RU84011U1 - COMPLEX OF EQUIPMENT FOR THE PRODUCTION OF VANADIUM PENTAOOXIDE AND THE DISPOSAL OF WASTE WASTE - Google Patents

Abstract

A complex of equipment for the production of vanadium pentoxide and the neutralization of waste generated, including a reactor with a stirrer for alkaline treatment of vanadium oxytrichloride, hermetically connected through a switchgear with a transported container with vanadium oxytrichloride, a tank for preparing a solution of sodium hydroxide, a tank for preparing a solution of ammonium chloride, a crystallizer tank ammonium metavanadate, filter-1 for separating from the suspension a precipitate of ammonium metavanadate and washing it, a calcining furnace, collecting tanks uterine solutions and ammonium metavanadate feed, ammonium metavanadate precipitate-repulse reactor connected to filter-1, a reactor for neutralizing mother liquors and ammonium metavanadate promoter connected to an iron (II) -containing solution dispenser and supply tank, and to a preparation tank a solution of sodium hydroxide, filter-2 for separation of precipitate of iron oxyhydrate with impurities of vanadium from the pulp, characterized in that the reactor for the decomposition of vanadium oxytrichloride has a connection with the tank for the preparation of a working solution ora of sodium hydroxide and with a tank containing a salt solution of sodium hydroxide, connected to the collection tank of filtrates after alkaline repulpation of the titanium cake-precipitate of titanium oxyhydrate with vanadium impurities, the lower discharge pipe of the pulp from the reactor for decomposition of technical vanadium oxytrichloride is directed through the pump and the shutoff-regulating fittings for filter-3, the output from filter-3 of a solution of ammonium metavanadate purified from the solid phase (titanium cake-precipitate of titanium oxyhydrate) is sent to a collection tank connected to the tank

Description

The proposed utility model relates to the field of chemical technology of inorganic substances, in particular to technological equipment for the hydrometallurgical processing of vanadium-containing raw materials and can be used at enterprises of non-ferrous and ferrous metallurgy and the chemical industry to obtain commercial V ₂ O ₅ from technical vanadium oxytrichloride containing up to 10- 70% TiCI ₄ and impurities of other metals.

A technical solution is known (see “Research and development of a technology for purifying vanadium from impurities to obtain commercial vanadium pentoxide” / Journal: Complex use of mineral raw materials, 1997, No. 1 p. 56-61), including a reactor for leaching technical vanadium pentoxide, a tank with alkali solution, filter-1 to isolate the insoluble residue, crystallizer NH ₄ VO ₃ , filter-2, calcination furnace.

A disadvantage of the known technical solution is a significant loss of vanadium with production waste, an unsatisfactory degree of extraction of vanadium from the feedstock into a marketable product, and environmental pollution with vanadium-containing production waste. Another disadvantage of this known technical solution is the lack in its composition of equipment for producing V ₂ O ₅ from technical vanadium oxytrichloride.

Of the known analogues, the closest in technical essence and the technical result achieved is the well-known "Hardware and technological complex for the production of vanadium pentoxide" (RF Patent ПМ No. 74636 by application No. 2008105007 with prior. Dated 11.02.2008. Reg. And publ. July 10, 2008, Bull. No. 19) - adopted as a PROTOTYPE.

The technical solution for the prototype includes the following main technological equipment: a reactor for alkaline treatment of the initial vanadium-containing materials, which is hermetically connected to a transported container with vanadium oxytrichloride, and the outlet of vanadium oxytrichloride from the transported tank is directed through a shut-off and control valve to a switchgear located in the reactor below the mixer. A reactor with a stirrer for alkaline treatment of the starting vanadium-containing materials is connected to a tank for preparing and supplying a solution of sodium hydroxide, a crystallization tank of ammonium metavanadate, having a connection with a series-installed metering tank and a storage tank for preparing and supplying a solution of ammonium chloride, the lid of the crystallizer tank has a loading hatch in which the outlet from the sodium chloride collection hopper is directed; after filter-1, a ammonium metavanadate-recovery tank is installed, a pipe the bottom discharge of the suspension, from which it has a connection with filter-1, for separating the precipitate of ammonium metavanadate from the suspension and washing it, a calcining furnace, a collection tank of mother liquors and an ammonium metavanadate feed, a reactor for neutralizing and neutralizing vanadium-containing wastewater, connected through a dispenser to a collection tank of iron (II) containing solutions and a tank for preparing and supplying a solution of sodium hydroxide, a reactor for neutralizing and neutralizing vanadium-containing wastewater is connected to a filter-2 for separation from

precipitate of iron (II and III) oxyhydrates with impurities of vanadium compounds.

