CN114226413B - Comprehensive treatment process of lithium slag - Google Patents
Comprehensive treatment process of lithium slag Download PDFInfo
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- CN114226413B CN114226413B CN202010940391.0A CN202010940391A CN114226413B CN 114226413 B CN114226413 B CN 114226413B CN 202010940391 A CN202010940391 A CN 202010940391A CN 114226413 B CN114226413 B CN 114226413B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a comprehensive treatment process of lithium slag, which comprehensively utilizes the waste slag generated after lithium extraction by a lithium ore sulfuric acid process by adopting an ore grinding treatment technology, a weak-strong magnetic separation iron removal technology, a solid-liquid two-phase desulfurization technology and a multistage annular water grading circulation technology. The invention can effectively separate the impurity components containing iron and sulfur from the silicon-aluminum components, and creates conditions for comprehensively utilizing the lithium slag to produce high added value products such as silicon-aluminum micropowder, tantalum-niobium concentrate and the like. Meanwhile, the problems of coarse product granularity, low yield, valuable metal waste, wastewater discharge and the like in the existing production process are solved, and the method has good popularization and application prospects.
Description
Technical Field
The invention relates to an industrial solid waste treatment technology, in particular to a comprehensive treatment process of lithium slag, and belongs to the field of comprehensive utilization of waste slag generated after lithium extraction by a sulfuric acid process of lithium ores.
Background
At present, with the rapid development of the lithium battery industry in China, the yield of metallurgical solid waste-lithium slag generated in the process is also increased, and the problem of environmental pollution is also continuously revealed, so that the requirement for comprehensive utilization of the lithium slag is also increased.
At present, research and application of comprehensive utilization of lithium slag are mostly remained in the field of building materials, and the added value of products is low. Recently, with the intensive research, lithium slag has been increasingly utilized as an existing application example.
The main chemical components of the lithium slag produced by the sulfuric acid method lithium extraction process are SiO 2 、Al 2 O 3 CaO and SO 3 . Amorphous silicon and aluminum make lithium slag intoIs a high-activity pozzolanic material. SiO in lithium slag 2 The content of (2) is 21-25%, al 2 O 3 The content of (2) is 60-67%, which is basically consistent with the component requirement of the silicon-aluminum micropowder for glass industry.
At present, there are domestic application examples of producing silicon-aluminum micropowder by flotation, strong magnetic separation and dehydration, and the product is used for replacing natural pyrophyllite to produce glass fibers. The produced by-products, namely flotation tailings and magnetic separation tailings, can be used for cement admixture, so that the high-value comprehensive utilization of lithium slag is realized. For example, chinese patent CN108273826a, a full-phase high-value recycling method for lithium slag: mixing and stirring the lithium slag to enable sulfate minerals in the lithium slag to be in a dispersed and suspended state; then the obtained product is subjected to reaction treatment and wet magnetic separation treatment by using soluble carbonate according to any sequence; and concentrating, filtering and drying the obtained slurry to obtain the pyrophyllite raw material for the glass fiber. The process flow diagram is shown in figure 2.
However, the existing technology for producing the silicon-aluminum micropowder by using the lithium slag has the following problems in the actual production process: 1. because the silicon-aluminum micropowder is not subjected to ore grinding treatment, the granularity of the produced silicon-aluminum micropowder is relatively coarse, and the substitution rate of the silicon-aluminum micropowder as a glass fiber production raw material for natural pyrophyllite is not high; 2. because the monomer of the iron-containing component in the lithium slag is insufficiently dissociated, the monomer can be in a continuous body with the silicon-aluminum component, and the silicon-aluminum component can enter the magnetic separation tailings along with the iron-containing component through strong magnetic separation, so that the yield of the silicon-aluminum micro powder is reduced; 3. the ferromagnetic iron-containing components in the raw materials are not removed in advance, and the raw materials can be tightly attached to a magnetic medium after entering a ferromagnetic machine, so that the ferromagnetic machine is easy to be blocked; 4. the tantalum-niobium content in the magnetic product after strong magnetic separation reaches industrial grade but is not reasonably utilized; 5. the product dehydration system increases the iron content of the silicon-aluminum micropowder due to the abrasion of the overcurrent iron-containing component; 6. the amount of sulfur and fine mud in the circulating water generated by the dehydration system is gradually increased along with production, so that periodic external discharge is required, and zero discharge of wastewater cannot be really realized.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a method for separating iron and silicon in lithium slag to realize comprehensive treatment of the lithium slag. The raw material ore grinding process is adopted, so that the granularity of the silicon-aluminum micro powder is reduced, the substitution rate of products for pyrophyllite in the subsequent glass fiber production is improved, meanwhile, iron-containing components in lithium slag are fully dissociated, the iron removal effect is better, and the yield and quality of the silicon-aluminum micro powder are improved. Meanwhile, a weak magnetic separation operation is added before the strong magnetic separation operation, so that the strong magnetic iron-containing components in the raw material lithium slag are removed in advance, and the blocking of a strong magnetic machine is prevented; the magnetic product obtained by the strong magnetic separation is further separated by adopting a flotation-gravity separation process to obtain tantalum-niobium concentrate, so that valuable resources are fully utilized; finally, dry magnetic separation is carried out by adding a magnetic separation grid before the product is packaged, so that the phenomenon that the iron content of the silicon-aluminum micropowder product is increased due to the abrasion of an overflow iron-containing component of a dehydration system is prevented; furthermore, the cyclic water generated by magnetic separation, gravity separation and flotation is recycled in a grading way, so that the zero emission of wastewater is truly realized.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a comprehensive treatment process of lithium slag comprises the following steps:
1) Grinding: and grinding the lithium slag to obtain grinding powder.
2) And (3) carrying out low-intensity magnetic separation treatment: and (3) carrying out low-intensity magnetic separation treatment on the ore grinding powder material obtained in the step (1) to obtain a magnetic material I and a material subjected to low-intensity magnetic separation.
