RU74636U1 - HARDWARE AND TECHNOLOGICAL COMPLEX FOR OBTAINING PANAOXIDE OF VANADIUM - Google Patents

Abstract

Instrumentation complex for producing vanadium pentoxide, including a reactor with a stirrer for alkaline treatment of the initial vanadium-containing materials, connected to a tank for preparing and supplying a solution of sodium hydroxide, a crystallizer tank of ammonium metavanadate, 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 the neutralization and neutralization of vanadium-containing wastewater, connected through a congestion 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, characterized in that the reactor for alkaline treatment of the initial vanadium-containing materials has a tight connection with a transported container with vanadium oxytrichloride, and the output of vanadium oxytrichloride from the transported tank through the shut-off and control valves is directed to a switchgear, p located in the reactor below the level of the mixer, the crystallizer tank has connections with a sequentially installed metering tank and a storage and storage tank for the 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 collector is directed , after the filter - 1, a ammonium metavanadate repulse tank is installed, the lower discharge pipe of the suspension has a connection with the filter - 1.

Description

The proposed utility model relates to the field of metallurgy and chemical technology and can be implemented in chemical and metallurgical industries, in particular for the production of commercial vanadium pentoxide (V ₂ O ₅ ) from vanadium-containing raw materials and materials, specifically from vanadium oxytrichloride (VOCl ₃ ).

The well-known "Production line for the production of vanadium pentoxide" (Certificate PM PM No. 23292 according to the application No. 2001130623/20 with prior, dated 16.11.2001. Regist. And publ. 06/10/2002. Bull. No. 16), which includes (Fig. 1): sequentially installed alkali solution tank (1), a reactor (2) for leaching technical vanadium pentoxide, a suction filter (3) to separate insoluble residue, a reactor-crystallizer (4), a filter press (5) and an oven (6) ) for the decomposition of ammonium metavanadate - NH ₄ VO ₃ to obtain vanadium pentoxide - V ₂ O ₅ ; the reactor for leaching the insoluble residue (8), equipped with a dosing tank (7) of sodium hypochlorite is installed between the suction filter (3) and the crystallizing reactor (4), connected to the alkali solution tank (1). The neutralizer tank (9), equipped with a reducing agent metering tank (10) installed on the drain line from the filter press.

The operation of the well-known "Production line for the production of vanadium pentoxide" is as follows. An alkali solution is supplied from the tank (1) to the reactor (2) and technical vanadium pentoxide is leached. At the end of the leaching process, the resulting suspension containing a solution of sodium metavanadate is fed to the nutsche filter (3). Particulate matter separation on the Nutsche filter

suspension from the solution. The solution is then sent to the reactor (4) for crystallization. The solid particles of the insoluble residue are sent to the reactor (8), into which sodium hypochlorite solution is supplied from the metering tank (7) and alkali is supplied from the tank (1) through an additionally mounted line. The resulting suspension is fed into the reactor (4) to obtain crystals of ammonium metavanadate. For this, ammonium chloride is fed into the reactor, resulting in the formation of solid particles of ammonium metavanadate. The suspension from the reactor is sent to a filter press (5), where crystals of ammonium metavanadate are separated from the mother liquor. The mother liquor is fed into the neutralizing tank (9), where it is treated with a reducing solution supplied from the tank (10), for example, sodium hydrosulfide solution to decompose the remaining sodium hypochlorite. The resulting and neutralized solution is discharged into the sewer. Ammonium metavanadate crystals are sent to the furnace (6), where, when heated, ammonium metavanadate decomposes to form the finished target product, vanadium pentoxide.

The disadvantage of this technical solution is the lack of equipment for the production of V ₂ O ₅ from UOSl ₃ in the "Technological line".

Of the known analogues, the closest in technical essence and the technical result achieved is the well-known “Production site for the production of commercial vanadium pentoxide” (RF Patent ПМ №41021 by application No. 2004116515/22 with prior, dated 01.06.2004. Register and publ. 10.10.2004. Bull. No. 28) - adopted as a PROTOTYPE.

