Comprehensive utilization method of clay type lithium ore

Abstract

The invention provides a comprehensive utilization method of clay type lithium ore, and relates to the field of hydrometallurgy. The comprehensive utilization method of the clay type lithium ore comprises the following steps: mixing the clay type lithium ore with concentrated sulfuric acid, and carrying out low-temperature roasting at the temperature of 100-300 DEG C to obtain a roasted cured material; adding water into the roasted and cured material, leaching, and carrying out solid-liquid separation to obtain a lithium-rich aluminum leaching solution; adsorbing the lithium-rich aluminum leaching solution by using an aluminum ion sieve adsorbent to obtain an aluminum-rich adsorbed solution and a lithium-loaded ion sieve; analyzing the lithium-loaded ion sieve to obtain a lithium-rich desorption solution; the lithium-rich desorption solution is sequentially subjected to purification and lithium precipitation, and battery-grade lithium carbonate is obtained; sequentially carrying out iron removal, purification and impurity removal on the aluminum-rich adsorption post-liquid to obtain iron slag and an aluminum sulfate solution; and sequentially carrying out aluminum precipitation and roasting on the aluminum sulfate solution to obtain the metallurgical-grade aluminum oxide. The method has the advantages of high-efficiency leaching of lithium and aluminum, high-efficiency separation of lithium and aluminum, environment friendliness, simple process and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of hydrometallurgy, in particular to a comprehensive utilization method of clay-type lithium ore. BACKGROUND

[0002] Clay-type lithium ore is a new lithium resource. This ore has two advantages: first, the total amount of resources is huge, which can effectively alleviate the problem of lithium resource scarcity; second, most of the ore deposits are open-pit ore bodies, and the mining cost is more economical than that of spodumene.

[0003] Currently, the extraction process of clay-type lithium ore mainly includes two technical routes: direct acid leaching and roasting. Direct acid leaching needs to be carried out under harsh conditions of high pressure and high concentration of sulfuric acid, which has problems such as high acid consumption, serious equipment corrosion, and low lithium leaching rate. Roasting changes the mineral structure of clay-type lithium ore at high temperature (usually 500-1200°C) to release lithium. Although this method can improve the leaching effect, it has high energy consumption, and valuable metal elements such as aluminum cannot be comprehensively utilized, resulting in high overall cost. In addition, the roasting method with additives introduced to accelerate the dissociation of lithium in clay-type lithium ore will increase the cost of raw materials and bring in more impurity elements, further increasing the difficulty of separation and purification of the solution in the later stage.

[0004] In summary, the existing utilization method of clay-type lithium ore cannot achieve efficient comprehensive utilization of valuable elements while controlling energy consumption. Therefore, it is of great significance to develop a comprehensive utilization method of clay-type lithium ore with low energy consumption, high selectivity, and simultaneous extraction of lithium and aluminum and other valuable elements. SUMMARY

[0005] The purpose of the present application is to provide a comprehensive utilization method of clay-type lithium ore to solve the above problems.

[0006] To achieve the above purpose, the following technical solutions are adopted: A comprehensive utilization method of clay-type lithium ore, comprising: mixing clay-type lithium ore with concentrated sulfuric acid, and carrying out low-temperature roasting at a temperature of 100-300°C to obtain roasted and cured material; adding water to the roasted and cured material to carry out leaching, and after solid-liquid separation, obtaining a lithium and aluminum-rich leaching solution; adsorbing the lithium and aluminum-rich leaching solution with an aluminum-based ion sieve adsorbent to obtain an aluminum-rich adsorbed solution and a lithium-loaded ion sieve; desorbing the lithium-loaded ion sieve to obtain a lithium-rich desorption solution; sequentially purifying and lithium precipitating the lithium-rich desorption solution to obtain battery-grade lithium carbonate; sequentially removing iron and purifying and removing impurities from the aluminum-rich adsorbed solution to obtain iron slag and aluminum sulfate solution; The aluminum sulfate solution is sequentially subjected to aluminum precipitation and calcination to obtain the metallurgical grade aluminum oxide.

[0007] According to the embodiment of the present application, the lithium content in the clay-type lithium ore is 0.1wt%-1wt%, the aluminum content is 15wt%-35wt%, the silicon content is 15wt%-20wt%, and the iron content is 1wt%-5wt%. According to the embodiment of the present application, the particles with a particle size of-0.150mm in the clay-type lithium ore account for more than 80% of the total mass.

[0008] According to the embodiment of the present application, the mass fraction of the concentrated sulfuric acid is 50-98%. The mass of the concentrated sulfuric acid is 0.5-2 times the mass of aluminum in the clay-type lithium ore.

[0009] According to the embodiment of the present application, the low-temperature calcination time is 0.5-10h.

[0010] According to the embodiment of the present application, when leaching, the liquid-solid mass ratio of the water to the calcined and matured material is 1-10:1.

[0011] According to the embodiment of the present application, the leaching time is 0.5-10h.

[0012] According to the embodiment of the present application, the preparation method of the aluminum-based ion sieve adsorbent comprises: mixing a lithium salt, an aluminum salt, and water to prepare a mixed salt solution, adding an inorganic alkali solution to the mixed salt solution to perform a co-precipitation reaction, and after the reaction is completed, adding dilute hydrochloric acid dropwise to adjust the pH until the pH of the system is 3-5, to generate an aluminum-based ion sieve adsorbent having lithium adsorption capacity. The lithium salt comprises LiCl, the aluminum salt comprises at least one of AlCl3 and AlCl3·6H2O, the inorganic alkali comprises at least one of NaOH and KOH, the mass ratio of the aluminum salt to the lithium salt is (1-5):1, the concentration of the inorganic alkali solution is 1-5mol / L, the temperature of the co-precipitation reaction is 30-80°C, and the time of the co-precipitation reaction is 0.5-5h. The time for which the lithium-rich aluminum leaching solution is adsorbed by the aluminum-based ion sieve adsorbent is 0.5-5h, and the temperature for which the lithium-rich aluminum leaching solution is adsorbed by the aluminum-based ion sieve adsorbent is 10-35°C.

