Method for recycling lithium-containing glass solid waste

Abstract

The invention relates to the technical field of solid waste resource recovery and regeneration, in particular to a lithium-containing glass solid waste resource utilization method which comprises the following steps: S1, after a lithium-containing glass solid waste raw material and acid liquor are mixed for reaction, solid-liquid separation is implemented or not implemented; and S2, adding alkali liquor and / or caustic soda flake solid into the leaching solution or the leaching slurry obtained in the step S1, adjusting the pH value to 12.5-14.5, adding calcium salt for reaction, and carrying out solid-liquid separation to obtain the lithium-containing purified solution. According to the method, simple inorganic acid leaching is matched with calcium salt addition under the specific alkalinity condition to remove aluminum, the problems that a traditional lithium-containing glass solid waste recycling reagent is high in operation cost, complex in process, poor in environmental protection property, large in lithium entrainment loss and the like are solved, and the economic benefits and the industrialization value of the lithium-containing glass solid waste recycling technology are remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of solid waste resource recycling and regeneration, and in particular to a method for resource utilization of lithium-containing glass solid waste. Background Art

[0002] The new energy industry has experienced rapid growth in recent years, with the development and utilization of strategically important lithium resources a key focus for various companies. Li₂O in lithium minerals and lithium compounds has a strong fluxing effect, positively impacting the density, thermal expansion coefficient, and mechanical properties of glass materials. Consequently, it has found widespread and stable application in the glass industry. With technological advancements, demand for new glass products is rapidly increasing, with applications spanning electronics, machinery, construction, and other fields. Consequently, the generation of lithium-containing glass solid waste is also increasing annually. Because waste glass has a low recycling value and, compared to other lithium-containing waste materials, is complex in crystal structure, highly stable, and difficult to handle, it is currently largely dumped. This not only consumes land resources but also resists natural degradation, posing a significant safety hazard to the surrounding environment. Therefore, developing an efficient, clean, and industrially viable method for recycling valuable elements such as lithium, aluminum, and silicon from glass solid waste could alleviate the shortage of lithium resources, reduce resource waste and production costs, and achieve sustainable resource utilization. Under current technological circumstances, research and application of technologies for lithium extraction and resource utilization from lithium-containing glass solid waste are limited. Expanding the recycling and application of glass solid waste holds great market potential and is a key measure in addressing energy conservation, emission reduction, and achieving the dual carbon goals. However, addressing the challenges of high costs, low returns, and complex recycling processes for glass solid waste remains a long-standing industry challenge.

[0003] For the separation and recovery of valuable elements such as lithium from lithium-containing glass waste, existing technologies have proposed some solutions, such as: Patent CN202310390085.8 discloses a method for extracting metallic lithium from waste glass. The waste glass powder is ground and sieved with a grinding agent and then subjected to high-temperature heat treatment at 500-750°C. The calcined material is heated and stirred with a mixed acid consisting of 15-20% hydrofluoric acid and 70-72% perchloric acid for leaching, so that lithium, sodium, potassium, and aluminum enter the leachate and are then separated and recovered. The use of high-temperature treatment in this process will increase energy consumption, and an exhaust gas treatment device must be equipped during implementation. The use of hydrofluoric acid and high-concentration perchloric acid not only worsens the leaching environment and increases the requirements for acid leaching equipment, but the harmless treatment of acid leaching wastewater is also a difficulty faced by this process. More importantly, the patent does not focus on the separation of aluminum and lithium in the leachate.

[0004] Patent CN202380010133.4 discloses a method for recycling waste lithium aluminum silicon glass-ceramics. The process uses citric acid and oxalic acid to assist ball milling activation, followed by hydrofluoric acid leaching treatment to convert lithium, aluminum, silicon, etc. into corresponding fluorides. Lithium, aluminum, and zirconium are then transferred to the liquid phase through a calcium chloride hydrochloric acid solution. Zirconium and aluminum are then separated in turn through solvent extraction and pH adjustment selective precipitation to obtain lithium-rich liquid and crude lithium carbonate. This process uses a variety of organic and inorganic acids such as citric acid, oxalic acid, hydrofluoric acid, and hydrochloric acid, as well as a variety of extraction reagents such as trioctylamine, tributyl phosphate, and sulfonated kerosene in the process of treating waste glass powder. The raw material and reagent costs are high, the process flow is complex, and the wastewater treatment is difficult.