The “production site for commercial vanadium pentoxide production” according to the prototype includes the following main technological equipment (Fig. 2):

- a heated reactor (for example, a steam with a jacket) with a stirrer for leaching the feedstock - technical vanadium pentoxide (1);

- a tank for the preparation and supply of a solution of alkali - sodium hydroxide (2);

- tank - dispenser of sodium hypochlorite solution (3);

- a filter (nutsche filter or press filter) for separating the insoluble residue after leaching from the mother liquor - sodium metavanadate solution (4);

- a crystallizer tank (5) for separating ammonium metavanadate from the solution into the solid phase, equipped with a hopper (and / or pipe) for loading ammonium chloride and / or ammonium nitrate into the crystallizer;

- a filter (nutsche filter or press filter) to separate the precipitate of ammonium metavanadate from the mother liquor (6);

- tank - a collection of uterine solutions and promotion of ammonium metavanadate (7);

- a reactor for the neutralization of vanadium-containing wastewater-uterine solutions from the allocation of NH ₄ VO ₃ and the promotion of ammonium metavanadate (8);

- tank - a collection (9) of solutions containing iron (II) salts, connected through a dispenser (10) to a reactor for the treatment of wastewater (8);

- capacity for alkaline solutions (NaOH and / or CaO, and / or CaO + H ₂ O, and / or MgO, and / or MgO + H ₂ O, etc.) - (11);

- filter - press (12) for separation of oxyhydrate sludge from vanadium-containing wastewater from the pulp after neutralization;

- screw feeder (13);

- mixer (14);

- bunker - dispenser of magnesium-containing oxide materials (MgO, brucite, magnesite and / or serpentinite, etc.) - (15);

- a hopper - a dispenser of inert fillers (various industrial wastes, sawdust, household or technological waste, etc.) - (16);

- hopper - dispenser of insoluble residue - after leaching of technical V ₂ O ₅ and separation of the mother liquor NaVO ₃ (17);

- a dispenser (18) of a solution containing magnesium chloride connected to a storage (consumable) container (19);

- knot molding, heat treatment and curing of the composite mixture (20);

- a false bottom absorber and ball nozzle for cleaning and neutralizing vanadium compounds from a dust-gas aerosol mixture leaving the calcining furnace (21);

- a circulation tank (22) with a solution of alkali - sodium hydroxide, connected to the tank (2) for the preparation and supply of alkali, connected to the spray device of the absorber (22).

The technical solution according to the prototype - “Production site for obtaining commercial vanadium pentoxide” is operated as follows: pour alkali solution and sodium hypochlorite solution up to 60-70% of the reactor volume from the tank (2) and the metering tank (3) into the reactor (1) (1), then, through the hatch and / or the reactor hopper, the calculated amount of the feedstock - technical vanadium pentoxide (60-95% V ₂ O ₅ ) is loaded into it with the stirrer turned _on . At the end of leaching, the suspension is fed to the filter (4), an insoluble residue containing impurities of the accompanying metals (and partially vanadium oxide) is separated from the mother liquor, the filter cake is washed, the NaVO ₃ solution and the washers are combined and sent to the collection tank, from where the solution is sent to the crystallizer tank (5). To separate ammonium metavanadate - НН ₄ О ₃ from the NaVO ₃ solution into the solid phase, ammonium chloride or nitrate is fed into the crystallizer tank with stirring. After crystallization, the suspension is fed to a filter press (7), the precipitate of ammonium metavanadate is separated from the mother liquor and washed. The mother liquor and wastewater (wastewater) are fed into the collection tank, from where they are sent to the reactor (8) to neutralize the effluents from the vanadium compounds, for this purpose to the reactor (8)

successively serves, from the collection tank (9), through the dispenser (10), solutions containing iron (II) salts, for example, concentrated solutions from hydraulic washing of spent melts of titanium chlorinators containing metal chlorides, including iron (II) chloride, manganese (II) ), chromium (III), potassium, sodium, magnesium, calcium, small amounts of rare and trace metals. If necessary, the resulting pulp is treated with high molecular weight flocculants (polyacrylamide, praestol, etc.). Then the suspension is fed to a filter press (12) to separate an oxyhydrate precipitate from the pulp. The filter cake is washed after filtering and, using a screw feeder (13), is sent to a mixer (14) to prepare a composite mixture suitable for solidifying waste. For this purpose, magnesium-containing oxide materials (MgO) are fed to the mixer (14), mainly non-utilizing production wastes containing magnesium oxide - waste from the production of brucite, magnesite, serpentinite, etc., inert fillers are also fed into the mixer from batchers (15 and 16) and an insoluble residue formed upon leaching of the starting technical vanadium pentoxide. To impart astringent properties to the composite mixture, a solution (and / or suspension, pulp) containing MgCl ₂ is introduced from the container (13) through the batcher (18), the composite mixture is thoroughly mixed and fed to the molding, heat-treating and curing unit (20) with the receipt and ultimately the "blocks" - environmentally friendly for long-term storage (storage).

