The chlorination of ferroniobium and device for its implementation
(57) Abstract:The invention relates to the metallurgy of rare metals, in particular to a device and method chlorine decomposition of tantalum - and niobium contained primary and technogenic raw materials. How is that ferroniobium in the form of pieces of size 10-100 mm load in charator layer thickness of 200-250 mm Chlorination is conducted at a temperature of 1100-1200oAnd the consumption of chlorine is 1:1.7 to 1.9 kg/kg of Melt addition hairout with putting him in sodium chloride. The ratio between the amounts of chlorine in the chlorination and dharitvena 9.5-10: 1, and the mass ratio of sodium chloride to ferric chloride is 1: 4-4,5. The device comprises a vertical water-cooled XLERATOR lined graphite, with a pipe for input of chlorine, pravilnik collection of ferric chloride with a pipe for input of sodium chloride, condenser, equipped with scrapers, pipe for output vapor-gas mixture, the camera defloriani from the inlet to the tangential input of chlorine installed on pravilnik and connected with chloroform conical furnace hearth with a hole for the output of products of chlorination. The furnace hearth filled with a nozzle made of fused silica. The diameter of the holes is equal to 45-50 mm Ratio visor up to 95-98%, to increase the degree of extraction of niobium and tantalum in the higher chlorides of niobium and tantalum by reducing the degree of recovery of niobium and tantalum to lower oxidation States and to reduce the content of non-volatile lower chlorides of niobium and tantalum with the output from the process with ferric chloride, and also to improve the chlorination apparatus through better timing and lack of local overheating due to the upper input of chlorine in the vertical charator. 2 c.p. f-crystals, 1 tab., 1 Il. The invention relates to the metallurgy of rare metals, in particular to a device and method chlorine decomposition of tantalum - and niobium contained primary and technogenic raw materials.The main task of the first stages of chlorination technology integrated Nb, Ta-containing raw material is the most complete extraction of niobium and tantalum in the bulk concentrate.Known chlorine method of processing of loparite concentrate /S. S. Korovin and other " Rare and trace elements. Chemistry and technology" -M: MISA, 1999, S. 324-332/. Chlorination is subjected briketirovannogo or powder charge. The method of chlorination is used for the first stage of the process. The total chlorination process loparite reflects the+NaCl+nCO2/CO
Conventionally, the process of chlorination of loparite can be viewed as the interaction of individual oxides with chlorine.A constructive solution of the staff of the chlorination is very important. It must meet the following requirements:
1) to ensure continuous operation within 12-18 months, almost complete absorption of chlorine with continuous output vapor-gas mixture and melt, as well as to ensure the desired decomposition concentrate;
2) the device must be adjustable both in heat mode, and performance;
3) the device must be stable with respect to small fluctuations of the charge composition, quality, chlorine and others;
4) to ensure full security for staff and perform basic ecological requirements.As one of the sources of raw materials for the production of compounds of niobium and tantalum are of interest mandalaybay alloys, in particular ferroniobium [U. D. Dgemric" Processes and devices of chemical and metallurgical technology of rare metals" - M Atomizdat, 1965, S. 62-64]. The chlorination process was conducted on a small scale (10-20 kg per load) in a horizontal tubular PE is I or graphite thickness of 2.5 see The lining of graphite better protection stainless steel from the effects of chlorine, since the surface of the graphite tube can more accurately process and to ensure a tight fit to the pipe of stainless steel. Ferroniobium were loaded into the furnace along the length of pieces ranging in size from 6.3 to 10 mm Nichrome coil furnace can heat the material prior to the reaction start temperature of 550oWith, and in the subsequent reaction with chlorine, the temperature was increased to 1000oC. Enter the chlorine was performed using a quartz tube, which was passed through the loaded material to the end of the furnace, almost to the condenser. In the end, and began the process of chlorination. As the reaction tube was slowly