WO2024040891A1

WO2024040891A1 - Treatment method for carbonate lithium clay

Info

Publication number: WO2024040891A1
Application number: PCT/CN2023/077473
Authority: WO
Inventors: 阮丁山; 李长东; 刘云涛; 张鹏; 郭萧轲
Original assignee: 广东邦普循环科技有限公司; 湖南邦普循环科技有限公司
Priority date: 2022-08-23
Filing date: 2023-02-21
Publication date: 2024-02-29
Also published as: CN115418498A; CN115418498B; CL2023001937A1

Abstract

The present application belongs to the technical field of mineral extraction, and disclosed is a treatment method for carbonate lithium clay. By means of repeated scrubbing and mixed material particle grading in the method, coarse-grained calcite in carbonate lithium clay can be effectively removed, and small-particle materials can be conveniently enriched; then effective secondary separation is conducted according to the particle size and the impurity content; particles with different compositions are distinguished and subjected to desulfurization and decarbonization, calcite removal and lithium flotation in a step-by-step manner, such that the content of impurities such as iron and calcium in a product is further reduced; and finally, the lithium enrichment multiple of the obtained lithium concentrate reaches twice or above, the comprehensive recovery rate of lithium reaches 75% or above, and the removal rate of impurity elements such as iron, calcium and sulfur is larger than 80%. The treatment method takes full advantage of the characteristics of the carbonate lithium clay and combines the scrubbing process with low investment and low operation cost with the flotation process with high adaptability and good separation performance according to the situation that the lithium content of the carbonate lithium clay is low, such that the applicable economy is high.

Description

A kind of processing method of lithium carbonate clay

Technical field

This application relates to the technical field of mineral refining, and specifically to a method for processing lithium carbonate clay.

Background technique

A major source of lithium resources is salt lake brine, but the mining and utilization of this source requires high industrial technology and can easily cause damage to the ecological environment.

In addition to salt lake brine resources, lithium resources can also come from hard rock lithium minerals. At present, the development of lithium minerals is mainly based on spodumene and lepidolite. After beneficiation and enrichment, the Li ₂ O content in the lithium concentrate can be increased to 3%-6%, and then through calcination, leaching, impurity removal and purification, and lithium precipitation After other processes, industrial grade or electronic grade lithium salt can be produced.

In recent years, people have discovered a kind of clay that contains highly enriched lithium content. It is predicted that the lithium carbonate equivalent can exceed one million tons and the lithium content reaches 0.1% to 0.3%. It is defined as lithium carbonate clay. According to the process mineralogy of this type of lithium clay, its main mineral composition includes calcite, lithium chlorite, illite, kaolinite, quartz, mica, pyrite, etc. For this new type of mineral soil, people have carried out preliminary exploration to extract lithium. They mainly use double salt roasting or sulfuric acid ripening to release lithium from the lithium clay into the solution. The resulting lithium-containing leachate is then subjected to impurity removal, concentration, and lithium precipitation processes to prepare lithium. Salt. However, due to the low lithium content in lithium clay, producing one ton of lithium salt often produces hundreds of tons of leaching residue. At the same time, smelting this raw material requires extremely high energy consumption. The lithium smelting plant has large investments, high operating costs, and is cost-effective. Extremely low, restricting the industrial development of this lithium carbonate clay.

Contents of the invention

The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the claims.

Based on the shortcomings of the existing technology, the purpose of this application is to provide a method for processing lithium carbonate clay, which removes coarse-grained calcite and minerals through multi-stage scrubbing, diversion, flotation and other processes. The improvement of lithium purity can ultimately increase the lithium enrichment factor to more than 2 times, and the lithium recovery rate can reach more than 75%. The mass yield of subsequent smelting lithium extraction processing materials only accounts for 30% to 40% of the lithium carbonate clay. At the same time, The requirements for equipment and reagents required for treatment are low, and there is no need to introduce high energy-consuming smelting processes, so industrial scale can be achieved.

In order to achieve the above purpose, the technical solutions adopted by this application are:

A method for processing lithium carbonate clay, including the following steps:

(1) After crushing the lithium carbonate clay to a particle size of ≤100mm, place it in a scrubbing machine for scrubbing, and then perform a vibrating wet sieving process to screen out the particles that cannot be sieved as tailings 1; The obtained particles with a particle size <1mm are screened out and placed in a hydrocyclone for primary cyclone to obtain underflow particles a and overflow particles b; the remaining particles are mixed with the underflow particles a, and the resulting mixture is scrubbed twice. , and then perform a vibrating wet sieving process with a screen aperture of 1 to 2 mm, and the resulting particles that cannot be sieved are screened out as tailings 2; the screened particles are placed in a hydrocyclone for secondary cyclone to obtain underflow particles. c and overflow particles d; the bottom material particles c are used as tailings 3 or are returned to the hydrocyclone to be mixed with the next batch of mixture for secondary scrubbing;