The technical solution according to the prototype provides the production of commercial vanadium pentoxide from commercial vanadium oxytrichloride (99.0-99.9% VOCl ₃ ) and makes it possible to neutralize wastewater (waste) from the production of vanadium pentoxide — mother liquors and wastes of ammonium metavanadate.

The disadvantage of the technical solution - "Hardware-technological complex" according to the prototype is the lack of the necessary equipment to obtain commercial vanadium pentoxide from technical vanadium oxytrichloride, containing in addition to VOCl ₃ up to 10-70% titanium tetrachloride - TiCl ₄ . Another disadvantage of the technical solution known from the prototype is the large volume of non-utilizable wastewater containing an increased amount of vanadium, which then, according to the prototype, goes into secondary waste - a precipitate of iron oxyhydrate.

The objective of the proposed utility model is the creation of a new technological complex, the combination of equipment of which makes it possible to obtain commercial vanadium pentoxide from technical vanadium oxytrichloride, while ensuring a high degree of vanadium extraction from the feedstock into commercial products.

The technical result that can be achieved by implementing the proposed model is to significantly reduce the loss of vanadium with waste and industrial products, increasing the "yield" of vanadium compounds in the finished commercial product - commercial vanadium pentoxide.

The problem is solved with the achievement of the above technical result by using the proposed utility model - "Complex equipment for the production of vanadium pentoxide and

the neutralization of waste generated ”, including a reactor (1) with a stirrer for alkaline treatment of vanadium oxytrichloride, hermetically connected through a dispenser (2) with a transported container (3) with vanadium oxytrichloride, tank (4) for preparing sodium hydroxide solution, tank (5) for the preparation of a solution of ammonium chloride, a crystallization tank (6) of ammonium metavanadate, filter-1 (7) for separating ammonium metavanadate from the suspension and washing it, a calcining furnace (9), a collection tank (10) of mother liquors and a metavan ammonium atat, reactor-repulpator (8) ammonium metavanadate precipitate connected to filter-1, (7), reactor (11) for neutralizing the mother liquors, and ammonium metavanadate feed connected to the dispenser (12) and the feed tank (13) iron ( II) -containing solutions, and with a tank for preparing a solution of sodium hydroxide, filter-2 (14) to isolate iron oxyhydrate with vanadium impurities from the precipitate.

New in the proposed technical solution is that the reactor (1) for the decomposition of vanadium oxytrichloride has a connection with a tank (25) for the preparation of a working solution of sodium hydroxide and with a tank (26) containing a saline solution of sodium hydroxide connected to a filtration tank (17) ) after alkaline repulpation of titanium cake-sediment of titanium oxyhydrate with vanadium impurities, the pipe bottom discharge of pulp from the reactor (1) for decomposition of technical vanadium oxytrichloride is directed through the pump and shut-off and control valves to the filter -3 (18), the output from filter-3 of a solution of ammonium metavanadate purified from the solid phase (titanium cake - titanium oxyhydrate precipitate) is sent to a collection tank (28) connected to the tank by a crystallizer (6) ammonium metavanadate, the filter trough (19) 3 (18) is connected through a discharge and distribution device (20) to a collection hopper (21) of a titanium cake (a precipitate of titanium oxyhydrate), the output of which is directed to a transported container (22), a discharge and distribution device

