Method of high-titanium-bearing foundry alloy production

FIELD: metallurgy; high-titanium-bearing foundry alloy production.

SUBSTANCE: the invention is dealt with the field of metallurgy, in particular, with production of the foundry alloy containing mainly titanium and also a small amount of other useful metals reduced from oxides of a charge together with the basic components of a foundry alloy. The method includes the following stages: after melting-down of the first portion of the charge representing an ilmenite concentrate formed on the rotating melt of the high-titanium-bearing foundry alloy and reduction by titanium and silicon of a part of oxides from the melted portion of ilmenite they use aluminum to reduce all oxides in a cinder melt. The obtained slag is added with the first portion of calcium oxide in the amount ensuring fluidity of the cinder. The second portion of the charge is introduced in the melt in the amount corresponding to the possibility of to reduce oxides by titanium. The produced titanium oxide is merged with the earlier produced cinder. A determined part of the produced melt in conditions of its rotation is poured out through a side tap hole. Using aluminum reduce titanium oxide from the merged cinder and the reduced titanium merge with the rest metal melt. In the formed final cinder enter the second portion of calcium oxide. A part of the produced foundry alloy is poured out through a side tap hole. Then a final cinder is also poured out and they feed a new portion of ilmenite onto the residue of the foundry alloy. The invention allows to reduce at least twice the power input used for reprocessing of the ilmenite concentrate, as in the process of reduction of the metals from oxides there are no endothermic reactions but exothermic reactions; to use ilmenite concentrates with a share of titanium oxide up to 45% and a strong metal reductant - aluminum, and also to realize a progressive technology of the liquid-phase reduction of metals from oxides in conditions of rotation of the melt by an electromagnetic field.

EFFECT: the invention allows to reduce at least twice the power input used for reprocessing of the ilmenite concentrate, to use ilmenite concentrates with a share of titanium oxide up to 45% and a strong metal reductant - aluminum, to realize a progressive technology of the liquid-phase reduction of metals from oxides.

5 cl, 1 ex, 1 dwg

 

The invention relates to the field of metallurgy, in particular to the production of alloys containing mainly titanium. The ligature may be a small amount of other minerals and metals recovered from the oxides of the charge together with the main components of ligatures.

In ilmenite concentrates with a high content of titanium oxide. For example, in the ilmenite concentrate Medvedev's deposits of titaniferous magnetite titanium oxide 40 to 45% [1, str, tbl]. Iron oxides in these concentrates 47-50%, other oxides have less than 10%.

Known Baskakova technology of complex processing of ore, which is obtained after enrichment of ilmenite concentrate okomkovaniya and ozelenyat or aglomerados, and later in elektrofotometricheskie receive first furnace steel semi-finished product, then alloy steel, and titanium slag, suitable for the production from or titanium sponge (after chlorination), or titanium oxide for pigment (after acid decomposition) [1, str, RES].

There is a method of processing vanadium bearing titaniferous magnetite ore tianity cast iron, vanadium slag and titanium-containing alloy [2]. According to this technology, together with other products get a titanium-containing alloy, titanium-containing virtually the ligature.

The above technology, a lot of twincity and sadasivam a large number of expensive process equipment.

Known technology for the production of ilmenite concentrate ferrotitanium [3, str-585; 4, str-618]suitable for deoxidation and alloying of steel, including acid resistant, corrosion resistant and heat resistant. Ferrotitanium is produced when aluminothermic secondary recovery of oxides of the charge, including ilmenite concentrate, aluminum powder, iron ore, ferrosilicon and small lime. Is essentially nicotianoideae ligature with a titanium content of 25-28%.

The prior art also taken for the prototype technology of smelting reduction of oxides of charge, suitable for recovery of oxides of ilmenite concentrates, including melting of the charge in the melting chamber of the unit on a rotating metal melt, the recovery of metals from the oxides of the charge, the fusion of recovered metals with a rotating metal melt, remove the newly formed molten metal, slag removal [5].

As the molten metal in the prototype it is recommended to use cast iron, and as a reductant is carbon, and the carbon recovery is recommended to take iron.