moved out of the reactor, until the entire loaded ferroniobium was not prochloron. Chlorine was applied in excess, and sintering, it is possible that during the formation of the lower chlorides, was prevented. The effectiveness of chlorine is not above 60-70%. Of the apparatus, the mixture of chlorides comes with a temperature above 350oC. In the main condenser it is reduced to 30oC. the Condenser is made in the form of three steel parallel pipes with a length of 60 cm and a diameter of 5 cm each. Pipe equipped with scrapers, managed through seals. From the bottom to the pipe is the ides of iron, Penta - and hexachloride tungsten. For cleaning pentachloride niobium and tantalum main condenser was immersed in an oil bath, which by the end of the primary process of condensation was heated to 220oC. a Mixture of chloride melts and flows into the displacer - vertical steel pipe with a length of 1.5 m and a diameter of 75 cm, also heated to 220oC. Steel cylinder moves from the top of the down tube, and a pipe with a constant velocity is filled with chlorides. From the displacer chlorides flowed in a short heated tube, evaporated and together with hydrogen was admitted to a horizontal steel reactor with a length of 1.2 m, diameter 23 see In this reactor at a temperature of 350oWith the ferric chloride is recovered to a non-volatile chlorides of bivalent iron. Chloride iron was going in the reactor and separated on the filter with the filter cloth from fiberglass.Main disadvantages:
- low level use /60-70%/ chlorine requires a strong system further capture and neutralization in order to avoid damage to the environment and staff;
with chloride of iron is lost up to 5% of niobium and tantalum in the restore him to nishizono lower chlorides of niobium and tantalum, prevents the reaction in the whole volume, making it difficult to remove the excess heat and reduces the efficiency of the process.The purpose of the invention:
1) increasing the degree of chlorine up to 95-98%, which leads to greater productivity and improve its environmental performance;
2) increasing the degree of extraction of niobium and tantalum in the higher chlorides of niobium and tantalum by reducing the degree of recovery of niobium (V) and tantalum (V) to lower degrees of oxidation and reduction of the non-volatile content of the lower chlorides of niobium and tantalum with the output from the process of chloride of iron.3) improving the performance of the apparatus chlorination by improved design process when holding it in a vertical chlorate with the upper input of chlorine, which allows use of the entire apparatus chlorination due to improved timing and lack of local overheating.The invention consists in the fact that a basically new method and apparatus for so-called "dry" chlorination of ferroniobium.Device for chlorination of ferroniobium (see drawing) consists of water-cooled chlorate provides for the filing of chlorine from above, XLERATOR made in the form of a vertical apparatus, consisting of two parts: the upper part of charator (1), and the lower part of declarator (5) containing conical furnace hearth (3) filled with irregular attachment of the fused silica and the outlet (4) with a diameter of 45-50 mm, and declarator provided with a nozzle tangential input of chlorine (6). The ratio of the upper and lower parts of the machine is 2.5-3:1.The device chlorination of ferroniobium equipped with pravilnik to collect chlorides of iron (7), socket for input of sodium chloride (8) and the condenser (9), equipped with scrapers (10) and pipe the output vapor-gas mixture (11).The device operates as follows.Ferroniobium without preliminary grinding, in the form of pieces of size 10-100 mm, load layer 200-250 mm on an irregular nozzle (3), made of fused quartz and located on the conical furnace hearth. The installation serves chlorine through a pipe (2), located in the top cover of charator (1). The chlorination process is carried out at a temperature of 1100-1200oWhen the flow rate of chlorine is 1: 1.7 to 1.9 kg/kg chlorine Consumption was regulated according to the testimony of a differential pressure gauge installed on echodrone in the lower part of chlarotera, and enters the chamber of defloriani (5), provided with a nozzle tangential input of chlorine (6). Introduced through pipe (6) chlorine dichloride fixed lower chlorides of niobium and tantalum up to their highest, volatile chlorides. The ratio