3) Strong magnetic separation: and (3) carrying out strong magnetic separation treatment on the low-intensity magnetic separation material obtained in the step (2) to obtain a magnetic material II and a high-intensity magnetic separation material.
4) And (3) flotation treatment: and (3) carrying out primary concentration and filtration on the strong magnetic separation material obtained in the step (3) and then carrying out flotation treatment to obtain sulfur-containing tailings and the material after flotation.
5) Alkali conversion treatment: adding soluble carbonate into the flotation material obtained in the step 4), and then carrying out secondary concentration and filtration to obtain a crude product of the silicon-aluminum micro powder.
2. The process according to claim 1, characterized in that: the process further comprises the following steps:
6) Drying and removing iron: and 5) drying the crude silicon-aluminum micropowder obtained in the step 5), and then carrying out iron removal treatment on the dried crude silicon-aluminum micropowder to obtain a fine silicon-aluminum micropowder.
Preferably, the process further comprises:
7) And (3) performing flotation treatment on the magnetic material II obtained in the step (3) to obtain a impurity material (generally a silicate component) and a sand material (mainly tantalum-niobium ore, containing a small amount of impurities). And then the sand material is subjected to reselection treatment to obtain a light sand material and a heavy sand material. And finally, carrying out primary concentration and filtration on the heavy sand material to obtain tantalum-niobium concentrate.
Preferably, the process further comprises:
8) Mixing the magnetic material I obtained in the step 2), the impurity material obtained in the flotation process in the step 7) and the light sand material obtained in the reselection process to obtain a mixture, and then carrying out primary concentration and filtration on the mixture to obtain the iron-containing tailings.
Preferably, fe in the material after the strong magnetic separation obtained in the step 3) 2 O 3 The content is 0.5% or less, preferably 0.45% or less. (mass fraction)
Preferably, SO in the crude silica-alumina micropowder obtained in step 5) 3 The content is 0.5% or less, preferably 0.45% or less. (mass fraction)
Preferably, in step 1), the ore grinding treatment adopts a closed circuit ore grinding process, specifically: and (3) feeding lithium slag into a ball mill (such as a long barrel type ball mill), grinding the lithium slag by the ball mill, discharging the ground lithium slag to a cyclone for classification, wherein overflow materials of the cyclone are grinding powder. And returning the cyclone sand setting to the ball mill for ore grinding.
Preferably, the particle size of the ground powder obtained after the grinding treatment is not less than 95% in terms of-45 μm, and preferably not less than 98% in terms of-45 μm.
Preferably, in step 1), a dispersant is added during the ore grinding treatment. Preferably, the dispersing agent is one or more of sodium silicate, soda and phosphate.
Preferably, the primary loop water is produced after the primary concentration filtration described in step 4), step 7) and step 8). Preferably, the primary circulating water is optionally used as the grinding treatment water in the step 1), the weak magnetic separation treatment water in the step 2), the strong magnetic separation treatment water in the step 3), or the floatation and reselection treatment water in the step 7).
Preferably, the secondary loop water is produced after the secondary concentration filtration described in step 5) of the alkaline shift treatment. Preferably, the secondary loop water is used as the flotation process water in step 4).
Preferably, during the alkaline conversion treatment of step 5), the pH of the slurry after addition of soluble carbonate to the post-flotation material is 7-14, preferably 8-12.
Preferably, the soluble carbonate is one or more of sodium carbonate, potassium carbonate and ammonium carbonate, preferably sodium carbonate or potassium carbonate.
Preferably, in step 6), the iron removal treatment is magnetic iron removal. And the magnetic iron removal is to remove iron from the dried crude silicon-aluminum micro powder by a magnetic grid to obtain a refined silicon-aluminum micro powder.
Preferably, the sulfur-containing tailings obtained in step 4) and/or the iron-containing tailings obtained in step 8) are used as cement admixture.
Preferably, in step 2), the weak magnetic separation treatment is performed by using a weak magnetic field separator.
Preferably, in step 3), the high-intensity magnetic separation treatment uses a high-intensity magnetic separator.
In the present invention, the "optionally" means one or more of all choices or any choices.
In the invention, the lithium slag is waste slag generated after lithium extraction by a lithium ore sulfuric acid method process.
In the prior art, the treatment of lithium slag has been mostly carried out in the field of construction materials. The added value of the product is extremely low. In the high-value comprehensive utilization process for the lithium slag, the lithium slag is not subjected to ore grinding treatment, so that the produced silicon-aluminum micropowder has coarse granularity, and the substitution rate of the silicon-aluminum micropowder as a glass fiber production raw material for natural pyrophyllite is not high. And because the monomer of the iron-containing component in the lithium slag is insufficiently dissociated, the monomer can be in a joint body with the silicon-aluminum component, and the silicon-aluminum component can enter the magnetic separation tailings along with the iron-containing component through strong magnetic separation, so that the yield of the silicon-aluminum micro powder is reduced. Because the ferromagnetic iron-containing components in the raw materials are not removed in advance, the ferromagnetic iron-containing components can be closely attached to a magnetic medium after entering a ferromagnetic machine, and further the ferromagnetic machine is easy to be blocked. The tantalum-niobium content in the magnetic product subjected to strong magnetic separation reaches industrial grade but is not reasonably utilized. The product dehydration system increases the iron content of the silicon-aluminum micropowder due to the abrasion of the overcurrent iron-containing component. The amount of sulfur and fine mud in the ring water generated by the dehydration system is gradually increased along with the production, and the ring water needs to be periodically discharged, so that the zero discharge of the wastewater can not be really realized.
