RU73872U1 - COMPLEX OF TECHNOLOGICAL EQUIPMENT FOR ELECTROLYTIC PRODUCTION OF MAGNESIUM AND MAGNETIC THERMAL PRODUCTION OF TITANIUM SPONGE - Google Patents

Abstract

The proposed utility model relates to the field of metallurgy, in particular metallurgy of non-ferrous metals, and can be used at titanium-magnesium enterprises for the production of magnesium and chlorine from carnallite and chloromagnesium raw materials and for the production of titanium metal - a titanium sponge by magnetothermal treatment of titanium tetrachloride with magnesium metal. The developed technical solution can also be used to create low-waste and non-waste technology for producing titanium and magnesium. The objective of the proposed utility model is the creation of such a complex of technological equipment for the electrolytic production of magnesium from carnallite raw materials and MgCl ₂ melts and a titanium sponge from ilmenite and / or ilmeno-rutile concentrates, the combination of which could provide the possibility of processing and utilization of chloride waste. The technical result that can be obtained by implementing the proposed utility model is to prevent the discharge of production waste into the environment and to obtain carnallite raw material on it, suitable for disposal directly in the existing “Complex” to produce additional commercial magnesium metal and anode chlorine, also implemented in the general technological scheme for the production of titanium and magnesium. The problem is solved with the achievement of the above technical result, the proposed utility model - “A set of technological equipment for the electrolytic production of magnesium and magnetothermal production of a titanium sponge”, including the redistribution of dehydration of carnallite raw materials, consisting of fluidized bed furnaces, carnallite chlorinators and mixers for collection

chloride sludge; Department-1 of electrolysis of dehydrated carnallite to produce salable metallic magnesium, anode chlorine and spent electrolyte collected in a transported container; compartment-2 of electrolysis of magnesium chloride to produce reverse metallic magnesium, used for the magnetothermal production of a titanium sponge and anode chlorine directed to the chlorination of titanium slags, an ore-thermal furnace for reducing electric melting of titanium-containing concentrates, for example, ilmenite and / or ilmeno-rutile and obtaining marketable cast iron titanium slag, salt chlorinator, equipped with a device for draining the spent melt, a chloride condensation system, technical cleaning department of titanium tetrachloride and redistribution of impurities from magnesium-producing titanium sponge to form a melt of magnesium chloride, directed into compartment 2 electrolysis. New in the developed technical solution is that the magnetothermic redistribution is equipped with cooling pads equipped with devices for discharging spent chloride melts into cooled molds and with plants for crushing chloride melts having functional-technological compounds with heated reactors with stirrers inside the reactors, false ones are located below the level of the stirrers bottoms with holes, on the lid of the reactor there is a loading hatch for chloride melts and a pipe for supplying circulating industrial solutions from the filter presses 1 and 2, the lower discharge pipe of the chloride suspension from the leaching reactor has a connection to the reactor for cleaning chloride solutions from impurities, on the lid of this reactor there is a pipe connected to the metering tank of the alkaline reagent solution, which has a connection with a supply tank, the lower discharge pipe of the suspension has a connection with a filter press - 1, the output of which is purified from the solid phase of the solution is sent to the collection of purified solutions of magnesium and potassium chloride, the salt chlorinator is equipped water removal bath connected to the circulation tank, lower

the discharge from which is directed to a reactor with a stirrer to neutralize and precipitate the amount of metal oxyhydrates, on the reactor cover there is a manhole with a loading cone connected to a hopper-dispenser of powdered magnesium-containing oxide materials, for example, caustic magnesite and / or serpentinite, a lower discharge pipe of the neutralization reactor connected to the filter press-2, the output of the solution purified from metal oxyhydrates is sent to the collection of purified solutions of magnesium and potassium chlorides connected to the evaporator, the output and which is directed into the furnace of the fluidized bed for dewatering raw carnallite.

Description

The proposed utility model relates to the field of metallurgy, in particular metallurgy of non-ferrous metals, and can be used at titanium-magnesium enterprises for the production of magnesium and chlorine from carnallite and chloromagnesium raw materials and for the production of titanium metal - a titanium sponge by magnetothermal treatment of titanium tetrachloride with magnesium metal. The developed technical solution can also be used to create low-waste and non-waste technology for producing titanium and magnesium.