(2) If the calcium content of the overflow particles b is ≤ 3wt%, then perform desulfurization, decarburization flotation and lithium flotation in sequence to obtain lithium concentrate 1; As tailings 4, the flotation foam obtained by the lithium flotation treatment is used as tailings 5; if the calcium content of the overflow particles b is >3wt%, the overflow particles b are subjected to the same process as the overflow particles d in step (3). deal with;

(3) The overflow particles d are sequentially subjected to desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment to obtain lithium concentrate 2; the flotation foam obtained by the desulfurization and decarburization flotation treatment is used as tail Ore 6, the flotation foam obtained by the calcite removal flotation is used as tailings 7, and the flotation foam obtained by the lithium flotation treatment is used as tailings 8.

In the processing method of lithium carbonate clay described in this application, through multiple scrubbing and mixing particle classification, the coarse-grained calcite in the lithium carbonate clay can be effectively eliminated, and small particle materials can be enriched. According to the particle size Effective secondary separation based on diameter size and impurity content, and step-by-step desulfurization, decarburization, calcite removal and lithium flotation to further reduce the content of iron, calcium and other impurities in the product, and ultimately achieve a lithium enrichment factor of 2 in the resulting lithium concentrate. More than times, the comprehensive recovery rate of lithium reaches more than 75%, and the removal rate of impurity elements such as iron, calcium, sulfur, etc. is greater than 80%. The mass yield of materials for subsequent lithium extraction processing in smelting only accounts for 30% to 40% of lithium carbonate clay. This treatment method makes full use of the characteristics of lithium carbonate clay. In view of its low lithium content, it combines the scrubbing process with low investment and low operating cost with the flotation process with strong adaptability and good sorting performance, reducing the need for mineral processing equipment. Investment and consumption of flotation reagents are low, and it is highly economical.

In the processing method of lithium carbonate clay described in this application, the physical and chemical properties of the screened particles are used to firstly remove sulfur-containing substances and carbonaceous matter in the particles to avoid interference with subsequent flotation; and if the particles If the calcium content is high, the pH value is further adjusted by alkali to remove the fine-grained calcite. Finally, after a large amount of acid-consuming calcite is removed, mixed acid is used to adjust the pH value of the slurry to the range of 1 to 2.5, and the slurry is effectively enriched through lithium flotation. To obtain lithium concentrate, the quality of different batches of lithium carbonate clay is fully taken into consideration, and different processing particles are treated differently with short-distance and long-distance routes to reduce the waste of process reagents and improve the overall product quality.

Optionally, the lithium content of the lithium carbonate clay in step (1) is ≥0.05wt%, and the calcium content is ≥5wt%.

Optionally, the particle size of the crushed lithium carbonate clay is ≤50 mm.

Optionally, the first scrubbing in step (1) is cylinder or vertical scrubbing, and the second scrubbing is vertical scrubbing.

More optionally, the scrubbing concentration of the first scrubbing and the second scrubbing is 50-80%.

Optionally, the agent used in the desulfurization and decarburization flotation treatment is at least one of an acidic pH adjuster, an inhibitor, a foaming agent, and a sulfur carbon collector.

More optionally, the acidic pH adjuster is at least one of sulfuric acid, phosphoric acid, hydrochloric acid and hydrofluoric acid; the inhibitor is at least one of sodium silicate, starch, dextrin and/or modified substances. kind; the foaming agent is at least one of No. 2 oil and methyl isobutyl carbinol; the sulfur carbon collector is xanthate and/or modified substance, black powder and/or modified substance, At least one of diesel and kerosene.

Optionally, the agent used in the calcite removal flotation treatment is at least one of an alkaline pH regulator, an inhibitor, and a calcite collector.

More optionally, the alkaline pH adjuster is a mixture of sodium carbonate and sodium hydroxide; the inhibitor is at least one of sodium silicate, starch, dextrin and/or modified substances; the calcite The collector is an anionic collector, and the anionic collector includes fatty acid soap and sulfonated fatty acid.

Optionally, the agent used in the lithium flotation is at least one of an acidic pH regulator and a lithium clay mineral collector.

More optionally, the lithium clay mineral collector is at least one of an etheramine collector and a polyamine collector.

Based on the characteristics of the impurities in the treated particles and the target mineral lithium, selecting the appropriate treatment environment and treatment chemicals can effectively enrich the lithium element and eliminate various types of impurities, thereby improving the purity of the final lithium concentrate.