[0005] Patent CN202310978528.5 discloses a method for resource utilization of lithium-containing glass waste. The method involves ultrasonically assisted alkaline leaching of the lithium-containing glass waste, with the addition of aluminate during leaching. The alkaline lithium-containing leachate is concentrated, cooled, and crystallized to produce a lithium hydroxide monohydrate product. While this process is simple to operate, it focuses solely on lithium recovery, leaving other valuable elements untreated. This results in limited resource recycling, and the maximum lithium recovery rate throughout the process is only 93.1%. The lithium hydroxide is of low purity and requires further processing before use. Furthermore, the process requires additional ultrasonic equipment, significantly increasing process investment and resulting in low overall economic and social benefits.

[0006] Patent CN202310283975.9 discloses a method for the comprehensive utilization of lithium-containing glass waste. The method involves calcining the lithium-containing glass waste with lithium porcelain stone, a reconstructing agent, and a fluorine-fixing agent, and then extracting lithium through water leaching. Although the lithium-containing glass waste can be processed in batches, it needs to be processed simultaneously with the lithium porcelain stone, which has high requirements for raw materials and poor universality. In addition, a large amount of reconstructing agent sulfate and fluorine-fixing agent calcium salt are used, which significantly increases the reagent cost and the calcination processing volume. In addition, the amount of slag is large, and a large amount of slag constitutes new solid waste storage, which does not achieve the purpose of resource utilization and green recycling. The single recovery of lithium further reduces the industrial efficiency.

[0007] For other lithium-containing raw materials, due to the significant differences in the properties, composition and recycling problems faced by the raw materials, the recycling of lithium-containing glass solid waste has no practical reference significance.

[0008] The inventors have actively explored this issue and found that traditional inorganic acid treatment can extract lithium from lithium-containing glass waste under simple and mild conditions, but it is also accompanied by the leaching of a large amount of aluminum. The conventional low pH adjustment for selective precipitation and separation of aluminum is accompanied by a large amount of lithium entrainment and loss, which cannot achieve a simple and effective lithium-aluminum separation effect, thereby significantly reducing the efficiency and industrial feasibility of the process. Therefore, a new method for resource utilization of lithium-containing glass solid waste is developed to achieve efficient separation and full recovery of valuable elements, especially high-value-added lithium elements, which provides a favorable premise for obtaining competitive high-value products and is of great significance to the industrial regeneration and recycling of lithium-containing glass solid waste. Summary of the Invention

[0009] The technical problem to be solved by the present invention is to provide a method for resource utilization of lithium-containing glass solid waste, realize the short-process, simple and efficient extraction of high-value element lithium in glass solid waste, and separate and recover or effectively enrich other valuable elements, thereby realizing high-efficiency and short-process recycling of lithium-containing glass solid waste with practical industrial significance.

[0010] The technical solution of the present invention is: A method for resource utilization of lithium-containing glass solid waste, comprising the following steps: S1. After mixing the lithium-containing glass solid waste raw material with the acid solution for reaction, perform or do not perform solid-liquid separation; S2. Adding alkali solution and / or solid caustic soda to the leachate or leachate slurry obtained in S1, adjusting the pH to 12.5-14.5, adding calcium salt for reaction, and performing solid-liquid separation to obtain a purified lithium-containing solution.

[0011] Preferably, the lithium-containing glass solid waste raw material is preferably powder, further preferably powder with a mesh size of 50-200, further preferably powder with a mesh size of 80-150, and more preferably powder with a mesh size of 100-120.

[0012] Preferably, the lithium content in the lithium-containing glass solid waste is 0.5%-4%, further 1%-3%, and further 1.5%-1.8%.

[0013] Preferably, the aluminum content in the lithium-containing glass solid waste is 5%-20%, further 7%-16%, and further 8.5%-15%.

[0014] Preferably, the calcium content in the lithium-containing glass solid waste is 0-4.5%, further 0.5%-2.5%, and further 0.9%-2.1%.