[0013] According to the embodiment of the present application, the lithium precipitation comprises: adding a lithium precipitation agent to the reaction system, the lithium precipitation agent comprising at least one of sodium carbonate and potassium carbonate.

[0014] According to the embodiment of the present application, the aluminum precipitation comprises: adding a precipitant to the aluminum sulfate solution to perform an aluminum precipitation reaction; and the precipitant comprises at least one of sodium carbonate, potassium carbonate, and sodium hydroxide.

[0015] Compared with the prior art, the beneficial effects of the present application include: The present application shortens the leaching process of clay-type lithium ore through the sulfuric acid curing low-temperature roasting-water leaching process, realizes the synchronous leaching of valuable elements lithium and aluminum, and the process of separately extracting lithium elements faces the challenge of high cost. The present application can significantly optimize the overall process flow and reduce production costs by utilizing aluminum resources in cooperation. The present application method can reduce the extraction cost of lithium by more than 65%, greatly improving the economic value and development feasibility of clay-type lithium ore. In addition, the present application has the advantages of simple process, high efficiency, energy saving, environmental friendliness and the like.

[0016] Specifically, through the curing roasting step, lithium and aluminum can be converted into soluble lithium sulfate and aluminum sulfate, and silicon in the clay-type lithium ore can be converted into crystalline silicon dioxide. Through the leaching step, lithium sulfate and aluminum sulfate can be left in the filtrate, and crystalline silicon dioxide can be left in the filter residue, realizing efficient separation of valuable elements lithium and aluminum from impurities. BRIEF DESCRIPTION OF DRAWINGS

[0017] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the present application, and therefore should not be regarded as a limitation on the scope of the present application.

[0018] Figure 1 The flow chart of the comprehensive utilization method of the clay-type lithium ore in the present application. DETAILED DESCRIPTION

[0019] As used herein: “Prepared from” is synonymous with “comprising”. The terms “comprising”, “including”, “having” or “containing” or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.

[0020] The conjunction “consisting of’ excludes any element, step, or ingredient not specified. If used in a claim, this phrase shall not be construed to mean that the claimed composition excludes materials not named in the specification. When the phrase “consisting of’ follows the introductory clauses “comprising”, “including”, or “containing”, it defines a product that is composed of the specified materials, and that can exclude unspecified materials. When the phrase “consisting of’ follows the introductory clauses “comprising”, “including”, or “containing”, it defines a product that is composed of the specified materials, and that can exclude unspecified materials.

[0021] When expressing amounts, concentrations, or other values or parameters of a substance in a range, preferably a range, or a series of upper preferred values and lower preferred values, it is to be understood that the disclosure specifically encompasses all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether that range is explicitly disclosed. For example, where a range "1-5" is disclosed, the disclosure is to be interpreted to include ranges such as "1-4," "1-3," "1-2," "1-2 and 4-5," "1-3 and 5," etc. When numerical ranges are disclosed, unless otherwise stated, the range is intended to include both the upper and lower values and all intervening values of the range, as well as the integers within the range.

[0022] In these embodiments, the parts and percentages described are by mass, unless otherwise indicated.

[0023] "Parts by mass" refers to a basic unit of measurement that represents the proportional relationship of the mass of multiple components, 1 part can represent any unit mass, such as 1 g, 2.689 g, etc. If we say that the mass of component A is a parts, and the mass of component B is b parts, it means that the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it means that the mass of component A is aK, and the mass of component B is bK (K is an arbitrary number, representing a multiple factor). It should not be misunderstood that, unlike parts by mass, the sum of the parts by mass of all components is not limited to 100 parts.

[0024] "and / or" is used to indicate that one or both of the described conditions can occur, for example, A and / or B includes (A and B) and (A or B).

[0025] A comprehensive utilization method of a clay-type lithium ore, with reference to Figure 1 , comprising: mixing the clay-type lithium ore with concentrated sulfuric acid, and performing low-temperature roasting at a temperature of 100-300°C to obtain a roasting and curing material; adding water to the roasting and curing material to perform leaching, and after solid-liquid separation, obtaining a lithium-rich aluminum leaching solution; using an aluminum ion sieve adsorbent to adsorb the lithium-rich aluminum leaching solution to obtain an aluminum-rich adsorbed solution and a lithium-loaded ion sieve; performing desorption on the lithium-loaded ion sieve to obtain a lithium-rich desorption solution; sequentially performing purification and lithium precipitation on the lithium-rich desorption solution to obtain battery-grade lithium carbonate; sequentially performing iron removal and impurity removal on the aluminum-rich adsorbed solution to obtain iron slag and an aluminum sulfate solution; sequentially performing aluminum precipitation and roasting on the aluminum sulfate solution to obtain metallurgical-grade aluminum oxide.

[0026] When clay-type lithium ore is mixed with concentrated sulfuric acid, the aluminum-containing minerals such as diaspore and chlorite, which are difficult to leach, are fully destroyed by the concentrated sulfuric acid in its presence, resulting in the accumulation of aluminum sulfate in the leachate. If the conventional roasting-acid leaching method is used, the aluminum in the ore reacts with oxygen in the air during the high-temperature roasting process to form corundum-structured alumina. This makes it difficult for the aluminum to be leached by sulfuric acid in the subsequent acid leaching process, and most of the aluminum-containing slag is discarded as tailings. This results in the inability to fully utilize the abundant aluminum resources in the ore, leading to a waste of resources. The sulfuric acid ripening process is relatively mild. Concentrated sulfuric acid acts as both a reactant and a heating medium, disrupting the stable crystal structure of minerals and converting the target metals lithium and aluminum into water-soluble sulfates. Meanwhile, impurity silicon forms water-insoluble compounds. Through water leaching, the target metals can be selectively transferred into the solution, achieving separation from impurities. This solves the problems of aluminum resource loss and the difficulty in separating silicon impurities from the solution, achieving synergistic leaching of lithium and aluminum ions and efficient extraction of aluminum resources. Lithium in the leachate is adsorbed by an aluminum-based ion sieve adsorbent, leaving aluminum in the solution. This avoids interference from other impurities such as potassium, calcium, and magnesium, achieving the separation of valuable elements lithium and aluminum, providing a strong guarantee for the subsequent production of battery-grade lithium carbonate from lithium sulfate. Iron removal is performed on the aluminum-rich adsorption solution using goethite or alum methods, efficiently separating impurity iron from the main metal element aluminum, resulting in a high-purity aluminum-rich solution, beneficial for the production of metallurgical-grade alumina.