The beneficial effect of this application is that this application provides a method for processing lithium carbonate clay. This method can effectively eliminate coarse-grained calcite in lithium carbonate clay through multiple scrubbings and mixing particle classification. It is convenient to enrich small particle materials, and then carry out effective secondary separation according to the particle size and impurity content. The particles of different compositions can be desulfurized, decarburized, calcite removed and lithium flotated step by step to further reduce the iron and calcium in the product. and other impurity content, ultimately achieving a lithium enrichment factor of more than 2 times in the lithium concentrate, a comprehensive recovery rate of lithium of more than 75%, and a removal rate of impurity elements such as iron, calcium, and sulfur greater than 80%; this treatment method makes full use of carbon According to the characteristics of lithium salt clay, in view of its low lithium content, the scrubbing process with low investment and low operating cost is combined with the flotation process with strong adaptability and good sorting performance. There is no need to introduce a high energy-consuming smelting process. It is suitable for Highly economical.

Other aspects will be apparent after reading and understanding the drawings and detailed description.

Description of drawings

The accompanying drawings are used to provide a further understanding of the technical solutions herein, and constitute a part of the specification. Together with the embodiments of the present application, they are used to explain the technical solutions herein, and do not constitute a limitation of the technical solutions herein.

Figure 1 is a schematic flow chart of the processing method of lithium carbonate clay described in this application.

Figure 2 is a mineral schematic diagram of the lithium carbonate clay used in Example 1 of the present application.

Figure 3 is an XRD test chart of the lithium carbonate clay used in Example 1 of the present application.

Figure 4 is a schematic flow chart of the processing method of lithium carbonate clay described in Example 1 of the present application.

Figure 5 is a schematic flow chart of the processing method of lithium carbonate clay described in Example 2 of the present application.

Figure 6 is a schematic flow chart of the processing method of lithium carbonate clay described in Example 3 of the present application.

Figure 7 is a schematic flow chart of the processing method of lithium carbonate clay described in Comparative Example 1 of the present application.

Figure 8 is a schematic flow chart of the processing method of lithium carbonate clay described in Comparative Example 2 of the present application.

Figure 9 is a schematic flow chart of the processing method of lithium carbonate clay described in Comparative Example 3 of the present application.

Detailed ways

The processing method of lithium carbonate clay described in this application includes the following steps:

The schematic flow chart of the processing method described in the present application is shown in Figure 1. In order to better explain the purpose, technical solutions and advantages of the present application, the present application will be further described below in conjunction with specific embodiments/comparative examples. The purpose is to explain in detail Understand the content of this application, but not the limitation of this application. All other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of this application. The experimental reagents, raw materials and instruments designed for the implementation and comparative examples of this application are all commonly used common reagents, raw materials and instruments unless otherwise specified.

Example 1

An embodiment of the processing method of lithium carbonate clay described in this application, as shown in Figure 4, includes the following steps:

(1) Collect lithium carbonate clay. Its mineral diagram is shown in Figure 2; its XRD test chart is shown in Figure 3. It can be seen that in addition to lithium chlorite, the mineral composition includes large-grained calcite Cc _1. Small particle size calcite Cc ₂ , quartz Q, etc. After the lithium carbonate clay is crushed to a particle size of ≤15mm, it is placed in a cylinder scrubbing machine and scrubbed once with a scrubbing concentration of 65%. Then, it is subjected to two-layer vibrating wet screening with sieve sizes of 10mm and 1mm. Particles with a particle size >10 mm are screened out as tailings 1; particles with a particle size <1 mm are screened out and placed in a hydrocyclone for primary cyclone to obtain underflow particles a and overflow particles b with a particle size of less than 38 μm. ; Mix the remaining particles with a particle size of 1 to 10 mm and the underflow particles a. The resulting mixture is placed in a vertical scrubbing machine for secondary scrubbing with a scrubbing concentration of 75%, and then vibrating wet screening with a screen aperture of 2mm is performed. , sieve out the particles with a particle size greater than 2mm that cannot be screened as tailings 2; place the sieved particles into a hydrocyclone for secondary cyclone to obtain underflow particles c and overflow particles d with a particle size below 250 μm. ;The bottom material particles c are used as tailings 3;

(2) The calcium content of the overflow particles b is ≤3wt%, and the desulfurization and decarburization flotation treatment and the lithium flotation treatment are carried out in sequence to obtain the lithium concentrate 1; the flotation foam obtained by the desulfurization and decarburization flotation treatment is used as tail Ore 4, the flotation foam obtained by the lithium flotation treatment is used as tailings 5;

Among them, the dosage of reagents used in desulfurization and decarburization flotation treatment and the corresponding treatment particle feed materials are: sulfuric acid 3kg/ton flotation feed material, starch 300g/ton flotation feed material, No. 2 oil 40g/ton flotation feed material, Ding The flotation feed is 100g/ton of base xanthate and 30g/ton of diesel; the flotation concentration of this desulfurization and decarburization flotation treatment is 30%;

