RU60529U1 - TECHNOLOGICAL LIMIT FOR THE PRODUCTION OF ZIRCONIUM OXIDE - Google Patents

Abstract

The proposed utility model relates to the field of chemical technology and, in particular, to technological conversions used in the technology of inorganic substances, plants, compartments and complexes for the production of metal oxides, in particular zirconium oxide ZrO ₂ used in the production of materials for radio electronics. The objective of the proposed utility model is to provide conditions for the production of zirconium dioxide suitable for the production of materials for electronic equipment, and to ensure the conditions for the processing, neutralization and disposal of generated waste and industrial products. The technical result that can be obtained by implementing the utility model is to increase the purity of the target product - zirconium dioxide and prevent environmental pollution by highly toxic production waste. The problem is solved with the achievement of the above technical result by the proposed utility model - “Technological redistribution for the production of zirconium oxide”, including a tank with a stirrer for the preparation of the initial solution of zirconium chloride, a hopper-dispenser of chloride and / or zirconium oxychloride having a sealed connection through a shut-off and control device with a tank loading hatch, a neutralizing reactor for precipitation from a solution of zirconium oxyhydrate, filtering equipment, a drying chamber, calcining one whose, in the new proposed technical solution is the fact that between the tank for preparing a starting solution of zirconium chloride and the reactor heated with stirring to precipitate zirconium oxyhydrate additionally installed reactor equipped with a heating jacket, a dispersing

ammonia-air mixture, connected through a pipeline with a heated container with ammonia water into which a bubbler of compressed air is placed, a rod with electrodes connected to a pH meter connected through a shut-off valve to the ammonia-air supply pipeline is installed in the reactor to clean the initial solution from impurities mixture, on the top cover of the reactor for cleaning the initial solution of impurities there is a loading hatch for supplying to the reactor part of the wet paste of zirconium oxyhydrate obtained in a heated reactor a catalyst for precipitation from a solution of zirconium chloride purified from impurities, a lower discharge pipe from the reactor for purification of the initial solution from impurities is connected through shut-off valves to the suction filter-I; the discharge from which the mother solutions of zirconium chloride, purified from impurities, is directed through shut-off valves to a neutralizing reactor to precipitate zirconium oxyhydrate, the suction filter-I has a connection to the pellet granulator, the outlet of which is directed to one of the collections of finished products, on the lid of a heated reactor The converter has a nozzle for supplying the ammonia-air mixture to the lower zone of the reactor through a disperser; a rod with electrodes connected to a pH meter and having an interface h shut-off valve with a pipeline for supplying ammonia-air mixture, the lower discharge pipe of the oxyhydrate pulp from the reactor-neutralizer has a connection with the suction filter-II the outlet of the mother liquor from which is directed to the collection tank, and the outlet of the wet paste of zirconium oxide from the suction filter is directed in a series-connected drying chamber, a calcining furnace and a collection of the target product.

Description

The proposed utility model relates to the field of chemical technology and, in particular, to technological conversions used in the technology of inorganic substances, plants, compartments and complexes for the production of metal oxides, in particular zirconium oxide ZrO ₂ used in the production of materials for radio electronics.

Known technological redistribution for the production of metal oxides (I.P. Mukhlenov, E.I.Dobkin, V.I. Deryuzhnin and others. Technology of catalysts: Chemistry, LO, 1989, pp. 92-120), including a container with initial solutions, a reactor for the deposition of metal hydroxides, containers with alkaline reagents, a decanter, filter equipment, a filtrate collector, a drying chamber, a calcining furnace, devices for granulating and / or tabletting, collections of the finished target product - catalysts based on metal oxides for various purposes.

A disadvantage of the known technological redistribution is the fact that it does not allow the production of zirconium dioxide for the electronics industry. Another disadvantage of the known technological redistribution is the lack of equipment for processing, neutralization and disposal of industrial wastes.

There is a known technological limit for the precipitation of hardly soluble compounds from aqueous solutions, including metal hydroxides and the production of metal oxides (S. S. Naboychenko, N. G. Ageev, A. P. Doroshchenko and others. Processes and apparatuses of non-ferrous metallurgy. Yekaterinburg, Izd. Ural State Technical University, 1997. p. 414-418).

A well-known technological redistribution includes a source solution collector, a precipitation reactor, a filter thickener, a clarified solution collector, a condensed pulp collector, a filter, a filtrate collector, cake repulators, a promptor collector and a metal-containing sludge (cake) collector.