Known and currently existing in Russia and a number of foreign countries complexes of technological equipment for the production of magnesium and titanium are based on the use of carnallite (MgCl ₂ · KCl · 6H ₂ O), ilmenite (FeTiO ₃ ) and / or ilmen rutile (FeTiO ₃ · TiO ₂₎ concentrate and include the following key equipment: oven fluidized bed chlorinators carnallite and carnallite for dehydration, compartment 1 and 2 - for the electrolytic production of magnesium metal anode and chloro of dehydrated carnallite (compartment 1) and the electrolysis of molten magnesium chloride (compartment 2).

The “Complexes” include ore-thermal furnaces for reducing electric melting of titanium-containing concentrates to produce cast iron, a commercial product and titanium slag (80-90% TiO ₂ ), salt chlorinators for chlorination of titanium slag anode chlorine in molten chlorides, in particular in spent electrolyte of magnesium electrolyzers fueled by carnallite raw materials, devices for the condensation of volatile chlorides removed from salt chlorinators in

as a gas-vapor mixture, a purification system (chemical and distillation) of technical titanium tetrachloride from impurities, a redistribution of the magnetothermal production of metallic titanium - a titanium sponge:

(one)

with the production of reverse magnesium chloride used in the electrolysis-2 compartment for the production of magnesium metal:

(2)

and anode chlorine directed to the chlorination of titanium slags (82-88% TiO ₂ and 12-18% of other metal oxides):

(3)

(See: Sagittarius H.L. Electrolytic production of magnesium. - M .: Metallurgy, 1972. - 336 s .; Aidenzon M.A. Metallurgy of magnesium and other light metals. - M.: Metallurgy, 1974. - 200 p. ; Lebedev O.A. Production of magnesium by electrolysis. - M .: Metallurgy, 1988. - 288 p .; Sergeev V.V., Galitsky N.V., Kiselev V.P., Kozlov V.M., Titanium metallurgy. M.: Metallurgy, 1971. - 320 pp .; Garmata V.A., Petrunko A.N., Galitsky N.V., Olesov Yu.G., Sandler R.A., Titanium. Properties, raw material base of titanium, physicochemical fundamentals and methods of production. M: Metallurgy, 1988. - 559 S. and others).

Famous - described in the technical literature, mastered and successfully operated at present, the complex of technological equipment provides high-quality metallic magnesium and sponge titanium in its composition and physicochemical properties that satisfy all modern requirements.

A disadvantage of the technical solutions known and described in the book, magazine and patent literature is the lack of a set of technological equipment for processing and rendering harmless of various wastes, in particular: spent molten salt titanium chlorinators, chloride oxide slurries of carnallite chlorinators, spent electrolytes of magnesium electrolyzers, etc. .

Of the known analogues, the closest in technical essence and the achieved result to the proposed utility model is the well-known (see Naboychenko S.A., Ageev N.G., Doroshkevich A.L. et al. Processes and apparatuses of non-ferrous metallurgy. Yekaterinburg: Ural State Technical University, 1997. - 648 p.) A set of technological equipment for the electrolytic production of magnesium and the magnetothermal production of metallic titanium - a titanium sponge based on the use of carnallite - MgCl ₂ · KCl · 6H ₂ O and ilmenite - FeTiO ₃ - was adopted as a PROTOTYPE as a feedstock.

Famous - on the prototype "Complex" includes the following main technological equipment:

- redistribution of dehydration of carnallite raw materials, consisting of fluidized bed furnaces, carnallite chlorinators and mixers for the collection of chloride sludge;

- Department-1 of electrolysis of dehydrated carnallite to produce salable metallic magnesium, anode chlorine and spent electrolyte collected in a transported container;

- separation-2 of the electrolysis of magnesium chloride to obtain reverse metallic magnesium used for the magnetothermal production of a titanium sponge and anode chlorine, directed to the chlorination of titanium slags;

- an ore-thermal furnace for reducing electric melting of titanium-containing concentrates, for example, ilmenite and / or ilmeno-rutile concentrates with the production of commodity cast iron and titanium slag;

- salt chlorinator, equipped with a device for draining the spent melt, a system of condensation of chlorides and purification of technical titanium tetrachloride from impurities;

- redistribution of the magnetothermal production of a titanium sponge with the formation of a magnesium chloride melt sent to the electrolysis compartment 2.