In general, silicon-aluminum micropowder for glass fiber has strict limitation on iron, a main harmful impurity, and generally requires Fe 2 O 3 The content is less than or equal to 0.5 percent (mass fraction). The iron in the fine silica alumina powder comes mainly from two aspects: 1. iron in the raw material lithium slag is derived from ore, mainly exists in the form of iron-containing aluminosilicate, and exists in the form of tantalite and niobite in a small amount; 2. iron pollution generated by abrasion of overflow equipment in the lithium slag processing process such as ore grinding, stirring and scattering operations.
In the invention, the lithium slag raw material is processed by adopting ore grinding, so that the main impurity-containing components in the lithium slag raw material are fully dissociated, and conditions are created for the follow-up magnetic separation iron removal and flotation sulfur removal; meanwhile, the granularity of the material is reduced through grinding, and the substitution rate of the product for pyrophyllite in the subsequent glass fiber production is improved. In the invention, the lithium slag grinding adopts a closed circuit grinding process: lithium slag is firstly fed into a long barrel type ball mill, mill discharge is pumped into a cyclone for classification, the cyclone overflows as a final grinding product to enter the next operation, and the cyclone sand setting returns to the ball mill for regrinding. The lithium slag adopts the ore grinding technology to cover the existing function of single dispersion stirring operation, simplifies the flow and creates conditions for expanding the productivity.
Further, dispersing agents are added in the ore grinding process, so that the dispersing agents are fully contacted with iron-containing and sulfur-containing impurity components in the lithium slag, a good suspension dispersion state is formed, and the effects of removing iron impurities through subsequent magnetic separation and removing sulfur impurities through floatation are improved.
In the present invention, for iron of different sources, wet is usedThe removal is carried out by two techniques of magnetic separation and dry magnetic separation. The wet magnetic separation technology comprises the following steps: the strong magnetic components in the materials are firstly removed by adopting a weak magnetic field magnetic separator (weak magnetic separation treatment) so as to prevent the strong magnetic components in the materials from entering the strong magnetic field magnetic separator, and the magnetic medium is blocked due to the fact that the magnetic adsorption force is too large and the materials are not easy to wash cleanly. The material after iron removal by weak magnetic field magnetic separation enters a strong magnetic field magnetic separator for further iron removal (strong magnetic separation treatment), and mainly the weak magnetic iron-containing components such as ferroaluminosilicate with larger content are removed. Then adopting a coarse one-sweep two-stage strong magnetic separation treatment operation to further remove the weak magnetic iron-containing component in the lithium slag, so that the Fe of the non-magnetic product (material after strong magnetic separation) 2 O 3 The content is reduced to below 0.5 percent (mass fraction). The dry magnetic separation technology comprises the following steps: because the produced silicon aluminum micropowder product particles have larger abrasiveness, iron pollution exists in the concentration-filtration-drying process, for example, when a flash evaporation dryer is adopted, a stirring impeller of the dryer is in close contact with materials, and the abrasion is larger, so that the iron pollution of the silicon aluminum micropowder can be caused. Through installing magnetic force grid in the overflow pipeline of the material after drying, can effectively get rid of the iron fillings that mix because of wearing and tearing, guarantee that the iron content of product (fine product of fine powder of aluminium and silicon does not exceed the standard.
Further, valuable metal elements such as tantalum and niobium are also enriched in the magnetic material II obtained in the strong magnetic separation iron removal operation, and the valuable metal elements exceed industrial exploitation indexes, so that the magnetic material II has comprehensive utilization value. The tantalum-niobium resource mainly exists in the form of tantalum iron ore and niobium iron ore, for the magnetic material II, a flotation process is adopted to remove silicate components (i.e. impurity materials) in the magnetic material II, then a gravity separation process is adopted to obtain a heavy sand product (tantalum-niobium coarse ore), the heavy sand product is tantalum-niobium concentrate after dehydration, the light sand product is combined with iron-containing components obtained by weak magnetic separation and silicate components obtained by flotation, and iron-containing tailings are obtained after dehydration, so that the heavy sand product can be used as a cement admixture.
In the present invention, a solid-liquid two-phase desulfurization technique is employed. Sulfur in lithium slag is mainly SO 4 2- In the form of ions, mostly of Ca 2+ The combined gypsum is present in the lithium slag. Since gypsum is slightly soluble in water, while other sulfates are readily soluble in water, during the production process, the liquorThe phase also contains a certain amount of SO 4 2- Ions and SO in liquid phase along with water recycling 4 2- The ions gradually reach saturation. The solid phase desulfurization adopts a floatation method, and the main target mineral is sulfate mineral mainly comprising gypsum, and is discharged along with foam in the floatation process, so that the purpose of solid phase desulfurization is achieved. And after solid phase desulfurization, liquid phase desulfurization can be carried out. The liquid phase desulfurization adopts a stirring and dewatering method, soluble carbonate is firstly added into slurry, the pH value of the slurry is controlled to be 7-14 (preferably 8-12), and SO in the slag phase of the slurry can be obtained through stirring and full reaction 3 The content is less than 0.5 percent (mass fraction). Concentrating, filtering and dewatering the reacted slurry to obtain qualified sulfur content material for the next operation.
In the invention, the zero emission of wastewater is realized by a cyclic water grading circulation technology. The circulating water obtained by the primary concentration, filtration and dehydration of each product in the magnetic separation iron-removing operation and the tantalum-niobium ore separation operation is slightly alkaline, has low impurity content, can be used as the primary circulating water for recycling in the ore grinding-magnetic separation-tantalum-niobium ore recovery operation section, does not need to be discharged, and can be supplemented to other operation sections such as flotation desulfurization and the like.
Further, the ring water obtained by dewatering each product of the flotation desulfurization operation and the alkaline conversion operation contains micro-fine particle gypsum, flotation agent and SO 4 2- The harmful components such as ions are more, the collected secondary circulating water is only recycled in the flotation-alkali conversion operation section, and when the content of the harmful components in the secondary circulating water reaches a certain concentration, the content is not increased any more, so that an equilibrium state is formed, and the secondary circulating water does not need to be discharged. The cyclic water grading circulation technology is adopted, so that the problems of water discharge and environmental pollution can be fundamentally solved, and the supplementing amount of new water is reduced.
