Lithium extraction system and method for lithium china stone, lithium-containing mother liquor and filling agent
阅读说明：本技术 锂瓷石的提锂系统、提锂方法、含锂母液和填充剂 (Lithium extraction system and method for lithium china 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系统、提锂方法、含锂母液和填充剂,其中,锂瓷石的提锂系统包括依次连通的研磨机构、回转窑、冷却窑、溶解机构和过滤机构,以及余热机构、用于向所述回转窑供热的加热管路、与所述加热管路连通的除硫机构,所述加热管路依次经过所述回转窑、所述余热机构和所述除硫机构,所述余热机构内用于盛放溶液,所述余热机构与所述溶液机构的连通并向所述溶解机构提供加热的溶液,所述除硫机构的底部与所述研磨机构连通。在本发明中,通过将通过余热机构可利用加热管路中的余热加热溶液,并将加热的溶液通入溶解机构,以增加溶解率；通过将除硫机构和研磨机构连通,可利用除硫机构产生的石膏,减少生产废料。(The invention discloses a lithium extraction system and a lithium extraction method of lithium china stones, lithium-containing mother liquor and a filling agent, wherein the lithium extraction system of the lithium china stones comprises a grinding mechanism, a rotary kiln, a cooling kiln, a dissolving mechanism and a filtering mechanism which are sequentially communicated, a waste heat mechanism, a heating pipeline for supplying heat to the rotary kiln and a sulfur removal mechanism communicated with the heating pipeline, the heating pipeline sequentially passes through the rotary kiln, the waste heat mechanism and the sulfur removal mechanism, a solution is contained in the waste heat mechanism, the waste heat mechanism is communicated with the solution mechanism and provides the heated solution for the dissolving mechanism, and the bottom of the sulfur removal mechanism is communicated with the grinding mechanism. In the invention, the solution can be heated by the waste heat in the heating pipeline through the waste heat mechanism, and the heated solution is introduced into the dissolving mechanism, so that the dissolving rate is increased; through with sulphur removal mechanism and grinding mechanism intercommunication, the gypsum that usable sulphur removal mechanism produced reduces production waste.)
1. The utility model provides a lithium system of carrying of lithium china stone, its characterized in that, including grinding mechanism, rotary kiln, cooling kiln, dissolving mechanism and the filtering mechanism who communicates in proper order to and waste heat mechanism, be used for to the heating pipeline of rotary kiln heat supply, with the sulphur removal mechanism of heating pipeline intercommunication, the heating pipeline passes through in proper order the rotary kiln waste heat mechanism with remove sulphur mechanism, be used for holding solution in the waste heat mechanism, waste heat mechanism with the intercommunication of solution mechanism and to it provides the solution of heating to dissolve the mechanism, remove sulphur mechanism's bottom with grind the mechanism intercommunication.
2. The lithium extraction system for lithium china stones according to claim 1, wherein the sulfur removal mechanism comprises a smoke exhaust pipe, a spraying device and a recovery device, the spraying device is used for spraying calcium carbonate into the smoke exhaust pipe, the recovery device is communicated with the rotary kiln, the recovery device is used for collecting gypsum generated by the spraying device and providing the gypsum for the grinding mechanism, and the rotary kiln is used for heating the lithium china stones, the gypsum and calcium oxide.
3. The lithium extraction system for lithionites of claim 1, wherein the solution contained in the waste heat mechanism is water.
4. A method for extracting lithium from lithium china stones by using the lithium extraction system for lithium china stones according to any one of claims 1 to 3, wherein the method for extracting lithium from lithium china stones comprises the following steps:
step one, respectively grinding lithium porcelain stone, calcium oxide and gypsum generated by the sulfur removal mechanism into powder, and mixing to prepare a mixture;
step two, granulating the mixture produced in the step one, putting the mixture into the rotary kiln, firing at the high temperature of 1000-1100 ℃, conveying the clinker to the cooling kiln for cooling, and conveying the clinker to the dissolving mechanism;
and step three, the waste heat mechanism introduces water with the temperature of more than 90 ℃ into the dissolving mechanism, the water is conveyed to the filtering mechanism for filtering after being stirred, the filtrate is taken as lithium-containing mother liquor, and the filter residue is taken as white filler.
5. The method for extracting lithium from lithium china stone as claimed in claim 4, 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.
6. The lithium extraction method of lithium china stone according to claim 4, wherein the second step comprises:
adding a granulating agent into the mixture produced in the step one for granulation, placing the mixture into the rotary kiln, firing at a high temperature of 1000-1100 ℃, conveying the clinker to the cooling kiln for cooling, and conveying the clinker to the dissolving mechanism.