It should be noted the following disadvantages technologies (way) of the prototype. The recovery of oxides of the slag phase is carbon, which kanshiram know, takes place when the cost of heat and the release of a large amount of gas, carrying a significant number of physical and chemical heat.

Since the process of the prototype is emitting large amounts of gas, the unit for implementing the method should join bulky exhaust and dust processing equipment, and this equipment is further complicated if the slag will need to restore magnesium oxide.

The novelty of the proposed method lies in the fact that after melting the first portion of the charge representing the ilmenite concentrate on rotating metal melt, representing wysokometanowego the ligature, and recovering the titanium and the silicon part of the oxides of the molten portion of ilmenite, aluminum restore all the oxides in the slag melt, in which the free energy of formation less than that of aluminum, the resulting slag add the first portion of the calcium oxide in an amount to provide the fluidity of the slag in the melt is injected second portion of the charge in an amount corresponding to restore titanium oxide, whose free energy of formation less than that of titanium formed the titanium oxide combined with the previously obtained slag established part of the obtained metal is a mini melt-in terms of its rotation is drained through the side tapped, aluminum restore the titanium oxide of the United slag and restored titanium combined with the left metal melt, formed in the final slag enter the second portion of the calcium oxide in an amount to provide the fluidity of the slag, the installed portion of the received vysokotekhnologicheskoi ligature is drained through the side tapped, the rest of the ligature through its rotation is placed on the edges of the melting chamber, open the Central tap-hole and the final slag is drained completely, tapped close up and resume feeding in the melting unit first portion of ilmenite.

Portions of ilmenite concentrate, it is advisable to apply in the melting unit is heated in the range of 100-500°C.

From the melting chamber a metal melt, which represents an iron with the addition of vanadium, silicon and manganese, it is recommended to drain in the number of 90-95%, and the discharge of molten metal may enter additional additives, and wysokometanowego the ligature is recommended to be merged within 70-90%.

When two plums from the melting Assembly for molten metal, it is recommended to leave in the melting chamber a different number of melt - 90-95% iron and 70-80% ligatures. This is explained in the following. If the ligature is desirable to have as much titanium (up to 100%), you have the drop off is as small as possible iron-containing alloy. If the ligature allow for a large amount of iron-containing alloy, then this number and left a mass of alloy.

Ligatures in the melting chamber, you need to leave more (70-90%) because, firstly, she is working on the process indicators in regard to Al is not affected, and secondly, if ligatures before removing 100% of the final slag will remain small, the conditions of the initial filing of the first portion of the charge in the melting chamber may be unfavorable (can happen freezing the rest of the ligature, which is unacceptable). The second portion of the charge is supplied to the melting chamber of the unit during the period when the camera is already formed part of the iron melt and has formed a slag having a high temperature.

In the melting chamber melting unit to the final slag is recommended to ensure that the temperature of 1600-1800°and, accordingly, the set temperature of the slag under the terms of his giacopelli in the final slag is injected calcium oxide and bring its content in the range of 20-30%.

Ilmenite concentrate according to the method proposed process on the titanium-containing alloys and other products without prior melting of iron-containing contaminants and, therefore, exclude expenses for the creation of technological equipment for iron-containing contaminants, and the iron-containing contaminants. But if the and the company has the equipment for iron-containing contaminants concentrate, the smelting better serve ozelenenie and not yet cooled concentrate. The economic effect will be greatest.

During recovery of the oxides of titanium and aluminum are exothermic reaction that generates heat. If the recovery of oxides will require a substantial amount of aluminum, the heat can be released so that it will be enough to heat the mixture to melting, and melting, and heating the melt to the desired temperature, which can occur redox reaction between the oxides and aluminum.

Recommendation to restore titanium oxides from the second portion of the charge does not reduce the consumption of Al the recovery of oxides ilmenite, because ultimately you have to pick up oxygen Titan took during recovery of the oxides of iron, silicon and manganese from the second portion of the charge, while aluminum will restore titanium from optionally formed of titanium oxide. However, the advantages of the proposed method are available. It becomes possible to serially feed the two portions ilmenite concentrate to get two metal melt. The first is iron with additives MT, Si and V, the second - vysokoshirotnaya ligature, in which the titanium content may be, for example, up to 90%. This content depends on the amount of iron that leaves Aut in the melting chamber while draining it from the melting unit. It is recommended to drain 90-95%.