Furthermore, as the material after alkali conversion contains sulfate ions, a procedure for removing sulfate ions can be added before secondary circulating water. In addition, sulfate ions can be removed by adding a reagent in the flotation operation, and the sulfate ions do not rise after reaching a certain concentration. The circulation of a small amount of sulfate ions in water does not affect the quality of the silicon-aluminum micropowder product.
In the invention, the content is the mass content, and the percentage is the mass percentage.
Compared with the prior art, the invention has the following beneficial technical effects:
1: according to the process, the raw material lithium slag is subjected to ore grinding treatment, so that the granularity of the produced silicon-aluminum micropowder product is finer, and the substitution rate of the product for pyrophyllite in the subsequent glass fiber production is improved; meanwhile, the ore grinding ensures that each impurity component in the lithium slag is fully dissociated, thereby creating conditions for improving the yield and quality of the silicon-aluminum micropowder.
2: the invention realizes the effective separation of iron and silicon in lithium slag by adopting the comprehensive magnetic separation treatment technology, improves the yield of main products, namely the fine silicon-aluminum powder, and effectively controls the content of iron impurities in the products.
3: the invention also effectively recovers the tantalum-niobium resources in the magnetic materials, realizes the reutilization of the waste resources and improves the economic benefit.
4: the invention adopts the solid-liquid two-phase desulfurization technology, so that the desulfurization is more thorough, and favorable conditions are created for ensuring the quality of products.
5: the invention realizes zero discharge of sewage by the multistage circulating water grading recycling technology, reduces the supplementing amount of new water and saves water resources.
Drawings
FIG. 1 is a flow chart of a comprehensive treatment process of lithium slag.
Fig. 2 is a flow chart of a prior art lithium slag treatment process.
Detailed Description
The following examples illustrate the technical aspects of the invention, and the scope of the invention claimed includes but is not limited to the following examples.
A comprehensive treatment process of lithium slag comprises the following steps:
1) Grinding: and grinding the lithium slag to obtain grinding powder.
2) And (3) carrying out low-intensity magnetic separation treatment: and (3) carrying out low-intensity magnetic separation treatment on the ore grinding powder material obtained in the step (1) to obtain a magnetic material I and a material subjected to low-intensity magnetic separation.
3) Strong magnetic separation: and (3) carrying out strong magnetic separation treatment on the low-intensity magnetic separation material obtained in the step (2) to obtain a magnetic material II and a high-intensity magnetic separation material.
4) And (3) flotation treatment: and (3) carrying out primary concentration and filtration on the strong magnetic separation material obtained in the step (3) and then carrying out flotation treatment to obtain sulfur-containing tailings and the material after flotation.
5) Alkali conversion treatment: adding soluble carbonate into the flotation material obtained in the step 4), and then carrying out secondary concentration and filtration to obtain a crude product of the silicon-aluminum micro powder.
2. The process according to claim 1, characterized in that: the process further comprises the following steps:
6) Drying and removing iron: and 5) drying the crude silicon-aluminum micropowder obtained in the step 5), and then carrying out iron removal treatment on the dried crude silicon-aluminum micropowder to obtain a fine silicon-aluminum micropowder.
Preferably, the process further comprises:
7) And (3) carrying out flotation treatment on the magnetic material II obtained in the step (3) to obtain an impurity material and a sand material. And then the sand material is subjected to reselection treatment to obtain a light sand material and a heavy sand material. And finally, carrying out primary concentration and filtration on the heavy sand material to obtain tantalum-niobium concentrate.
Preferably, the process further comprises:
8) Mixing the magnetic material I obtained in the step 2), the impurity material obtained in the flotation process in the step 7) and the light sand material obtained in the reselection process to obtain a mixture, and then carrying out primary concentration and filtration on the mixture to obtain the iron-containing tailings.
Preferably, fe in the material after the strong magnetic separation obtained in the step 3) 2 O 3 The content is 0.5% or less, preferably 0.45% or less. (mass fraction)
Preferably, SO in the crude silica-alumina micropowder obtained in step 5) 3 The content is 0.5% or less, preferably 0.45% or less. (mass fraction)
Preferably, in step 1), the ore grinding treatment adopts a closed circuit ore grinding process, specifically: and (3) feeding lithium slag into a ball mill (such as a long barrel type ball mill), grinding the lithium slag by the ball mill, discharging the ground lithium slag to a cyclone for classification, wherein overflow materials of the cyclone are grinding powder. And returning the cyclone sand setting to the ball mill for ore grinding.
Preferably, the particle size of the ground powder obtained after the grinding treatment is not less than 95% in terms of-45 μm, and preferably not less than 98% in terms of-45 μm.
Preferably, in step 1), a dispersant is added during the ore grinding treatment. Preferably, the dispersing agent is one or more of sodium silicate, soda and phosphate.
Preferably, the primary loop water is produced after the primary concentration filtration described in step 4), step 7) and step 8). Preferably, the primary circulating water is optionally used as the grinding treatment water in the step 1), the weak magnetic separation treatment water in the step 2), the strong magnetic separation treatment water in the step 3), or the floatation and reselection treatment water in the step 7).
Preferably, the secondary loop water is produced after the secondary concentration filtration described in step 5) of the alkaline shift treatment. Preferably, the secondary loop water is used as the flotation process water in step 4).
Preferably, during the alkaline conversion treatment of step 5), the pH of the slurry after addition of soluble carbonate to the post-flotation material is 7-14, preferably 8-12.
Preferably, the soluble carbonate is one or more of sodium carbonate, potassium carbonate and ammonium carbonate, preferably sodium carbonate or potassium carbonate.