[0015] Preferably, the acid solution in S1 is an acidic liquid containing one of hydrochloric acid, sulfuric acid, nitric acid, or any combination thereof; preferably, the acid solution concentration is 10-25%, further 12-20%, and further 15-18%; Preferably, the solid-liquid mass ratio in S1 is 1:2-10, further 1:2-8; further 1:3-5; Preferably, the reaction temperature of S1 is 10-99 ℃, preferably 20-95 ℃, further 50-90 ℃; Preferably, the reaction time of S1 is 0.5-3 h, preferably 1-2.5 h, more preferably 1.5-2 h; Preferably, the lithium ion concentration in the S1 leaching slurry or solution is 0.5-10 g / L, further 1.0-8 g / L, further 2.0-6 g / L; Preferably, the aluminum ion concentration in the S1 leaching system is 10-45 g / L, further 12.0-35 g / L, further 15-30 g / L, further 18-25 g / L; Preferably, solid-liquid separation is performed after leaching in S1 to obtain leachate and leach residue; Preferably, the leached residue is washed and then dried to obtain silicon slag by-product 1; Preferably, the alkali solution in S2 is a solution of sodium hydroxide, potassium hydroxide or a combination thereof with a molar concentration of 3-10M, preferably 4-9M, more preferably 5M-8M; Preferably, the pH in S2 is adjusted to 13.0-14.5, further to 13.5-14.3, and further to 14.0-14.2; Preferably, the molar amount of calcium in the calcium salt added in S2 is 2-6 times the molar amount of aluminum in the system, preferably 2.4-4 times, more preferably 3-3.5 times the molar amount of calcium salt added; Preferably, the calcium salt in S2 is one or any combination of calcium chloride, calcium hydroxide, calcium carbonate, and calcium oxide; Preferably, S2 is carried out at ambient temperature, specifically -10-50°C, preferably 5-40°C, more preferably 10-35°C; Preferably, the reaction time of S2 is 15-60 min, preferably 25-40 min, more preferably 30-35 min; Preferably, the stirring rate during the reaction of S1 and / or S2 is 0-1500 rpm, preferably 200-1200 rpm, preferably 500-1000 rpm, preferably 650-900 rpm; Preferably, the impurity-removed residue obtained by solid-liquid separation in S2 is washed and then dried to obtain the aluminum-calcium compound by-product 2; Preferably, the method further includes the following steps: S3, directly extracting lithium from the lithium-containing purified liquid or extracting lithium after further purification to obtain a lithium salt product.

[0016] The main elements in the leachate obtained after the acid leaching treatment of the lithium-containing glass solid waste of the present invention are Li, Al, and Ca, and the leaching rate of valuable elements is as high as 98% or more, among which the aluminum content level is significantly higher than the lithium content level, which is an aluminum-rich lithium-containing system. Studies have found that the lithium-containing aluminum-rich system will cause a large amount of lithium adsorption and entrainment loss (lithium loss is as high as 40% or more) by adjusting the low pH to form aluminum hydroxide precipitation to remove aluminum, and the impurity-removed system is viscous and pasty, and solid-liquid separation is difficult. In addition, other solution systems with calcium salts for assisted aluminum removal are directly applied to the leaching system of the present application, that is, simply adjusting the pH to within the range of aluminum hydroxide precipitation and adding calcium salts. The method of removing impurities by calcium aluminate precipitation is also accompanied by a large amount of lithium loss. The problem of poor aluminum-lithium separation and difficult solid-liquid separation in the lithium-containing glass leaching system remains unsolved. The occurrence of the above phenomenon may be related to the solubility product K of substances such as lithium hydroxide, calcium aluminum compounds and calcium hydroxide. SP Related, K SP There will be differences in precipitation priorities, and the components of the system and their mutual influences are complex, making the impurity removal process difficult to control.

[0017] Through in-depth research, the inventors have found that in response to the above problems existing in the lithium-containing aluminum-rich solution system obtained by leaching lithium-containing glass solid waste, under high pH conditions, the selective precipitation and removal of substances in the form of calcium-aluminum compounds, which are different from the existing calcium metaaluminate, supplemented by the addition of calcium salts, can significantly reduce the lithium element entrainment during the precipitation of aluminum-containing compounds. Without introducing new impurity elements, the aluminum ions in the solution are removed in the form of special calcium-aluminum compounds. This method effectively reduces the lithium entrainment loss during the dealuminization process, and the fluidity of the impurity removal system is significantly optimized, with good filterability, effectively improving the impurity removal effect and production efficiency. On this basis, by optimizing the form and addition method of the alkali in the system, the initial reaction pH and the amount of calcium salt used, further optimized dealumination and lithium loss reduction effects are achieved.