(20) the trough (19) of filter-3 (18) also has a connection with a heated tank (23) for alkaline repulpation of a titanium cake (a precipitate of titanium oxyhydrate), on the cover of this tank there is a hatch (24.1) for loading the titanium cake and a pipe (24.2) ) connected to the tank (25) with a working solution of sodium hydroxide, having a connection with the tank (4) for preparing the initial concentrated solution of sodium hydroxide and a distribution line for distilled water, draining the pulp from the tank (23) for alkaline repulping of titanium cake through the lower discharge pipe , pump and piping water is directed to filter-3 (18), the output from filter-3 (18) of an alkaline solution containing sodium metavanadate after titanium cake repulpation is sent to a collection tank (17) having a connection with a tank (4) to prepare the initial concentrated sodium hydroxide solution and a tank (26) for sodium hydroxide salt solution, a lower discharge pipe (27) of sodium hydroxide salt solution is connected by a pipeline to the reactor (1) for alkaline treatment of technical vanadium oxytrichloride, the crystallizer tank (6) of ammonium metavanadate has a connection with the collection tank of the mother liquor (9) after isolating the ammonium metavanadate precipitate from the suspension on filter-1 (7), there is a pipe on the lid of the collecting tank (9) to connect to the tank (5) to prepare the initial concentrated solution of ammonium chloride, output promv ammonium metavanadate and parts (40-60%) of the mother liquor from filter-1 (7) are sent to a collection tank (10) connected to the reactor (11) for the neutralization of the mother liquors and the promotion of ammonium metavanadate from vanadium compounds. The output from filter-2 (14) of the sodium metavanadate solution purified from the solid phase (titanium cake - titanium oxyhydrate precipitate) is sent to a collection tank (29), and the output of iron oxyhydrate precipitate with vanadium impurities from filter-2 (14) is directed through a trough ( 15) and the unloading and distributing device (16) in the tank-repulpator (30) connected to the filter-2 (14) and the collecting hopper (31) unloaded into the transported container (32), the output of the commodity

Vanadium pentoxide from the calcining furnace (9) is directed to a storage and storage tank (33) connected in a filling machine (34).

Implementation of the proposed utility model

The proposed technical solution "Complex of equipment for the production of vanadium pentoxide and the disposal of waste generated" works and is operated in the following way (see. Fig.).

In a reactor (1) with a stirrer for alkaline treatment of vanadium oxytrichloride, sodium chloride (NaOH + NaCI) reverse salt solution from a tank (26) having a connection with a tank (4) is preliminarily filled (or pumped) to prepare the initial (concentrated - up to 20 -30% NaOH) of sodium hydroxide solution and also filtrates connected to the collection tank (17) after alkaline repulpation of titanium cake-precipitate of titanium oxyhydrate with vanadium impurities.

Note 1. During the start-up of the “Complex ...” (site, department, redistribution, etc.) in operation ie in the absence (at the beginning) of the "Complex ..." (site) of circulating alkaline solutions (NaOH + NaCI) in the tank (17), the working solution is initially poured (pumped) from the tank (25) into the reactor (1) to decompose VОСI ₃ (25) (5-15%) sodium hydroxide (obtained by diluting with distilled water the initial concentrated NaOH solution from the tank (4)).

When the mixer is switched on, the reactor (1) through the distribution device (2) under the layer of alkaline solution serves from the transported container (3) the initial technical vanadium oxytrichloride containing 30-90% VOCI ₃ and up to 10-70% TiCI ₄ and impurities of other metal chlorides . The resulting pulp is mixed, as a result of which chemical reactions of the decomposition of vanadium oxytrichloride occur in the reactor (1) with the formation of water-soluble sodium metavanadate and the precipitation of titanium oxyhydrates - TiO (OH) ₂ , Ti (OH) ₄ , TiO ₂ · H ₂ O, etc. pulp is fed (pumped) to filter-3 (18), which is mainly used as a filter press. Sodium Metavanadate Solution