[0027] Concentrated sulfuric acid can dehydrate the amorphous silicon in clay-type lithium ore, transforming it into insoluble crystalline or polymeric silicates, thus "fixing" it in the slag phase and preventing it from entering the solution during leaching to form harmful silica gel. Under heating and the dehydration effect of concentrated sulfuric acid, amorphous silicon (SiO2·nH2O) loses its structural water, and the silicon-oxygen network rearranges, transforming into crystalline silicon dioxide with higher crystallinity and stronger chemical inertness. This makes it difficult for concentrated sulfuric acid to continue leaching, and the silicon is retained in the slag. The reaction equation is as follows: SiO2·nH2O + H2SO4→ SiO2 (crystalline state) + (n+1)H2O↑ + SO3↑ High concentrations of sulfuric acid exhibit strong reactivity under heating conditions, effectively disrupting the crystal structure of stable minerals such as gibbsite. The mineral lattice is opened, making aluminum easier to leach. Specifically, the target metal lithium is converted into soluble lithium sulfate, and aluminum is converted into aluminum sulfate.

[0028] This application enables calcination at a lower temperature, which has the advantages of high efficiency and energy saving. It avoids the process of high-temperature calcination followed by acid leaching in traditional processes, shortens the process flow, and combines calcination and acid leaching to complete the synergistic leaching of lithium and aluminum in one step.

[0029] The chemical reaction equation involved in the process is as follows: Li2O + H2SO4→ Li2SO4+ H2O Diaspore (α-AlO(OH)) will first decompose under the action of concentrated sulfuric acid, and then undergo a sulfation reaction. The reaction equation is as follows: 2α-AlO(OH) + 3H2SO4(concentrated)→ Al2(SO4)3+ 4H2O The present application combines acid leaching with roasting, and uses the concentrated sulfuric acid curing method to mineral dissociation of the refractory low-grade clay-type lithium ore, and the valuable elements lithium and aluminum are simultaneously leached, and the lithium is adsorbed by the aluminum ion sieve adsorbent, so that the lithium and aluminum in the solution are separated, and the problem that other adsorbents may be dissolved in the solution to increase the impurity content is avoided. In the process, the lithium leaching rate is more than 97%, the aluminum leaching rate is more than 90%, the lithium and aluminum are efficiently extracted, the main impurity silicon of the mineral is not leached, the impurities are effectively inhibited in the leaching process, and good economic value is obtained.

[0030] The present application ingeniously uses the aluminum ion sieve adsorbent to specifically adsorb lithium under the condition of an acidic lithium and aluminum containing high-impurity solution, so that efficient separation of lithium and aluminum is achieved. The lithium sulfate solution obtained after desorption of the lithium ion sieve has a low impurity content, and after purification, battery-grade lithium carbonate can be directly prepared, and the process has the characteristics of short process and high recovery rate, and the lithium recovery rate in the whole experimental process is as high as more than 76%.

[0031] The present application can remove iron impurities in an acidic solution through the iron removal step to obtain an iron-removed solution and an iron-containing residue. The method has the characteristics of efficient impurity removal and simple process, and the valuable element aluminum and the impurity iron are efficiently separated. The iron-removed solution is purified to obtain an aluminum-rich solution (aluminum sulfate solution) with a low impurity content, and a high-purity aluminum hydroxide is produced by adding a precipitating agent, and metallurgical-grade aluminum oxide is obtained after calcination. The total aluminum recovery rate is as high as more than 75%.

[0032] In some embodiments, the low-temperature roasting is performed in a roasting furnace.

[0033] The temperature of the low-temperature roasting is 100-300°C, for example, the temperature of the low-temperature roasting is 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, or any value between 100-300°C.

[0034] According to the embodiments of the present application, the lithium content in the clay-type lithium ore is 0.1wt%-1wt%, the aluminum content is 15wt%-35wt%, the silicon content is 15wt%-20wt%, and the iron content is 1wt%-5wt%; For example, the lithium content in the clay-type lithium ore is 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, or any value between 0.1 wt% and 1 wt%; the aluminum content in the clay-type lithium ore is 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, or any value between 15 wt% and 35 wt%; the silicon content in the clay-type lithium ore is 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, or any value between 15 wt% and 20 wt%; and the iron content in the clay-type lithium ore is 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or any value between 1 wt% and 5 wt%.

[0035] In some embodiments, the lithium content in the clay-type lithium ore is preferably 0.1 wt% to 0.4 wt%; and the aluminum content in the clay-type lithium ore is preferably any value between 15 wt% and 28 wt%.

[0036] In some embodiments, the clay-type lithium ore can further contain Ti and Mg elements, the Ti content in the clay-type lithium ore is about 1.02 wt%, and the Mg content in the clay-type lithium ore is about 0.22 wt%.

[0037] In some embodiments, the clay-type lithium ore contains lithium chlorite, diaspore, kaolinite, and a small amount of iron oxide ore and anatase, as analyzed by X-ray diffraction.

[0038] According to embodiments of the present application, the particles with a particle size of -0.150 mm account for more than 80% of the total mass in the clay-type lithium ore. When the particle size of the clay-type lithium ore is within the above range, the clay-type lithium ore has a large specific surface area, and the solid-liquid contact area is large during leaching, which can effectively improve the leaching rate of the target elements.

[0039] According to embodiments of the present application, the mass fraction of the concentrated sulfuric acid is 50% to 98%; It should be noted that the mass fraction of the concentrated sulfuric acid refers to the mass fraction of the concentrated sulfuric acid aqueous solution.

[0040] For example, the mass fraction of the concentrated sulfuric acid is 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 98%, or any value between 50% and 98%.

[0041] The mass of the concentrated sulfuric acid is 0.5-2 times the mass of aluminum in the clay-type lithium ore.

[0042] For example, the mass of the concentrated sulfuric acid is 0.5 times, 1 times, 1.5 times, 2 times, or any value between 0.5-2 times the mass of aluminum in the clay-type lithium ore.

