CN112723393B - Method for preparing high-purity tantalum pentachloride/niobium and lithium chloride from waste tantalum/lithium niobate - Google Patents
Method for preparing high-purity tantalum pentachloride/niobium and lithium chloride from waste tantalum/lithium niobate Download PDFInfo
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Abstract
The invention discloses a method for preparing high-purity tantalum pentachloride/niobium and lithium chloride from waste tantalum/lithium niobate, which is characterized in that waste tantalum/lithium niobate treated by acid-base cleaning is taken as a tantalum/lithium niobate metal source, petroleum coke, activated carbon and carbon black are taken as carbon sources, crushed and uniformly mixed according to a certain proportion, after plasma activation, the mixture is put into a chlorination furnace, the temperature is increased, high-purity chlorine is introduced for reaction, the temperature of the produced mixture is controlled to 280-400 ℃, the mixture is removed by high-temperature dust and iron is removed by a filtering section, the mixture is cooled and recycled in a material receiving section with the temperature controlled to 150-220 ℃, and the high-purity lithium chloride is recycled by water immersion of the residue of the chlorination furnace. The invention realizes the preparation of high-purity tantalum pentachloride/niobium and lithium chloride, solves the problems of low product purity, low recovery rate, complex process and the like commonly existing in the traditional waste tantalum/lithium niobate recovery process, and has the outstanding advantages of simple process equipment, complete utilization of raw materials, low cost, cleanness and environmental protection.
Description
Technical Field
The invention relates to a method for preparing high-purity tantalum pentachloride/niobium and lithium chloride from waste tantalum/lithium niobate, belonging to the field of rare material recovery and re-preparation.
Background
Tantalum pentachloride is a white crystal with a boiling point as low as 242 ℃, and the difference between the boiling point and the chloride of the impurity element is utilized to facilitate the separation of the impurity element such as silicon, aluminum, titanium, iron, calcium, manganese, nickel and the like. As an important precursor of superfine high-purity tantalum powder and high-purity tantalum coating, the high-purity tantalum powder and the high-purity tantalum coating have been widely applied to the fields of capacitors, artificial bones, ultra-high temperature materials and high corrosion resistant materials; niobium pentachloride is a pale yellow crystal with the boiling point as low as 250 ℃, is an important precursor of superfine high-purity niobium powder and high-purity niobium coating, and is mainly applied to the fields of superconducting materials, corrosion-resistant high-temperature-resistant materials and other high-performance materials; lithium chloride is an inorganic compound of lithium, and can be widely applied to the field of lithium electric materials, and also used as soldering flux, drying agent and the like in the field of air conditioning.
The common recovery methods of spent tantalum/lithium niobate introduce new materials such as aluminum or sodium, both pyrogenic and wet. The purity of the metal tantalum/niobium prepared by the pyrogenic process is low, high-temperature electron beam melting is needed to obtain a tantalum/niobium rod with relatively high purity, the subsequent process treatments such as hydrogenation powder preparation are needed, the process flow is long, the energy consumption is high, and the high-quality extraction of lithium is difficult to realize; the wet method adopts high-temperature alkali fusion, water washing and acid washing, the water consumption is large, the purity of the separated tantalum/niobium is only 98%, and the purity of lithium is also only about 96%. The traditional recovery method of the waste tantalum/lithium niobate only realizes the recycling of tantalum/niobium and lithium, and is difficult to realize the high-quality application. Therefore, the development of a method for preparing high-purity tantalum pentachloride/niobium and lithium chloride by using waste tantalum/lithium niobate in a high-quality mode is particularly important.
Disclosure of Invention
The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing high purity tantalum pentachloride/niobium pentachloride and lithium chloride; the invention realizes the high-quality recovery of waste tantalum/lithium niobate and the preparation of high-purity tantalum pentachloride/niobium and lithium chloride, saves resources, and does not obviously increase energy compared with the traditional preparation method of high-purity tantalum pentachloride/niobium.
