阅读说明：本技术 锂瓷石的提锂方法、含锂母液和填充剂 (Method for extracting lithium from lithium porcelain stone, lithium-containing mother liquor and filling agent ) 是由 魏绪春 魏东东 廖新 于 2019-11-07 设计创作，主要内容包括：本发明公开一种锂瓷石的提锂方法、含锂母液和填充剂,其中,锂瓷石的提锂方法包括：取锂瓷石、石膏和氧化钙分别研磨成粉,混合制成混合物；将所述混合物造粒,放入回转窑,1000～1100℃高温灼烧,烧成的熟料；取温度为90℃以上的水加入制备的熟料中,搅拌后,过滤,取过滤液为含锂母液,取滤渣为白色填充剂。在本发明中,通过将锂瓷石、石膏和氧化钙一同煅烧,从而可获得Li<Sub>2</Sub>SO<Sub>4</Sub>,将Li<Sub>2</Sub>SO<Sub>4</Sub>溶于高温水中,从而获得含锂母液,实现锂的提取,与现有技术比较,提锂步骤简单,提取率高；产生的废料主要为白色铝硅酸钙,可进一步用于涂料中充当填充剂或制作白色水泥,有利于环境保护。(The invention discloses a lithium extraction method of lithium china stone, lithium-containing mother liquor and a filling agent, wherein the lithium extraction method of the lithium china stone comprises the following steps: respectively grinding lithium porcelain stone, gypsum and calcium oxide into powder, and mixing to prepare a mixture; granulating the mixture, putting the mixture into a rotary kiln, and firing at a high temperature of 1000-1100 ℃ to obtain a fired clinker; adding water with temperature above 90 deg.C into the prepared clinker, stirring, filtering, collecting filtrate as lithium-containing mother liquor, and collecting filter residue as white filler. In the present invention, Li can be obtained by calcining together lithium porcelain stone, gypsum and calcium oxide 2 SO 4 Introduction of Li 2 SO 4 Dissolving in high-temperature water to obtain mother liquid containing lithium, extracting lithium, and other stepsCompared with the prior art, the lithium extraction step is simple, and the extraction rate is high; the generated waste materials are mainly white calcium aluminosilicate, and can be further used as a filler in coatings or for preparing white cement, thereby being beneficial to environmental protection.)

1. A lithium extraction method for lithium china stones is characterized by comprising the following steps:

step one, taking the lithium porcelain stone, the gypsum and the calcium oxide, respectively grinding into powder, and mixing to prepare a mixture;

step two, granulating the mixture produced in the step one, putting the mixture into a rotary kiln, and firing at a high temperature of 1000-1100 ℃ to obtain a fired clinker;

and step three, adding water with the temperature of more than 90 ℃ into the clinker prepared in the step two, stirring, filtering, taking filtrate as lithium-containing mother liquor, and taking filter residue as a white filler.

2. The method for extracting lithium from lithium china stone as claimed in claim 1, wherein the first step includes:

by mass fraction, 55-60 parts of lithium porcelain stone, 30-40 parts of gypsum and 5-10 parts of calcium oxide are respectively ground into powder with the particle size of 150-250 meshes, and the powder is mixed to prepare the mixture.

3. The method for extracting lithium from lithium china stone as claimed in claim 1, wherein the gypsum in the first step is flue gas desulfurization gypsum.

4. The method for extracting lithium from lithium china stone according to claim 3, wherein the gypsum in the first step is ground into 200 meshes with water content of 7-10%.

5. The method for extracting lithium from lithium china stone as claimed in claim 1, wherein the second step includes:

adding the mixture produced in the first step into a granulating agent for granulation;

and (3) placing the granules into a rotary kiln, and firing at a high temperature of 1000-1100 ℃ to obtain the fired clinker.

6. The lithium extraction method of lithium china stone as claimed in claim 5, wherein the granulating agent is polyacrylamide and/or polyaluminium chloride.

7. The lithium extraction method of lithium china stone according to claim 5, wherein the third step comprises:

and (3) adding water with the temperature of more than 90 ℃ into the clinker prepared in the second step, stirring for 30min, filtering by using a plate frame, taking the filtrate as the lithium-containing mother liquor, and taking the filter residue as the white filler.

8. A lithium-containing mother liquor prepared by the lithium extraction method of the lithium china stone as claimed in any one of claims 1 to 7.

9. A white filler prepared by the method for extracting lithium from lithium china stone as claimed in any one of claims 1 to 7.