It should be noted that if, for example, from granular ilmenite concentrate Medvedev's deposits of titaniferous magnetite [1, str, tbl] only aluminum to restore Ti, Fe, Si, Mn and V from their oxides, in the resulting alloys titanium can be up to 40%. If the first Fe, mn and V from their oxides to restore silicon obtained iron with the addition of Mn and V drain, then Ti and Si from their oxides to recover aluminum, the obtained alloys titanium can be up to 65%.

In the melting process of the proposed method it is possible to count on an almost full recovery from concentrate ilmenite Fe, Si, Mn and V from their oxides. Full recovery of titanium oxide may not be as part of titanium oxide in the slag can log in trudnoustranim connection. In this case, there will be less spent aluminum on the recovery of titanium and will increase the proportion of Al in the reduction of iron, the price is significantly less than the price of titanium. This reduces the economic effect from the implementation of the method, but still the effect is significant.

Two enter into the slag melt of calcium oxide allows, firstly, to reduce the melting point of the slag melt, making it fluid, and secondly, to contribute to the decline of education in the slag trudnoustranim compounds, including titanium oxide.

The PE the first metal melt (iron with a small amount of Si, Mn and V) merges overheated 250-300°due to the fact that the slag in the melting chamber of the unit should have a temperature of about 1750-1800°C. it is Advisable to use this overheating due to input into the receiving ladle any useful additives, such as carbon (get steel or cast iron), steel scrap (increase the weight of the metal in the ladle), etc.

Incomplete plums from the melting chamber of the first unit of iron, and then ligatures, especially in terms of their rotation have the following positive aspects:

- portions of the mixture are introduced on a liquid substrate or of iron, or ligatures, and it is generally accepted in staleplavilnymi positive operation;

- rotation of minor amounts of leave in the melting chamber of the metal phase of iron or ligature allows you to place this number in the area of the magnetic field obtained from crucible induction melting part of the unit. To metal, therefore, due to the induced currents can enter the maximum amount of energy, and this prevents freezing of the refractory alloy in the melting chamber in the event of any delay to its drain;

- rotate left in the melting chamber ligatures frees the Central part of the bottoms from the ligatures known method to reveal the Central tap-hole and a tapped drain shall be in the bucket of the final slag - the product is of high value;

- featured plum iron and ligatures through the side tapped in terms of rotation in the melting chamber allows, first, to drain the iron and alloys free from slag inclusions that the discharge will tesnyatsya to the center, and, secondly, plum will be accelerated, which reduces the cycle time of the processing of the two portions of the charge;

rotation of the metal phase of the electromagnetic field generated by MHD devices, which are placed on the bottom of the melting unit, ensures good mixing of the metal due to the rotation, and due to the constant rise and plum on the metal walls of the melting chamber by the action of centrifugal forces. The latter is especially useful because it allows you to have accelerated mussalman between the metal and slag phases, for example, when Ti from the metal phase will be to restore the oxides of the molten second portion of the charge.

Importantly, the proposed method:

1. From the first portion of the charge aluminum oxide restores in the metallic phase of Fe, Ti, Si, Mn and V, and in the beginning of this portion of the charge Ti from nakitai part ligatures recovers from oxides of Fe, Si, mn and V.

2. Obtained from the first portion of the mixture of titanium-containing master alloy with a relatively low content of Ti is not merged, and the titanium used is for the recovery of metals from oxides, contained in the second portion of the charge, resulting in the metal melt is released from Ti and becomes mainly in the iron melt with additions of Si, Mn and V. This melt is a second metal product. This product is mostly from the melting chamber of the unit merges and frees space for then produced from the slag of the first product - vysokotekhnologicheskoi ligatures.

3. Subsequent recovery of titanium oxide aluminum makes the first metal product in wysokometanowego the ligature.

4. The final slag is suitable for the production of a high quality cement or alumina.

Important is the fact that most of the reduction reactions in the proposed method, go without the formation of gas phase, which dramatically reduces the cost of gas exhaust equipment and allows you to create in the melting chamber, if necessary, an inert atmosphere, preventing, for example, undesirable oxidation of Al at its input on recovery operations and other

Technological scheme of production vysokotekhnologicheskoi ligatures shown in the drawing. An example of the proposed method is implemented in this scheme.