Preferably, in step 6), the iron removal treatment is magnetic iron removal. And the magnetic iron removal is to remove iron from the dried crude silicon-aluminum micro powder by a magnetic grid to obtain a refined silicon-aluminum micro powder.
Preferably, the sulfur-containing tailings obtained in step 4) and/or the iron-containing tailings obtained in step 8) are used as cement admixture.
Preferably, in step 2), the weak magnetic separation treatment is performed by using a weak magnetic field separator.
Preferably, in step 3), the high-intensity magnetic separation treatment uses a high-intensity magnetic separator.
In the present invention, the "optionally" means one or more of all choices or any choices.
In the invention, the lithium slag is waste slag generated after lithium extraction by a lithium ore sulfuric acid method process.
Example 1:
for lithium Slag (SiO) generated by preparing lithium carbonate by using spodumene as raw material and adopting sulfuric acid method in Sichuan lithium salt enterprises 2 ：61.50％、Al 2 O 3 ：20.95％，SO 3 ：7.27％、Fe 2 O 3 :0.81%, particle size: -45 μm content: less than or equal to 45 percent), firstly grinding by adopting a ball mill, and simultaneously adding dispersant sodium silicate, wherein the grinding concentration is as follows: 35%; the ore grinding product (the grain diameter is-45 mu m and the ratio is more than or equal to 98 percent) is firstly subjected to weak magnetic separation to remove iron, and the weak magnetic separation magnetic field strength is 0.3T; then a coarse magnetic separator with a two-section strong magnetic field with a magnetic field strength of 1.5T for coarse separation and a magnetic field strength of 1.8T for scavenging are adopted for removing iron, and the magnetic material slurry obtained by the strong magnetic separation is subjected to floatation and reselection to obtain tantalum-niobium concentrate for sale. The magnetic material-containing slurry obtained by the weak magnetic separation and tailings after flotation and reselection (the flotation and reselection treatment of the magnetic material-containing slurry after the strong magnetic separation) are mixed and dehydrated, and then the mixture can be sold as a cement production admixture. The non-magnetic material slurry obtained by strong magnetic separation adopts floatation desulfurization; the flotation adopts a primary roughing process and a secondary scavenging process, the flotation collector is oleic acid, the flotation foam product is gypsum after dehydration, and the gypsum can be sold as a retarder for cement production; adding sodium carbonate into the slurry subjected to flotation desulfurization to adjust the pH to 10, concentrating, filtering and drying, and removing iron through a magnetic grid to obtain a silicon-aluminum micropowder product.
The main components of the silicon-aluminum micropowder product are as follows: al (Al) 2 O 3 ：25.37％，SiO 2 ：68.52％，Fe 2 O 3 ：0.39％，SO 3 :0.29%, yield: 71.5 percent, and meets the quality requirement of partially replacing pyrophyllite for producing glass fibers. The production wastewater is recycled in a grading way, and no discharge exists.
Example 2:
for lithium Slag (SiO) generated by preparing lithium carbonate by using spodumene as raw material and adopting sulfuric acid method in Sichuan lithium salt enterprises 2 ：61.50％、Al 2 O 3 ：20.95％，SO 3 ：7.27％、Fe 2 O 3 :0.81%, particle size: -45 μm content: less than or equal to 45 percent), firstly grinding by adopting a ball mill, and simultaneously adding dispersant sodium silicate, wherein the grinding concentration is as follows: 40%; the ore grinding product (the grain diameter is-45 mu m and the ratio is more than or equal to 98 percent) is firstly subjected to weak magnetic separation to remove iron, and the weak magnetic separation magnetic field strength is 0.3T; then a coarse magnetic separator with a two-section strong magnetic field with a magnetic field strength of 1.5T for coarse separation and a magnetic field strength of 2.5T for scavenging are adopted for removing iron, and the magnetic material slurry obtained by the strong magnetic separation is subjected to floatation and reselection to obtain tantalum-niobium concentrate for sale. The magnetic material-containing slurry obtained by the weak magnetic separation and tailings after flotation and reselection (the flotation and reselection treatment of the magnetic material-containing slurry after the strong magnetic separation) are mixed and dehydrated, and then the mixture can be sold as a cement production admixture. The non-magnetic material slurry obtained by strong magnetic separation adopts floatation desulfurization; the flotation adopts a primary roughing process and a secondary scavenging process, the flotation collector is oleic acid, the flotation foam product is gypsum after dehydration, and the gypsum can be sold as a retarder for cement production; adding sodium carbonate into the slurry subjected to flotation desulfurization to adjust the pH to 11, concentrating, filtering and drying, and removing iron through a magnetic grid to obtain a silicon-aluminum micropowder product.
The main components of the silicon-aluminum micropowder product are as follows: al (Al) 2 O 3 ：25.42％，SiO 2 ：68.57％，Fe 2 O 3 ：0.28％，SO 3 :0.30%, yield: 73.1 percent, and meets the quality requirement of partially replacing pyrophyllite for producing glass fibers. The production wastewater is recycled in a grading way, and no discharge exists.