The well-known - on the prototype "Complex", well mastered by the domestic titanium-magnesium industry (AVISMA branch of VSMPO-AVISMA Corporation OJSC, Berezniki, Perm Territory), provides high-quality titanium sponge and metallic magnesium used for the production of aerospace alloys destination.

A disadvantage of the well-known prototype of the “Complex” is that its composition does not include equipment, sections, departments and processes for the processing and disposal of chloride waste generated at various stages of the production of magnesium metal and upon receipt of titanium tetrachloride and titanium sponge. There is also no equipment for utilization and processing of part (5-10%) of the magnesium chloride melt (see reaction equation 1) formed in the process of obtaining a titanium sponge. Many years of experience in operating equipment for the magnetothermal reduction of a titanium sponge showed that in the MgCl ₂ melt, heavy metal impurities (mainly nickel) accumulate from the walls of the equipment from the walls of the equipment to accumulate impurities of heavy metals. In this regard, this melt must be periodically withdrawn from the production cycle, otherwise, these impurities during the electrolysis of the MgCl ₂ melt are transferred to metallic magnesium and then, during the magnetothermal treatment of titanium tetrachloride, enter the titanium sponge, which substantially worsens its quality and, essentially, prevents the use of such a sponge for the subsequent production of structural materials for aerospace purposes. However, the existing and well-known prototype complex lacks the necessary equipment for the preparation and utilization of a part (5-10%) of the chloride melt - MgCl ₂ melt - in connection with which this melt is usually disposed of in a dump - to a landfill.

The objective of the proposed utility model is the creation of such a complex of technological equipment for electrolytic

production of magnesium from carnallite raw materials and MgCl ₂ melts and a titanium sponge from ilmenite and / or ilmeno-rutile concentrates, the combination of which could provide the possibility of processing and disposal of chloride waste.

The technical result that can be obtained by implementing the proposed utility model is to prevent the discharge of production waste into the environment and to obtain carnallite raw material on it, suitable for disposal directly in the existing “Complex” to produce additional commercial magnesium metal and anode chlorine, also implemented in the general technological scheme for the production of titanium and magnesium.

The problem is solved with the achievement of the above technical result, the proposed utility model - “A complex of technological equipment for the electrolytic production of magnesium and magnetothermal production of a titanium sponge”, including the redistribution of dehydration of carnallite raw materials, consisting of fluidized bed furnaces (1), carnallite chlorinators (2) and mixers (3) to collect chloride sludge; Department-1 of electrolysis of dehydrated carnallite (4) to produce salable metallic magnesium, anode chlorine and spent electrolyte collected in a transported container (5); compartment-2 of electrolysis of magnesium chloride (6) to produce reverse metallic magnesium used for the magnetothermal production of a titanium sponge and anode chlorine directed to the chlorination of titanium slags, an ore-thermal furnace (7) for the reduction electric melting of titanium-containing concentrates, for example, ilmenite and / or ilmen rutile with the production of commercial iron and titanium slag, salt chlorinator (8), equipped with a device for draining the spent melt (9), a condensation system of chlorides (10), separation Technical impurities from titanium tetrachloride (11) and redistribution obtain magnesium-titanium sponge (12) to form a melt of magnesium chloride, directed into compartment 2 electrolysis.

