UA113351C2 - METHOD AND INSTALLATION FOR THE PRODUCTION OF TITANIUM SLAUGHTER FROM ILLENITE - Google Patents

Abstract

A method of producing titanium slag from ilmenite involves the operations of: a) partial recovery of granular ilmenite with a reducing substance in the reactor (6) recovery at a temperature of at least 900 ° C; b) transfer of partially recovered hot ilmenite obtained in operation a) to an electric furnace (12 ), c) melting of ilmenite in an electric furnace (12) in the presence of a reducing substance to form liquid iron and titanium slag, and d) unloading titanium slag from an electric furnace (12). The exhaust gas from the recovery reactor (6) is introduced into the heat recovery boiler (20).

Description

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The field of technology

The present invention relates to a method of producing titanium slag from ilmenite, and to the corresponding installation.

Ilmenite, which contains titanium dioxide and iron oxides, is one of the most important starting materials for the recovery of titanium metal and titanium compounds, for example, titanium dioxin for the production of pigments. Iron is separated from coal because the electrosmelting of ilmenite in a metallurgical furnace is always used to restore ilmenite, and iron oxides are reduced to metallic iron, which is precipitated from slag containing titanium dioxide.

The main disadvantage of this method is the significant consumption of electrical energy, which is approximately 2200 kWh per ton of titanium slag and is the main item of production costs.

Until now, titanium slag plants are economically feasible only in countries where the cost of energy is low, mainly in countries where hydropower is available, such as in Canada or Norway, or where energy is obtained from low-cost coal, such as in the South Africa The increase in energy costs and the restriction of energy supply for energy-intensive industries led to a negative impact on the economic situation of slag producers. Currently, approximately half of the world's titanium slag production is provided by the use of energy produced from coal, and the other half - by the use of hydropower. Furnaces of various designs are in operation, for example, rectangular or circular, with pre-fired or self-sintering electrodes, hollow or solid electrodes, with the supply of materials through the hollow electrode or through the furnace vault, alternating or direct current to ensure the melting power.

Most of the plants work according to the traditional melting technology, when cold raw ilmenite is fed for remelting.

It was proposed to produce titanium slag based on pre-reduced ilmenite, where ilmenite and a solid reducing agent, such as coal or semi-coke, are introduced into a drum furnace that serves as a reduction reactor. The hot exhaust gas from the drum furnace is sent to the next combustion chamber, in which carbon monoxide and hydrogen contained in the exhaust gases are burned, and then the exhaust gas, which has a temperature of 900-10007C, is fed to the heat recovery boiler for steam production. Because of the high temperatures obtained in the chamber

From the next combustion, it is necessary to pump water to avoid the formation of layers on the walls of the chamber of the next combustion. Equipment costs are quite high, and energy efficiency is unsatisfactory.

The applicant proposed in the international publication ULO 2006/048283 JSC a method of obtaining titanium slag from ilmenite, in which granular ilmenite is first partially reduced with a reducing agent in a reduction reactor, and then the hot material, which has an inlet temperature of 500-900"7С, is fed into an electric furnace and melted there in the presence of a reducing agent to form liquid iron and titanium slag. The reduction reactor has a fluidized bed into which the ore that has undergone several preheating stages and a carbonization reactor are introduced. From the fluidized bed reduction reactor, a mixture of partially reduced ilmenite and semi-coke is taken at temperature of approximately 1000 and cooled to approximately 700"C before being loaded into a magnetic separator, where the fraction enriched in titanium dioxide and metallic iron is separated as a magnetic product from the non-magnetic fraction. The magnetic fraction is loaded into an electric melting furnace, which operates at about 1700 "C, and produces titanium slag, which has a mass fraction of 75-90 95 titanium dioxide, and liquid iron, which has a mass fraction of more than 94 95 metallic iron. The waste gas from the electric furnace , which contains a volume fraction of more than 90 95 carbon monoxide, after dust removal, is burned in the next combustion chamber. The hot waste gas is fed to a gas heater to heat the fluidized gas that is introduced into the recovery reactor. Although in the system disclosed in the international publication MLO 2006/048283 JSC, a significant reduction in energy consumption during the production of titanium slag has already been foreseen, there is still potential for further improvement.

