RU84383U1 - FLOW TECHNOLOGICAL LINE FOR PROCESSING VANADIUM OXYTICHLORIDE WITH PRODUCTION OF VANADIUM PENTAOXIDE AND DISPOSAL OF PRODUCTION WASTE - Google Patents

Abstract

The proposed utility model relates to the field of metallurgy and chemical technology of inorganic substances, in particular to technological production lines for complex hydrometallurgical processing and technical vanadium oxytrichloride, with the production of commercial V ₂ O ₅ , neutralization and disposal of the resulting solid and liquid wastes. The developed technical solution can be used at the enterprises of non-ferrous and ferrous metallurgy and the chemical industry to obtain marketable, in addition to V ₂ O _5, from technical vanadium oxytrichloride containing VOCl ₃ titanium tetrachloride and impurities of other metal chlorides. The objective of the proposed technical solution is to create a new in-line technological line, 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 VOCl ₃ in V ₂ O ₅ . The technical result that can be achieved by implementing the proposed utility model is to significantly reduce the loss of vanadium with waste and industrial products, increasing the “yield” of vanadium compounds in commercial products - vanadium pentoxide. The problem is solved with the achievement of the above technical result in the implementation of the proposed utility model - “In-line production line for processing vanadium oxytrichloride to obtain vanadium pentoxide and disposal of production waste”, including a reactor for the decomposition of vanadium oxytrichloride in an alkaline solution, connected through a distribution device with a transported tank for vanadium oxytrichloride, a tank with a stirrer for preparing the initial alkali solution alkali metal metavanadate solution, a tank with a mixer for preparing the initial solution of ammonium chloride distilled water distribution line, ammonium metavanadate crystallizer tank, filter-1 for isolating ammonium metavanadate from the suspension, calcining furnace equipped with a filling unit, collection tanks of vanadium-containing mother liquors and promvod, installation for extracting from the mother liquor and promvod vanadium compounds, which includes tank equipment, reactors, chemical dispenser, filters, pipelines, a drying chamber and / or a calcining furnace, pumps, shut-off and control valves, a collection tank for chloride solutions purified from vanadium compounds.

New in the proposed technical solution is that the reactor for the decomposition of vanadium oxytrichloride has a connection with a tank for the preparation and supply of a salt solution of potassium hydroxide connected to a filter press-2 and a tank with an initial solution of potassium hydroxide, a crystallization tank of ammonium metavanadate is connected to a prefabricated - a flow tank of filtrates - solutions of potassium metavanadate after separation of the precipitate of titanium oxyhydrate and with a tank for the preparation and supply of a mixed solution of ammonium and potassium chlorides, the lower discharge pipe bullets Fe from the reactor for the decomposition of technical vanadium oxytrichloride in a potassium hydroxide salt solution is connected to the inlet of the filter press-2, the outlet of which of the solid phase, the precipitate of titanium oxyhydrate, is directed through the trough of the filter press-2 to the titanium oxyhydrate recovery tank connected to the tank for the preparation and supply of potassium hydroxide solution, the output of the solid phase from the filter press-2 is also directed through a shut-off switchgear to a collection and consumable sediment hopper having an unloading hatch, a collection tank for cleaning solutions of potassium and ammonium chlorides exited from vanadium, it is connected to a heated reactor with a stirrer equipped with a loading hatch, into which the magnesium and / or potassium salt waste wastes are dispensed from the bunker, containing potassium, magnesium and other metal impurities, discharge concentrated chloride solutions from a heated reactor with a stirrer is directed to an evaporator, a vacuum crystallization unit, the discharge unit of which has connections to a mixed chlorine drying unit ide ammonium, potassium and magnesium, the output of the dryer is directed to ready-feed bin commodity output coupled to the filling machine.

Description

The proposed utility model relates to the field of metallurgy and chemical technology of inorganic substances, in particular to production lines for hydrometallurgical processing of technical vanadium oxytrichloride to produce marketable V ₂ O ₅ , rendering harmless and disposing of solid and liquid wastes generated. The developed technical solution can be used at the enterprises of non-ferrous and ferrous metallurgy and the chemical industry to obtain commercial V ₂ O ₅ from technical vanadium oxytrichloride containing, in addition to VOCl _3, titanium tetrachloride and impurities of other metal chlorides.