[0018] Beneficial effects (1) Using a pure wet process, the valuable elements Li, Al, and Ca can be efficiently leached from lithium-containing glass solid waste by treating it with simple inorganic acid, without being restricted by the various limitations of selective leaching.

[0019] (2) Using calcium salt as an impurity remover, the main elements Al and Ca in the leachate are removed in the form of specific calcium-aluminum compounds within a specific pH range, effectively reducing lithium loss during the aluminum removal process of the lithium-rich aluminum solution. At the same time, the introduction of additional impurity ions is avoided, reducing the tedious steps in the subsequent deep impurity removal treatment. Through the solution of the present invention, the lithium loss of the aluminum-rich lithium solution is significantly reduced compared to the traditional low pH aluminum removal method.

[0020] (3) In aluminum-rich and lithium-containing systems, the fluidity of the impurity removal scheme of the present invention is significantly better than that of the traditional slurry system in which low pH is adjusted to dealumination with aluminum hydroxide, and the lithium loss and filterability are also significantly improved.

[0021] (4) Compared with the combination of pyrolysis and wet processing or multi-reagent collaborative treatment, the process flow is short and simple to operate, with low material cost and low energy consumption, no waste gas is generated, and the wastewater generated can be easily recycled after treatment.

[0022] (5) The slag obtained by leaching and dealuminization can be reused in production without waste residue accumulation. The insoluble silicon slag obtained by leaching can be recycled and directly used in the preparation of cement, ceramics, glass and other products. The aluminum-calcium compounds obtained by impurity removal can be recycled and used in materials, construction, ceramics, electronics, environmental protection and other fields. The lithium salts such as lithium carbonate obtained by directly extracting lithium from the impurity-rich solution or further treating it can be used as raw materials for the production of lithium-ion battery materials. This effectively improves the lithium extraction process of lithium-containing glass solid waste, makes full use of the valuable elements such as lithium, aluminum, silicon, and calcium in lithium-containing glass solid waste, reduces environmental pollution caused by the stacking of glass waste, reduces production costs and industrialization difficulties, improves economic benefits, and provides an effective way to achieve full resource recycling of lithium-containing solid waste. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 XRD of lithium-containing glass solid waste raw materials.

[0024] Figure 2 This is the XRD pattern of calcium-aluminum precipitate.

[0025] Figure 3 This is the state of the impurity removal system under different pH conditions. DETAILED DESCRIPTION

[0026] The raw materials used in the following embodiments are lithium-containing glass solid waste powder that has passed through a 100-mesh sieve, and the main components are as follows: Li% Al% Ca% Mg% Fe% K% Na% 1.775 12.614 1.116 0.979 0.076 0.231 1.422 P% Zn% Ni% B% Mn% Cr% Ti% 0.023 0.012 0.014 0.013 0.005 0.006 0.007 Example 1 S1. Lithium-containing glass solid waste powder was mixed with 18% hydrochloric acid solution at a solid-liquid ratio of 1:5, stirred and reacted at 70°C for 3 hours, and solid-liquid separation was performed to obtain leachate and leach residue. The leach residue was washed and dried to obtain insoluble silicon slag. The leaching effect of this embodiment is as follows: S2, add 5M sodium hydroxide solution to the leachate to adjust the pH of the system to 14.2, add calcium hydroxide according to n(Ca):n(Al)=2:1, stir at room temperature for 30 minutes and filter to obtain the impurity-removed liquid and impurity-removed residue, impurity removal slag After washing and drying, a calcium-aluminum-containing byproduct 2 is obtained. The impurity removal effect is as follows: The lithium-containing liquid after impurity removal is further subjected to lithium extraction to obtain lithium carbonate product.

[0027] In this embodiment, the aluminum removal rate is 36.76%, the lithium entrainment loss is 2.05%, the impurity removal system has good solid-liquid separation, and the magnesium co-precipitation removal effect is excellent.

[0028] Example 2 S1 leaching operation is the same as in Example 1; S2, add 5M sodium hydroxide solution to the leachate to adjust the pH of the system to 14.2, add calcium carbonate according to n(Ca):n(Al)=2:1, stir at room temperature for 30 minutes and filter to obtain the impurity-removed liquid and impurity-removed residue, impurity removal slag After washing and drying, a calcium-aluminum-containing byproduct 2 is obtained. The impurity removal effect is as follows: In this embodiment, the aluminum removal rate is 30.35%, the lithium entrainment loss is 3.46%, the impurity removal system has good solid-liquid separation, and the calcium co-precipitation removal effect is better.