Technical Field

The invention relates to the technical field of waste manufacturing, in particular to a method for extracting lithium from lithium china stone, lithium-containing mother liquor and a filling agent.

Background

Lithium is an important rare metal element, lithium sulfate or lithium carbonate is an important chemical raw material, and with the emergence of the development plan of new national energy, the new lithium battery energy becomes one of the energy industries which are key in national support development; lithium sulfate or lithium carbonate is used as an important basic raw material for the development of new energy of lithium batteries, and the demand of the lithium sulfate or the lithium carbonate is larger and higher, and the price of the lithium sulfate or the lithium carbonate is higher and higher.

The lithium porcelain stone explored in China has low taste, and Li₂The content of O is between 0.8 and 1.8 percent, the average content is 1.61 percent, the extraction is difficult, and the lithium porcelain stone resource cannot be utilized with high added value. In the prior art, the lithium is extracted from the laponite ore, and the laponite is generally extracted from the laponite ore by natural dissociation, flotation and purification, and then the lithium is extracted from the laponite ore. In the process of extracting lepidolite from the lithium porcelain stone, a large amount of tailings are generated in the process, a large amount of energy and manpower are consumed, and the production cost is increased; on the other hand, the recovery rate of lithium in the process of extracting lepidolite from the lepidolite can only reach 70% -80%, the recovery rate of lithium in the process of extracting lithium from the lepidolite is 80% -90%, the recovery rate of comprehensive lithium is only 60% -70%, and a large amount of lithium resources are wasted. The process is complex, long in flow, low in lithium recovery rate, high in processing cost and poor in effect.

Therefore, there is a need to provide a new lithium extraction method from lithium china stone to solve the above technical problems.

Disclosure of Invention

The invention mainly aims to provide a lithium extraction method of lithium china stones, lithium-containing mother liquor and a filling agent, and aims to solve the technical problems of complex lithium extraction process and low recovery efficiency of the existing lithium china stones.

In order to achieve the purpose, the invention provides a lithium extraction method of lithium china stone, which comprises the following steps:

step one, taking the lithium porcelain stone, the gypsum and the calcium oxide, respectively grinding into powder, and mixing to prepare a mixture;

step two, granulating the mixture produced in the step one, putting the mixture into a rotary kiln, and firing at a high temperature of 1000-1100 ℃ to obtain a fired clinker;

and step three, adding water with the temperature of more than 90 ℃ into the clinker prepared in the step two, stirring, filtering, taking filtrate as lithium-containing mother liquor, and taking filter residue as a white filler.

Preferably, the first step includes:

by mass fraction, 55-60 parts of lithium porcelain stone, 30-40 parts of gypsum and 5-10 parts of calcium oxide are respectively ground into powder with the particle size of 150-250 meshes, and the powder is mixed to prepare the mixture.

Preferably, the gypsum in the first step is flue gas desulfurization gypsum.

Preferably, in the first step, the gypsum with the water content of 7-10% is ground into 200 meshes.

Preferably, the second step includes:

adding the mixture produced in the first step into a granulating agent for granulation;

and (3) placing the granules into a rotary kiln, and firing at a high temperature of 1000-1100 ℃ to obtain the fired clinker.

Preferably, the granulating agent is polyacrylamide and/or polyaluminium chloride.

Preferably, the third step includes:

and (3) adding water with the temperature of more than 90 ℃ into the clinker prepared in the second step, stirring for 30min, filtering by using a plate frame, taking the filtrate as the lithium-containing mother liquor, and taking the filter residue as the white filler.

The invention also provides a lithium-containing mother liquor prepared by the lithium extraction method of the lithium china stone.

The invention also provides a white filler prepared by the lithium extraction method of the lithium china stone.

In the present invention, Li can be obtained by calcining together lithium porcelain stone, gypsum and calcium oxide₂SO₄Introduction of Li₂SO₄Dissolving in high-temperature water to obtain lithium-containing mother liquor, and extracting lithium, wherein compared with the prior art, the lithium extraction step is simple and the extraction rate is high; the generated waste material is mainly white calcium aluminosilicate, and can be further used in coating as filler or for making whiteAnd the cement is beneficial to environmental protection.

Drawings

Fig. 1 is a schematic flow chart of a lithium extraction method for lithium china stones according to an embodiment of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.

Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.