New in the developed technical solution is that the magnetothermal redistribution is equipped with cooling pads (13) equipped with devices for discharging spent chloride melts into cooled molds (14) and plants (15) for crushing chloride melts having functional technological connections with heated reactors ( 16) with stirrers inside the reactors, false bottoms with holes are located below the level of the stirrers, on the reactor cover there is a loading hatch (18) for chloride melts and a pipe (19) for supply of reverse washing solutions from filter presses 1 and 2, the pipe (20) of the lower discharge of the chloride suspension from the leaching reactor has a connection with the reactor (21) for cleaning chloride solutions from impurities, on the lid of this reactor there is a pipe (22) connected to the tank - to a dispenser (23) of an alkaline reagent solution having a connection with a supply tank (24), the lower discharge pipe of the suspension has a connection with a filter press-1 (25), the output of which is purified from the solid phase of the solution is directed to the collection (26) of purified solutions magnesium chloride and potassium, the salt chlorinator (8) is equipped with a hydro-removal bath having a connection to the circulation tank, the lower discharge from which is directed to the reactor with a stirrer to neutralize and precipitate the amount of metal oxyhydrates, on the reactor cover there is a hatch with a loading cone (30) connected to the hopper -doser (31) of powdered magnesium-containing oxide materials, for example, caustic magnesite and / or serpentinite, the lower discharge pipe of the reactor for neutralization is connected to filter press-2 (32), the output of metal free of oxyhydrates solution is directed into the collection (26) purified magnesium chloride solutions and potassium coupled to the evaporator (33), the output of which is directed into the fluidized bed furnace (1) for dewatering raw carnallite.

IMPLEMENTATION OF THE SUGGESTED USEFUL MODEL

The developed technical solution - "The complex of technological equipment for the electrolytic production of magnesium and the magnetothermic production of a titanium sponge" works and is operated as follows.

The initial carnallite raw material (MgCl ₂ · KCl · 6H ₂ O) is fed to the dehydration redistribution, in particular, first to the fluidized bed furnace (1), then to the carnallite chlorinator (2). Chloride sludge generated in the carnallite chlorinator (2) is collected in a mixer (3) and transferred to a cooling pad (13-1). Dehydrated carnallite is fed to electrolysis unit 1. The spent electrolyte (70-80% KCl, the rest MgCl ₂ , NaCl, MgO, etc.) is collected in a transported container (5) and transferred to a cooling pad (13-2).

The metal magnesium formed during the electrolysis is fed to the redistribution of the magnetothermal production of a titanium sponge, the excess of the metal magnesium obtained is realized as a commercial product (in the form of "ingots"). The anodic chlorine released during electrolysis is sent to a salt furnace (8) for chlorination of titanium slag obtained in an ore-thermal furnace (7) during reduction smelting of titanium-containing concentrates, which use ilmenite (FeTiO ₃ ) and / or ilmeno-rutile concentrates (FeTiO ₃ · TiO ₂ ).

Volatile metal chlorides in the form of a gas-vapor mixture are sent from a salt chlorinator (8) to a condensation system (10), from where technical titanium tetrachloride is sent to the stage of purification from foreign impurities. The purified titanium tetrachloride is sent to the redistribution (12) of the magnetothermal production of the titanium sponge, which simultaneously receives metallic magnesium from compartment-1 and compartment-2 of electrolysis of magnesium-containing chloride melts.

The spent chloride melt from the salt chlorinator (8) is periodically poured through a special device (9) into the hydraulic removal bath (27), where water and / or reverse chloride solutions are continuously supplied from the circulation tank (28). The circulation is carried out until the solutions are saturated with the total amount of metal chlorides, after which these solutions are fed into the reactor (29) with a stirrer to neutralize the solution and precipitate the sum of metal oxyhydrates from it. Powdered magnesium-containing materials, which are used as caustic magnesite and / or serpentinite and / or other magnesium-containing oxide powdery materials, are added to the reactor (29) with continuous stirring in portions through a loading hatch (30), from the hopper (31): / or intermediate products.

The oxyhydrate pulp formed in the reactor (29) is thoroughly mixed and fed to the filter press 2. The solution of potassium and magnesium chlorides purified from impurities of heavy metals and solid phase is pumped from the filter press 2 into the collector (26).