[0029] Example 3 S1 leaching operation is the same as in Example 1; S2, add 5M sodium hydroxide solution to the leachate to adjust the pH of the system to 14.2, add calcium hydroxide according to n(Ca):n(Al)=2.5:1, stir at room temperature for 30 minutes and filter to obtain the impurity-removed liquid and impurity-removed residue, impurity removal slag After washing and drying, a calcium-aluminum-containing byproduct 2 is obtained. The impurity removal effect is as follows: In this embodiment, the aluminum removal rate is 44.2%, the lithium entrainment loss is 1.58%, the impurity removal system has good solid-liquid separation, and the co-precipitation effect of magnesium and iron is excellent.

[0030] Example 4 S1 leaching operation is the same as in Example 1; S2, add 5M sodium hydroxide solution to the leachate to adjust the pH of the system to 14.2, add calcium hydroxide according to n(Ca):n(Al)=3:1, stir at room temperature for 30 minutes and filter to obtain the impurity-removed liquid and impurity-removed residue, impurity removal slag After washing and drying, a calcium-aluminum-containing byproduct 2 is obtained. The impurity removal effect is as follows: In this embodiment, the aluminum removal rate is 43.8%, the lithium entrainment loss is 1.49%, the impurity removal system has good solid-liquid separation, and the co-precipitation effect of magnesium and iron is excellent.

[0031] Example 5 S1 leaching operation is the same as in Example 1; S2, add 5M sodium hydroxide solution to the leachate to adjust the pH of the system to 14.2, add calcium hydroxide according to n(Ca):n(Al)=3.5:1, stir at room temperature for 30 minutes and filter to obtain the impurity-removed liquid and impurity-removed residue, impurity removal slag After washing and drying, a calcium-aluminum-containing byproduct 2 is obtained. The impurity removal effect is as follows: In this embodiment, the aluminum removal rate is 44.96%, the lithium entrainment loss is 1.26%, the impurity removal system has good solid-liquid separation, and the co-precipitation effect of magnesium and iron is excellent.

[0032] Example 6 S1. Mix the lithium-containing glass solid waste powder with 18% hydrochloric acid solution at a solid-liquid ratio of 1:5, stir and react at 65°C for 3 hours, separate the solid and liquid to obtain leachate and leach residue, wash the leach residue and dry it to obtain insoluble silicon residue. The leaching effect of this embodiment is as follows: S2, add solid caustic soda to the leachate, add water to dilute 1.5 times, adjust the system pH to 12.56, add calcium hydroxide according to n (Ca): n (Al) = 3.5: 1, stir at room temperature for 30 minutes and filter to obtain the impurity-removed liquid and impurity-removed residue, impurity removal slag After washing and drying, a calcium-aluminum-containing byproduct 2 is obtained. The impurity removal effect is as follows: The lithium-containing liquid after impurity removal is further subjected to lithium extraction to obtain lithium carbonate product.

[0033] In this embodiment, the aluminum removal rate is 82.28%, the lithium entrainment loss is 16.91%, the impurity removal system has good solid-liquid separation, and the calcium co-precipitation removal effect is better.

[0034] Example 7 S1. The lithium-containing glass solid waste powder was mixed with 18% hydrochloric acid solution at a solid-liquid ratio of 1:5, and stirred at 75°C for 2.5 hours. The solid and liquid were separated to obtain a leachate and a leachate residue. The leachate residue was washed and dried to obtain an insoluble silicon residue. The leaching effect of this embodiment is as follows: S2, add solid caustic soda to the leachate, add water to dilute 1.5 times, adjust the system pH to 13.74, add calcium hydroxide according to n (Ca): n (Al) = 3.5: 1, stir at room temperature for 30 minutes and filter to obtain the impurity-removed liquid and impurity-removed residue, impurity removal slag After washing and drying, a calcium-aluminum-containing byproduct 2 is obtained. The impurity removal effect is as follows: The lithium-containing liquid after impurity removal is further subjected to lithium extraction to obtain lithium carbonate product.

[0035] In this embodiment, the aluminum removal rate is 88.13%, the lithium entrainment loss is 9.06%, the impurity removal system has good solid-liquid separation, and the calcium co-precipitation removal effect is excellent.