Description of the invention

Thus, the task of the present invention is to further reduce energy consumption during the production of titanium slag. In addition, CO emissions will be reduced."

According to the present invention, a method is proposed, which includes the features given in clause 1 of the claims. For the production of titanium slag from ilmenite, granulated ilmenite is partially reduced with a reducing agent in a reduction reactor at a temperature of at least 900°C, in particular 1000-11507°C. The partially reduced hot ilmenite is then fed into an electric furnace, where it melts in the presence of a reducing agent to form liquid cast iron and titanium slag, which are removed from the electric furnace. In the context of this application, the terms "electric furnace", "electric recovery furnace" and "melting furnace" are used synonymously to describe the same means. According to the invention, the waste gas of the reduction reactor is fed to heat recovery boiler Preferably, there is a direct connection between the heat recovery boiler and the recovery reactor.

In contrast to known methods, the waste gas from the reduction reactor is not fed to the subsequent combustion chamber, in which the carbon monoxide and hydrogen contained in the waste gas are burned, and then the waste gas with a temperature of 900-11007C is fed to the heat recovery boiler to generate steam. More precisely, the invention proposes to abandon the chamber of subsequent combustion, and to connect a heat recovery boiler with a recovery reactor. Thus, equipment costs can be significantly reduced. In addition, it is possible to dispense with the necessary injection of water into the afterburner chamber for adequate cooling. In a preferred embodiment of the present invention, the reduction reactor is a drum furnace into which, in particular, coal and/or semi-coke is fed as a solid reducing agent. In an alternative embodiment of the invention, the reduction reactor may have a fluidized bed, as described in UMO 2006/048283

A1, moreover, a gas containing carbon or hydrogen is used as a reducing agent.

In order to further increase the energy efficiency of the process, the waste gas of the electric furnace is also introduced into the heat recovery boiler.

Preferably, the waste gas of the electric furnace is cooled and/or cleaned before being introduced into the heat recovery boiler.

In particular, when coal and/or semi-coke is used as a reducing agent, the partially reduced ilmenite is preferably subjected to magnetic separation before loading the material into an electric furnace to separate the magnetic fraction, which contains titanium dioxide and iron oxides, from the non-magnetic fraction, which contains a significant amount of ash and excess semi-coke, if it is used as a reducing agent. Only the magnetic fraction obtained by magnetic separation is fed into the electric furnace. In this case, the temperature of the partially reduced material used during the magnetic separation is preferably about 7009 C. According to the invention, the magnetic fraction is then fed into an electric melting furnace without cooling or heating. Thus, the energy required to heat the material fed to the electric furnace to the operating temperature in the furnace is minimized without significant re-oxidation

From partially recovered material before entering the electric furnace.

The energy efficiency of the process is further increased if the excess solid fuel (semi-coke) from the recovery reactor and/or carbon containing fine waste separated by magnetic separation is fed into the heat recovery boiler and burned in it. Thus, the calorific value of these materials can also be used in this process.

The installation according to the invention, which is acceptable for the implementation of the method described above, has features according to clause 7 of the claims. In particular, the installation includes a reduction reactor for the partial recovery of granular ilmenite, a magnetic separator for separating the reduced ilmenite and non-magnetic fraction by magnetic separation, and an electric furnace for melting ilmenite in the presence of a reducing agent to obtain titanium slag and pig iron. At the same time, the heat recovery boiler is connected to the recovery reactor.

Preferably, the heat recovery boiler has a radiation heat transfer section and a convection heat transfer section, and the radiation heat transfer section is connected to the recovery reactor.

In the most preferred version, in the side wall of the heat recovery boiler there are additional burners for burning solid carbon residues introduced into the heat recovery boiler.

Preferably, the recovery reactor is a drum furnace. In an alternative embodiment of the invention, the recovery reactor has a fluidized bed.

A cooler may be provided behind the recovery reactor. Preferably, the cooler is a drum cooler in which indirect cooling occurs by heat exchange with water to cool the solid material leaving the recovery reactor at a temperature of about 10007°C to a temperature of about 700°C before loading it into the magnetic separator.

In a heat recovery boiler, steam generation is carried out in a generally known way in this area. Preferably, a turbogenerator for generating electricity is located behind the heat recovery boiler.