A technical solution is known (“Research and development of a technology for purifying vanadium from impurities to produce commercial vanadium pentoxide. // Journal.“ Complex use of mineral raw materials ”1997, No. 1 (99), pp. 56-61), including: a technical leach reactor vanadium pentoxide, a NaOH solution tank connected thereto, a filter for separating the insoluble residue, a crystallizer for separating from the NH ₄ VO ₃ solution, the outlet of which is connected to a filter for separating the ammonium metavanadate precipitate from the mother liquor and a decomposition furnace and calcining ammonium metavanadate to give marketable V ₂ O ₅ .

The disadvantages of the known technical solutions are significant losses 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. A disadvantage of this known technical solution is the lack of equipment for processing technical vanadium oxytrichloride in its composition.

Of the known analogues, the closest in technical essence and the technical result achieved is the well-known "Hardware-technological complex for the production of vanadium pentoxide" (RF Patent ПМ No. 74636 by application No. 2008105007 with prior, dated 11.02.2008; Zareg. 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, a transported container with vanadium oxytrichloride, shut-off and control valves, a switchgear located in the reactor below the mixer, a tank for the preparation and supply of sodium hydroxide solution, ammonium metavadanate crystallizer tank, having a connection with a series-installed metering tank and a storage tank for preparation and supply of a solution of ammonium chloride, on the lid of the crystallizer tank there is a loading hatch in which the outlet from the sodium chloride collection hopper is directed, after filter-1, an ammonium metavadanate recovery tank is installed, the lower discharge pipe of the suspension has a connection with filter-1 for isolation ammonium metavadanate sediment from the suspension and its washing, calcining furnace, mother liquor collection tanks and ammonium metavadanate feed, a reactor for the neutralization and neutralization of vanadium-containing wastewater, connected through an ator with 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 to separate Fe (II) and Fe (III) oxyhydrates from the sludge with impurities of vanadium compounds.

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

The disadvantage of the technical solution - "Hardware-technological complex ..." according to the prototype is the lack of the necessary equipment to produce commercial vanadium pentoxide from technical vanadium oxytrichloride, which in addition to VOCI ₃ contains up to 10-70% titanium tetrachloride - TiCl ₄ and impurities of other metals.

Another disadvantage of the technical solution according to the prototype is the formation of a large volume of non-utilized wastewater containing an increased amount of vanadium, which goes into the sediment of iron oxyhydrate when the wastewater is treated with Vestma toxic secondary waste.

The objective of the proposed technical solution is the creation of a new "In-line technological line ...", 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 VOCI ₃ in V ₂ O ₅ .

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

The problem is solved with the achievement of the above technical result in the implementation of the proposed utility model - "In-line production line for processing vanadium oxytrichloride to obtain vanadium pentoxide and disposal of industrial waste", including a reactor (1) for the decomposition of vanadium oxytrichloride in an alkaline solution, connected through a distribution device ( 2) with a transported container (3) for vanadium oxytrichloride, a tank (4) with a stirrer for preparing the initial alkali solution, prefabricated an alkaline metal metavanadate solution tank (5), a tank (6) with a stirrer for preparing the initial solution of ammonium chloride, a distillation water distribution line (8), a crystallization tank (9) of ammonium metavanadate, filter-1 (10) to isolate from a suspension of ammonium metavanadate sludge, a calcining furnace (11) equipped with a filling unit (11.1), collection tanks of vanadium-containing mother liquors (12) and a promvod (13), a plant (14) for extracting vanadium compounds from the mother liquor and promvod, which includes tank equipment, reactors, national team ki, batchers of chemical reagents, filters, piping, drying and / or calcining furnace, pumps, shut-off control valves, the collecting container (15) for the purified compounds of vanadium chloride solutions.