purified from the solid phase - suspended particles (titanium cake-titanium oxyhydrate) are collected in a collection tank (28), titanium cake (precipitate of titanium oxyhydrate with impurities of vanadium compounds) is discharged from filter-3 (18) into a trough (19), from where this precipitate through a discharge and distribution device (20) it enters a collection hopper (21), or it is sent through a loading hatch (24.1) to a heated tank (23) with an agitator for repulping titanium cake (a precipitate of titanium oxyhydrate) in sodium hydroxide solution - in order to recover from sediment of vanadium compounds. Repulpation is carried out at W: T = 2 ÷ 5, T = 60-80 ° for 0.5-2 hours. The pulp is then pumped to filter-3 (18), the alkaline solution, purified from the precipitate of titanium oxyhydrate, from filter-3 (18), is collected in a collection tank (17), from where the solution enters the tank (26) and then through the lower discharge pipe (27) to the reactor (1). The precipitate of titanium oxyhydrate on the filter-3 (18), if necessary, is washed with a solution of sodium hydroxide and / or water, then this precipitate is discharged from the filter-3 (18) into the trough (19), from where this precipitate is through the unloading and distribution device (20) unload in a collection hopper (21), then in a transported container (22), with the help of which they are transported and loaded for further processing and disposal. Promoters diluted with NaOH and with a low concentration of vanadium from filter-3 (18) are sent to the collection tank (10) for their subsequent neutralization from vanadium in the reactor (11).

In order to obtain a precipitate of ammonium metavanadate and then vanadium pentoxide from a NaVO ₃ solution, the sodium metavanadate solution from the collection tank (28) is sent to the crystallizer tank (6), into which a reverse solution (NH ₄ CI +) is supplied (poured) from the tank (9). NaCI), obtained as a result of "before strengthening" - according to NH ₄ CI - mother liquors (after separation of the precipitate from the suspension (NH ₄ VO ₃ )) obtained in previous operations of the technological cycle of processing technical VOCI ₃ and obtaining NH ₄ NO ₃ and V ₂ O ₅ .

Note 2. When commissioning the "Complex ..."("Section" of the department) into operation, i.e. in the absence of reverse solutions (NaCI + NH ₄ CI) in the tank (9), an ammonium chloride solution is initially supplied from the tanks (5) or (5.1) to the crystallization tank (6).

After processing the sodium metavanadate solution in a crystallizer tank (6) with a solution containing NH ₄ CI, ammonium metavanadate NH ₄ VO ₃ is precipitated and a suspension is formed, which is fed to filter-1 (7) to isolate the ammonium metavanadate precipitate. The precipitate on filter-1 (7) is washed with 1-3 volumes of a diluted solution of NH ₄ CI - from the tank (5.1). Then, the NH ₄ VO ₃ precipitate is discharged from filter-1 (7) into a “trough” from which the precipitate is fed through the unloading and separation device to the reactor-repulpator (8), into which the diluted solution is poured (pumped) from the tank (5.1) ammonium chloride. The suspension after repulpation from the reactor-repulpator (8) is pumped onto filter-1 (7), the filter cake is washed again (washed with NaCI) with diluted NH ₄ CI solution, the washed cake of NH ₄ VO ₃ from filter-1 (7) is discharged and sent to a calcining furnace (9). After calcining the precipitate, the resulting powdered commercial vanadium pentoxide is discharged into a storage and storage tank (33), from which commercial V ₂ O _{5 is} packed into a sealed container using a filling machine (34) and shipped to consumers.

Stock solutions - after separation of the precipitate from the suspension, NH ₄ VO ₃ on filter-1 (7) is divided into two parts (into two volumes), one of which is fed into the solution preparation tank (NH ₄ CI + NaCI + (Na-NH ₄ ) VO ₃ ), then used to crystallize NH ₄ VO ₃ in the crystallizer tank (6). Another part of the mother liquors (containing vanadium compounds) and ammonium metavanadate promoters, as well as other vanadium-containing effluents (formed during various operations of the general technological scheme) are collected in a collection tank (10 combined assembly-averaging tanks), from which

the combined vanadium-containing chloride solutions and wastewater are fed to the reactor to neutralize the vanadium compounds. To this end, with the stirrer switched on, first a solution containing a ferrous iron salt: FeCI ₂ or FeSO _{4 is} first sequentially fed from the dispenser connected to the supply tank (13), then sodium hydroxide solution is supplied from the tank (25) to the reactor (11), the resulting oxyhydrate pulp is carefully transferred and pumped onto filter-2 (14). The precipitate of iron oxyhydrate with vanadium impurities is separated from the chloride solution, which is sent to a collection tank (29). The precipitate from filter-2 (14) is discharged into a trough (15) and sent through a discharge distributor (16) to a recovery tank (30), after repulpation in water, the precipitate is pumped to filter-2 (14), washed with water, they are discharged from filter-2 (14) into a collection hopper (31), from which the precipitate is discharged into a transportable container (32) and sent for further processing, for example, for drying and calcining with subsequent sale of the precipitate as technogenic iron-vanadium raw materials.