[0036] Example 8 S1 leaching operation is the same as in Example 7; S2, add solid caustic soda to the leachate, add water to dilute 1.5 times, adjust the system pH to 14.2, add calcium hydroxide according to n (Ca): n (Al) = 3.5: 1, stir at room temperature for 30 minutes and filter to obtain the impurity-removed liquid and impurity-removed residue, impurity removal slag After washing and drying, a calcium-aluminum-containing byproduct 2 is obtained. The impurity removal effect is as follows: In this embodiment, the aluminum removal rate is 90.31%, the lithium entrainment loss is 6.5%, the impurity removal system has good solid-liquid separation, and the calcium-magnesium co-precipitation removal effect is excellent.

[0037] Example 9 S1. The lithium-containing glass solid waste powder was mixed with 18% hydrochloric acid solution at a solid-liquid ratio of 1:4, and stirred at 80°C for 2 hours. The solid and liquid were separated to obtain a leachate and a leachate residue. The leachate residue was washed and dried to obtain an insoluble silicon residue. The leaching effect of this embodiment is as follows: S2, add solid caustic soda to the leachate, add water to dilute 1.5 times, adjust the system pH to 14.2, add calcium hydroxide according to n (Ca): n (Al) = 3.5: 1, stir at room temperature for 30 minutes and filter to obtain the impurity-removed liquid and impurity-removed residue, impurity removal slag After washing and drying, a calcium-aluminum-containing byproduct 2 is obtained. The impurity removal effect is as follows: The lithium-containing liquid after impurity removal is further subjected to lithium extraction to obtain lithium carbonate product.

[0038] In this embodiment, the aluminum removal rate is 89.75%, the lithium entrainment loss is 5.3%, the impurity removal system has good solid-liquid separation, and the calcium-magnesium co-precipitation removal effect is excellent.

[0039] Comparative Example 1 No calcium salt was added to S2, and the rest was the same as in Example 1. The impurity removal effect was as follows: It can be seen from Comparative Example 1 that without adding calcium salt to assist dealumination, the lithium entrainment loss increases from 2.05% to 12.1%.

[0040] Comparative Example 2 In S2, solid caustic soda flakes were added to the leachate, and then water was added to dilute it 1.5 times. The pH of the system was adjusted to 5.35, and no calcium salt was added. The rest was the same as in Example 1. The impurity removal effect was as follows: From Comparative Example 2, it can be seen that the glass leaching system containing aluminum and lithium is removed by conventional low pH aluminum hydroxide precipitation, and the lithium entrainment loss is as high as 40.21%. Figure 3 It can be seen that the impurity removal system is in a viscous paste and solid-liquid separation is difficult.

[0041] Comparative Example 3 In S2, the leachate is added to the alkali solution, and the pH of the system is adjusted to 14.09. The rest is the same as in Example 1. The impurity removal effect is as follows: It can be seen from Comparative Example 3 that adjusting the impurity removal and liquid addition method has a significant effect on the removal of aluminum and the entrainment of lithium. That is, the method of adding alkaline solution to the leachate to adjust the pH cannot overcome the defect of lithium entrainment loss.

[0042] Comparative Example 4 S1 is the same as Example 6; S2, add solid caustic soda to the leachate, add water to dilute 1.5 times, adjust the system pH to 10.88, add calcium hydroxide according to n (Ca): n (Al) = 3.5: 1, stir at room temperature for 30 minutes and filter to obtain the impurity-removed liquid and impurity-removed residue, impurity removal slag After washing and drying, a calcium-aluminum-containing byproduct 2 is obtained. The impurity removal effect is as follows: As can be seen from Comparative Example 4, the problem of high lithium entrainment loss cannot be solved even when the pH is higher than that of conventional aluminum hydroxide or even when metaaluminate exists, but not within the pH range specified in this application; and Figure 2 It can be seen that there is a difference in the diffraction peaks between Comparative Example 4 and Example 8, indicating that pH affects the formation of calcium aluminum precipitates.

[0043] The contents illustrated in the above embodiments should be understood as these embodiments are only used to more clearly illustrate the present invention, and are not used to limit the scope of the present invention. After reading the present invention, various equivalent modifications of the present invention by those skilled in the art shall fall within the scope defined by the claims attached to this application.