The disadvantage of this known technological redistribution is that it lacks the necessary equipment for the production of zirconium dioxide, suitable for the production of electronic equipment and equipment for the disposal and disposal of generated waste and industrial products.

The objective of the proposed utility model is to provide conditions for the production of zirconium dioxide suitable for the production of electronic equipment materials, and to ensure the conditions for processing the disposal and disposal of the resulting gaseous production wastes.

The technical result that can be obtained by implementing the utility model is to increase the purity of the target product - zirconium dioxide and prevent environmental pollution by highly toxic industrial waste.

A well-known technological redistribution includes a source solution collector, a precipitation reactor, a filter thickener, a clarified solution collector, a condensed pulp collector, a filter, a filtrate collector, cake repulators, a promo collector, and a container for a metal-containing precipitate (cake).

The disadvantage of this known limit is that it lacks the necessary equipment for the production of zirconium dioxide, suitable for the production of electronic equipment and equipment for the disposal and disposal of generated waste and industrial products.

Of the known analogues, the closest in technical essence and achievable technical result to the utility model proposed in this application is the well-known technological redistribution for the production of zirconium dioxide (Research and development of technological processes and their hardware design for the production of inorganic materials for special purposes // Basic Research , 2006, No. 1, p.81) - adopted as a PROTOTYPE.

The technological redistribution of the prototype includes a tank with a stirrer and a loading door for preparing the initial aqueous solution of zirconium chloride; ZrOCl ₂ and / or ZrCl ₄ metering hopper having a tight connection through shut-off and control valves with the loading hatch of the agitator tank; a reactor for the deposition of zirconium oxyhydrate (reactor-converter) on the upper cover of the reactor there are nozzles connected to the tank for the preparation of the initial solution of zirconium chloride / oxychloride and with a tank for the preparation of alkali solution (NaOH, NH ₄ OH, etc.); discharge from the reactor is directed to a filter press to separate the precipitate of zirconium oxyhydrate from the mother liquor; The trough of the filter press has connections with the drying chamber and the calcining furnace connected in series with each other.

This hardware and technological redistribution provides the production of inorganic sorbents, collectors and carriers from ZrOCl ₂ and / or ZrCl ₄ for the subsequent production of general-purpose catalysts.

The objective of the proposed utility model is to provide conditions for the production of zirconium dioxide suitable for the production of materials for electronic equipment, and to ensure the conditions for the processing, neutralization and disposal of generated waste and industrial products.

The technical result that can be obtained by implementing a utility model is to increase the purity of the target product -

zirconium dioxide and the prevention of environmental pollution by highly toxic waste products.

The problem is solved with the achievement of the above technical result by the proposed utility model - “Technological redistribution for the production of zirconium oxide”, including (Fig. 1) a tank (1) with a stirrer and a loading hatch for preparing the initial aqueous solution of zirconium chloride, a hopper (2) zirconium chloride and / or oxychloride, which is tightly connected through shut-off and control valves with the loading hatch of the tank (1) with a stirrer, reactor-neutralizer (3) for precipitation from zirconium oxyhydrate, filter udovanie, the drying chamber (4) and a calcining furnace (5). New in the proposed model is that between the tank (1) for preparing the initial solution of zirconium chloride / oxychloride and the heated reactor (3) with a stirrer, a heated reactor (6) is additionally equipped, equipped with a heated jacket, dispersant (7) of ammonia-air mixture, connected through a pipeline (8) with a heated container (9) into which a bubbler (10) of compressed air is placed, a rod (11) with electrodes connected to a pH meter (12) is installed in the reactor (6) to clean the initial solution from impurities pairing cut-off valve (13) with a pipeline line (8) for supplying ammonia-air mixture to the reactors; on the top cover of the reactor (6) for cleaning the initial solution of zirconium chloride / zirconium oxychloride there is a loading hatch (14) for feeding into the reactor (6 ) parts (3-10%) of zirconium oxyhydrate sediment from the surface of the suction filter-II (27), the lower discharge pipe (15) from the impurity purification reactor of the initial solution is connected through shut-off valves (16) to the suction filter-I (17) , the discharge from which mother solutions of zirconium chloride purified from impurities is directed through apornuyu valve (18) to the reactor-converter (3) for the deposition of the cleaning solution of zirconium oxyhydrate precipitate suction filter I (17)