[0043] According to an embodiment of the present application, the low-temperature roasting time is 0.5-10 h.

[0044] For example, the low-temperature roasting time is 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, or any value between 0.5-10 h.

[0045] According to an embodiment of the present application, when leaching, the liquid-solid mass ratio of water to the roasting and curing material is 1-10:1.

[0046] For example, when leaching, the liquid-solid mass ratio of water to the roasting and curing material is 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or any value between 1-10:1.

[0047] According to an embodiment of the present application, the leaching time is 0.5-10 h.

[0048] For example, the leaching time is 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, or any value between 0.5-10 h.

[0049] According to an embodiment of the present application, the preparation method of the aluminum-based ion sieve adsorbent comprises: mixing a lithium salt, an aluminum salt, and water to prepare a mixed salt solution, adding an inorganic alkali solution to the mixed salt solution, performing a co-precipitation reaction, adding dilute hydrochloric acid dropwise to adjust the pH until the pH of the system is 3-5, and generating an aluminum-based ion sieve adsorbent having lithium adsorption capacity; The lithium salt comprises LiCl, the aluminum salt comprises at least one of AlCl3 and AlCl3·6H2O, the inorganic alkali comprises at least one of NaOH and KOH, the mass ratio of the aluminum salt to the lithium salt is (1-5):1, the concentration of the inorganic alkali solution is 1-5 mol / L, the temperature of the co-precipitation reaction is 30-80°C, and the time of the co-precipitation reaction is 0.5-5 h. For example, the mass ratio of the aluminum salt to the lithium salt is 1:1, 2:1, 3:1, 4:1, 5:1, or any value between 1-5:1. The concentration of the inorganic base solution is 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, 5 mol / L, or any value between 1-5 mol / L. The temperature of the co-precipitation reaction is 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, or any value between 30-80°C. The time of the co-precipitation reaction is 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h, or any value between 0.5-5 h. The end point pH of the reaction is 2, 2.5, 3, 3.5, 4, or any value between 2-4.

[0050] The time for which the lithium-rich aluminum leaching solution is adsorbed by the aluminum-based ion sieve adsorbent is 0.5-5 h, and the temperature for which the lithium-rich aluminum leaching solution is adsorbed by the aluminum-based ion sieve adsorbent is 10-35°C.

[0051] For example, the time for which the lithium-rich aluminum leaching solution is adsorbed by the aluminum-based ion sieve adsorbent is 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, or any value between 0.5-5 h. The temperature for which the lithium-rich aluminum leaching solution is adsorbed by the aluminum-based ion sieve adsorbent is 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, or any value between 10-35°C.

[0052] In some embodiments, desorbing the lithium-loaded ion sieve includes adding dilute sulfuric acid to the lithium-loaded ion sieve to obtain a lithium-rich desorption solution.

[0053] According to embodiments of the present application, the lithium precipitation includes adding a lithium precipitation agent to the reaction system, the lithium precipitation agent including at least one of sodium carbonate and potassium carbonate.

[0054] In some embodiments, the method for removing iron from the aluminum-rich adsorption solution includes any one of the goethite method and the jarosite method. When the method for removing iron is the goethite method, the addition coefficient is 1-5 times according to the iron content in the mineral.

[0055] The present application uses the goethite method and the jarosite method to remove iron and other impurities in an acidic solution to obtain an iron-removed solution (aluminum sulfate solution) and iron slag. This method has the characteristics of efficient impurity removal and simple process, and efficiently separates the valuable element aluminum and the impurity iron. The equations involved are shown below: Fe 3+ + 2H2O → FeOOH↓ + 3H + According to the embodiment of the present application, the aluminum precipitation comprises: adding a precipitant into an aluminum sulfate solution to carry out an aluminum precipitation reaction to obtain aluminum hydroxide; the precipitant comprises at least one of sodium carbonate, potassium carbonate and sodium hydroxide.

[0056] The calcination comprises: calcining the aluminum hydroxide to obtain the metallurgical grade aluminum oxide.

[0057] The embodiments of the present application will be described in detail below with specific examples, but those skilled in the art will understand that the following examples are only for illustration of the present application and should not be regarded as limiting the scope of the present application. If the specific conditions are not specified in the examples, the conventional conditions or the conditions recommended by the manufacturer are carried out. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0058] The aluminum-based ion sieve adsorbent used in the examples and comparative examples is prepared by the following method: AlCl3 and LiCl are weighed according to a mass ratio of 3:1, anhydrous AlCl3, LiCl and water are mixed to obtain a mixed salt solution, 2 mol / L NaOH solution is slowly added to the mixed salt solution, and the mixture is stirred at a temperature of 50°C for 1 hour to carry out a co-precipitation reaction. After the reaction is completed, the pH of the system is adjusted by using dilute hydrochloric acid, and the reaction end point pH is 3 to obtain the aluminum-based ion sieve adsorbent.

[0059] Example 1 Example 1 provides a comprehensive utilization method of clay-type lithium ore, comprising the following steps: S1, 30 g of clay-type lithium ore (containing Li 0.31wt%, Al 23.89wt%, Si 16.89wt%, Fe 2.86wt%, and particle size of-0.150 mm accounting for more than 80%) is uniformly mixed with 98% concentrated sulfuric acid, the mass ratio of the mass of concentrated sulfuric acid to the mass of aluminum in the clay-type lithium ore is 1:1, to obtain a first step mixture; S2, the mixture is loaded into a crucible and placed in a calcination furnace, the calcination temperature is 240°C, and the reaction time is 2h to obtain a calcined and cured material; S3, the calcined and cured material is taken out, water is added under normal temperature conditions for leaching, the liquid-solid mass ratio of leaching is 5:1, the leaching time is 2h, and after solid-liquid separation, a lithium and aluminum rich leaching solution is obtained, the leaching rate of lithium is 98.98%, and the leaching rate of aluminum is 96.48%; S4, the lithium and aluminum rich leaching solution is adsorbed by an aluminum-based ion sieve adsorbent to obtain an aluminum rich adsorbed solution and a lithium ion sieve, and a lithium sulfate desorption solution is obtained by desorption, and the concentration of the lithium solution is enriched to 5 g / L.

