al≤11%, 4.5%≤Si≤24%; The mass percentages of Ca, Ba and Sr in the calcined material satisfy the following requirements: 6%≤Ca+Sr+Ba≤8%; The lithium extraction coefficient A of the calcined material satisfies the following relationship: 52≤A≤119, A=(M·B) / 3(b·p); M is the mass content ratio of at least one of Ca, Ba, and Sr to S in the calcined material; B is the specific surface area of ​​the calcined material, in m 2 / g; b is the bulk density of the calcined material, in g / cm 3 ; p is the total single-point adsorption pore volume of the calcined material, in cc / g; The specific surface area of ​​the calcined material is 1~2m 2 / g, average pore radius is 8~15nm, and bulk density is 0.2~0.8g / cm 3 The total pore volume of single-point adsorption is 0.005~0.009cc / g.

2. The roasting material according to claim 1, wherein The mass content ratio of at least one of Ca, Ba, and Sr to S is 0.75-0.

84.

3. The roasting material according to claim 1, wherein The mass percentages of Li, S, Na, K, Al and Si in the calcined material satisfy the following requirements: 0.7%≤Li≤1%, 5%≤S≤10%, 1.5%≤Na≤9%, 4%≤K≤8%, 7.5%≤Al≤13%, 11.5%≤Si≤16.5%; The mass percentages of Ca, Ba and Sr in the calcined material satisfy the following requirements: 6%≤Ca+Sr+Ba≤10%.

4. The roasting material according to claim 1, wherein The mass percentages of Li, S, Na, K, Al and Si in the calcined material satisfy the following requirements: 1%≤Li≤1.4%, 5%≤S≤10%, 1.5%≤Na≤2.5%, 5%≤K≤10%, 11%≤Al≤13%, 21%≤Si≤24%; The mass percentages of Ca, Ba and Sr in the calcined material satisfy the following requirements: 1.5%≤Ca+Sr+Ba≤5%.

5. The roasting material according to claim 1, wherein The mass percentages of Li, S, Na, K, Al and Si in the calcined material satisfy the following requirements: 0.23%≤Li≤0.7%, 12%≤S≤13.5%, 5%≤Na≤10%, 4%≤K≤6%, 5.2%≤Al≤11%, 16%≤Si≤19%; The mass percentages of Ca, Ba and Sr in the calcined material satisfy the following requirements: 8%≤Ca+Sr+Ba≤10%.

6. The roasting material according to claim 1, wherein The calcined material further comprises 0.1-0.6% Mg, 0.15-0.75% Rb, 0.1-0.4% Cs, 0.01-0.5% Cl, 0.1-0.5% Fe and 0.15-6% F in mass percentage.

7. The roasting material according to claim 1, wherein When the mesh number of the calcined material is -100 mesh accounting for 80%, the specific surface area is 1~1.5m 2 / g, average pore radius is 10~12nm, and bulk density is 0.5~0.7g / cm 3 .

8. The method for preparing a calcined material for extracting lithium from a lithium-containing raw ore material according to any one of claims 1 to 7, wherein: The following steps are involved: The lithium-containing ore material is crushed, mixed with a roasting aid and a lithium conversion agent, placed in a roasting device and roasted, and crushed to -100 mesh accounting for 80%, thereby obtaining the roasted material.

9. The preparation method according to claim 8, wherein The lithium-containing ore material is at least one of lepidolite, spodumene, and lithium-containing ore waste; and the lithium oxide mass content of the lithium-containing ore material is 0.5-4.5wt%.

10. The preparation method according to claim 8, characterized in that The lithium conversion agent is at least one of sodium sulfate and potassium sulfate, and the roasting aid is at least one of calcium sulfate, barium sulfate, and strontium sulfate; the mass ratio of the lithium-containing ore material, the lithium conversion agent, and the roasting aid is: (lithium-containing ore material): (lithium conversion agent): (roasting aid) = 100: (6~25): (8~35).

11. The preparation method according to claim 8, characterized in that The roasting device is a rotary kiln.

12. The preparation method according to claim 11, characterized in that The preparation method is: The lithium-containing ore material is crushed into a -100 mesh powder accounting for 80%, and then mixed with a roasting aid and a lithium conversion agent. The resulting mixture is placed in a rotary kiln and calcined at 450-550° C. for 1.5-2.5 hours. During the calcination, fluorine is removed by exhausting. The mixture is then heated to 1100-1110° C. and calcined at a rotary kiln rotation speed of 2.5-3.5 r / min for 3.5-4.5 hours to obtain the roasted material.

13. The preparation method according to claim 8, wherein The roasting device is a roller kiln.

14. The preparation method according to claim 13, wherein The preparation method is: The lithium-containing ore material is crushed into a -100 mesh powder accounting for 80%, and then mixed with a roasting aid and a lithium converter. The resulting mixture is then pressed into blocks of designed size and placed in a roller kiln for calcination at 800-1100°C for 5.5-6.5 hours to obtain the roasted material.

15. The preparation method according to claim 14, wherein The mixed material is in block shape before being placed into the roller kiln, with a length of 450-550 mm, a width of 400-450 mm, and a thickness of 40-50 mm.

16. The preparation method according to claim 8, characterized in that The roasting device is a tunnel kiln.

17. The preparation method according to claim 16, wherein The preparation method is: The original lithium-containing ore material is crushed into a -100 mesh powder accounting for 80% of the mesh, and then mixed with a roasting aid and a lithium conversion agent. The resulting mixture is then pressed into blocks of designed size and placed in a tunnel kiln for calcination at 800-1100°C for 5.5-6.5 hours to obtain the roasted material.

18. The preparation method according to claim 17, wherein The mixed material is in block shape before being placed into the tunnel kiln, with a length of 200-300 mm, a width of 50-150 mm, and a thickness of 40-60 mm.

19. The preparation method according to claim 8, wherein The roasting device is a vertical kiln.

20. The preparation method according to claim 19, wherein The preparation method is: The lithium-containing ore material is crushed into a -100 mesh powder accounting for 80%, and then mixed with a roasting aid and a lithium converter. The resulting mixture is then pressed into balls of designed size and placed in a vertical kiln for calcination at 800-1100°C for 5.5-6.5 hours to obtain the roasted material.

21. The preparation method according to claim 20, characterized in that The mixed material is in a spherical shape with a diameter of 30-35 mm before being placed in the vertical kiln.

22. Use of a roasted material for extracting lithium from lithium-containing raw ore materials as claimed in any one of claims 1 to 7 in industrial lithium extraction.

23. The use according to claim 22, characterized in that The industrial lithium extraction process includes the steps of crushing, lithium leaching, impurity removal, and concentrated precipitation of lithium carbonate.

24. A method for extracting lithium from a calcined material, characterized in that: The following steps are involved: The calcined material for extracting lithium from lithium-containing ore materials as claimed in any one of claims 1 to 7 is crushed into a -100 mesh powder accounting for 80%, and then placed in water and the pH of the resulting mixed solution is maintained at 6.5-7.

5. The mixture is stirred for leaching, and the filtrate is collected, concentrated after impurities are removed, and a lithium precipitating agent, sodium carbonate, is added to precipitate and separate the lithium carbonate product.

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