Example 3:
for the lithium slag in example 1, water is added to pulp first, and the pulp concentration is adjusted: 30, adding dispersant water glass at the same time; firstly, deironing lithium slag ore pulp by adopting a weak magnetic field (magnetic field strength: 0.3T) magnetic separator, and then deironing the lithium slag ore pulp by adopting a strong magnetic field (magnetic field strength: 1.5T) magnetic separator; grinding the iron-removed material by adopting a ball mill, wherein the grinding concentration is as follows: 35%; the ore grinding product (the grain diameter is-45 mu m with the proportion of more than or equal to 98 percent) is deironing by adopting a strong magnetic field (the magnetic field strength is 1.8T) magnetic separator; and carrying out flotation and reselection on the magnetic material-containing slurry obtained by strong magnetic separation (magnetic field strength: 1.8T) to obtain tantalum-niobium concentrate for sale. The magnetic material slurry obtained by the weak magnetic separation is mixed with tailings after flotation and reselection (the flotation and reselection treatment are carried out on the magnetic material slurry after the strong magnetic separation), and the mixture is dehydrated and can be used as cement production admixture for sale, and the non-magnetic material slurry obtained by the strong magnetic separation (the magnetic field strength is 1.8T) is desulfurized by flotation; the flotation adopts a primary roughing process and a secondary scavenging process, the flotation collector is oleic acid, the flotation foam product is gypsum after dehydration, and the gypsum can be sold as a retarder for cement production; adding potassium carbonate into the slurry subjected to flotation desulfurization to adjust the pH to 10, concentrating, filtering and drying, and removing iron through a magnetic grid to obtain a silicon-aluminum micropowder product.
The main components of the silicon-aluminum micropowder product are as follows: al (Al) 2 O 3 ：25.58％，SiO 2 ：69.72％，Fe 2 O 3 ：0.35％，SO 3 :0.31%, yield: 69.7% of the glass fiber, and meets the quality requirement of partially replacing pyrophyllite for producing glass fiber. The production wastewater is recycled in a grading way, and no discharge exists.
Example 4:
for the lithium slag in example 1, water is added to pulp first, and the pulp concentration is adjusted: 30, adding dispersant water glass at the same time; firstly, deironing lithium slag ore pulp by adopting a weak magnetic field (magnetic field strength: 0.5T) magnetic separator, and then deironing the lithium slag ore pulp by adopting a strong magnetic field (magnetic field strength: 2.0T) magnetic separator; grinding the iron-removed material by adopting a ball mill, wherein the grinding concentration is as follows: 40%; the ore grinding product (the grain diameter is-45 mu m with the proportion of more than or equal to 98 percent) is deironing by adopting a strong magnetic field (the magnetic field strength is 2.5T) magnetic separator; and carrying out flotation and reselection on the magnetic material-containing slurry obtained by strong magnetic separation (magnetic field strength: 2.5T) to obtain tantalum-niobium concentrate for sale. The magnetic material slurry obtained by the weak magnetic separation is mixed with tailings after flotation and reselection (the flotation and reselection treatment are carried out on the magnetic material slurry after the strong magnetic separation), and the mixture is dehydrated and can be used as cement production admixture for sale, and the non-magnetic material slurry obtained by the strong magnetic separation (the magnetic field strength is 1.8T) is desulfurized by flotation; the flotation adopts a primary roughing process and a secondary scavenging process, the flotation collector is oleic acid, the flotation foam product is gypsum after dehydration, and the gypsum can be sold as a retarder for cement production; adding potassium carbonate into the slurry subjected to flotation desulfurization to adjust the pH to 11, concentrating, filtering and drying, and removing iron through a magnetic grid to obtain a silicon-aluminum micropowder product.
The main components of the silicon-aluminum micropowder product are as follows: al (Al) 2 O 3 ：25.64％，SiO 2 ：69.77％，Fe 2 O 3 ：0.22％，SO 3 :0.33%, yield: 70.2% of the glass fiber, and meets the quality requirement of partially replacing pyrophyllite for producing glass fiber. The production wastewater is recycled in a grading way, and no discharge exists.
Example 5:
for the lithium slag in example 1, adding water into the raw materials for size mixing, and adjusting the concentration of ore pulp: 30, adding dispersant water glass at the same time; firstly, carrying out flotation desulfurization on ore pulp, adopting a primary roughing and secondary scavenging flotation process, wherein a flotation collector is oleic acid, and a flotation foam product is gypsum after dehydration, so that the ore pulp can be sold as a retarder for cement production; dewatering the non-foam product in the flotation operation, reducing the water content to below 15%, and grinding by adopting a ball mill, wherein the grinding concentration is as follows: 35%; the ore grinding product (the grain diameter is-45 mu m and the ratio is more than or equal to 98 percent) is firstly subjected to weak magnetic separation to remove iron, and the weak magnetic separation magnetic field strength is 0.3T; and then a coarse magnetic separator with a two-section strong magnetic field with a magnetic field strength of 1.5T for coarse separation and a magnetic field strength of 1.8T for scavenging are adopted for removing iron, and the magnetic material slurry obtained by the strong magnetic separation is subjected to floatation and reselection to obtain tantalum-niobium concentrate for sale. The magnetic material-containing slurry obtained by the weak magnetic separation and tailings after flotation and reselection (the flotation and reselection treatment of the magnetic material-containing slurry after the strong magnetic separation) are mixed and dehydrated, and then the mixture can be sold as a cement production admixture. Adding ammonium carbonate into the non-magnetic material slurry obtained by strong magnetic separation to adjust the pH value to 10, concentrating, filtering and drying, and removing iron through a magnetic grid to obtain the silicon-aluminum micropowder product.
The main components of the silicon-aluminum micropowder product are as follows: al (Al) 2 O 3 ：26.15％，SiO 2 ：68.95％，Fe 2 O 3 ：0.37％，SO 3 :0.28%, yield: 65.8 percent, and meets the quality requirement of partially replacing pyrophyllite for producing glass fibers. The production wastewater is recycled in a grading way, and no discharge exists.