The precipitate of ammonium metavanadate after separation on the filter (6) from the mother liquor and washing from salts (NaCl, NH ₄ Cl) is fed to a calcining furnace to decompose ammonium metavanadate: . Commercial vanadium pentoxide is discharged from the furnace, packaged and sent to consumers. Exhaust gases from the furnace in the form of waste are sent to the absorber (21) with a false bottom and a ball nozzle equipped with a spray device

alkalis supplied from the circulation tank (22). The spent vanadium-containing circulation solution is sent to the reactor (1) for leaching the initial technical vanadium pentoxide, thereby ensuring the utilization of trapped vanadium and ultimately providing an increase in the degree of its extraction from the feedstock into a marketable product.

The production site of the prototype allows with high efficiency to process technical vanadium pentoxide (70-90% V ₂ O ₅ ) to obtain marketable V ₂ O ₅ .

The disadvantage of the technical solution for the prototype is the lack of equipment for the processing of vanadium oxytrichloride (VOCl ₃ ) in the composition of the “Production Site” to produce commercial vanadium pentoxide.

Another disadvantage of the technical solution of the prototype is a significant loss of vanadium with mother liquors during crystallization of ammonium metavanadate.

The objective of the proposed utility model is the creation of a hardware-technological complex that provides the possibility of processing vanadium oxytrichloride, an industrial product of production, forming in the production of titanium, in particular during the purification of technical titanium tetrachloride from impurities of vanadium compounds.

The technical result that can be achieved by implementing the developed technical solution is to increase the degree of vanadium release - in the form of NH ₄ VO ₃ from the solution into the solid phase, increase the degree of vanadium extraction into the commercial product and reduce the irreversible loss of vanadium with mother liquors.

The problem is solved with the achievement of the above technical result by the proposed utility model - “Hardware-technological complex for the production of vanadium pentoxide”, including (Fig. 3) a reactor (1) with an agitator for alkaline treatment of the initial vanadium-containing materials connected to the tank (2) for

preparation and supply of a sodium hydroxide solution, a tank - a crystallizer of ammonium metavanadate (3), a filter - 1 (4) for separating a precipitate of ammonium metavanadate from a suspension and washing it, a tank - a collection of mother liquors and an ammonium metavanadate washer (5), a reactor for neutralizing and neutralization of vanadium-containing wastewater (6), connected through a dispenser (7) to a tank - collector (8) of iron (II) -containing solutions and a tank (2) for preparing and supplying sodium hydroxide solution, a reactor (6) for neutralizing and neutralizing vanadium-containing waste x water is connected to the filter - 2 (9), and after the filter - 1 (4) a calcination furnace (10) is installed. New in the proposed utility model is that the reactor (1) for alkaline treatment of the initial vanadium-containing materials has a tight connection with the transported tank (11) with vanadium oxytrichloride, and the output of vanadium oxytrichloride from the transported tank through the shut-off and control valves (12) is directed to the distribution device (13) located in the reactor below the level of the mixer. The crystallizer tank (3) has connections with a sequentially installed metering tank (14) and an accumulating storage tank (15) for preparing and supplying a solution of ammonium chloride; there is a loading hatch (16) on the lid of the crystallizer tank, into which the outlet is directed from the hopper - collector (17) sodium chloride, after the filter - 1 (4) a tank is installed - a repulpator (18) of ammonium metavanadate, the lower discharge pipe of the suspension has a connection to the filter - 1 (4).

IMPLEMENTATION OF THE SUGGESTED USEFUL MODEL

The proposed technical solution - "Hardware-technological complex for the production of vanadium pentoxide" works and is operated as follows.

A solution (20-200 g / dm ³ ) of sodium hydroxide is pumped (or by gravity) into a reactor (1) with a stirrer from a dispenser (2-1) connected to a tank (2) and

then, when the mixer is switched _on, vanadium oxytrichloride - VOCl ₃ is supplied from the transported container (11) through a switchgear (13). The feed rate is regulated by valves. In the reactor (1), "decomposition" of vanadium oxytrichloride occurs with the formation of a sodium vanadate solution.