The method for preparing high-purity tantalum pentachloride and lithium chloride from waste lithium tantalate or preparing high-purity tantalum pentachloride and lithium chloride from waste lithium niobate comprises the following specific steps:
1) Waste tantalum/lithium niobate pretreatment
Washing the waste lithium tantalate/lithium tantalate particles with pure water and hydrochloric acid to remove surface impurity ash, and drying for later use.
2) Pretreatment of carbon source
Crushing the carbon source to more than 100 meshes, washing with pure water and hydrochloric acid to remove impurities, and drying for later use.
3) Material mixing and activation
And (2) mixing the waste tantalum/lithium niobate obtained in the step (1) with the carbon source obtained in the step (2), and then performing plasma activation to break the crystal structure of the tantalum/lithium niobate and realize grain refinement and carburization.
4) Chlorination reaction
Placing the waste tantalum/lithium niobate and carbon mixture prepared in the step 3) into a chlorination furnace, vacuumizing and replacing the chlorination furnace with argon, finally introducing high-purity chlorine when the temperature of the chlorination furnace is raised to more than 700 ℃ to make the mixture undergo chlorination reaction, enabling generated tantalum pentachloride/niobium and carbon oxide to enter a high-temperature dust removing section with the temperature of more than 400 ℃ in the form of steam, removing carried tantalum/lithium niobate, carbon and lithium chloride-free dust, cooling the gas to 255-300 ℃, entering a filtering iron removing section to remove ferrous chloride, cooling the gas to 150-220 ℃ in a material receiving section, and collecting cooled and crystallized tantalum pentachloride/niobium powder, wherein the purity of the tantalum pentachloride/niobium is not less than 99.7%.
5) Lithium chloride separation
Washing the residue and dust in the high-temperature dust removing section in the step 4) by pure water, dissolving the generated lithium chloride in an aqueous solution, and concentrating and crystallizing to obtain lithium chloride powder with the purity of not less than 99.7%.
According to the invention, waste tantalum/lithium niobate is carburized by plasma, the crystal structure and the material composition of tantalum/lithium niobate are broken, the activation energy of tantalum/lithium niobate is enhanced, the later chloridizing difficulty is reduced, high-temperature dust removal and medium-temperature iron removal are carried out in the gas product collecting stage, high-boiling substances such as lithium chloride, ferric chloride, tantalum/lithium niobate, carbon powder, nickel chloride and the like are directly separated from tantalum pentachloride/niobium, the tantalum pentachloride/niobium does not need secondary purification, and the thermal insulation control of a material receiving section realizes the separation of tantalum pentachloride/niobium from low-boiling substances such as silicon chloride, titanium chloride, aluminum chloride and the like. The lithium chloride mainly stays in the chlorination furnace, liquid lithium chloride after deslagging can be rapidly agglomerated and solidified to be separated from most of unreacted carbon and a small amount of lithium tantalate, separation of the lithium chloride is realized through water dissolution, and then high-purity lithium chloride is obtained through concentration and crystallization.
The invention realizes the high-quality recovery of waste tantalum/lithium niobate and the collaborative preparation of high-purity tantalum pentachloride/niobium and lithium chloride. On one hand, the invention solves the problems that the traditional waste lithium tantalate can only be simply recycled, the purity and recovery rate of products are not high, and the process is complex, the reaction activation energy of the tantalum/lithium niobate is improved by the tantalum/lithium niobate through plasma carburization, the chlorination reaction temperature and the reaction difficulty are reduced, the tantalum/lithium niobate can be completely reacted and recovered basically, and the obtained products are high-purity tantalum pentachloride/niobium and lithium chloride. On the other hand, a novel synergistic preparation method is developed for the preparation of high-purity tantalum pentachloride/niobium and lithium chloride, the impurities of waste tantalum/lithium niobate are mainly on the surface, the surface cleaning of tantalum/lithium niobate is realized through water washing and acid washing, the tantalum/lithium niobate can be used as a preparation raw material of the high-purity tantalum pentachloride/niobium and lithium chloride, the reduction of high-boiling-point substance impurities in the tantalum pentachloride/niobium is realized through high-temperature dust removal and medium-temperature iron removal sections, the high-purity tantalum pentachloride/niobium is obtained in one step, meanwhile, lithium chloride generated by the reaction is easy to dissolve in water and has large solubility in water, and the high-purity lithium chloride can be obtained through concentration crystallization from unreacted tantalum/lithium niobate and carbon. In conclusion, the scheme of the invention has the advantages of simple operation, short flow, less energy consumption, low cost and environmental friendliness, is favorable for the maximum utilization of resources and meets the needs of industrial development.