[0060] S5, purifying and removing impurities from 5 g / L lithium sulfate desorption solution, specifically including: adding 20 wt% sodium carbonate solution to 5 g / L lithium sulfate desorption solution to control the pH of the solution to 3.5, purifying and removing impurities, obtaining high-purity lithium sulfate purification solution, wherein the content of calcium, magnesium, iron, aluminum and other impurities is less than 0.5 mg / L, the purification solution is concentrated to a concentration of 12 g / L, industrial-grade lithium carbonate is prepared by adding sodium carbonate, industrial-grade lithium carbonate is added to a pure water solution, the liquid-solid mass ratio is 20:1, CO2 is introduced at room temperature, the flow rate of CO2 is 2 L / min, the introduction time is 1 h, the lithium carbonate is dissolved, after dissolution, a lithium bicarbonate solution is obtained, the room temperature lithium bicarbonate solution is heated to 90°C, a white precipitate is obtained, after filtration, the precipitate is dried by hot air at 400°C and air flow crushing, battery-grade lithium carbonate (Li2CO3≥99.5%) is obtained, the comprehensive recovery rate of lithium in the process is 82%, and the pyrolysis direct recovery rate of refined battery-grade lithium carbonate is 50%.

[0061] S6, removing iron from the aluminum-rich adsorption solution by goethite method, specifically including: adding 10 wt% sodium carbonate solution to the aluminum-rich adsorption solution to adjust the pH of the system to 2.5 at 90°C, slowly hydrolyzing to generate goethite precipitate, the Fe in the solution is 10 ppm, an aluminum-rich solution with high purity is obtained, aluminum hydroxide solution is obtained by adding sodium carbonate, and metallurgical-grade alumina (Al2O3≥98.4%) is obtained after calcination, and the recovery rate of aluminum is 85%.

[0062] Example 2 Example 2 provides a comprehensive utilization method of clay-type lithium ore, including the following steps: S1, uniformly mixing 30 g of clay-type lithium ore (containing Li 0.31 wt%, Al 23.89 wt%, Si 16.89 wt%, Fe 2.86 wt%, particle size of -0.150 mm accounting for more than 80%) with 80% concentrated sulfuric acid, the mass ratio of the mass of concentrated sulfuric acid to the mass of aluminum in the clay-type lithium ore is 3:1, to obtain a first step mixed material; S2, loading the mixed material into a crucible and placing it in a calcination furnace, the calcination temperature is 220°C, and the reaction time is 2 h, to obtain a calcined and cured material; S3, taking out the calcined and cured material, adding water under room temperature conditions for leaching, the liquid-solid mass ratio of leaching is 5:1, the leaching time is 2 h, after solid-liquid separation, an aluminum-rich leaching solution is obtained, the leaching rate of lithium is 90.86%, and the leaching rate of aluminum is 90.09%; S4, adsorbing the aluminum-rich leaching solution with an aluminum ion sieve adsorbent to obtain an aluminum-rich adsorption solution and a lithium-loaded ion sieve, and desorbing to obtain a lithium sulfate desorption solution, the concentration of the lithium sulfate desorption solution is enriched to 5 g / L.

[0063] S5, purifying and removing impurities from 5 g / L lithium sulfate desorption solution, specifically including: adding 20 wt% sodium carbonate solution to 5 g / L lithium sulfate desorption solution to control the pH of the solution to 3.5, purifying and removing impurities, obtaining high-purity lithium sulfate purification solution, wherein the content of impurities such as calcium, magnesium, iron and aluminum is less than 0.5 mg / L, the purification solution is concentrated to a concentration of 12 g / L, industrial-grade lithium carbonate is prepared by adding sodium carbonate, industrial-grade lithium carbonate is added to a pure water solution, the liquid-solid mass ratio is 20:1, CO2 is introduced at room temperature, the flow rate of CO2 is 2 L / min, and the introduction time is 1 h, the lithium carbonate is dissolved, and after dissolution, a lithium bicarbonate solution is obtained, the lithium bicarbonate solution at room temperature is heated to 90℃, a white precipitate is obtained, after filtration, the precipitate is dried by hot air at 400℃ and is pulverized by airflow, obtaining battery-grade lithium carbonate (Li2CO3≥99.5%), the comprehensive recovery rate of lithium in the process is 76%, and the direct pyrolysis yield of refined battery-grade lithium carbonate is 55%.

[0064] S6, removing iron from the aluminum-rich adsorption solution by goethite method, specifically including: adding 10 wt% sodium carbonate solution to the aluminum-rich adsorption solution to adjust the pH of the system to 2.5 at 90℃, slowly hydrolyzing to generate goethite precipitate, the Fe in the solution is 10 ppm, obtaining a solution with high purity and containing aluminum, adding sodium hydroxide to obtain an aluminum hydroxide solution, and calcining to obtain metallurgical-grade aluminum oxide (Al2O3≥98.4%), the recovery rate of aluminum is 75%.

[0065] Example 3 Example 3 provides a comprehensive utilization method of clay-type lithium ore, including the following steps: S1, uniformly mixing 30 g of clay-type lithium ore (containing Li 0.31 wt%, Al 23.89 wt%, Si 16.89 wt%, Fe 2.86 wt%, and particle size of-0.150 mm accounting for more than 80%) with 90% concentrated sulfuric acid, the mass ratio of the mass of concentrated sulfuric acid to the mass of aluminum in the clay-type lithium ore is 2:1, to obtain a first-step mixed material; S2, loading the mixed material into a crucible and placing it into a calcination furnace, the calcination temperature is 200℃, and the reaction time is 1 h, to obtain a calcined and cured material; S3, taking out the calcined and cured material, adding water under room temperature conditions for leaching, the liquid-solid mass ratio of leaching is 10:1, the leaching time is 2 h, and after solid-liquid separation, an aluminum-rich leaching solution is obtained, the leaching rate of lithium is 99.15%, and the leaching rate of aluminum is 92.83%; S4, adsorbing the aluminum-rich leaching solution with an aluminum-based ion sieve adsorbent to obtain an aluminum-rich adsorption solution and a lithium-loaded ion sieve, and desorbing to obtain a lithium sulfate desorption solution, the concentration of the lithium sulfate desorption solution is enriched to 5 g / L.