For example, the mass of the first portion supplied to the smelting of ilmenite concentrate is assumed to be 3 tons is m The chemical composition of ilmenite concentrate will accept the way it is shown in [1, str, table, column 2].

The following composition, %: Fetotal- 36,30; FeO - 34,37; Fe2About3- 13,30; Tio2- 44,90; SiO2- 2,80; Al2About3to 0.92; CaO - 0,62; MgO - 0,62; V2About5to 0.21; MnO - 0,79; CR2O3- 0,03; P - 0,05; S - 0,91.

We adopt the following assumptions, which only slightly affect the final result of the calculation.

1. Introduced into the melting unit for recovery of oxides of aluminum fully consumed in the slag phase is not dissolved in the metal phase and is not oxidized by the oxygen of the atmosphere, because the melting process is carried out in conditions when in the melting chamber Assembly created non-oxidizing atmosphere.

2. Not considered a reduction of the yield of titanium in the alloy because of the possible nedoustanovlennoy oxides of titanium and aluminum.

3. The oxides of magnesium and calcium aluminum is not restored.

4. The presence of chromium and phosphorus is not considered because of their smallness.

5. It is assumed that the majority of the sulphur will be contacted with calcium oxide, and its amount in the iron-containing product is valid.

In order from the first portion of the charge weight 3T to recover aluminum, Fe, Ti, Si, Mn and V, it is necessary from their oxides pick 933 kg of oxygen, and it takes 1050 kg of aluminum.

In the metallic phase after vos is Stanovlenie oxides will be: Fe - 1089 kg; Ti - 808,2 kg; Si - 39,2 kg; Mn - 18.3 kg; V - 3,5 kg

In the primary slag will be: Al2About3- 2010,2 kg; MgO - 18,6 kg

So in the primary slag was not less than 20% of Cao, it is necessary in the slag to enter 500 kg Cao.

Since the reduction reaction of aluminum oxide exothermic, i.e. heat, as the recovery of Fe, Ti, Si, Mn and V will be released heat, which would be enough to melt the input 500 kg Cao and to the temperature of the slag melt was about 1750-1800°C (at this temperature the slag is fluid). One kg of aluminium in the oxidation of oxygen in the oxide allows to obtain 4-4,5 kW·h energy 2050 kg aluminum will get 4000-5000 kW·h energy.

Specified amounts of energy almost enough to melt the first portion of the charge, filed simultaneously with the filing of aluminum, in order to have the desired temperature of the slag, and also to compensate for the heat loss in the melting unit. If energy is not enough, the crucible portion of the melting unit this shortfall will be offset.

After melting the first portion of the charge in the melting unit at a set time, depending on the speed of recovery of the oxides of the charge titanium, enter the second portion of the charge. The weight of the mixture shall conform to the ability of titanium to restore those oxides in the charge that t is an can recover. In this case, the titanium will restore from the second portion of Fe, Si, Mn and V. Recoverable metals will be launched in the metallic phase, and titanium from this phase will be to leave oxidized into the slag phase.

If the whole of titanium metal phase will be spent, according to the calculations of the second portion of the ilmenite concentrate should have a weight of approximately 4 tons.

Metal phase after restoring with titanium oxide of 4 tonnes of concentrate will be: Fe - 2532 kg (94,7%); Si is 91.5 kg (3.6%); Mn - 42,7 kg (1,6%); V - 8,2 (0,3%). All of the metal phase will be 2674,4 kg the mass of the slag phase will increase and it will be 2010 kg Al2O3, 500 kg Cao; 43,4 kg MgO and 3143 Tio2.

If according to the technological scheme of the melting chamber to drain 90% of the iron-containing alloy, the camera will remain 267 kg of this alloy, in which: Fe - 253 kg; Si - 9.1 kg; Mn - 4.3 kg; V - 0,82.