Drawings
FIG. 1 is a process flow diagram of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the claims.
Example 1
Weighing a certain amount of waste lithium tantalate, washing with 1 time of water and 1 time of 2% by mass of dilute hydrochloric acid, drying at 120 ℃ after washing with 1 time of water, weighing a proper amount of activated carbon, crushing to 200 meshes, washing with 1 time of water and 1 time of 2% by mass of dilute hydrochloric acid, drying at 120 ℃ after washing with 1 time of water, mixing with the treated lithium tantalate in a mixer for 10min, transferring to a 50kW plasma for activation for 10min, then delivering to a boiling furnace for chlorination, wherein the molar ratio of the waste lithium tantalate, the activated carbon and chlorine is 1:2:3.5, the feeding rate of the waste lithium tantalate is 500g/min, the reaction temperature is 700-800 ℃, the temperature is controlled at 400 ℃ in a high-temperature dedusting section, the temperature is controlled at 300 ℃, the purity of the obtained tantalum pentachloride is 99.88%, the content of iron elements is lower than 50ppm, the content of elements such as silicon and aluminum is lower than 20ppm, the dust content of the lithium chloride block in the residue collected after cooling in the boiling furnace is lower than 50ppm, the dust content of the high-temperature dedusting section is 20ppm, the purity of the nickel chloride is lower than 20.98% and the purity of the pure water is lower than 20.98% of the impurity impurities such as copper, and the purity is lower than 20.98% by concentration.
Example 2
Weighing a certain amount of waste lithium niobate, washing with 2 times of water and 2 times of 2% of diluted hydrochloric acid, drying at 120 ℃ after 2 times of water washing, weighing a proper amount of activated carbon, crushing to 250 meshes, washing with 2 times of water and 2% of diluted hydrochloric acid, drying at 120 ℃ after 2 times of water washing, mixing with the treated lithium niobate in a mixer for 15min, transferring to a power 55kW plasma for activation for 10min, feeding into a fluidized bed for chlorination, feeding hydrogen into an iron removing section, controlling the molar ratio of waste lithium niobate, activated carbon and chlorine to be 1:2.5:4, controlling the temperature of the iron removing section to be 280 ℃ at the reaction temperature of 800-900 ℃, controlling the temperature of the material collecting section to be 180 ℃, obtaining niobium pentachloride purity of 99.91%, the content of iron element to be lower than 40ppm, the content of silicon element, the content of the element elements such as aluminum to be lower than 20ppm, collecting lithium chloride blocks in residues after cooling of the fluidized bed, and the water of the high purity of the lithium chloride to be lower than 98.38 ppm, and the purity of the crystal nickel to be lower than 98.98% by using pure water, and the purity of the impurities such as lithium chloride to be lower than 98.38 ppm, and the purity of the impurities to be lower than the purity of the crystal impurities to be 98.98.38% of the manganese is obtained after the concentration.
Example 3
Weighing a certain amount of waste lithium tantalate, washing with 2 times of water and 2 times of 2% by mass of dilute hydrochloric acid, drying at 120 ℃ after washing with 2 times of water, weighing a proper amount of activated carbon, crushing to 350 meshes, washing with 2 times of water and 2% by mass of dilute hydrochloric acid, drying at 120 ℃ after washing with 2 times of water, mixing with the treated lithium tantalate in a mixer for 15min, transferring to a power 60kW plasma for activation for 20min, feeding into a boiling furnace for chlorination, feeding hydrogen into an iron removing section, controlling the molar ratio of the waste lithium tantalate, the activated carbon and chlorine to be 1:3:5, feeding the waste lithium tantalate at 500g/min, controlling the temperature of a high-temperature dust removing section to be 450 ℃, controlling the temperature of a material collecting section to be 195 ℃, obtaining tantalum pentachloride at 99.93%, the content of iron elements being lower than 30ppm, the content of silicon, the content of aluminum element being lower than 20ppm, the lithium chloride block in the residue after cooling of the boiling furnace, the high-temperature dust removing section being lower than 20ppm, the pure water content of the lithium chloride being lower than 98.98% and the purity of the copper, the purity being lower than 8.98% of the impurity, and the purity of the crystal nickel being lower than the purity of the lithium ion storage being lower than 98.98.98% after being concentrated.