A complex of equipment for the production of vanadium pentoxide and the disposal of waste

1. A reactor with a stirrer for alkaline treatment of technical vanadium oxytrichloride.

2. Switchgear for uniform distribution (VOCI ₃ + TiCI ₄ ) in the lower zone of the reactor (1).

3. Transported container with the original vanadium oxytrichloride (VOCI ₃ + TiCI ₄ ).

4. A tank with a stirrer for preparing the initial concentrated (30-40%) sodium hydroxide solution.

5. Tank with a stirrer for preparing the initial concentrated solution of ammonium chloride.

5.1. Tank with a working (diluted) solution of ammonium chloride.

6. A crystallizer tank of ammonium metavanadate (with a “jacket” for cooling the suspension).

7. Filter-1 for separation of the precipitate NH ₄ VO ₃ from the suspension and its washing.

8. The reactor-repulpator sediment NH ₄ VO ₃ in a dilute solution of ammonium chloride.

9. A calcination furnace for the decomposition of ammonium metavanadate and the production of commercial vanadium pentoxide V ₂ O ₅ .

10. Tank-collector (prefabricated-averaging capacity) production of ammonium metavanadate and parts (40-60%) of the mother liquor, after separation of the precipitate NH ₄ VO ₃ from the suspension

11. A reactor for the neutralization of vanadium compounds from mother liquors and the promotion of ammonium metavanadate.

12. Dispenser of iron (II) -containing solutions (FeCl ₂ or FeSO ₄ ).

13. Consumption tank with an iron (II) -containing solution (FeCI ₂ or FeSO ₄ ).

14. Filter-2 for the precipitation of iron oxyhydrate from the pulp with impurities of vanadium compounds.

15. Trough of filter-2 (14).

16. 3-head distribution (unloading) device.

17. A collection tank of filtrates - solutions (NaCI + NaOH + NaVO ₃ ) after alkaline (NaOH) repulpation of titanium cake - a precipitate of titanium oxyhydrite with vanadium impurities isolated from pulp after alkaline treatment of technical vanadium oxytrichloride (VOCI ₃ + TiCI ₄ ).

18. Filter-3 for isolating from the pulp (after alkaline treatment - decomposition of technical VOCI ₃ ) the solid phase (titanium cake - precipitate of titanium oxyhydrite with impurities of vanadium compounds).

19. "Trough" of filter-3 (18) for unloading from the filter-3 precipitate of titanium oxyhydrate.

20. The discharge and distribution device of the trough (19) filters-3 (18), which supplies the precipitate of titanium oxyhydrate to the collection hopper (21) of the titanium cake, either through the hatch (24.1) or into the heating tank (23) for alkaline repulpation of titanium Keka is a precipitate of titanium oxyhydrite.

21. Prefabricated bunker of titanium cake - a precipitate of titanium oxyhydrate, with impurities of vanadium compounds.

22. Transported container for sending titanium cake for processing and disposal, with the receipt of marketable products suitable for sale at the consumer.

23. A heating tank with a stirrer for alkaline (NaOH) titanium cake repulpation - with the aim of retrieving vanadium compounds (NaVO ₃ ) and returning them to the production of commercial vanadium pentoxide.

24.1 Hatch on the tank lid (23) for loading titanium cake for the purpose of its subsequent alkaline repulpation.

24.2 Pipe for supplying NaOH solution to the tank (23) for repulping titanium cake.

25. Tank for the preparation and supply of a working solution (5-15%) of sodium hydroxide intended for alkaline repulpation of titanium cake, for washing on a filter-3 of titanium cake and for decomposition of technical VOCI ₃ .

26. Tank for the preparation of saline (NaCI) sodium hydroxide solution, designed for the decomposition of technical VOCI ₃ .

27. The lower discharge pipe of the saline solution (NaOH + NaCI) from the collection tank (26).

28. Collective capacity of a solution of sodium metavanadate obtained after isolation on the filter-3 (18), a precipitate of titanium oxyhydrate formed in the reactor (1).