To the mass of the alloy after reduction with aluminum 3143 kg Tio2added to 1890 kg titanium and just vysokotekhnologicheskoi ligatures will be 2157 kg, in which: Ti - 87,6%; Fe - 11,73%; Si - 0,42%; Mn - 0,2%; V - 0,039%.

Aluminum recovery of titanium oxide will be spent 1414 kg, and only after remelting of the two portions of the charge 2464 kg

In the final slag oxide Al will 4654 kg, Mg oxide - 43,4 kg To end the slag of calcium oxide was not less than 20%, already put 500 kg Cao should add more porjadka kg Cao. The weight of the final slag will be 6090 kg, which will be: Al2About3Is 77.5%; CaO - 21,7%; MgO Is 0.72%. Such a slag suitable for the manufacture of him high-alumina cement, for example, the brand VHC-1, and to extract the alumina.

Calculations of the efficiency of the proposed method show that excluding the cost of production from the processing of the final slag profit from recycling 1 ton of ilmenite concentrate can make up to$200, and when you consider the cost of products that can be obtained from the final slag, the profit can be up to 400$ per 1 ton of concentrate.

Remelting of the two portions of the charge in the developed multifunctional melting unit (MPA) presumably can be made for 1 year. If the MPA will work, for example, 6000 hours per hour, during this time you will be processing about 40 thousand tonnes of ilmenite concentrate and to have an annual profit of from 8 to 16 million dollars.

To implement the method, it is recommended to apply the developed multifunctional melting unit (MPA) [6].

MPA includes two energy node (crucible node to heat the molten metal to a temperature of 1800°and site MHD machinery to ensure the rotation of the melt in the melting chamber and the site drainage and the supply of metal melt in the melting chamber. The capacity of the crucible host up to 6 MW. Power is here MHD technology to 0.6 MW.

On MPA practicable all necessary operations according to the present method (appropriate supply of ilmenite concentrate for smelting, input reductant oxide, to create the rotation of the metal and the slag melt, regulated power supply, plum products smelting and so on).

MPA suitable for efficient melting of previously obtained iron to free him from sulphur, if it is in the gland above the permissible limits according to GOST.

Titanium, as is known, has a high reactivity at elevated temperatures, particularly with respect to oxygen, nitrogen and carbon. The presence of even small amounts of these substances leads to the formation of oxides, carbides and nitrides of titanium. The proposed technology and the proposed technologies MPA eliminates the contact of titanium with these substances.

The technical result from application of the proposed method is as follows:

Not less than two times the energy consumption is reduced to the processing of ilmenite concentrate, because in the process for recovering metals from oxides are not endothermic reaction (heat absorption)and exothermic (heat).

Used the fact that the high content of titanium oxide in ilmenite concentrates (up to 45%) allowing due to the high price the OIC difference in the cost of titanium, on the one hand, and the value of Al, on the other hand, with a positive effect, use a strong metal reducing agent, such as Al, resulting in several times reduces the payback period of technological equipment, sadasivaiah for the implementation of the proposed method.

Implemented practically waste-free technology.

Implemented advanced technology of liquid-phase recovery of metals from oxides under the conditions of rotation of the melt electromagnetic field which is applied, for example: it is useful to use a centrifugal effect; rapidly melt supplied to the smelting ilmenite concentrate and rapidly implement after melting the mass transfer between the slag and metal phases, the more that it becomes possible to introduce a reductant into the slag phase through the metal phase; simplify operations by periodically removing the metal and slag phases of the furnace Assembly.

The process is carried out without or almost without releasing gas from the melt, which simplifies the design of the melting unit and eliminates the need for equipment removal and gas cleaning.

Sources of information:

1. Leontiev L.I., Vatolin N.A., Shavrin SV, Chumanov NS Pyrometallurgical processing of complex ores. M.: metallurgy, 1997, s.

2. Pat the NT of the Russian Federation No. 2206630. A method of processing vanadium bearing titaniferous magnetite ore tianity cast iron, vanadium slag and titanium-containing alloy / kites E.A., P.A. Smirnov, Burkin S. p., Deryabin Y.A., Loginov YU.N., Mironov, GV, IPC With 22 33/00, 37/00, Appl. 31.05.2001, publ. 20.04.2001, Bulletin No. 11.