Distilled water (from the shop line) and a solution of NH ₄ Cl are sequentially pumped (or fed by gravity) into the crystallization tank (3). Sodium chloride is charged from the reactor (1) with the stirrer turned on into the crystallizer tank (3) through the loading hatch (16) and the collection hopper (17) in an amount that ensures obtaining a saturated (or close to saturated) sodium chloride solution, and then from a storage tank (15) through a metering tank (14), a solution of ammonium chloride is fed into the crystallizer tank. Ammonium chloride solution is supplied with the stirrer switched on, the resulting suspension is cooled and kept, as a result of which a crystalline precipitate of ammonium metavanadate is separated from the solution into the solid phase:

The suspension is then fed to a filter - 1 (4), which can be used with suction filters, filter press (manual and / or automatic), drum vacuum filters, etc. The precipitate of ammonium metavanadate is separated from the mother liquor, which is collected in a collection tank (5). Filter cake - 1 (4) is washed with a diluted (1-3%) solution of ammonium chloride, in an amount of 2-3 volumes per 1 volume of sediment. Promotions are collected in a collection tank (5). Then the precipitate from the filter - 1 (4) is discharged into the repulpator tank (18), into which a diluted (1-3%) solution of ammonium chloride is preliminarily poured (pumped). The precipitate NH ₄ VO _{3 is} repulped at a ratio of W: T = (10-30): 1, the suspension is pumped onto a filter - 1, the filtrate is collected in a collection tank (5). Filter cake - 1 (4) is again washed with diluted (1-3%) solution

ammonium chloride. All promotions are collected in a collection tank (5). Washed (“washed” from sodium chloride) precipitate NH ₄ VO _{3 is} discharged from filter - 1 (4) and loaded into the calcined furnace (10), which is mainly used as a cylindrical rotary furnace installed at a slight (1-10 °) slope to the horizontal axis and having along the entire length several heating and calcining zones and various temperatures from 100-150 ° C to 500-550 ° C. As the NH ₄ VO ₃ precipitate passes from the “inlet” (loading hatch) to the exit (to the loading hatch), ammonium metavanadate decomposes to produce marketable powdered vanadium pentoxide.

In this case, the released ammonia is mainly oxidized to nitrogen. Vanadium pentoxide in this case, apparently, plays the role of a catalyst. At the end of the calcination process, the resulting vanadium pentoxide is discharged from the calcining furnace (10), packaged in bags and shipped to consumers.

To neutralize from vanadium all vanadium-containing wastewater generated at the Complex, mother liquors, the washer, the combined effluent from the collection tank (5) are pumped into the reactor (6), then, with the stirrer turned on, it is fed sequentially from the batcher (7) and tank - collector (8) a solution of ferrous salt - FeCl ₂ or FeSO ₄ and, then - from the dispenser (2-1) and tank (2) sodium hydroxide solution. The pulp in the reactor (6) is mixed and pumped onto the filter - 2 (9). The precipitate of iron oxyhydrate containing vanadium recovered from the effluent is separated from the purified (deactivated) solution from vanadium chloride (NaCl, NH ₄ Cl) solution, washed on the filter with water, discharged from the filter - 2 (9) and disposed of, for example, dried, calcined and sent to the additional extraction of vanadium by one of the previously developed methods. The filtrate and wastewater purified from vanadium are discharged into the sewer

Claims (1)

Instrumentation complex for producing vanadium pentoxide, including a reactor with a stirrer for alkaline treatment of the initial vanadium-containing materials, connected to a tank for preparing and supplying a solution of sodium hydroxide, a crystallizer tank of ammonium metavanadate, 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 the neutralization and neutralization of vanadium-containing wastewater, connected through a congestion 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, characterized in that the reactor for alkaline treatment of the initial vanadium-containing materials has a tight connection with a transported container with vanadium oxytrichloride, and the output of vanadium oxytrichloride from the transported tank through the shut-off and control valves is directed to a switchgear, p located in the reactor below the level of the mixer, the crystallizer tank has connections with a sequentially installed metering tank and a storage and storage tank for the preparation and supply of ammonium chloride solution, on the lid of the crystallizer tank there is a loading hatch in which the outlet from the sodium chloride collector is directed , after the filter - 1, a ammonium metavanadate repulse tank is installed, the lower discharge pipe of the suspension has a connection with the filter - 1.