29. Collective container purified from the solid phase (precipitate of iron oxyhydrate with impurities of vanadium) and neutralization of chloride solutions and wastewater from vanadium.

30. Tank-repulpator precipitate of iron oxyhydride with impurities of vanadium.

31. Precast hopper sediment iron oxyhydrate.

32. A transported tank for loading sludge from the hopper (31) and its direction for processing to produce marketable products.

33. Storage and storage capacity for commercial vanadium pentoxide.

34. 3-filling machine - to ensure the packaging and shipment of commodity V ₂ O _{5 to} consumers.

Claims (1)

A complex of equipment for the production of vanadium pentoxide and the neutralization of waste generated, including a reactor with a stirrer for alkaline treatment of vanadium oxytrichloride, hermetically connected through a switchgear with a transported container with vanadium oxytrichloride, a tank for preparing a solution of sodium hydroxide, a tank for preparing a solution of ammonium chloride, a crystallizer tank ammonium metavanadate, filter-1 for separating from the suspension a precipitate of ammonium metavanadate and washing it, a calcining furnace, collecting tanks uterine solutions and ammonium metavanadate feed, ammonium metavanadate precipitate-repulse reactor connected to filter-1, a reactor for neutralizing mother liquors and ammonium metavanadate promoter connected to an iron (II) -containing solution dispenser and supply tank, and to a preparation tank a solution of sodium hydroxide, filter-2, for separating from the pulp a precipitate of iron oxyhydrate with impurities of vanadium, characterized in that the reactor for the decomposition of vanadium oxytrichloride has a connection with a tank for preparing a working solution ora of sodium hydroxide and with a tank containing a salt solution of sodium hydroxide, connected to the collection tank of filtrates after alkaline repulpation of the titanium cake-precipitate of titanium oxyhydrate with vanadium impurities, the lower discharge pipe of the pulp from the reactor for decomposition of technical vanadium oxytrichloride is directed through the pump and the shutoff-regulating fittings for filter-3, the output from filter-3 of a solution of ammonium metavanadate purified from the solid phase (titanium cake-precipitate of titanium oxyhydrate) is sent to a collection tank connected to the tank by the ammonium metavanadate crystallizer, the filter-3 trough is connected to the collecting hopper of the titanium cake (titanium oxyhydrate precipitate) through a discharge and distribution device, the outlet from which is directed to a transportable container, the filter-3 discharge and distribution device also has a connection to a heated alkaline repulse tank titanium cake (precipitate of titanium oxyhydrate), on the lid of this tank there is a hatch for loading titanium cake and a pipe connected to the tank with a working solution of sodium hydroxide having a connection to the tank for preparing the initial concentrated sodium hydroxide solution and a distilled water distribution line, draining the pulp from the tank for alkaline repulpation of titanium cake through the lower discharge pipe, the pump and pipeline are directed to filter-3, the output from filter-3 of the alkaline solution containing After the titanium cake is repulped, the sodium metavanadate is sent to a collection tank having a connection with the tank for preparing the initial concentrated sodium hydroxide solution and the tank for the saline solution sodium oxide, the lower discharge pipe of the sodium hydroxide salt solution is connected by a pipeline to the reactor for the alkaline treatment of technical vanadium oxytrichloride, the ammonium metavanadate crystallizer tank has a connection with the mother liquor collection tank after precipitation of ammonium metavanadate from the suspension on filter-1, on the lid of the collecting tank there is a nozzle for connection to the tank for the preparation of the initial concentrated solution of ammonium chloride, the output is the promotion of ammonium metavanadate and parts of the mother liquor and from filter-1 it was sent to a collection tank connected to a reactor for neutralizing the mother liquors and washing ammonium metavanadate from vanadium compounds, the output from filter-2 of a sodium metavanadate solution purified from the solid phase (titanium cake-precipitate of titanium oxyhydrate) was sent to a collection tank, and the output of the precipitate of iron oxyhydrate with vanadium impurities from the filter-2 is directed through the trough and the unloading and distribution device to the recovery tank connected to the filter-2, and a collection hopper discharged into the transported tank , Marketable yield of vanadium pentoxide calcining furnace is directed in the flow-collecting tank connected to the bagger machine.