New in the proposed technical solution is that the reactor (1) for the decomposition of vanadium oxytrichloride has a connection with a tank (17) for the preparation and supply of a saline solution of potassium hydroxide connected to a filter-2 (16) and a tank (4) with an initial solution of potassium hydroxide , the crystallization tank (9) of ammonium metavanadate is connected to a collecting and flow tank of filtrates - solutions of potassium metavanadate after separating the precipitate of titanium oxyhydrate on filter press-2 (16) and to the tank (12) for preparing and supplying the initial mixed solution of ammonium chlorides and potassium, the lower discharge pipe of the pulp from the reactor (1) for the decomposition of technical vanadium oxytrichloride in a potassium hydroxide salt solution is connected to the inlet of the filter press-2 (16), the output of which is the solid phase - the precipitate of titanium oxyhydrate through the trough of the filter press -2 (16.1), sent to the titanium oxyhydrate repulse tank (18), connected to the tank (19) for the preparation and supply of potassium hydroxide solution, the output of the solid phase from filter press-2 (16) is also directed through a shut-off and distribution device (20) to the collection hopper ( 21) a wet precipitate of titanium oxyhydrate connected to a transported tank (22) having a discharge unit (22.1), the collection tank (15) for solutions of potassium or ammonium chloride cleared of vanadium has a connection to a heating reactor (23) with a stirrer equipped with a loading hatch (24), to which the magnesium and / or potassium salt production waste products containing potassium, magnesium and micro-impurities of other metals are sent from the metering hopper (25), draining the resulting concentrated chloride solutions from a heated reactor (23) with a stirrer is directed to an evaporator (26), a vacuum crystallization unit (27), the discharge unit of which is connected to a drying unit (28) of mixed ammonium, potassium and magnesium chlorides, the output from the drying unit (28) is sent to -consumption hopper (29) of commercial products connected to the filling machine (30).

IMPLEMENTATION OF THE SUGGESTED USEFUL MODEL

The developed technical solution “In-line technological line for processing vanadium oxytrichloride to produce vanadium pentoxide and disposal of production waste” works and is operated as follows.

For the decomposition of technical vanadium oxytrichloride, potassium hydroxide (KOH + KCI) is preliminarily fed from the tank (17) to the reactor (1); ) Then, the initial technical vanadium oxytrichloride (30-90% VOCI ₃ + 10-30% TiCI ₂ , etc.) is sent from the transported container (3) to the reactor (1) when the mixer is switched on, from the transported container (3). As a result of chemical reactions in the reactor (1), VOCI ₃ decomposes to form a KVO ₃ solution and precipitates titanium oxyhydrate - TiO ₂ · nH ₂ O in the solid phase; TiO (OH) ₃ ; Ti (OH) ₄ and others. The resulting pulp is pumped to a filter press 2 (16) to separate the precipitate of titanium oxyhydrate from a solution of potassium metavanadate - a filtrate, which is transferred to the tank (17) to “strengthen” along KOH, i.e. . for the preparation of a salt (KCI) potassium hydroxide solution. This solution (KOH + KCI) is fed, as already mentioned above, into the VOCI ₃ decomposition reactor (1). When the mixer is switched on, when the mixer is switched on, it is discharged from the filter press-2 (16) through the trough of the filter press-2 (16.1) unloading devices (20), the precipitate of titanium oxyhydrate, mixing of the resulting pulp is carried out for 0.5-2 hours at temperature 60-90 °. A significant part of the vanadium compounds in this case passes from the precipitate phase of titanium oxyhydrate to an alkaline (KOH + KCI) solution. The pulp is then fed (for example, pumped) to a filter press 2 (16), the filtrate is sent to a collection and delivery tank (5) and then sent to a crystallizer tank (9) to crystallize ammonium metavanadate.

The precipitate of titanium oxyhydrate (after repulpation) containing a small amount of vanadium from the filter press-2 (16) and dumped from the trough of the filter press-2 (16.1) through the unloading device (20) and fed into the collecting hopper (21), from which wet Ti (V) -containing sludge is fed into a transportable container (22) equipped with an unloading hatch (22.1) and sent for further processing and disposal in the form of commercial titanium-vanadium concentrates sold to extract titanium and vanadium, for example, by chlorination in salt chlorinators to obtain m technical TiCI ₄ and technical VOCI _3. In another embodiment, the wet (Ti-V) precipitate is sent to produce granular vanadium-containing catalysts used in organic synthesis processes.

A solution of potassium metavanadate, purified from the filter press-2 from the solid phase - titanium oxyhydrate precipitate, from the tank (5), as already noted, is sent to the ammonium metavanadium crystallizer tank (9). To isolate vanadium from the solution into the solid phase, i.e. for crystallization of NH ₄ VO ₃ in the crystallizer tank (9), a salt (KCl) solution of ammonium chloride obtained from the tank (19) obtained in the tank (19) by mixing the mother liquors of NH ₄ VO ₃ from the previous crystallization of NH ₄ VO ₃ , is supplied from the tank (19), and the estimated amount of a concentrated "reserve" solution of ammonium chloride from the tank (6). The resulting suspension in the crystallizer tank (9) is cooled (through a water-cooling “shirt”) —for more complete separation of the solid phase from the solution — NH ₄ VO ₃ .