The dosage of reagents used in lithium flotation treatment and the corresponding treated particle feed materials are: sulfuric acid 5kg/ton flotation feed, hydrofluoric acid 2kg/ton flotation feed, ether amine modified collector 300kg/ton flotation feed;

(3) The overflow particles d are sequentially subjected to desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment to obtain lithium concentrate 2; the flotation foam obtained by the desulfurization and decarburization flotation treatment is used as tail Ore 6, the flotation foam obtained by the calcite removal flotation is used as tailings 7, and the flotation foam obtained by the lithium flotation treatment is used as tailings 8;

Among them, the dosage of reagents used in desulfurization and decarburization flotation treatment and the corresponding particle feed materials are: sulfuric acid 6kg/ton flotation feed, starch 600g/ton flotation feed, No. 2 oil 50g/ton flotation feed, Ding The flotation feed is 150g/ton of base xanthate and 50g/ton of diesel; the flotation concentration of this desulfurization and decarburization flotation treatment is 30%;

The calcite removal flotation treatment stage includes rough flotation and fine flotation stages. The dosage of reagents used in the rough flotation stage and the corresponding treated particle feed materials are: sodium carbonate 2kg/ton of flotation feed, sodium hydroxide 2kg/ton of flotation feed. Selective feed, sodium silicate 3kg/ton flotation feed, modified oxidized paraffin soap 3kg/ton flotation feed; fine flotation stage includes sodium hydroxide 0.5kg/ton flotation feed, sodium silicate 0.5kg /ton flotation feed, modified oxidized paraffin soap 0.5kg/ton flotation feed;

The dosage of reagents used in lithium flotation treatment and the corresponding treated particle feed materials are: 10kg/ton of sulfuric acid flotation feed, 4kg/ton of hydrofluoric acid flotation feed, and 500kg/ton of etheramine modified collector Feed.

The element content and yield of the products at each stage were calculated. Lithium concentrates 1 and 2 were combined, tailings 5 and 8 were combined, tailings 4 and 6 were combined, and tailings 1 to 3 were combined. The test results are shown in Table 1. .

Table 1

It can be seen that the yield of lithium concentrate obtained by the treatment method described in Example 1 reaches 45%, and the distribution rate of lithium element reaches 88.62%. The tailings obtained by the mineral processing at each stage are of low grade, and the lithium extraction efficiency is high. At the same time, it can be seen that the yield of tailings 1 to 3 after simple scrubbing is about 30%, the Li grade is increased from 0.25% of the original ore to 0.34%, and the enrichment is 1.36 times; the subsequent flotation feed only accounts for 70% of the original ore. , and then remove pyrite, carbonaceous, calcite, quartz, etc. through flotation, further increasing the concentrate grade to 0.50%. Compared with some existing processes that use physical scrubbing alone for processing (raw ore crushing efficiency is low, scrubbing concentration is low, and high-concentration scrubbing, roughening, and selective grinding cannot be achieved), this technical solution has higher processing efficiency. , further improving the final grade of lithium.

Example 2

An embodiment of the processing method of lithium carbonate clay described in the present application, as shown in Figure 5, includes the following steps:

(1) After crushing the lithium carbonate clay to a particle size of ≤100mm, place it in a cylinder scrubber for scrubbing with a scrubbing concentration of 70%, and then conduct a two-layer vibrating wet sieve with sieve sizes of 40mm and 1mm. Process, sieve out the particles with a particle size > 40 mm as tailings 1; sieve out the particles with a particle size < 1 mm and put them into a hydrocyclone for one cyclone to obtain underflow particles a and overflow particles with a particle size below 250 μm. Flow particles b; mix the remaining particles with a particle size of 1 to 40 mm with the underflow particles a. The resulting mixture is placed in a vertical scrubbing machine for secondary scrubbing with a scrubbing concentration of 55%, and then vibrated with a screen aperture of 2mm. Wet sieving process, sieve out the particles with a particle size greater than 2mm that cannot be sieved as tailings 2; put the screened particles into a hydrocyclone for secondary cyclone to obtain underflow particles c and a particle size of less than 250 μm. The flow particles d; the bottom material particles c are used as tailings 3;

(2) The calcium content of the overflow particles b is >3wt%. Combine it with the overflow particles d and perform desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment in sequence to obtain lithium concentrate 2; The flotation foam obtained by the desulfurization and decarbonization flotation treatment is used as tailings 6, the flotation foam obtained by the decalcite flotation is used as tailings 7, and the flotation foam obtained by the lithium flotation treatment is used as tailings 8;