has compounds with a sediment granulator (19), the output of which is directed to one of the product collections (granular inorganic commercial sorbents and / or “carriers” for subsequent production of catalysts, for example, organic synthesis catalysts, oil cracking catalysts, etc., on the cover of the heated reactor-converter (3) with a stirrer to neutralize the solution purified from impurities and deposit zirconium oxyhydrate there is a pipe (21) for connection with a filter press II (17), a pipe for feeding into the lower zone the reactor (3) through the dispersant (22) of the ammonia-air mixture, a rod (23) with electrodes is placed in the reactor (3), connected to a pH meter (24), which is interfaced via a shut-off valve (25) with a pipeline (8) for supplying ammonia-air mixture leaving the tank (9) with aqueous ammonia, the pipe (26) of the lower discharge of the oxyhydrate pulp from the reactor (3) has a connection with the suction filter II (27), the output of the mother liquor of ammonium chloride from which is directed to the collection tank (28) - for the subsequent shipment of this solution to consumers, the output of the solid phase is a loose sediment of zirconium oxyhydrate from the suction filter II (27) is sent to the drying chamber (4), the calcining furnace (5) and the collection (23) of the target product - high-purity zirconium oxide (> 99.99%) suitable for the production of special materials, for example for radio ceramics.

The combination of the above equipment, which is part of the "Technological redistribution for the production of zirconium oxide" according to the proposed technical solution provides, as shown by the results of experimental and industrial tests, the solution of the problem and the achievement of the technical result, which consists, in particular, in ensuring the conditions for obtaining zirconium dioxide, suitable for the production of materials for electronic equipment, ensuring the conditions for processing, disposal and disposal of industrial products waste duction in enhancing purity of the desired product (ZrO ₂₎ and

prevention of environmental pollution by toxic waste products.

Implementation of a utility model.

The proposed utility model - "Technological redistribution for the production of zirconium oxide" works as follows:

A certain (not more than 70-80% of the tank volume) distilled water is poured into the tank (1) with the mixer from the “distribution” line, then when the mixer is switched on, the calculated amount of ZrCl _{2 is} loaded into the tank (1) through the hopper (2) and / or ZrOCl ₂ . Stirring is carried out until complete dissolution to obtain the initial solution of zirconium chloride (oxychloride, zirconyl zirconium chloride), after which from the tank (1) the initial solution is poured into a heated reactor (6) equipped with a heated jacket and dispersant (8) of an ammonia-air mixture . The initial solution in the reactor is heated (mainly to 60-90 ° C) with stirring, which leads to further hydrolysis of zirconium ions and the formation of polynuclear hydroxocomplexes [Zr (OH) ₈ ] ⁸⁺ and others in the solution and the release of hydrochloric acid into the solution. With the heated hydrolyzed zirconium-containing solution, then, with the stirrer turned on, a wet (50-80% hyd.) Paste of zirconium oxyhydrate obtained in the reactor (3) in the previous operation (in the previous cycle of the ZrO ₂ production process) is loaded through the loading hatch (14) - from filter II (27). The amount of paste loaded into the solution (6) is 5-10% of the total volume (or mass) of the wet paste of zirconium oxyhydrate obtained by neutralizing (pH 5-8) a zirconium-containing solution in the reactor (3) and filtered on a suction filter (27) in the previous operation, in the previous technological cycle of processing the initial zirconium-containing solution to obtain the target product - ZrO ₂ . The pulp (suspension) formed in the reactor (6) is stirred with heating (60-90 ° C) for 0.5-1 hours. When this happens

partial dissolution of the paste as a result of the interaction of free hydrochloric acid in solution due to the hydrolysis of the zirconium salt with a precipitate of zirconium oxyhydrate, in addition, sorption of microimpurities of foreign metals present in the initial zirconium-containing solution by precipitation of zirconium oxide occurs. For a more complete removal of these microimpurities from the solution and a deeper purification of the solution from microimpurities (mainly heavy non-ferrous metals), an ammonia-air mixture is supplied to the reactor (6) through a bubbler (7) from the pipeline (8) with the mixer turned on. The flow of the ammonia-air mixture is carried out for 0.5-1 hours until the pH in the pulp reaches 1.0-2.5. The pH value in the pulp is controlled by a pH meter (12), which has “mates” with a shut-off valve (13) installed on the pipeline (8) for supplying the ammonia-air mixture. Upon reaching a predetermined pH in the pulp, the valve (13) "works" and the flow of ammonia-air mixture into the reactor (6) is stopped. After that, the pulp in the reactor is stirred for 0.5-1.0 hours and maintained without stirring for 1-3 hours. As a result of these operations in the reactor (6), the initial zirconium-containing solutions are purified from trace elements (to a purity of 99.99%) due to the combination of sorption, precipitation, and coprecipitation processes. After sedimentation, the pulp from the reactor (6) is fed (by gravity or using a pump - not shown in Fig.) To the Nutsche filter I (17), the mother liquor is a solution of chloride (oxychloride, zirconyl chloride) of zirconium, purified of trace elements through a shut-off the reinforcement (18) is sent to a neutralizing reactor for subsequent precipitation from a purified solution of a precipitate of zirconium oxyhydrate - intermediate products to obtain the target ZrO ₂ . The precipitate on the Nutsche filter I (17) is washed with water and discharged into a granulator (19), in which using well-known technological methods, devices and devices, for example, by extrusion combined with heat treatment of the precipitate, a granular commodity product is obtained -