[0066] S5, purifying and removing impurities from 5 g / L lithium sulfate desorption solution, specifically including: adding 20wt% sodium carbonate solution to 5 g / L lithium sulfate desorption solution to control the pH of the solution to 3.5, purifying and removing impurities, obtaining high-purity lithium sulfate purification solution, wherein the content of calcium, magnesium, iron, aluminum and other impurities is less than 0.5 mg / L, the purification solution is concentrated to a concentration of 12 g / L, industrial-grade lithium carbonate is prepared by adding sodium carbonate, industrial-grade lithium carbonate is added to a pure water solution, the liquid-solid mass ratio is 20:1, CO2 is introduced at room temperature, the flow rate of CO2 is 2 L / min, the CO2 introduction time is 1 h, the lithium carbonate is dissolved, and after dissolution, a lithium bicarbonate solution is obtained, the room temperature lithium bicarbonate solution is heated to 90℃, a white precipitate is obtained, after filtration, the precipitate is dried by hot air at 400℃ and air flow crushing, battery-grade lithium carbonate (Li2CO3≥99.5%) is obtained, the comprehensive recovery rate of lithium in the process is 85%, and the pyrolysis direct recovery rate of refined battery-grade lithium carbonate is 45%.

[0067] S6, removing iron from the aluminum-rich adsorption solution by using the jarosite method, specifically including: adding potassium sulfate at 95℃ and pH 1.5 to generate a composite sulfate precipitate, the Fe in the solution is 15 ppm, an aluminum-rich solution with high purity is obtained, sodium carbonate is added to obtain an aluminum hydroxide solution, and metallurgical-grade alumina (Al2O3≥98.4%) is obtained after calcination, and the recovery rate of aluminum is 82%.

[0068] Example 4 Example 4 provides a comprehensive utilization method of clay-type lithium ore, including the following steps: S1, uniformly mixing 30 g of clay-type lithium ore (containing Li 0.38wt%, Al 25.75wt%, Si 15.58wt%, Fe 2.24wt%, and particle size of-0.150 mm accounting for more than 80%) with 98% concentrated sulfuric acid, the mass ratio of the mass of concentrated sulfuric acid to the mass of aluminum in the clay-type lithium ore is 1.5:1, to obtain a first-step mixed material; S2, loading the mixed material into a crucible and placing it in a calcination furnace, the calcination temperature is 260℃, and the reaction time is 2 h, to obtain a calcined and cured material; S3, taking out the calcined and cured material, adding water under room temperature conditions for leaching, the liquid-solid mass ratio of leaching is 10:1, the leaching time is 1 h, and after solid-liquid separation, an aluminum-rich leaching solution is obtained, the leaching rate of lithium is 97.40%, and the leaching rate of aluminum is 91.75%; S4, adsorbing the aluminum-rich leaching solution with an aluminum-based ion sieve adsorbent to obtain an aluminum-rich adsorption solution and a lithium-loaded ion sieve, and desorbing to obtain a lithium sulfate desorption solution, the concentration of the lithium sulfate desorption solution is enriched to 5 g / L.

[0069] S5, purifying and removing impurities from 5 g / L lithium sulfate desorption solution, specifically including: adding 20 wt% sodium carbonate solution to 5 g / L lithium sulfate desorption solution to control the pH of the solution to 3.5, purifying and removing impurities, obtaining high-purity lithium sulfate purification solution, wherein the content of impurities such as calcium, magnesium, iron and aluminum is less than 0.5 mg / L, the purification solution is concentrated to a concentration of 12 g / L, industrial-grade lithium carbonate is prepared by adding sodium carbonate, industrial-grade lithium carbonate is added to a pure water solution, the liquid-solid mass ratio is 20:1, CO2 is introduced at room temperature, the flow rate of CO2 is 2 L / min, and the introduction time is 1 h, the lithium carbonate is dissolved, and after dissolution, a lithium bicarbonate solution is obtained, the lithium bicarbonate solution at room temperature is heated to 90℃, a white precipitate is obtained, and after filtration, the precipitate is dried by hot air at 400℃ and pulverized by airflow, obtaining battery-grade lithium carbonate (Li2CO3≥99.5%), the comprehensive recovery rate of lithium in the process is 86%, and the direct pyrolysis yield of refined battery-grade lithium carbonate is 40%.

[0070] S6, removing iron from the aluminum-rich adsorption solution by goethite method, specifically including: adding 10 wt% sodium carbonate solution to the aluminum-rich adsorption solution at 90℃ to adjust the pH of the system to 2.5, slowly hydrolyzing to generate goethite precipitate, the Fe in the solution is 8 ppm, obtaining a solution with high purity and containing aluminum, adding sodium hydroxide to obtain an aluminum hydroxide solution, and calcining to obtain metallurgical-grade aluminum oxide (Al2O3≥98.4%), the recovery rate of aluminum is 75%.

[0071] Example 5 Example 5 provides a comprehensive utilization method of clay-type lithium ore, including the following steps: S1, uniformly mixing 30 g of clay-type lithium ore (containing Li 0.27 wt%, Al 27.69 wt%, Si 16.56 wt%, Fe 2.31 wt%, and particle size of-0.150 mm accounting for more than 80%) with 70% concentrated sulfuric acid, the mass ratio of the mass of concentrated sulfuric acid to the mass of aluminum in the clay-type lithium ore is 5:1, to obtain a first step mixed material; S2, loading the mixed material into a crucible and placing it into a calcination furnace, the calcination temperature is 200℃, and the reaction time is 5 h, to obtain a calcined and cured material; S3, taking out the calcined and cured material, adding water under room temperature conditions for leaching, the liquid-solid mass ratio of leaching is 5:1, the leaching time is 2 h, and after solid-liquid separation, an aluminum-rich leaching solution is obtained, the leaching rate of lithium is 90.90%, and the leaching rate of aluminum is 89.56%; S4, adsorbing the aluminum-rich leaching solution with an aluminum-based ion sieve adsorbent to obtain an aluminum-rich adsorption solution and a lithium-loaded ion sieve, and desorbing to obtain a lithium sulfate desorption solution, the concentration of the lithium sulfate desorption solution is enriched to 5 g / L.