7. The lithium extraction method of lithium china stone as claimed in claim 6, wherein the granulating agent is polyacrylamide and/or polyaluminium chloride.
8. The lithium extraction method of lithium china stone according to claim 4, wherein the third step comprises:
and the waste heat mechanism introduces water with the temperature of more than 90 ℃ into the dissolving mechanism, conveys the water to the filtering mechanism for filtering after stirring for 30min, takes the filtrate as lithium-containing mother liquor and takes the filter residue as white filler.
9. A lithium-containing mother liquor prepared by the lithium extraction method of the lithium china stone as claimed in any one of claims 4 to 8.
10. A white filler prepared by the method for extracting lithium from lithium china stone as claimed in any one of claims 4 to 8.
Technical Field
The invention relates to the technical field of waste manufacturing, in particular to a lithium extraction system and method for 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 system and method for lithium china stone, lithium-containing mother liquor and a filling agent, and aims to solve the technical problems of complex lithium extraction process and more waste materials of the existing lithium china stone.
In order to achieve the purpose, the lithium extraction system for the lithium china stones comprises a grinding mechanism, a rotary kiln, a cooling kiln, a dissolving mechanism and a filtering mechanism which are sequentially communicated, a waste heat mechanism, a heating pipeline for supplying heat to the rotary kiln and a sulfur removal mechanism communicated with the heating pipeline, wherein the heating pipeline sequentially passes through the rotary kiln, the waste heat mechanism and the sulfur removal mechanism, the waste heat mechanism is used for containing solution, the waste heat mechanism is communicated with the solution mechanism and provides heated solution for the dissolving mechanism, and the bottom of the sulfur removal mechanism is communicated with the grinding mechanism.
Preferably, the desulfurization mechanism includes exhaust pipe, spray set and recovery unit, spray set be used for to spray calcium carbonate in the exhaust pipe, recovery unit with the rotary kiln intercommunication, recovery unit is used for collecting the gypsum that spray set produced and to grind the mechanism and provide the gypsum, the rotary kiln is used for heating lithium china stone, gypsum and calcium oxide.
Preferably, the solution contained in the waste heat mechanism is water.
The chlorphenamine also provides a lithium extraction method for the lithium china stone by adopting the lithium extraction system for the lithium china stone, which is characterized by comprising the following steps of:
step one, respectively grinding lithium porcelain stone, calcium oxide and gypsum generated by the sulfur removal mechanism into powder, and mixing to prepare a mixture;
step two, granulating the mixture produced in the step one, putting the mixture into the rotary kiln, firing at the high temperature of 1000-1100 ℃, conveying the clinker to the cooling kiln for cooling, and conveying the clinker to the dissolving mechanism;
and step three, the waste heat mechanism introduces water with the temperature of more than 90 ℃ into the dissolving mechanism, the water is conveyed to the filtering mechanism for filtering after being stirred, the filtrate is taken as lithium-containing mother liquor, and the filter residue is taken as 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 second step includes:
adding a granulating agent into the mixture produced in the first step for granulation, placing the mixture into the rotary kiln, firing at a high temperature of 1000-1100 ℃, conveying the clinker to the cooling kiln for cooling, and conveying the clinker to the dissolving mechanism;
preferably, the granulating agent is polyacrylamide and/or polyaluminium chloride.
Preferably, the third step includes:
and the waste heat mechanism introduces water with the temperature of more than 90 ℃ into the dissolving mechanism, conveys the water to the filtering mechanism for filtering after stirring for 30min, takes the filtrate as lithium-containing mother liquor and takes the filter residue as 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 invention, the solution can be heated by the waste heat in the heating pipeline through the waste heat mechanism, and the heated solution is introduced into the dissolving mechanism, so that the dissolving rate is increased; through with sulphur removal mechanism and grinding mechanism intercommunication, the gypsum that usable sulphur removal mechanism produced reduces production waste.
Drawings
Fig. 1 is a schematic structural diagram of a lithium extraction system 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 utility model provides a lithium system of carrying of lithium china stone, including
In this embodiment, the solution contained in the residual heat mechanism 6 is water.
Further,
In the invention, the solution can be heated by the waste heat in the
The invention provides a lithium extraction method of lithium china stone, which comprises the following steps:
step S1, respectively grinding the lithium porcelain stone, the gypsum and the calcium oxide into powder, 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 generatedxCay(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.
The process is carried out by calcining α -type lithium porcelain stone to obtain β -type which has loose structure and easy reaction with sulfate, converting lithium into lithium sulfate, filtering, obtaining mother liquid containing lithium hydroxide, filter residue containing silicon-aluminum-calcium, filter residue being used to prepare white cement, or being used as white filler in paint, etc. calcium fluoride can increase the glossiness of 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
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