The reagent system used in the desulfurization and decarburization flotation treatment is: 2kg/ton of sodium silicate as flotation feed, 100g/ton of methyl isobutyl methanol as flotation feed, and 250g/ton of amyl xanthate as flotation feed; Desulfurization and decarbonization flotation treatment The flotation concentration is 28%;

The calcite removal flotation treatment includes one rough flotation stage and two fine flotation stages. The dosage of reagents used in the rough flotation stage and its corresponding treatment particle feed is: sodium carbonate 4kg/ton flotation feed, sodium hydroxide 4kg/ton flotation feed, starch 1kg/ton flotation feed, oxidized paraffin soap and oleic acid soap mixture 3.5kg/ton flotation feed; the first fine flotation stage chemicals include sodium hydroxide 0.5kg/ Ton of flotation feed, sodium silicate 0.75kg/ton of flotation feed, mixture of oxidized paraffin soap and oleic acid soap 0.75kg/ton of flotation feed; the second fine flotation stage chemicals include 0.5kg of sodium hydroxide /ton of flotation feed, sodium silicate 0.25kg/ton of flotation feed, mixture of oxidized paraffin soap and oleic acid soap 0.25kg/ton of flotation feed;

The dosage of reagents used in lithium flotation treatment and the corresponding treated particle feed materials are: 15kg/ton of sulfuric acid flotation feed, 4kg/ton of hydrofluoric acid flotation feed, and 800kg/ton of etheramine modified collector Feed.

The element content, yield, etc. of the products at each stage were calculated. Tailings 1 to 3 were combined. The test results are shown in Table 2.

Table 2

It can be seen that the yield of lithium concentrate obtained by the treatment method described in Example 2 reaches 33%, and the distribution rate of lithium element reaches 75.30%. The tailings obtained from smelting at each stage have low grades, and the lithium extraction efficiency is high. At the same time, it can be seen that the yield of tailings 1 to 3 after simple scrubbing is about 40%, the Li grade is increased from 0.15% of the original ore to 0.22%, and the enrichment is 1.47 times; the subsequent flotation feed only accounts for 60% of the original ore. , and then remove pyrite, carbonaceous, calcite, quartz, etc. through flotation, further increasing the concentrate grade to 0.34%.

Example 3

An embodiment of the processing method of lithium carbonate clay described in this application, as shown in Figure 6, includes the following steps:

(1) After crushing the lithium carbonate clay to a particle size of ≤30mm, place it in a cylinder scrubber for scrubbing with a scrubbing concentration of 65%, and then perform a two-layer vibrating wet sieving process with sieve sizes of 15mm and 1mm. , sieve out the particles with a particle size >15mm as tailings 1; sieve out the particles with a particle size <1mm and put them into a hydrocyclone for one cyclone to obtain underflow particles a and overflow particles with a particle size below 38 μm. Particle b; mix the remaining particles with a particle size of 1 to 15 mm and the underflow particles a. The resulting mixture is placed in a vertical scrubbing machine for secondary scrubbing with a scrubbing concentration of 75%, and then vibrated and wetted with a screen aperture of 1mm. Sieve treatment, sieve out the particles with a particle size greater than 1 mm that cannot be sieved as tailings 2; place the screened particles into a hydrocyclone for secondary cyclone to obtain underflow particles c and overflow with a particle size below 38 μm. Particle d; the bottom material particle c is put back into the vertical scrubbing machine and mixed with subsequent particles for secondary scrubbing;

The desulfurization and decarburization flotation treatment includes a rough flotation stage and a fine flotation stage. The dosage of reagents used in the rough flotation stage and the corresponding treated particle feed materials are: 300g/ton of starch/ton of flotation feed, 100g/ton of No. 2 oil tons of flotation feed, butyl xanthate 250g/ton of flotation feed, diesel 100g/ton of flotation feed; the agent used in the fine flotation stage is 100g/ton of starch flotation feed, the desulfurization and decarbonization flotation treatment The flotation concentration is 32%;

The calcite removal flotation process includes a rough flotation stage and a fine flotation stage. The dosage of reagents used in the rough flotation stage and the corresponding treatment particle feed materials are: sodium hydroxide 5kg/ton flotation feed, starch 0.6kg/ton The flotation feed, the mixture of oxidized paraffin soap and oleic acid soap is 3.5kg/ton of flotation feed; the fine flotation stage chemicals include sodium hydroxide 0.25kg/ton of flotation feed and starch 0.25kg/ton of flotation feed. , a mixture of oxidized paraffin soap and oleic acid soap 0.5kg/ton flotation feed;

The dosage of reagents used in lithium flotation treatment and the corresponding treated particle feed materials are: sulfuric acid 20kg/ton flotation feed, hydrofluoric acid 6kg/ton flotation feed, etheramine modified collector 700kg/ton flotation Feed.