[0072] S5, purifying and removing impurities from 5 g / L lithium sulfate desorption solution, specifically including: adding 20wt% sodium carbonate solution to 5 g / L lithium sulfate desorption solution to control the pH of the solution to 3.5, purifying and removing impurities, obtaining high-purity lithium sulfate purification solution, wherein the content of calcium, magnesium, iron, aluminum and other impurities is less than 0.5 mg / L, the purification solution is concentrated to a concentration of 12 g / L, industrial-grade lithium carbonate is prepared by adding sodium carbonate, industrial-grade lithium carbonate is added to a pure water solution, the liquid-solid mass ratio is 20:1, CO2 is introduced at room temperature, the flow rate of CO2 is 2 L / min, the introduction time is 1 h, the lithium carbonate is dissolved, after dissolution, a lithium bicarbonate solution is obtained, the room temperature lithium bicarbonate solution is heated to 90℃, a white precipitate is obtained, after filtration, it is dried by hot air at 400℃ and pulverized by airflow, obtaining battery-grade lithium carbonate (Li2CO3≥99.5%), the comprehensive recovery rate of lithium in the process is 78%, and the pyrolysis direct recovery rate of refined battery-grade lithium carbonate is 50%.

[0073] S6, removing iron from the aluminum-rich adsorption solution by using the iron alum method, specifically including: adding potassium sulfate at 95℃ and pH 1.5 to generate a composite sulfate precipitate, the Fe in the solution is 18 ppm, obtaining an aluminum solution with high purity, adding sodium carbonate to obtain an aluminum hydroxide solution, and obtaining metallurgical-grade alumina (Al2O3≥98.4%) after calcination, the recovery rate of aluminum is 85%.

[0074] Example 6 Example 6 provides a comprehensive utilization method of clay-type lithium ore, including the following steps: S1, uniformly mixing 30 g of clay-type lithium ore (containing Li 0.27wt%, Al 27.69wt%, Si 16.56wt%, Fe 2.31wt%, particle size of-0.150 mm accounting for more than 80%) with 85% concentrated sulfuric acid, the mass ratio of the mass of concentrated sulfuric acid to the mass of aluminum in the clay-type lithium ore is 2:1, to obtain a first step mixed material; S2, loading the mixed material into a crucible and placing it into a calcination furnace, the calcination temperature is 220℃, and the reaction time is 5 h, to obtain a calcined and cured material; S3, taking out the calcined and cured material, adding water under room temperature conditions for leaching, the liquid-solid mass ratio of leaching is 10:1, the leaching time is 5 h, after solid-liquid separation, an aluminum-rich leaching solution is obtained, the leaching rate of lithium is 96.60%, and the leaching rate of aluminum is 91.23%; S4, adsorbing the aluminum-rich leaching solution with an aluminum ion sieve adsorbent to obtain an aluminum-rich adsorption solution and a lithium-loaded ion sieve, and desorbing to obtain a lithium sulfate desorption solution, the concentration of the lithium sulfate desorption solution is enriched to 5 g / L.

[0075] S5, the 5 g / L lithium sulfate desorption solution is purified and impurities are removed, specifically including: adding a 20 wt% sodium carbonate solution to the 5 g / L lithium sulfate desorption solution to adjust the pH of the solution to 3.5, purifying and removing impurities, and obtaining a high-purity lithium sulfate purification solution, wherein the content of impurities such as calcium, magnesium, iron, and aluminum is less than 0.5 mg / L; the purification solution is concentrated to a concentration of 12 g / L, and industrial-grade lithium carbonate is prepared by adding sodium carbonate; the industrial-grade lithium carbonate is added to a pure water solution, the liquid-solid mass ratio is 20:1, CO2 is introduced at room temperature, the flow rate of CO2 is 2 L / min, and the introduction time is 1 h; the lithium carbonate is dissolved, and after dissolution, a lithium bicarbonate solution is obtained; the lithium bicarbonate solution at room temperature is heated to 90°C, and a white precipitate is obtained; after filtration, the precipitate is dried by hot air at 400°C and pulverized by airflow, and a battery-grade lithium carbonate (Li2CO3≥99.5%) is obtained; the comprehensive recovery rate of lithium in the process is 82%, and the direct pyrolysis yield of the refined battery-grade lithium carbonate is 52%.

[0076] S6, the aluminum-rich adsorption solution is treated by the goethite method to remove iron, specifically including: adding a 10 wt% sodium carbonate solution to the aluminum-rich adsorption solution at 90°C to adjust the pH of the system to 2.5, and slowly hydrolyzing to generate a goethite precipitate; the Fe content in the solution is 10 ppm, and an aluminum solution with high purity is obtained; aluminum hydroxide solution is obtained by adding sodium carbonate, and metallurgical-grade alumina (Al2O3≥98.4%) is obtained after calcination; the recovery rate of aluminum is 80%.

[0077] Comparative Example 1 Comparative Example 1 provides a comprehensive utilization method of clay-type lithium ore, including the following steps: S1, 30 g of clay-type lithium ore (containing Li 0.31 wt%, Al 23.89 wt%, Si 16.89 wt%, Fe 2.86 wt%, and particle size of -0.150 mm accounting for more than 80%) is loaded into a crucible and placed in a calcination furnace, the calcination temperature is 200°C, and the reaction time is 2 h, to obtain a calcined and cured material; S3, the calcined and cured material is taken out and immersed in 5 mol / L sulfuric acid at room temperature, the liquid-solid mass ratio of immersion is 10:1, the immersion time is 5 h, and the leaching solution is obtained after solid-liquid separation; the leaching rate of lithium is 78.98%, and the leaching rate of aluminum is 36.78%.

[0078] As can be seen from the results, without adding concentrated sulfuric acid for curing and direct calcination, the leaching rate of aluminum in the mineral is only 36.78% at 200°C, which may be due to the fact that aluminum in the clay-type lithium ore does not form corundum, and low-temperature calcination without the addition of sulfuric acid cannot destroy the mineral lattice, resulting in a lower aluminum leaching rate in Comparative Example 1.