According to the invention, there is a return pipe to transfer the waste gas from the electric furnace to the heat recovery boiler, so that the heat of this waste gas is also used in this process.

Next, the invention will be described in more detail on the example of the preferred embodiment of the invention and the attached drawings. All described and/or shown features form the subject matter of the present invention by itself or in any combination, regardless of their inclusion in the claims or their back reference.

Brief description of the drawings

In fig. 1 shows a diagram of the installation according to the present invention.

In fig. 2 shows a diagram comparing the capacities, CO emissions and energy consumption of prior art installations and the installation of the present invention.

In fig. C shows the possible annual savings in energy costs if this invention is applied in an existing installation for the production of titanium slag.

Description of the best implementation options

In the method of producing titanium slag from ilmenite (Fig. 1), a mixture of ilmenite and coal and/or semi-coke is fed from bunkers 1, 2, Z to a roller feeder 4 or an equivalent feeding device and then fed to a gas-tight double pendulum valve 5, and from there to the inlet sections of reactor 6 recovery, in particular, the drum furnace. The drum furnace preferably has a slope of 1-3 95 to ensure solid material movement through the reactor. Process air is introduced into the drum furnace through air fans 7 in the reactor shell. Additional coal for temperature regulation and/or sulfur, if necessary for partial removal of manganese, and air are injected countercurrently through nozzle 8. In the reduction reactor 6, ilmenite is partially restored with the help of reducing substances, in particular, coal and semi-coke, at a temperature of 1000-11507C, in particular about 1100"C, to a degree of metallization of about 70 95, based on the iron content.

From the recovery reactor, the mixture of partially reduced ilmenite and excess semi-coke at a temperature of approximately 1100"С is continuously discharged through the chute 9 into the drum cooler 10, where it is indirectly cooled with water to a temperature of approximately 700"С. Like the drum furnace, the drum cooler 10 is slightly inclined to allow movement of the material flow. At the outlet end of the drum cooler 10, the larger lumps of ore are removed, for example by means of a sieve, crushed and treated separately to recover the titanium and iron.

The remaining material is loaded into the magnetic separator 11 at a temperature of approximately 700 °C, where the magnetic material (titanium dioxide and metallic iron) is separated from the non-magnetic materials by hot magnetic separation. The non-magnetic materials include, in particular, ash and excess semi-coke, which are not used for recovery in reactor 6 recovery.

The magnetic fraction (reduced ilmenite) is then loaded into an electric reduction furnace 12 (melting furnace) which operates at approximately 17007°C to produce titanium slag having a mass fraction of 75-90 95 titanium dioxide and liquid iron having a mass fraction of more 94 95 metallic iron.

The waste gas from the recovery reactor 6 is introduced into the heat recovery boiler 20, which has a section 21 of heat transfer by radiation and a section 22 of heat transfer by convection. The recovery reactor 6 is directly connected to the heat transfer site 21 by the radiation of the heat recovery boiler. Additional solid fuel, in particular, excess semi-coke returned from the magnetic separator 11 and air is also introduced into the heat recovery boiler 20 to promote combustion. Waste gas from the electric recovery furnace 12, which contains a significant amount of volume fraction often more than 90 95 carbon monoxide, after dust removal, is preferably returned to the heat recovery boiler 20 through the return pipeline 23.

Additional burners 24 can be installed in the side wall of the heat recovery boiler 20 to burn the carbon contained in the material. Emergency valve 25 is activated during off-duty operation. The dust deposited in the lower part of the heat recovery boiler 20 is removed and returned to the recovery reactor 6 along the line 26. The exhaust gas is removed from the heat recovery boiler 20 through the outlet 27 and cleaned in the electrostatic precipitator (ESD) 28 before being discharged through the flue pipe 29. The remaining dust can be returned to the recovery reactor 6 or returned to the mine as waste.

The heat produced in the heat recovery boiler 20 is used to obtain high-pressure steam in the steam drum 30 at a pressure of 40-60 bar and a temperature of 350-600"C, preferably 400-5407C. The steam is additionally heated by passing it through the heat transfer section 22 by convection of the heat recovery boiler 20 and fed to the turbine generator 31 to generate electricity. The expanded steam is condensed in the cooler 32, which is connected to the cooling tower 33. The water thus obtained is deaerated in the deaerator 34 before being fed to the feed tank 35 for use in production Additional fresh water can be added after demineralization in the demineralizer 36. The water is then passed through the convection heat transfer section 22 of the heat recovery boiler 20 to preheat it before entering the steam drum 30.