Example 4
Weighing a certain amount of waste lithium niobate, washing with 2 times of water and 2 times of 2% of diluted hydrochloric acid, drying at 120 ℃ after washing with 2 times of water, weighing a proper amount of activated carbon, crushing to 350 meshes, washing with 2 times of water and 2% of diluted hydrochloric acid, drying at 120 ℃ after washing with 2 times of water, mixing with the treated lithium niobate in a mixer for 15min, transferring to a power 60kW plasma for activation for 20min, feeding into a boiling furnace for chlorination, feeding hydrogen into a de-ironing section, feeding waste lithium niobate, activated carbon and chlorine at a molar ratio of 1:4:6:0.005, feeding waste lithium niobate at a feeding rate of 500g/min, reacting at 1000-1100 ℃, controlling the temperature of 450 ℃ in a high-temperature dedusting section, controlling the temperature to 255 ℃ in a material collecting section, controlling the temperature to 195 ℃, obtaining niobium pentachloride at a purity of 99.92%, the content of iron element being lower than 20ppm, the content of elements such as silicon and aluminum being lower than 20ppm, cooling the obtained lithium pentachloride block and residue in the boiling furnace, collecting residue after cooling, and filtering the lithium chloride at a purity of the lithium chloride being lower than 99.99.45 ppm, and the purity of the lithium chloride being lower than 20.99.45% and the purity of the impurities being lower than the purity of the lithium chloride is higher than 20.45%, and the purity of the impurities being equal to that of the lithium chloride is lower than the purity is equal to 20.45% and the purity is higher than the purity of the impurities.
Claims (8)
1. A method for preparing high-purity tantalum pentachloride and lithium chloride from waste lithium tantalate, which is characterized by comprising the following steps:
1) Waste lithium tantalate pretreatment
Washing the waste lithium tantalate particles by pure water and washing off the waste lithium tantalate particles by hydrochloric acid to remove the surface impurity ash;
2) Pretreatment of carbon source
Crushing a carbon source to more than 100 meshes;
3) Material mixing and activation
Mixing the waste lithium tantalate obtained in the step 1) with the carbon source obtained in the step 2), and then performing plasma activation to break the crystal structure of the lithium tantalate and realize grain refinement and carburization; carburization to LiTaO 3-X C X Wherein x=0-3; the molar ratio of the waste lithium tantalate to the carbon source is 1:1.5-5;
4) Chlorination reaction
Placing the waste lithium tantalate and carbon mixture prepared in the step 3) into a chlorination furnace, vacuumizing and replacing argon in the chlorination furnace, introducing high-purity chlorine when the temperature of the chlorination furnace is raised to more than 700 ℃ finally, enabling the mixture to carry out chlorination reaction, enabling generated tantalum pentachloride and carbon oxide to enter a high-temperature dust removing section with the temperature of more than 400 ℃ in a steam form, removing carried lithium tantalate, carbon and lithium chloride dust, cooling gas to 255-300 ℃, entering a filtering iron removing section to remove ferric chloride, cooling gas into a material collecting section to 150-220 ℃, and collecting cooled and crystallized tantalum pentachloride powder, wherein the purity of tantalum pentachloride is not less than 99.7%;
5) Lithium chloride separation
Washing the residue and dust in the high-temperature dust removing section in the step 4) by pure water, dissolving the generated lithium chloride in an aqueous solution, and concentrating and crystallizing to obtain lithium chloride powder with the purity of not less than 99.7%.