Example 6:
for the lithium slag in example 1, adding water into the raw materials for size mixing, and adjusting the concentration of ore pulp: 30, adding dispersant water glass at the same time; firstly, carrying out flotation desulfurization on ore pulp, adopting a primary roughing and secondary scavenging flotation process, wherein a flotation collector is oleic acid, and a flotation foam product is gypsum after dehydration, so that the ore pulp can be sold as a retarder for cement production; dewatering the non-foam product in the flotation operation, reducing the water content to below 15%, and grinding by adopting a ball mill, wherein the grinding concentration is as follows: 40%; the ore grinding product (the grain diameter is-45 mu m and the ratio is more than or equal to 98 percent) is firstly subjected to weak magnetic separation to remove iron, and the weak magnetic separation magnetic field strength is 0.3T; and then a coarse magnetic separator with a two-section strong magnetic field with a magnetic field strength of 2.0T for coarse separation and a magnetic field strength of 2.5T for scavenging are adopted for removing iron, and the magnetic material slurry obtained by the strong magnetic separation is subjected to floatation and reselection to obtain tantalum-niobium concentrate for sale. The magnetic material-containing slurry obtained by the weak magnetic separation and tailings after flotation and reselection (the flotation and reselection treatment of the magnetic material-containing slurry after the strong magnetic separation) are mixed and dehydrated, and then the mixture can be sold as a cement production admixture. Adding ammonium carbonate into the non-magnetic material slurry obtained by strong magnetic separation to adjust the pH value to 11, concentrating, filtering and drying, and removing iron through a magnetic grid to obtain the silicon-aluminum micropowder product.
The main components of the silicon-aluminum micropowder product are as follows: al (Al) 2 O 3 ：26.22％，SiO 2 ：68.99％，Fe 2 O 3 ：0.24％，SO 3 :0.30%, yield: 68.8% of the glass fiber, and meets the quality requirement of partially replacing pyrophyllite for producing glass fibers. The production wastewater is recycled in a grading way, and no discharge exists.
Comparative example 1:
for lithium Slag (SiO) generated by preparing lithium carbonate by using spodumene as raw material and adopting sulfuric acid method in Sichuan lithium salt enterprises 2 ：60.50％、Al 2 O 3 ：21.52％，SO 3 ：7.00％、Fe 2 O 3 :0.78%, particle size: -45 μm content: less than or equal to 50 percent), adding water into the raw materials for size mixing, and the concentration of ore pulp is as follows: 30, adding dispersant water glass at the same time; firstly, carrying out flotation desulfurization on ore pulp, adopting a primary roughing and secondary scavenging flotation process, wherein a flotation collector is oleic acid, and a flotation foam product is gypsum after dehydration, so that the ore pulp can be sold as a retarder for cement production; the non-foam product of flotation operation adopts a section of strong magnetic field magnetic separator to remove iron, and rougher magnetic fieldThe strength is 1.5T, the magnetic material slurry obtained by magnetic separation can be sold as a cement production admixture after dehydration, and the non-magnetic material slurry is concentrated, filtered and dried to obtain the silicon-aluminum micropowder product.
The main components of the silicon-aluminum micropowder product are as follows: al (Al) 2 O 3 ：25.47％，SiO 2 ：72.59％，Fe 2 O 3 ：0.7％，SO 3 :0.5%, yield: 45 percent, can be used as a raw material for producing ceramics, and can not meet the quality requirement of partially replacing pyrophyllite as a raw material for producing glass fibers. Overflow of flotation froth concentration operation has high sulfur content, cannot be recycled, and is discharged after periodic treatment, so that pressure is caused to the environment.
Comparative example 2:
for lithium Slag (SiO) generated by preparing lithium carbonate by using spodumene as raw material and adopting sulfuric acid method in Sichuan lithium salt enterprises 2 ：60.50％、Al 2 O 3 ：21.52％，SO 3 ：7.00％、Fe 2 O 3 :0.78%, particle size: -45 μm content: less than or equal to 70 percent), adding water into the raw materials for size mixing, and the concentration of ore pulp is as follows: 30, adding dispersant water glass at the same time; firstly, carrying out flotation desulfurization on ore pulp, adopting a primary roughing and secondary scavenging flotation process, wherein a flotation collector is oleic acid, and a flotation foam product is gypsum after dehydration, so that the ore pulp can be sold as a retarder for cement production; the non-foam product of flotation operation adopts a section of strong magnetic field magnetic separator to remove iron, the intensity of a roughing magnetic field is 2.0T, the magnetic material slurry obtained by magnetic separation can be sold as a cement production admixture after dehydration, and the non-magnetic material slurry is concentrated, filtered and dried to obtain the silicon-aluminum micropowder product.
The main components of the silicon-aluminum micropowder product are as follows: al (Al) 2 O 3 ：25.49％，SiO 2 ：72.61％，Fe 2 O 3 ：0.65％，SO 3 :0.51%, yield: 46.9 percent of the glass fiber composite material can be used as a raw material for producing ceramics, and the quality requirement of partially replacing pyrophyllite as a raw material for producing glass fibers is not met. Overflow of flotation froth concentration operation has high sulfur content, cannot be recycled, and is discharged after periodic treatment, so that pressure is caused to the environment.
Claims (24)
1. A comprehensive treatment process of lithium slag is characterized in that: the process comprises the following steps:
1) Grinding: grinding the lithium slag to obtain grinding powder;
2) And (3) carrying out low-intensity magnetic separation treatment: carrying out weak magnetic separation on the ore grinding powder material obtained in the step 1) to obtain a magnetic material I and a material after weak magnetic separation;
3) Strong magnetic separation: carrying out strong magnetic separation on the low-intensity magnetic separation material obtained in the step 2) to obtain a magnetic material II and a high-intensity magnetic separation material;
4) And (3) flotation treatment: carrying out primary concentration and filtration on the strong magnetic separation material obtained in the step 3) and then carrying out floatation treatment to obtain sulfur-containing tailings and a material after floatation;
5) Alkali conversion treatment: adding soluble carbonate into the flotation material obtained in the step 4), and then obtaining a crude product of the silicon-aluminum micro powder after secondary concentration and filtration;
6) Drying and removing iron: drying the crude silicon-aluminum micropowder obtained in the step 5), and then carrying out iron removal treatment on the dried crude silicon-aluminum micropowder to obtain a fine silicon-aluminum micropowder;
7) Carrying out flotation treatment on the magnetic material II obtained in the step 3) to obtain an impurity material and a sand material; then, carrying out reselection treatment on the sand material to obtain a light sand material and a heavy sand material; finally, carrying out primary concentration and filtration on the heavy sand material to obtain tantalum-niobium concentrate;
8) Mixing the magnetic material I obtained in the step 2), the impurity material obtained in the flotation process in the step 7) and the light sand material obtained in the reselection process to obtain a mixture, and then carrying out primary concentration and filtration on the mixture to obtain the iron-containing tailings.