between the amounts of chlorine introduced the actual chlorination (2) and dharitvena (6), 9.5-10:1.Formed during chlorination volatile pentachloride niobium and tantalum chlorides and iron come into the condenser (9), where as lowering the temperature of the iron dichloride forms a volatile ingredients melt that flows into pravilnik iron dichloride (7), provided with a socket input of sodium chloride (8). Introduction into the melt of sodium chloride is necessary for binding trichloride iron, which in small amounts can be formed during chlorination and defloriani in non-volatile, thermally stable complex NaFeCl4. The mass ratio of the injected sodium chloride to ferric chloride is 1: 4-4,5. The introduction of sodium chloride also allows you to hold the molten aluminum in the form of a complex NaAlCl4. From pravilnik (7) the melt is periodically brought out through the lower tapped and sent for further processing.The amount of easily volatile pentachloride the mixture, where is condensed and fed to further processing in order to obtain individual pentachloride niobium and tantalum.Example 1
Lumpy ferroniobium size 10-100 mm) is fed into the upper part of charator sector through the feeder on an irregular nozzle, made of fused silica layer 200-250 mm Chlorine is fed through a nozzle located on the top cover of charator. Chlorine consumption adjust the readings of the differential pressure gauge installed on the expenditure puck. Calibration gas exits through the outlet which is located at the bottom of chlarotera, and enters the chamber of defloriani. The ratio of chlorine to the chlorination and dharitvena 9.5-10:1. The chlorination process is carried out at a temperature of 1100-1200oAnd the consumption of chlorine is 1:1.7 to 1.9 kg/kg Volatile pentachloride niobium and tantalum chlorides and iron come into the condenser, where as lowering the temperature of the iron dichloride forms a volatile ingredients melt and flow into pravilnik dichloride iron, which introduces the sodium chloride in the ratio of 1:4-4,5. Pentachloride of niobium and tantalum (PHL) pass through the condenser and in the form of steam is supplied into the system of condensation, where it is condensed and fed to further processing with a the capacity balance of the chlorination process of ferroniobium according to the results of the pilot facility is attached. 1. The chlorination of ferroniobium, including the loading of ferroniobium in the form of pieces in charator, chlorination at a given temperature, homogenization of chloride metals containing iron chloride, characterized in that the pieces of ferroniobium size 10-100 mm load in charator layer thickness of 200-250 mm, the chlorination is carried out at a temperature of 1100-1200oAnd the consumption of chlorine is 1: 1.7 to 1.9 kg/kg and the melt is additionally glorious with putting him in sodium chloride, the ratio of the amounts of chlorine in the chlorination and dharitvena 9.5-10: 1, and the mass ratio of sodium chloride to ferric chloride is 1: 4-4,5.2. Device for chlorination of ferroniobium containing vertical water-cooled XLERATOR lined graphite, with a pipe for input of chlorine, located on the lid of chlarotera, condenser, equipped with scrapers, pipe for output vapor-gas mixture, characterized in that it is provided with pravilnik collection of ferric chloride with a pipe for input of sodium chloride and Luggage defloriani from the inlet to the tangential input of chlorine installed on pravilnik and connected with chloroform conical furnace hearth with a hole for the output of products of chlorination, sepolgen the options defloriani is 2.5-3: 1.
SUBSTANCE: invention relates to hydrometallurgy, in particular to the technology of processing of ore concentrates of niobium and tantalum. The method of producing of niobium and tantalum oxides from columbite (tantalite) concentrate includes its opening by ammonium fluorides and sulphuric acid, subsequent release, purification and separation of niobium and tantalum salts by extraction. Note that the concentrate is fluorinated by melting of a mix of fluorides of ammonium at a temperature of 110-240°C within 0.5-5 hours, the discharged gases are absorbed by water with producing of an ammonia solution.
EFFECT: invention provides the cost-saving and low-waste method of processing of niobium and tantalum ore concentrates, and also low specific consumption of chemicals.
4 cl, 1 dwg, 2 ex