The magnesium chloride formed by the reaction equations (1) during magnetothermal production of a titanium sponge is sent to electrolysis compartment 2 (6) to obtain magnesium metal used in redistribution (12) for the next operation of magnetothermal treatment of TiCl ₄ to obtain a titanium sponge. Periodically, as heavy metal chlorides accumulate in the melt, this melt is removed from the technological cycle, for which the MgCl ₂ melt is collected in a special container and placed on a cooled site (13-3). At cooled sites (13-1, 13-2, 13-3), chloride melts are poured using devices (14) from prefabricated mixers and / or transported containers into cooled molds. After cooling and crystallization of these melts, they are discharged from the molds into crushing plants. From where the crushed melt is fed through the loading hatch (18) to a heated reactor (16) equipped with a stirrer and equipped with a false bottom (17) with openings. Prior to loading the melt, this reactor is preliminarily fed or pumped into this reactor.

Promotions from FP-1 and FP-2 filter presses (25) and (32). The suspension in the reactor (16) is stirred, the density of the resulting solution of MgCl ₂ + KCl is periodically measured. The leaching process with periodic loading into the reactor (16) through the loading hatch (18) of the crushed melt is carried out until a solution is concentrated that is saturated with the total amount of metal chlorides, after which the solution is fed from the reactor (16) through the lower discharge pipe (20) to the reactor (21) ) with a stirrer. To remove foreign metal impurities, a solution (70-150 g / dm ³ ) of NaOH is supplied from the dispenser (23) to the combined chloride solution in the reactor (26) through the pipe (22) placed on the cover of the reactor (16). After treatment with a sodium hydroxide solution, the suspension from the reactor (16) is pumped to a filter press (1), where the solid phase is separated from the solutions of magnesium chloride and potassium, which is sent to the collector (26). The solution of magnesium chloride purified from impurities from the collection (26) is fed to the evaporator (32), from where the synthetic carnallite raw material is sent to the fluidized bed furnace (1).

The implementation of the utility model in the electrolytic production of metallic magnesium and the magnetothermal production of a titanium sponge using the combination of technological equipment provided for in the developed Complex ensures almost complete utilization of all chloride melts formed at various stages of the general technological scheme of production, and on the basis of production wastes they get synthetic carnallite used to produce metallic magnesium and chlorine, which allows for ganizovat steady and stable operation of the whole complex - independent of supply carnallite raw material from other companies (mine group of OJSC "Uralkali" and OJSC "Silvinit").

COMPLEX OF TECHNOLOGICAL EQUIPMENT FOR ELECTROLYTIC PRODUCTION OF MAGNESIUM AND MAGNETIC THERMAL PRODUCTION OF TITANIUM SPONGE

1 - fluidized bed furnace (stage I dehydration of carnallite MgCl ₂ · KCl · 6H ₂ 0);

2 - carnallite chlorinator (stage II carnallite dehydration);

3 - mixer-collection of chloride sludge carnallite chlorinators;

4 - Department-1 electrolysis of dehydrated carnallite;

5 - transported capacity for spent electrolyte of magnesium electrolysis cells;

6 - compartment-2 of the electrolysis of a melt of magnesium chloride;

7 - ore-thermal furnace for reducing smelting of titanium-containing concentrates (for example, ilmenite (FeTiO ₃ ) and / or ilmeno-rutile (FeTiO ₃ · TiO ₂ )) to produce marketable cast iron and titanium slag (82-88% Ti0 ₂ );

8 - salt chlorinator for chlorination with anode chlorine (from magnesium electrolysis) of titanium slag in a chloride melt - in spent electrolyte of carnallite electrolysis compartment-1;

9 - a device for draining spent chloride melt from a salt chlorinator;

10 - condensation system of volatile chlorides leaving the salt chlorinator in the form of a vapor-gas mixture;

11 - Department of cleaning technical titanium tetrachloride from impurities;

12 - redistribution of the magnetothermal production of a titanium sponge (TiCl ₄ + 2Mg → Ti + 2MgCl ₂ );

13 - cooling pads for cooling and crystallizing sludges of carnallite chlorinators (13-1), spent electrolyte of compartment-1 of carnallite electrolysis (13-2) and part of the magnesium chloride melt formed during the magnetothermic production of a titanium sponge (13-3);