The element content, yield, etc. of the products at each stage were calculated. Tailings 1 and 2 were combined. The test results are shown in Table 3.

table 3

It can be seen that the yield of lithium concentrate obtained by the treatment method described in Example 3 reaches 40%, and the distribution rate of lithium element reaches 83.54%. However, the tailings obtained by beneficiation at each stage have low grades, and the lithium extraction efficiency is high. At the same time, the yield of tailings 1 to 2 after simple scrubbing is about 35%, and the Li grade is increased from 0.20% of the raw ore to 0.29%, enriched 1.45 times; the subsequent flotation feed only accounts for 65% of the raw ore, and then through flotation The pyrite, carbonaceous, calcite, quartz, etc. are removed separately and further improved to a concentrate grade of 0.42%.

Comparative example 1

A comparative example of the processing method of lithium carbonate clay described in this application, as shown in Figure 7, includes the following steps:

(1) After crushing the lithium carbonate clay to a particle size ≤ 40mm, place it in a cylinder scrubber for scrubbing with a scrubbing concentration of 65%, and then conduct a two-layer vibrating wet sieve with sieve sizes of 10mm and 3mm. Process, sieve out the particles with a particle size > 10 mm as tailings 1; sieve out the particles with a particle size < 3 mm and put them into a hydrocyclone for one cyclone to obtain underflow particles a and overflow particles b; The remaining particles with a particle size of 3 to 10 mm are mixed with the underflow particles a. The resulting mixture enters the ball mill for grinding. The grinding concentration is 65%. The overflow of the mill is placed in a hydrocyclone for secondary cyclone to obtain the underflow particles c and The overflow particles d with a particle size below 250 μm; the bottom material particles c are returned to the ball mill to continue grinding;

The desulfurization and decarburization flotation treatment includes a rough flotation stage and a fine flotation stage. The dosage of reagents used in the rough flotation stage and the corresponding treated particle feed materials are: 500g/ton of starch/ton of flotation feed, 300g/ton of No. 2 oil Ton flotation feed, butyl xanthate 350g/ton flotation feed, diesel 200g/ton flotation feed; the agent used in the fine flotation stage is 200g/ton starch flotation feed, the desulfurization and decarbonization flotation treatment The flotation concentration is 30%;

The calcite removal flotation treatment includes a rough flotation stage and a fine flotation stage. The dosage of reagents used in the rough flotation stage and the corresponding treatment particle feed materials are: sodium hydroxide 5kg/ton flotation feed, starch 0.7kg/ton The flotation feed, the mixture of oxidized paraffin soap and oleic acid soap is 4.5kg/ton of flotation feed; the fine flotation stage chemicals include sodium hydroxide 0.5kg/ton of flotation feed and starch 0.3kg/ton of flotation feed. , the mixture of oxidized paraffin soap and oleic acid soap is 0.8kg/ton of flotation feed;

The dosage of reagents used in lithium flotation treatment and the corresponding treated particle feed materials are: sulfuric acid 10kg/ton flotation feed, hydrofluoric acid 8kg/ton flotation feed, ether amine modified collector 800kg/ton flotation Feed.

The element content, yield, etc. of the products at each stage were analyzed, and the test results are shown in Table 4.

Table 4

It can be seen that the lithium concentrate yield obtained by the treatment method described in Comparative Example 1 is 30%, and the distribution rate (recovery rate) of lithium element is only 62.61%, which is much lower than Examples 1, 2 and 3. This comparative example only uses a section of cylinder scrubbing. The yield of tailings 1 is about 15% after scrubbing. The Li grade is increased from 0.14% of the raw ore to 0.16%, which is only enriched 1.14 times. After scrubbing, the particle size of the 3 to 10mm material under the sieve is relatively coarse. , not suitable for direct flotation, which increases the grinding and classification operation with high equipment investment; and the overflow product generated by materials smaller than 3mm entering the cyclone 1 has excessive Ca content and must enter route 2; the subsequent flotation feed accounts for The yield of raw ore is as high as 85%, and then pyrite, carbonaceous, calcite, quartz, etc. are removed through flotation, further increasing to a concentrate grade of 0.29%, but the dosage of flotation reagents increases significantly.