2. The process according to claim 1, characterized in that: fe in the material obtained in the step 3) after the strong magnetic separation 2 O 3 The content is less than or equal to 0.5 percent; and/or
SO in the crude silicon-aluminum micropowder obtained in step 5) 3 The content is less than or equal to 0.5 percent.
3. The process according to claim 2, characterized in that: fe in the material obtained in the step 3) after the strong magnetic separation 2 O 3 The content is less than or equal to 0.45%; and/or
SO in the crude silicon-aluminum micropowder obtained in step 5) 3 The content is less than or equal to 0.45 percent.
4. A process according to any one of claims 1-3, characterized in that: in the step 1), the ore grinding treatment adopts a closed circuit ore grinding process, and specifically comprises the following steps: feeding lithium slag into a ball mill, grinding by the ball mill, discharging the ground lithium slag into a cyclone for classification, wherein overflow materials of the cyclone are ground powder; and returning the cyclone sand setting to the ball mill for ore grinding.
5. The process according to claim 4, wherein: the grain size of the ore grinding powder obtained after the ore grinding treatment is less than 45 mu m and the proportion is not less than 95 percent.
6. The process according to claim 5, wherein: the grain size of the ore grinding powder obtained after the ore grinding treatment is less than 45 mu m and the proportion is not less than 98 percent.
7. The process according to claim 6, wherein: in the step 1), a dispersing agent is added in the ore grinding treatment process.
8. The process according to claim 7, wherein: the dispersing agent is one or more of sodium silicate, soda and phosphate.
9. A process according to any one of claims 1-3, 5-8, characterized in that: the primary circulating water is generated after the primary concentration and filtration in the step 4), the step 7) and the step 8).
10. The process according to claim 4, wherein: the primary circulating water is generated after the primary concentration and filtration in the step 4), the step 7) and the step 8).
11. The process according to claim 9, characterized in that: the primary circulating water is optionally used as the treatment water for one or more steps of the grinding treatment of the step 1), the low-intensity magnetic separation treatment of the step 2), the high-intensity magnetic separation treatment of the step 3), the flotation treatment of the step 7) and the reselection treatment.
12. The process according to claim 10, wherein: the primary circulating water is optionally used as the treatment water for one or more steps of the grinding treatment of the step 1), the low-intensity magnetic separation treatment of the step 2), the high-intensity magnetic separation treatment of the step 3), the flotation treatment of the step 7) and the reselection treatment.
13. The process according to any one of claims 1-3, 5-8, 10-12, characterized in that: the secondary water is generated after the secondary concentration and filtration in the alkali conversion treatment in the step 5).
14. The process according to claim 4, wherein: the secondary water is generated after the secondary concentration and filtration in the alkali conversion treatment in the step 5).
15. The process according to claim 13, wherein: the secondary loop water is used as flotation process water in step 4).
16. The process according to claim 14, wherein: the secondary loop water is used as flotation process water in step 4).
17. The process according to any one of claims 1-3, 5-8, 10-12, 14-16, characterized in that: in the alkaline conversion treatment process of the step 5), the pH value of the slurry after adding the soluble carbonate into the material after flotation is 7-14; and/or
The soluble carbonate is one or more of sodium carbonate, potassium carbonate and ammonium carbonate.
18. The process according to claim 4, wherein: in the alkaline conversion treatment process of the step 5), the pH value of the slurry after adding the soluble carbonate into the material after flotation is 7-14; and/or
The soluble carbonate is one or more of sodium carbonate, potassium carbonate and ammonium carbonate.
19. The process according to claim 17, wherein: the pH value of the slurry is 8-12 after adding soluble carbonate into the material after flotation; and/or
The soluble carbonate is sodium carbonate or potassium carbonate.
20. The process according to claim 18, wherein: the pH value of the slurry is 8-12 after adding soluble carbonate into the material after flotation; and/or
The soluble carbonate is sodium carbonate or potassium carbonate.
21. The process according to any one of claims 1-3, 5-8, 10-12, 14-16, 18-20, characterized in that: in the step 6), the iron removal treatment is magnetic iron removal; and the magnetic iron removal is to remove iron from the dried crude silicon-aluminum micro powder by a magnetic grid to obtain a refined silicon-aluminum micro powder.
22. The process according to claim 4, wherein: in the step 6), the iron removal treatment is magnetic iron removal; and the magnetic iron removal is to remove iron from the dried crude silicon-aluminum micro powder by a magnetic grid to obtain a refined silicon-aluminum micro powder.
23. The process according to any one of claims 1-3, 5-8, 10-12, 14-16, 18-20, 22, characterized in that: using the sulfur-containing tailings obtained in step 4) and/or the iron-containing tailings obtained in step 8) as a cement admixture; and/or
In the step 2), a weak magnetic field magnetic separator is adopted in the weak magnetic separation treatment; and/or
In the step 3), a strong magnetic field magnetic separator is adopted for the strong magnetic separation treatment.
24. The process according to claim 4, wherein: using the sulfur-containing tailings obtained in step 4) and/or the iron-containing tailings obtained in step 8) as a cement admixture; and/or
In the step 2), a weak magnetic field magnetic separator is adopted in the weak magnetic separation treatment; and/or
In the step 3), a strong magnetic field magnetic separator is adopted for the strong magnetic separation treatment.
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