The suspension is then pumped onto filter-1 (10), the NH ₄ VO ₃ precipitate is separated from the mother liquor and washed on the filter with a diluted solution of ammonium chloride from the tank (7). The mother liquors are collected in a tank (12) and then used for the subsequent preparation of a saline solution (NH ₄ Cl + KCl) to crystallize another portion of NH ₄ VO ₃ .

The precipitate of NH ₄ VO ₃ after washing with filter-1 (10) is sent to a calcining furnace (11), in which NH ₄ VO ₃ is decomposed to produce commercial vanadium pentoxide, which is shipped through the unloading unit (11.1) to consumers.

Ammonium metavanadate and other waste water containing vanadium compounds formed at various stages and stages of the general technological scheme for processing technical VOCI ₃ to produce marketable V ₂ O _{5 are} pumped into a collection and averaging tank (12). To extract vanadium compounds from solutions, and neutralize wastewater (waste) water from vanadium compounds, all combined solutions and wastewater are sent to a plant (14). The chloride (KCI + NH ₄ CI) solutions purified from vanadium in the apparatus (14) are sent to a collection tank (15) connected to a heating reactor (23) equipped with a loading hatch (24). Through this loading hatch (24), in the heated reactor (23) with the stirrer switched on, salt (waste) of magnesium and / or potassium production containing potassium, magnesium chlorides and impurities of chlorides and oxychlorides of other metals is loaded (in crushed or crushed form) from the hopper (25) . The resulting composite saline solution (KCI, NH ₄ CI, MgCI ₂ , etc.) is sent from the reactor (23) to the sequentially installed evaporator (26) and vacuum crystallization unit (27), from which mixed crystals (KCI + NH ₄ CI) is loaded into a drying unit (28) for the dehydration of mixed potassium, ammonium and magnesium chlorides. Crystals of potassium, ammonium and magnesium chlorides are discharged from the drying unit into a collecting and consuming hopper (29) of a commercial product and then into a filling machine (30) for subsequent shipment to consumers as a complex composite mineral fertilizer.

1. A reactor for the decomposition of technical vanadium oxytrichloride containing 30-90% VOCI ₃ , 10-70% TiCI ₄ and impurities of chlorides and oxychlorides of other metals;

2. Switchgear for supplying technical vanadium oxytrichloride under a layer of alkaline solution (KOH + KCI);

3. Transported container with the original technical vanadium oxytrichloride;

4. A tank with a stirrer, a loading hatch and a pipe for supplying distilled water, intended for the preparation and subsequent supply of the initial concentrated (“reserve”) KOH solution;

5. The collection tank for a solution of potassium metavanadate obtained after decomposition of technical VOCI ₃ and the allocation of titanium oxyhydrate from the sludge;

6. Tank with a stirrer for preparing the initial solution of ammonium chloride;

7. A tank with a stirrer, a loading hatch and a pipe for supplying distilled water (intended for the preparation and subsequent supply of a diluted (1-3%) solution of ammonium chloride for washing the precipitate of ammonium metavanadate);

8. Distribution line of distilled (desalted) water - for the preparation of initial solutions of KOH, NH ₄ CI; for washing precipitation.

9. The crystallizer tank of ammonium metavanadate;

10. Filter-1 for separation of ammonium metavanadate precipitate from the suspension - NH ₄ VO ₃ ;

11. Calcination furnace for the decomposition of NH ₄ VO ₃ to obtain marketable V ₂ O ₅ ;

11.1 Feeding unit calcination furnace;

12. Tank collection of vanadium-containing mother liquors of ammonium metavanadate;

13. Tank collection promvod ammonium metavanadate, parts of mother liquors and other vanadium-containing waste - wastewater generated at various stages and stages of processing technical VOCI ₃ and obtaining marketable V ₂ O ₅ ;

14. Installation for extracting from mother liquors and treating ammonium metavanadate, vanadium compounds (“vanadium wastewater treatment plant”), which includes tank equipment, reactors, collectors, chemical dispensers, filters, pipelines, pumps, shut-off valves control apparatus, drying chamber and / or calcining furnace;