3. Tarasov A.V., Utkin P.I. General metallurgy. M.: metallurgy, 1997, s.

4. Edneral FP electrometallurgy of steel and ferroalloys. M: Metallurgizdat, 1963, s.

5. The patent of Russian Federation № 2165461. Method for the production of pig iron and slag / kites E.A., P.A. Smirnov, Burkin S. p., Tarasov A.G., Loginov YU.N., Sarapulov FN. MKI With 21 In 11/00, Appl. 27.05.99, publ. 20.04.2001, Bulletin No. 11.

6. Application for patent of the RF No. 2001113326/02 (013744) dated 14.05.2001. The melting unit. Authors: E. Korshunov, Sarapulov F.N., The Burkin S. p., Tarasov A.G., Arakelyan O.A., Tretyakov B.C.

1. Method of manufacturing vysokotekhnologicheskoi ligatures, including the melting of portions of the charge in the melting chamber of the unit on a rotating metal melt, the recovery of metals from the oxides of the charge, the fusion of recovered metals with a rotating metal melt, remove newly-formed metallic melts, remove slag, characterized in that after deposition of the first portion of the charge representing the ilmenite concentrate on rotating metal melt, representing vyskot anastasiadou the ligature, and restore with titanium and silicon part oxides from molten portions of ilmenite, aluminum restore all the oxides in the slag melt, in which the free energy of formation less than that of aluminum in the resulting slag add the first portion of the calcium oxide in an amount to provide the fluidity of the slag in the melt is injected second portion of the charge in an amount corresponding to restore titanium oxide, whose free energy of formation less than that of titanium, the resulting titanium oxide combined with the previously obtained slag established part of the obtained molten metal in terms of its rotation is drained through the side tapped, aluminum restore the titanium oxide of the United slag and restored titanium combined with the left metal melt, formed in the final slag enter the second portion of the calcium oxide in an amount to provide the fluidity of the slag, the installed portion of the received vysokotekhnologicheskoi ligature is drained through the side tapped, the rest of the ligature through its rotation is placed on the edges of the melting chamber, open the Central tap-hole and the final slag is drained, tapped close up and resume feeding in the melting unit first portion of ilmenite.

2. The method according to claim 1, characterized in that the melting chamber metal is a mini-melt, representing the iron with the addition of vanadium, silicon and manganese, merge in the number of 90-95%.

3. The method according to claims 1 or 2, characterized in that the discharge of molten metal in him introduce additional additives.

4. The method according to claim 1, characterized in that the melting chamber is drained 70-90% vysokotekhnologicheskoi ligatures.

5. The method according to claim 1, characterized in that the melting chamber melting unit to the final slag provide a temperature in the range of 1600-1800°and, accordingly, the set temperature of the slag under the terms of his giacopelli in the final slag is injected calcium oxide and bring its contents up to 20-30%.



 

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2 tbl, 4 ex

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3 cl, 3 tbl, 1 ex

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2 ex

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2 cl, 4 ex, 3 tbl

FIELD: iron metallurgy, in particular steel smelting industry.

SUBSTANCE: claimed material contains (mass %): viterite concentrate 40-42; aluminum 38-40; lime 5-12; magnesium 6-8; titanium 1-2. Invention allows increasing the refining ability of material due to modification low valence sulfur and phosphorus compounds in metal melt.

EFFECT: steel of improved quality.

1 tbl, 1 ex

The invention relates to the field of metallurgy, in particular to the development of complex alloys for deoxidation and alloying of steel and cast iron

The invention relates to the field of metallurgy and foundry

The invention relates to the field of metallurgy, namely to free the ligatures used for reduction, refinement and modification during secondary treatment liquid metal at its release from the melting furnace to a pouring ladle
The invention relates to metallurgy and can be used for alloying steels and alloys

FIELD: iron metallurgy, in particular steel smelting industry.

SUBSTANCE: claimed material contains (mass %): viterite concentrate 40-42; aluminum 38-40; lime 5-12; magnesium 6-8; titanium 1-2. Invention allows increasing the refining ability of material due to modification low valence sulfur and phosphorus compounds in metal melt.

EFFECT: steel of improved quality.

1 tbl, 1 ex

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