When using preheated, reduced ilmenite, as well as heat from the recovery reactor b and the electric furnace 12, the energy consumption of the recovery electric furnace 12 can be reduced by approximately 60 95 in comparison with the usual melting of raw ilmenite. In addition, it is possible to significantly increase the throughput of the electric furnace 12 and improve product quality by reducing the amount of ash introduced into the melting furnace.

Examples

In fig. 2 shows the influence of the use of pre-reduced ilmenite and the use of latent heat from various devices of the installation on power, CO emissions? and energy consumption in the titanium slag production plant.

In fig. 2, option A refers to the standard method, in which ilmenite is introduced into the melting furnace at room temperature (25"7C) and with zero metallization. In option B, the degree of metallization is 70 95, but still ilmenite is fed at a temperature of 25"C, and in in option C, the temperature is additionally increased to 65092 C. Option OO refers to a concept similar to option C, where the heat from the waste gas of the furnace is used in a heat recovery boiler. In the variant

E, additionally, the excess semi-coke, which is removed from the drum furnace, is burned in the heat recovery boiler, and in option B, the waste gas from the electric furnace 12 is also returned and used in the heat recovery boiler.

The size of the electric recovery furnace (melting furnace) and the power of the corresponding electric transformers are the same for all options A - P. The greatest impact on energy reduction is provided in options C (use of reduced ilmenite with 70 95 metallization and a supply temperature of 650") and O (additional use latent heat from the waste gas of the drum furnace for the production of electricity.) Option E additionally includes the burning of excess semi-coke of the furnace discharge, and option E also includes the burning of cooled and purified carbon monoxide (CO) and hydrogen (H»g), which are in waste gas from an electric furnace.

In addition, energy optimization could be achieved by using the physical heat of those exhaust gases that leave the electric furnace at a temperature of approximately 1400 - 1500" C in a separate heat recovery boiler.

Basic option A corresponds to the currently most common conventional technology for the production of titanium slag. The supply of pre-reduced and pre-heated ilmenite according to option C reduces the electric energy consumption at the electrodes of the electric reduction furnace to about 58 95 of the value required in option A. Thanks to this, the productivity of the electric reduction furnace can be increased by about 73 95.

By additional energy utilization of the flue gases and excess semi-coke of the drum furnace, as well as the flue gases of the electric furnace for power generation, the total energy consumption of the electric furnace per ton of titanium slag can be further reduced to about 39 95 of the value in option A. This already provides the energy required for preliminary recovery in a drum furnace and electricity production.

The obtained values for options A - E can be seen from Table 1. The calculations were made based on an electric melting furnace with cold feed, which has an annual output of 250,000 tons, as in option A. To feed preheated (650"C) and of pre-reduced ilmenite with 70 95 metallization, the productivity of an electric melting furnace of the same size increases to 432,000 t/year.

Table 1

Energy consumption of an electric melting furnace for the production of titanium slag about Warrant | | | And | In | C | 0 | E | in

In this example, option U provides a power reduction of 1134 kWh per ton of titanium slag. If the price is 1.0 US cents/kWh, this results in a cost reduction of 11.34 US cents per ton of slag . Assuming a more realistic price of 5.0 US cents/kWh, this results in a cost reduction of $56.70 per ton, or approximately $24.5 million per year Figure C shows the potential annual savings in options C-E, based on the difference in energy prices.

Another important advantage of the combination of a drum furnace with an electric melting furnace is the reduction of COg emissions, which is for option E only 69 95 COg emissions of option A. This reduces CO emissions: at the level of approximately 1000 kg per ton of slag. Option B provides a moderate reduction in COg emissions only due to additional CO2 emissions from the recovery unit. This largely offsets the reduced CO2 emissions achieved by reducing the energy requirements of the electric melting furnace. Real CO reduction is achieved by feeding heated ilmenite and using latent heat to generate electricity. Table 2 shows estimated CO emissions: for options A - E.