The invention provides a lithium extraction method of lithium china stone, which comprises the following steps:

step S1 grinding the lithium porcelain stone, the gypsum and the calcium oxide into powder respectively, and mixing to prepare a mixture;

specifically, 55-60 parts by mass of lithium porcelain stone, 30-40 parts by mass of gypsum and 5-10 parts by mass of calcium oxide are respectively ground into powder with the particle size of 150-250 meshes and mixed to prepare the mixture. In the step S1, the gypsum is ground into 200 mesh with a water content of 7% to 10%.

Lithium porcelain stone with SiO₂、Ai₂O₃、Li₂O、K₂O、Na₂O and the like. In this embodiment, the gypsum can be purchased industrial gypsum waste, or flue gas desulfurization gypsum generated in the flue gas desulfurization process.

S2, granulating the mixture produced in the step S1, putting the mixture into a rotary kiln, and firing at a high temperature of 1000-1100 ℃ to obtain a fired clinker;

specifically, the mixture produced in step S1 is added to a granulating agent for granulation; the granulating agent has enough viscosity to ensure that the mixture has good formability and mechanical strength; the granulating agent can be completely volatilized by high-temperature calcination, and no or little residual impurities of the granulating agent are left in the clinker. In this embodiment, the granulating agent is polyacrylamide and/or polyaluminium chloride.

And (3) placing the granules into a rotary kiln, and firing at a high temperature of 1000-1100 ℃ to obtain the fired clinker. The granulating agent is polyacrylamide and/or polyaluminium chloride.

Li in lithium porcelain stone₂O、K₂O、Na₂The content of O is high, so that the flux has strong fluxing capacity; selecting 1000-1100 ℃ to make SiO₂·Ai₂O₃·Li₂O can be in CaSO₄And CaO, and the new substances are generated in the presence of the CaO, and the new substances do not further decompose to generate calcium silicate. In the presence of CaSO alone₄In the case of (2), li is generated_xCa_y(SO₄)_z(ii) a Adding CaSO₄And CaO, with SiO due to the addition of calcium oxide₂、Ai₂O₃And the like, thereby improving the melting point of the lithium porcelain stone, shortening the calcination time, increasing the content of lithium ions in lithium-containing mother liquor, and increasing the content of lithium ions in CaSO₄In the presence of Li₂SO₄. CaO acts as a fluorine-fixing agent, thereby generating calcium fluoride with octahedral and cubic crystals.

And S3, adding water with the temperature of more than 90 ℃ into the clinker prepared in the step S2, stirring, filtering, taking filtrate as lithium-containing mother liquor, and taking filter residue as a white filler.

And concretely, adding water with the temperature of more than 90 ℃ into the clinker prepared in the second step, stirring for 30min, filtering by using a plate-and-frame filter, taking filtrate as the lithium-containing mother liquor, and taking filter residue as the white filler.

By calcining, the lithium porcelain stone is converted from alpha-type into beta-type which has a loose structure and is easy to react with sulfate, so that lithium in the lithium porcelain stone is converted into lithium sulfate. After filtering, the filtrate is mother liquor containing lithium sulfate, the main component of the filter residue is silicon-aluminum-calcium-containing, and the filter residue can be used for preparing white cement; or as a white filler in a mixture such as paint. Calcium fluoride can increase the glossiness of the filter residue.

In the present invention, Li can be obtained by calcining together lithium porcelain stone, gypsum and calcium oxide₂SO₄Introduction of Li₂SO₄Dissolving in high-temperature water to obtain lithium-containing mother liquor, and extracting lithium, wherein compared with the prior art, the lithium extraction step is simple and the extraction rate is high; the generated waste materials are mainly white calcium aluminosilicate, and can be further used as a filler in coatings or for preparing white cement, thereby being beneficial to environmental protection.

The invention also provides a lithium-containing mother liquor prepared by the lithium extraction method of the lithium china stone. Calcium hydroxide can be added into the lithium-containing mother liquor for further deslagging, so that the lithium content is improved.

The invention also provides a white filler prepared by the lithium extraction method of the lithium china stone. The white filler can be used for manufacturing decorative paint and the like.

The method for extracting lithium from lithium china stone provided by the invention is specifically described by the following specific examples, wherein the lithium china stone is collected from the western union, the city of the country, and the main components of the lithium china stone are as follows:

	％		％
				Li2O	1.63	Cs2O	0.74
SiO2	55.78	Na2O	6.12
				Al2O3	21.34	Rb2O	2.20
K2O	6.27	Fe2O3	0.41