Comparative example 2

A comparative example of the processing method of lithium carbonate clay described in this application, as shown in Figure 8, includes the following steps:

(1) After crushing the lithium carbonate clay to a particle size of ≤15mm, place it in a cylinder scrubber for scrubbing with a scrubbing concentration of 65%, and then conduct a two-layer vibrating wet sieve with sieve sizes of 10mm and 3mm. Process, sieve out the particles with a particle size >10mm as tailings 1; sieve out the particles with a particle size <3mm and put them into a hydrocyclone for one cyclone to obtain underflow particles a and overflow particles with a particle size below 250 μm. Flow particles b; mix the remaining particles with a particle size of 3 to 10 mm with the underflow particles a. The resulting mixture is placed in a vertical scrubbing machine for secondary scrubbing with a scrubbing concentration of 75%, and then vibrated with a screen aperture of 2mm. Wet sieving process, sieve out the particles with a particle size greater than 2mm that cannot be sieved as tailings 2; put the screened particles into a hydrocyclone for secondary cyclone to obtain underflow particles c and a particle size of less than 250 μm. The flow particles d; the bottom material particles c are used as tailings 3;

The reagent system used in the desulfurization and decarburization flotation treatment is: 2kg/ton of sodium silicate as flotation feed, 100g/ton of methyl isobutyl methanol as flotation feed, and 250g/ton of amyl xanthate as flotation feed; The flotation concentration of desulfurization and decarbonization flotation treatment is 28%;

The calcite removal flotation treatment includes one rough flotation stage and two fine flotation stages. The dosage of reagents used in the rough flotation stage and its corresponding treatment particle feed is: sodium carbonate 4kg/ton flotation feed, sodium hydroxide 4kg/ton of flotation feed, 3kg/ton of sodium silicate, 4.5kg/ton of a mixture of oxidized paraffin soap and oleic acid soap; the first fine flotation stage chemicals include 0.5 sodium hydroxide kg/ton of flotation feed, sodium silicate 0.75kg/ton of flotation feed, mixture of oxidized paraffin soap and oleic acid soap 0.75kg/ton of flotation feed; the second fine flotation stage chemicals include sodium hydroxide 0.5kg/ton of flotation feed, 0.25kg/ton of sodium silicate, 0.25kg/ton of mixture of oxidized paraffin soap and oleic acid soap;

The element content, yield, etc. of the products at each stage were calculated, among which tailings 1 to 3 were combined. The test results are shown in Table 5.

table 5

It can be seen from the statistics of the test results of the two schemes of Example 1 and Comparative Example 2 that in the treatment method described in Comparative Example 2, the first group of cyclones feed materials with a particle size of <3 mm, and the overflow product is Fine mud with a particle size of less than 250 μm has a high Ca content and must be processed in Route 2, resulting in a decrease in scrubbing tailings yield from 30% to 26%, and an increase in flotation tailings 7 yield from 10% to 17%. In terms of mineral processing costs such as reagent consumption, the lithium concentrate yield dropped from 45% to 40%, and the concentrate Li grade and Li recovery rate dropped from 0.50% and 88.62% to 0.44% and 81.75% respectively.

Comparative example 3

A comparative example of the processing method of lithium carbonate clay described in this application, as shown in Figure 9, includes the following steps:

(1) After crushing the lithium carbonate clay to a particle size of ≤15mm, place it in a cylinder scrubber for scrubbing with a scrubbing concentration of 65%, and then conduct a two-layer vibrating wet sieve with sieve sizes of 10mm and 1mm. Process, sieve out the particles with a particle size > 10 mm as tailings 1; sieve out the particles with a particle size < 1 mm and put them into a hydrocyclone for one cyclone to obtain underflow particles a and overflow particles with a particle size below 38 μm. Flow particles b; mix the remaining particles with a particle size of 1 to 10 mm with the underflow particles a. The resulting mixture enters the ball mill for grinding. The grinding concentration is 65%. The overflow of the mill is placed in a hydrocyclone for secondary cyclone , to obtain underflow particles c and overflow particles d with a particle size below 250 μm; the bottom material particles c are returned to the ball mill to continue grinding;

Among them, the dosage of reagents used in desulfurization and decarburization flotation treatment and the corresponding treatment particle feed materials are: sulfuric acid 6kg/ton flotation feed material, starch 600g/ton flotation feed material, No. 2 oil 100g/ton flotation feed material, Ding The flotation feed is 250g/ton of base xanthate and 100g/ton of diesel; the flotation concentration of this desulfurization and decarbonization flotation treatment is 30%;

The calcite removal flotation treatment stage includes rough flotation and fine flotation stages. The dosage of reagents used in the rough flotation stage and the corresponding particle feed materials are: sodium carbonate 2kg/ton flotation feed, sodium hydroxide 4kg/ton flotation. Selective feed, sodium silicate 5kg/ton flotation feed, modified oxidized paraffin soap 6kg/ton flotation feed; fine flotation stage includes sodium hydroxide 0.5kg/ton flotation feed, sodium silicate 0.5kg /ton flotation feed, modified oxidized paraffin soap 0.75kg/ton flotation feed;

The dosage of reagents used in lithium flotation treatment and the corresponding treated particle feed materials are: sulfuric acid 8kg/ton flotation feed, hydrofluoric acid 8kg/ton flotation feed, etheramine modified collector 850kg/ton flotation Feed.