14 - a device for draining chloride melts into cooled molds;

15 - installation for crushing cooled and crystallized melts;

16 - heated reactors with mixers for leaching of chloride melts;

17 - false bottom of the leaching reactor;

18 - reactor loading port for loading crushed chloride melts into it;

19 - pipe for supplying circulating washing solutions from filter presses (FP-1 and FP-2);

20 - pipe lower discharge of the chloride suspension from the reactor for leaching;

21 - reactors with mixers for cleaning chloride melts from impurities of heavy metals and solid inclusions (metal oxides and oxyhydrates);

22 - pipe on the lid of the reactor (21) connected to the metering tank of the NaOH solution;

23 - a tank metering solution of sodium hydroxide;

24 - consumable tank with a stirrer for preparing the initial NaOH solution and its supply to the metering tank (23);

25 - filter press 1 for separation of a solid phase from a suspension;

26 - a collection of purified solutions of magnesium chloride and potassium (with impurities of NaCl);

27 - a hydro-removal bath for spent chloride melt from a salt chlorinator (8);

28 - circulation tank;

29 - a reactor with a stirrer to neutralize and precipitate metal oxyhydrates (Fe, Cr, Mn, Ae, Sc, Th, Ti, Zr, etc.);

30 - loading cone;

31 - bunker-dispenser of powdered magnesium-containing oxide materials (caustic magnesite and / or serpentinite, etc.);

32 - filter press-2 for the selection of the amount of metal oxyhydrates from the chloride suspension of the precipitate and their washing;

33 - evaporator.

Claims (1)

A set of technological equipment for the electrolytic production of magnesium and the magnetothermal production of a titanium sponge, including the redistribution of dehydration of carnallite raw materials, consisting of a fluidized bed furnace, carnallite chlorinator and a mixer for collecting chloride sludge, separation-1 of electrolysis of dehydrated carnallite to produce salable metal magnesium, anode chlorine and spent the electrolyte collected in the transported container, compartment-2 of the electrolysis of magnesium chloride to obtain reverse metal magnesium, used for the magnetothermal production of a titanium sponge and anode chlorine, used for chlorination of titanium slags, an ore-thermal furnace for reducing electric melting of titanium-containing concentrates, for example, ilmenite and / or ilmeno-rutile, to obtain marketable cast iron and titanium slags, a salt chlorinator, discharge of the spent melt, a chloride condensation system, a system for purifying technical titanium tetrachloride from impurities, and redistribution of magnetothermal production titanium sponge with the formation of a magnesium chloride melt sent to the electrolysis compartment-2, characterized in that the compartment-1 and the magnesium thermal redistribution are equipped with cooling pads equipped with devices for draining spent chloride melts into cooled molds and with plants for crushing and / or granulating chloride melts having functional technological connections with heated reactors with stirrers for leaching chloride melts inside the reactors below the level of the stirrer wives are false bottoms with holes, on the reactor lid there are loading hatches for chloride melts and nozzles for supplying reverse washing solutions from filter presses 1 and 2, the lower discharge nozzles of the chloride suspension from the leaching reactors have connections to the reactor for cleaning chloride melts from impurities, on the lid of this reactor there is a pipe connected to a metering tank of an alkaline reagent solution having a connection to a supply tank, a lower discharge pipe has a connection to a filter press 1, the outlet of which The solution, purified from the solid phase, is sent to the collection of purified solutions of magnesium and potassium chlorides, the salt chlorinator is equipped with a hydro-removal bath connected to a circulation tank, the lower discharge from which is sent to the reactor with a stirrer to neutralize and precipitate the amount of metal oxyhydrates, there is a hatch on the reactor lid with a loading cone connected to a hopper-dispenser of powdered magnesium-containing oxide materials, for example caustic magnesite and / or serpentinite, a lower discharge pipe of the reactor d I neutralization is connected to a filter press 2, the output from the purified metal oxyhydrates solution is directed to the collection of purified solutions of magnesium and potassium chlorides, coupled to the evaporator, the output of which is directed into the furnace of the fluidized bed for dewatering raw carnallite.