inorganic sorbent for the purification of various technological solutions and wastewater from toxic substances, for the extraction of radionuclides, etc .; or the resulting granular product is then used as a carrier for the production of various catalysts used, for example, in fine organic synthesis, etc. The zirconium-containing solution purified from microimpurities in the reactor (3) is neutralized to pH 5-8 by feeding it into the lower mixer the reactor zone through the dispersing device (22) of the ammonia-air mixture - from the pipeline (8) exiting from the heated tank (9) with ammonia water - an aqueous solution of NH ₄ OH, in the lower zone of which a bubbler (10) of compressed air, the supply of ammonia-air mixture in the reactor (3) is carried out until the pH value in the pulp is 5-8. The pH value is measured and monitored with a pH meter using electrodes located in a rod (23) connected to a pH meter (24). When the specified pH value (in the range from 5 to 8) is reached in the pulp - in the reactor (3), a shut-off valve (25), coupled with a pH meter (24), is activated on the line - pipeline (8); the flow of ammonia-air mixture into the reactor is then stopped. After that, to obtain a chemically homogeneous paste of zirconium oxyhydrate, the pulp in the reactor (3) is stirred for 0.5-2 hours, and then, through the lower discharge pipe (26), the oxyhydrate pulp is fed to suction filter II (27), the mother liquor (solution NH ₄ Cl), sent to the collection (28), from where it is shipped to consumers.

The precipitate of zirconium oxyhydrate on a suction filter-II (27) is washed from the mother liquor with distilled water and first placed in a drying chamber (4), and then in a calcining furnace (5). The finished target commercial product, high-purity zirconium oxide ZrO _{2, is} discharged from the calcining furnace (5) into a collector (29) for cooling and subsequent packaging and shipping to consumers - for the production of special-purpose materials, for example, electronics materials.

Claims (1)

A hardware-technological complex for the production of zirconium oxide, including a tank with a stirrer for preparing the initial solution of zirconium chloride, a hopper-dispenser of chloride and / or zirconium oxychloride, which has a sealed connection through a shut-off control device with a loading hatch of the tank, a reactor-neutralizer for sedimentation from solution zirconium oxyhydrate, filter equipment, drying chamber, calcining furnace, characterized in that between the tank for preparing the initial solution of zirconium chloride and heated a reactor with a stirrer for precipitating zirconium oxyhydrate is additionally equipped with a reactor equipped with a heated jacket, an ammonia-air dispersant, connected through a pipeline with a heated tank with ammonia water, into which a compressed air bubbler is placed, a rod with electrodes is installed in the reactor for cleaning the initial solution from impurities connected to a pH meter coupled through a shut-off valve to the ammonia-air mixture supply pipe on the top cover of the reactor to clean the feed of impurities there is a loading hatch for feeding into the reactor part of the wet paste of zirconium oxyhydrate obtained in a heated neutralizing reactor for precipitation from a solution of zirconium chloride purified from impurities, the lower discharge pipe from the reactor for purification of the initial solution from impurities is connected through a shut-off valve to the suction filter I; the discharge from which the mother solutions of zirconium chloride, purified from impurities, is directed through shut-off valves to a neutralizing reactor to precipitate zirconium oxyhydrate, the suction filter-I has a connection to the pellet granulator, the outlet of which is directed to one of the collections of finished products, on the lid of a heated reactor The converter has a nozzle for supplying the ammonia-air mixture to the lower zone of the reactor through a disperser; a rod with electrodes connected to a pH meter and having an interface h shut-off valve with a pipeline for supplying ammonia-air mixture, the lower discharge pipe of the oxyhydrate pulp from the reactor-neutralizer has a connection with the suction filter-II, the outlet of the mother liquor from which is directed to the collection tank, and the outlet of the wet paste of zirconium oxide from the suction filter is II is sent to a drying chamber, a calcining furnace and a target product collector connected in series.