The element content, yield, etc. of the products at each stage were calculated. Lithium concentrates 1 and 2 were combined, tailings 5 and 8 were combined, and tailings 4 and 6 were combined. The test results are shown in Table 6.

Table 6

It can be seen from the test results of the two methods of Example 1 and Comparative Example 3 that only one stage of scrubbing is used in the treatment method described in Comparative Example 3, resulting in a scrubbing tailings 1 yield of only 15% and a flotation tailings 7 yield. The increase from 10% to 30% significantly increased the grinding cost and pharmaceutical cost. The lithium concentrate yield decreased from 45% to 40%. The concentrate Li grade and Li recovery rate decreased from 0.50% and 88.62% to 0.44% and 0.44% respectively. 78.81%.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and do not limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that The technical solution of the present application may be modified or equivalently substituted without departing from the essence and scope of the technical solution of the present application.

Claims

A method for processing lithium carbonate clay, which includes the following steps:

(1) After crushing the lithium carbonate clay to a particle size of ≤100mm, place it in a scrubbing machine for scrubbing, and then perform a vibrating wet sieving process to screen out the particles that cannot be sieved as tailings 1; The obtained particles with a particle size <1mm are screened out and placed in a hydrocyclone for primary cyclone to obtain underflow particles a and overflow particles b; the remaining particles are mixed with the underflow particles a, and the resulting mixture is scrubbed twice. , and then perform a vibrating wet sieving process with a screen aperture of 1 to 2 mm, and the resulting particles that cannot be sieved are screened out as tailings 2; the screened particles are placed in a hydrocyclone for secondary cyclone to obtain underflow particles. c and overflow particles d; the bottom material particles c are used as tailings 3 or are returned to the hydrocyclone to be mixed with the next batch of mixture for secondary scrubbing;

(2) If the calcium content of the overflow particles b is ≤ 3wt%, then perform desulfurization, decarburization flotation and lithium flotation in sequence to obtain lithium concentrate 1; As tailings 4, the flotation foam obtained by the lithium flotation treatment is used as tailings 5; if the calcium content of the overflow particles b is >3wt%, the overflow particles b are subjected to the same process as the overflow particles d in step (3). deal with;

(3) The overflow particles d are sequentially subjected to desulfurization and decarburization flotation treatment, calcite removal flotation treatment and lithium flotation treatment to obtain lithium concentrate 2; the flotation foam obtained by the desulfurization and decarburization flotation treatment is used as tail Ore 6, the flotation foam obtained by the calcite removal flotation is used as tailings 7, and the flotation foam obtained by the lithium flotation treatment is used as tailings 8.
The method for treating lithium carbonate clay according to claim 1, wherein in the step (1), the lithium content of the lithium carbonate clay is ≥0.05wt% and the calcium content is ≥5wt%.
The processing method of lithium carbonate clay according to claim 1, wherein the primary scrubbing in step (1) is cylinder or vertical scrubbing, and the secondary scrubbing is vertical scrubbing; the primary scrubbing and the secondary scrubbing are vertical scrubbing. The scrubbing concentration for scrubbing is 50 to 80%.
The method of treating lithium carbonate clay according to claim 1, wherein the agent used in the desulfurization and decarburization flotation treatment is at least one of an acidic pH regulator, an inhibitor, a foaming agent, and a sulfur carbon collector. .
The method for treating lithium carbonate clay according to claim 4, wherein the acidic pH regulator is at least one of sulfuric acid, phosphoric acid, hydrochloric acid and hydrofluoric acid; the inhibitor is sodium silicate, starch, At least one of dextrin and/or modified products; the foaming agent is at least one of No. 2 oil and methyl isobutyl carbinol; the sulfur carbon collector is xanthate and/or modified At least one of chemical substances, black powder and/or modified substances, diesel oil, and kerosene.
The method for treating lithium carbonate clay according to claim 1, wherein the agent used in the calcite removal flotation treatment is at least one of an alkaline pH regulator, an inhibitor, and a calcite collector.
The processing method of lithium carbonate clay according to claim 6, wherein the alkaline pH adjuster is a mixture of sodium carbonate and sodium hydroxide; the inhibitor is sodium silicate, starch, dextrin and/or At least one of the modified products; the calcite collector is an anionic collector, and the anionic collector includes fatty acid soap and sulfonated fatty acid.
The method for treating lithium carbonate clay according to claim 1, wherein the agent used in the lithium flotation is at least one of an acidic pH regulator and a lithium clay mineral collector.
The method for treating lithium carbonate clay according to claim 8, wherein the lithium clay mineral collector is at least one of an etheramine collector and a polyamine collector.