15. The combined capacity of purified and neutralized from vanadium compounds chloride solution (N ₂ O-KCI-NH ₄ CI);

16. Filter press-2 for separation from the pulp after alkaline (KOH) decomposition of technical vanadium oxytrichloride (VOCI ₃ + TiCI ₄ ) precipitate of titanium oxyhydrate and its washing;

16.1. Trough filter press-2 for unloading a precipitate of titanium oxyhydrate;

17. Tank with a stirrer for the preparation (and subsequent supply to the reactor (1) for the decomposition of VOCI ₃ ) of a saline solution (KCI + KOH) of potassium hydroxide;

18. Tank for preparation from a concentrated solution of NH ₄ CI - a diluted (1-3%) solution of ammonium chloride for washing and repulping a precipitate of ammonium metavanadate;

19. Tank for the preparation of initial (working) KOH solutions;

20. Locking and distribution device;

21. The collection and supply hopper of the precipitate of titanium oxyhydrate after its repulpation in a solution of potassium hydroxide and filtering on a filter press-2 (FP-2);

22. Transported sediment capacity of titanium oxyhydrate;

22.1 Unloading hatch for unloading and shipment further processing to produce commercial titanium-vanadium products, for example, vanadium-containing granular organic synthesis catalysts;

23. Heated reactor with stirrer, equipped with a loading hatch (24), to obtain concentrated salt solutions (KCI + NH ₄ CI, impurities MgCI ₂ and trace metals chlorides of other metals);

24. Loading hatch of a heated reactor (23);

25. The bunker-dispenser of salt waste from magnesium and / or potash production containing potassium and / or magnesium chlorides, impurities of chlorides of other metals;

26. Evaporator;

27. Vacuum crystallization unit;

28. Drying unit - for dehydration of crystals of potassium chloride, ammonium and magnesium;

29. Collapsible bunker of commodity products;

30. Filling machine of complex mineral fertilizers based on KCI, NH ₄ CI and MgCl ₂ .

Claims (1)

Production line for processing vanadium oxytrichloride to produce vanadium pentoxide and disposal of production waste, including a reactor for the decomposition of vanadium oxytrichloride in an alkaline solution, connected through a switchgear with a transportable container for vanadium oxytrichloride, a tank with a stirrer for preparing the initial alkali solution, a collection and consumable container alkali metal metavanadate solution, a tank with a stirrer for preparing the initial solution of ammonium chloride, dist distraction distribution line water, a crystallizer tank of ammonium metavanadate, a filter - 1 for isolating ammonium metavanadate from a suspension, a calcining furnace equipped with a filling unit, collection tanks of vanadium-containing mother liquors and a prompter, a plant for extracting vanadium compounds from the mother liquor and prompter, in which includes tank equipment, reactors, chemical dispenser, filters, pipelines, drying chamber and / or calcining furnace, pumps, shut-off and control valves, prefabricated container for peeled from soybeans distillation of vanadium chloride solutions, characterized in that the reactor for the decomposition of vanadium oxytrichloride has a connection to a tank for preparing and supplying a potassium hydroxide saline solution connected to a filter press - 2 and a tank with an initial potassium hydroxide solution, an ammonium metavanadate crystallizer tank is connected - a flow tank of filtrates - solutions of potassium metavanadate after separation of the precipitate of titanium oxyhydrate and with a tank for preparing and supplying a mixed solution of ammonium and potassium chlorides, a lower discharge pipe ice from the reactor for the decomposition of technical vanadium oxytrichloride in a potassium hydroxide salt solution is connected to the inlet of the filter press - 2, the output of which of the solid phase - the precipitate of titanium oxyhydrate through the trough of the filter press - 2, is sent to the titanium oxyhydrate recovery tank connected to the tank for the preparation and supply of a solution of potassium hydroxide, the output of the solid phase from the filter press - 2 is also directed through a shut-off and distribution device into a collection and consumable sediment hopper having an unloading hatch, a collection tank for solutions of potassium and ammonium chlorides searched for from vanadium, it is connected to a heated reactor with a stirrer equipped with a loading hatch, into which the magnesium and / or potassium salt waste wastes are dispensed from the bunker, containing potassium, magnesium and other metal impurities, discharge concentrated chloride solutions from a heated reactor with a stirrer is directed to the evaporator, a vacuum crystallization unit, the discharge unit of which has connections with the drying unit are mixed x chlorides of ammonium, potassium and magnesium, the output from the drying unit is directed to a collection and consumable bunker of marketable products connected to the filling machine.