Claims

1. A method for resource utilization of lithium-containing glass solid waste, characterized in that: The steps include: S1. After mixing the lithium-containing glass solid waste raw material with the acid solution for reaction, perform or do not perform solid-liquid separation; S2. Adding alkali solution and / or solid caustic soda to the leachate or leachate slurry obtained in S1, adjusting the pH to 12.5-14.5, adding calcium salt for reaction, and performing solid-liquid separation to obtain a purified lithium-containing solution.

2. The method for resource utilization of lithium-containing glass solid waste according to claim 1, characterized in that: The lithium-containing glass solid waste raw material is preferably a powder, further a powder with a mesh size of 50-200, further a powder with a mesh size of 80-150, and more preferably a powder with a mesh size of 100-120. Preferably, the lithium content of the lithium-containing glass solid waste is 0.5%-4%, further 1%-3%, and further 1.5%-1.8%. Preferably, the aluminum content of the lithium-containing glass solid waste is 5%-20%, further 7%-16%, and further 8.5%-15%. Preferably, the calcium content of the lithium-containing glass solid waste is 0-4.5%, further 0.5%-2.5%, and further 0.9%-2.1%.

3. The method for resource utilization of lithium-containing glass solid waste according to claim 1, characterized in that: The acid solution described in S1 is an acidic liquid containing one of hydrochloric acid, sulfuric acid, and nitric acid, or any combination thereof; preferably, the acid solution concentration is 10-25%, further 12-20%, and further 15-18%; preferably, the solid-liquid mass ratio in S1 is 1:2-10, further 1:2-8; further 1:3-5; preferably, the S1 reaction temperature is 10-99°C, preferably 20-95°C, and further 50-90°C; preferably, the S1 reaction time is 0.5~3h, preferably 1-2.5h, and more preferably 1.5-2h.

4. The method for resource utilization of lithium-containing glass solid waste according to claim 1, characterized in that: The lithium ion concentration in the S1 leaching slurry or solution is 0.5-10 g / L, further 1.0-8 g / L, further 2.0-6 g / L; preferably, the aluminum ion concentration in the S1 leaching system is 10-45 g / L, further 12-35 g / L, further 15-30 g / L, further 18-25 g / L.

5. The method for resource utilization of lithium-containing glass solid waste according to claim 1, characterized in that: Preferably, after leaching in S1, solid-liquid separation is performed to obtain leachate and leach residue, and the leach residue is washed and dried to obtain silicon slag by-product 1.

6. The method for resource utilization of lithium-containing glass solid waste according to claim 1, characterized in that: The alkali solution in S2 is a solution of one of sodium hydroxide and potassium hydroxide or a combination thereof with a molar concentration of 3-10M, preferably 4-9M, more preferably 5M-8M; preferably, the alkali is solid flake alkali, solid flake alkali is added and diluted with water to adjust the pH; preferably, the dilution ratio with water is 0.5-2.5 times; preferably, the pH in S2 is adjusted to 13.0-14.5, further to 13.5-14.3, and further to 14.0-14.

2.

7. The method for resource utilization of lithium-containing glass solid waste according to claim 1, characterized in that: Calcium salt is added to S2 so that the molar amount of calcium in the added calcium salt is 2-6 times, preferably 2.4-4 times, and more preferably 3-3.5 times the molar amount of aluminum in the system; preferably, the calcium salt in S2 is one or any combination of calcium chloride, calcium hydroxide, calcium carbonate, and calcium oxide.

8. The method for resource utilization of lithium-containing glass solid waste according to claim 1, characterized in that: S2 is carried out at ambient temperature, specifically -10-50°C, preferably 5-40°C, more preferably 10-35°C; preferably, the reaction time of S2 is 15-60 min, preferably 25-40 min, more preferably 30-35 min.

9. The method for resource utilization of lithium-containing glass solid waste according to claim 1, characterized in that: The stirring rate during the reaction of S1 and / or S2 is 0-1500 rpm, preferably 200-1200 rpm, preferably 500-1000 rpm, preferably 650-900 rpm; preferably, the impurity-removed residue obtained by solid-liquid separation in S2 is washed and dried to obtain the aluminum-calcium compound by-product 2.

10. The method for resource utilization of lithium-containing glass solid waste according to claim 1, characterized in that: The following steps are also included: S3. Lithium is extracted directly from the lithium-containing purified liquid or further purified to obtain a lithium salt product.

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