[0079] Comparative Example 2 The comparative example 2 provides a comprehensive utilization method of the clay type lithium ore, comprising the following steps: S1, 30g of the clay type lithium ore (containing Li 0.31wt%, Al 23.89wt%, Si 16.89wt%, Fe 2.86wt%, and the particle size is more than 80% of-0.150mm) is loaded into a crucible and placed into a calcination furnace, the calcination temperature is 600℃, the reaction time is 2h, and the calcined and cured material is obtained; S3, the calcined and cured material is taken out, and 5mol / L sulfuric acid is added under normal temperature conditions for leaching, the liquid-solid mass ratio of leaching is 10:1, the leaching time is 5h, and the leaching liquid is obtained after solid-liquid separation, the leaching rate of lithium is 78.34%, and the leaching rate of aluminum is 16.79%.

[0080] It can be seen from the results that without adding concentrated sulfuric acid for curing and direct calcination, the leaching rate of aluminum in the mineral is only 16.78% under the condition of 600℃, compared with the comparative example 1, the leaching rate decreases, which indicates that corundum has been generated at this time, making it difficult to destroy the mineral crystal lattice in the subsequent acid leaching process, so the leaching rate of aluminum decreases.

[0081] The application skillfully destroys the mineral crystal structure by adding concentrated sulfuric acid for curing, so that the minerals in the raw ore that are difficult to be dissociated by conventional acid leaching are dissociated, and the leaching process is strengthened. The method has the characteristics of high efficiency, mild reaction, high recovery rate, etc., avoids the energy consumption problem caused by high temperature calcination in the traditional process, and ensures the co-leaching of lithium and aluminum under low temperature calcination and curing conditions. The impurities silicon contained in the raw ore are retained in the slag.

[0082] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, but not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

[0083] In addition, those skilled in the art can understand that although some embodiments herein include certain features included in other embodiments rather than other features, the combination of features of different embodiments means to be within the scope of the present application and form different embodiments. For example, in the above claims, any one of the claimed embodiments can be used in any combination. The information disclosed in the background section is only intended to deepen the understanding of the overall background of the present application, and should not be regarded as acknowledging or implying in any form that the information constitutes prior art known to those skilled in the art.

Claims

1. A method for the comprehensive utilization of clay-type lithium ore, characterized in that, include: Clay-type lithium ore is mixed with concentrated sulfuric acid and then roasted at a low temperature of 100-300℃ to obtain roasted and calcined material. The roasted and cooked material is added to water for leaching. After solid-liquid separation, a lithium-rich aluminum leachate is obtained. The lithium-rich aluminum leachate was adsorbed with an aluminum-based ion sieve adsorbent to obtain an aluminum-rich adsorbed liquid and a lithium-loaded ion sieve. The lithium-ion-loaded sieve is desorbed to obtain a lithium-rich desorption solution; The lithium-rich desorption solution was purified and lithium precipitated sequentially to obtain battery-grade lithium carbonate. The aluminum-rich adsorbed liquid was subjected to iron removal and purification processes in sequence to obtain iron slag and aluminum sulfate solution. The aluminum sulfate solution was subjected to aluminum precipitation and calcination in sequence to obtain metallurgical grade alumina.

2. The comprehensive utilization method of clay-type lithium ore according to claim 1, characterized in that, The clay-type lithium ore contains 0.1wt%-1wt% lithium, 15wt%-35wt% aluminum, 15wt%-20wt% silicon, and 1wt%-5wt% iron.

3. The comprehensive utilization method of clay-type lithium ore according to claim 2, characterized in that, In the clay-type lithium ore, particles with a size of -0.150 mm account for more than 80% of the total mass.

4. The comprehensive utilization method of clay-type lithium ore according to claim 1, characterized in that, The concentrated sulfuric acid has a mass fraction of 50-98%. The mass of the concentrated sulfuric acid is 0.5-2 times the mass of aluminum in the clay-type lithium ore.

5. The comprehensive utilization method of clay-type lithium ore according to claim 1, characterized in that, The low-temperature calcination time is 0.5-10 hours.

6. The method for comprehensive utilization of clay-type lithium ore according to claim 1, characterized in that, During leaching, the liquid-to-solid mass ratio of the water to the roasted and cooked material is 1-10:

1.

7. The comprehensive utilization method of clay-type lithium ore according to claim 4, characterized in that, The leaching time is 0.5-10 hours.

8. The method for comprehensive utilization of clay-type lithium ore according to claim 1, characterized in that, The preparation method of the aluminum-based ion sieve adsorbent includes: mixing lithium salt, aluminum salt and water to prepare a mixed salt solution, adding an inorganic alkaline solution to the mixed salt solution to carry out a co-precipitation reaction, and after the reaction is completed, adding dilute hydrochloric acid to adjust the pH until the pH of the system is 3-5, thereby generating an aluminum-based ion sieve adsorbent with lithium adsorption capacity. The lithium salt includes LiCl, the aluminum salt includes at least one of AlCl3 and AlCl3·6H2O, the inorganic base includes at least one of NaOH and KOH, the mass ratio of the aluminum salt to the lithium salt is (1-5):1, the concentration of the inorganic base solution is 1-5 mol / L, the temperature of the coprecipitation reaction is 30-80°C, and the time of the coprecipitation reaction is 0.5-5 h; And / or, the adsorption time of the lithium-rich aluminum leachate with the aluminum-based ion sieve adsorbent is 0.5-5h, and the adsorption temperature of the lithium-rich aluminum leachate with the aluminum-based ion sieve adsorbent is 10-35℃.

9. The method for comprehensive utilization of clay-type lithium ore according to claim 1, characterized in that, The lithium precipitation process includes adding a lithium precipitation agent to the reaction system, wherein the lithium precipitation agent includes at least one of sodium carbonate and potassium carbonate.

10. The method for comprehensive utilization of clay-type lithium ore according to claim 1, characterized in that, The aluminum precipitation process includes: adding a precipitant to an aluminum sulfate solution to carry out an aluminum precipitation reaction; the precipitant includes at least one of sodium carbonate, potassium carbonate, and sodium hydroxide.

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