2. The method for preparing high purity tantalum pentachloride and lithium chloride from waste lithium tantalate according to claim 1, wherein the carbon source in step 2) is activated carbon, petroleum coke or carbon black.
3. The method for preparing high purity tantalum pentachloride and lithium chloride from waste lithium tantalate according to claim 1, wherein the molar ratio of waste lithium tantalate to chlorine in the chlorination reaction in the step 4) is 1:3-5.
4. The method for preparing high purity tantalum pentachloride and lithium chloride from waste lithium tantalate according to claim 1, wherein the chlorination reaction temperature in step 4) is 700-1200 ℃.
5. A method for preparing high-purity niobium pentachloride and lithium chloride from waste lithium niobate, which is characterized by comprising the following steps:
1) Pretreatment of waste lithium niobate
Washing the waste lithium niobate particles by pure water and washing off the waste lithium niobate particles by hydrochloric acid to remove the surface impurity ash;
2) Pretreatment of carbon source
Crushing a carbon source to more than 100 meshes;
3) Material mixing and activation
Mixing the waste lithium niobate obtained in the step 1) with the carbon source obtained in the step 2), and then performing plasma activation, wherein the power of the plasma activation is 55kW, the activation is 10min, or the power is 60kW, the activation is 20min, the crystal structure of the lithium niobate is broken, and the particle refinement and carburization are realized; the molar ratio of the waste lithium niobate to the carbon source is 1:1.5-5;
4) Chlorination reaction
Placing the waste lithium niobate and carbon mixture prepared in the step 3) into a chlorination furnace, vacuumizing and replacing argon in the chlorination furnace, introducing high-purity chlorine when the temperature of the chlorination furnace is raised to more than 700 ℃ finally, enabling the mixture to carry out chlorination reaction, enabling generated niobium pentachloride and carbon oxide to enter a high-temperature dust removing section with the temperature of more than 400 ℃ in a steam form, removing carried lithium niobate, carbon and lithium chloride dust, cooling gas to 255-300 ℃, entering a filtering iron removing section to remove ferric chloride, cooling gas into a material receiving section to 150-220 ℃, and collecting cooled and crystallized niobium pentachloride powder;
5) Lithium chloride separation
Washing the residue and dust in the high-temperature dust removing section in the step 4) by pure water, dissolving the generated lithium chloride in an aqueous solution, and concentrating and crystallizing to obtain lithium chloride powder with the concentration of not less than 99.7%.
6. The method for preparing high purity niobium pentachloride and lithium chloride from waste lithium niobate according to claim 5, wherein the carbon source in the step 2) is activated carbon, petroleum coke or carbon black.
7. The method for preparing high purity niobium pentachloride and lithium chloride from waste lithium niobate according to claim 5, wherein the molar ratio of the waste lithium niobate and chlorine gas in the chlorination reaction in the step 4) is 1:3-5.
8. The method for preparing high purity niobium pentachloride and lithium chloride from waste lithium niobate according to claim 5, wherein the chlorination reaction temperature in step 4) is 700-1200 ℃.
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| CN109207746A (en) * | 2018-09-25 | 2019-01-15 | 内蒙古扎鲁特旗鲁安矿业有限公司 | A kind of fused salt chlorimation extracting method of low-grade niobium concentrate |
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| US4446115A (en) * | 1980-02-15 | 1984-05-01 | Tokyo Shibaura Denki Kabushiki Kaisha | Method of recovering tantalum from silicon-containing tantalum scrap |
| JPH0328334A (en) * | 1989-06-27 | 1991-02-06 | Tosoh Corp | Method for recovering high purity tantalum and its derivative from tantalum scrap |
| CN108264088A (en) * | 2018-03-30 | 2018-07-10 | 西安瑞鑫科金属材料有限责任公司 | It is a kind of that the method that tantalic chloride is prepared in slag is enriched with from titanium tantalum |
| CN109207746A (en) * | 2018-09-25 | 2019-01-15 | 内蒙古扎鲁特旗鲁安矿业有限公司 | A kind of fused salt chlorimation extracting method of low-grade niobium concentrate |
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