Table 2

Emission of CO" during the production of titanium slag about Warrant | | / A | in ' HER with | 0 | E | EE

Regarding the above example, approximately 0.4 tons of pig iron is simultaneously produced per ton of titanium slag. Thus, it is also necessary to consider the corresponding emission of COg during the external production of cast iron. Standard values are approximately 1,500 kg of CO2 per ton of cast iron. This further reduces CO2 emissions from approximately 600 kg CO2 to approximately 1,700 kg

Saturday"; per ton of titanium slag.

List of references 1 - feed hopper (ilmenite) 2 - feed hopper (coal)

C - feed hopper (semi-coke) 4 - feeder 5 - double pendulum valve b - recovery reactor 7 - air fan in the reactor shell 8 - nozzle 9 - chute 10 - cooler 11 - magnetic separator 12 - electric recovery furnace (melting furnace) 20 - heat recovery boiler 21 - radiation heat transfer section 22 - convection heat transfer section 23 - return pipeline 24 - burner 25 - emergency valve 26 - line 27 - outlet 28 - electrostatic dust collector 29 - smoke pipe 30 - steam drum 31 - turbogenerator 32 -- refrigerator 33 - cooling tower 34 - deaerator 35 - feeding tank 36 - demineralizer

Claims (14)

FORMULA OF THE INVENTION 1. The method of producing titanium slag from ilmenite, which consists in: 50 a) partially reducing granulated ilmenite with a reducing agent in the reactor (b) reduction at a temperature of at least 900 "C, b) transfer partially reduced hot ilmenite obtained in operation a) to an electric furnace (12), c) melt ilmenite in an electric furnace (12) in the presence of a reducing agent to form liquid iron and titanium slag, and d) discharge titanium slag from electric furnace (12), which differs in that the waste gas from the recovery reactor (b) is introduced into the heat recovery boiler (20). 2. The method according to claim 1, which is characterized by the fact that the recovery reactor is a drum furnace or a reactor containing a circulating fluidized bed. Q. The method according to claim 1 or claim 2, which differs in that the waste gas of the electric furnace (12) is introduced into the heat recovery boiler (20). 4. The method according to any of the previous items, which is characterized by the fact that the waste gas of the electric furnace (12) is cooled and/or cleaned before entering the heat recovery boiler (20). 5. The method according to any of the preceding points, which is characterized by the fact that before feeding into the electric furnace (12), the partially reduced hot ilmenite is subjected to magnetic separation, and the magnetic fraction obtained in this way is loaded into the electric furnace (12). 6. The method according to any of the previous clauses, which differs in that the excess solid fuel from the recovery reactor (b), separated by magnetic separation, is introduced into the heat recovery boiler (20) and burned in it. 7. Installation for the production of titanium slag from ilmenite, in particular, for the implementation of the method according to any of the previous items, which has: a recovery reactor (6) for partial recovery of granular ilmenite at a temperature of at least 900 "C, a magnetic separator (11) for separation reduced ilmenite from the non-magnetic fraction by magnetic separation, and an electric furnace (12) for smelting ilmenite in the presence of a reducing agent to obtain titanium slag and cast iron, which is characterized by the fact that a heat recovery boiler (20) is connected to the recovery reactor (b). Zo 8. The installation according to claim 7, which differs in that the heat recovery boiler (20) has a radiation heat transfer section (21) and a convection heat transfer section (22), and the radiation heat transfer section (21) is connected to the reactor ( 6) recovery. 9. Installation according to claim 7 or claim 8, which differs in that the additional burners (24) are installed in the side wall of the heat recovery boiler (20). 10. Installation according to any of claims 7-9, which is characterized in that the recovery reactor (6) is a drum furnace. 11. Installation according to any of claims 7-9, which is characterized in that the recovery reactor (6) has a circulating fluidized bed. 12. Installation according to any of claims 7-11, which is characterized by the fact that a cooler (10) is located behind the recovery reactor (6). 13. Installation according to any one of claims 7-12, which is characterized by the fact that behind the heat recovery boiler (20) there is a steam drum (30) and a turbogenerator (31) for obtaining energy. 14. Installation according to any one of claims 7-13, which is characterized by the fact that it has a return pipe (23) for transferring the waste gas from the electric furnace (12) to the heat recovery boiler (20). 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