KR20090034386A - Method and apparatus for reducing metal containing materials to reducing products - Google Patents

Abstract

The present invention is directed to a method for reducing a metal containing material to a reducing product and an apparatus for reducing a metal containing material to a reducing product.

Description

METHOD AND APPARATUS FOR REDUCING METALLIFEROUS MATERIAL TO A REDUCTION PRODUCT}

The present invention relates to a method for reducing a metalliferous material to a reducing product. The invention also relates to an apparatus for reducing a metal containing material to a reducing product.

Reduction of metal-containing materials such as metal-oxygen compounds, metal-oxides, for example iron oxides, is carried out in large scale reduction furnaces. The blast furnace in the reduction of iron-oxygen compounds has been a convenient device for producing pig iron from metal-containing materials such as iron-oxygen compounds or iron ores for over a century. The source of chemical energy and the first reducing agent in this blast furnace was coke.

Coke is produced by baking coal in the absence of oxygen to remove volatile hydrocarbons and to give the coke an important characteristic for stable blast furnace operation. Coke production is problematic from an environmental point of view because many volatile hydrocarbons are harmful. Also, not all types of coal are suitable for coke production. The demand for by-products of coke production has also been reduced. Therefore, reducing coke consumption and overall fuel consumption of blast furnaces is a major focus of recent developments. Direct injection of coal into the blast furnace is one of these developments. In addition, new technologies have been developed to overcome the blast furnace process, such as the direct reduction of iron ore.

The direct reduction method is to produce iron by reducing the iron ore with a reducing agent which may be a gas reducing agent or a solid reducing agent at a temperature below the melting point of iron. The solid reducing agent may be coal of any size instead of coke. Examples of gas reducing agents are natural gas, hydrogen and carbon monoxide (CO).

The direct reduction of iron ore can be combined with the final reduction product in the form of solid direct-reducing iron, or with a melting device to produce a liquid product. The final reduction product of the direct reduction process can be discharged into the second reactor for melting and optionally further refining, or cooled and stored for later use.

Dust and sludge from integrated steel operations are currently recycled as raw material for the ore manufacturing stage. Often referred to as 'fines', these wastes may contain iron-containing compounds such as iron oxide. However, due to the metal content such as zinc or zinc-compounds in the fines, the accumulation of the element and the limitation of the amount of the metal to fill the blast furnace, the waste has to be recycled or disposed of in another way, thus adding additional cost. Occurs or is an environmental burden.

 The process in WO2005 / 116273 includes supplying solid carbonaceous materials such as coal and oxygen-containing gas to the fluidized bed of the first vessel, generating heat, converting coal to char, and It is known to reduce iron ore based on releasing a hot off-gas stream containing CO which is formed by partially oxidizing the charcoal. CO, charcoal, and unavoidable remaining solid particles (such as ash) are then transferred to a second vessel to reduce some or all of the metal-containing material. Solid reduction products containing some or all reduced iron ore fines can be further treated, if necessary, for example in the fluidized bed for the second reduction step to increase the degree of reduction. As a result of the high processing temperatures above 900 ° C., iron ore fines show a tendency to accretions and agglomerates. This sticking behaviour is controlled by forming excess charcoal in the first container. Another disadvantage is the formation of bulky complexes and the generation of dangerous hydrocarbons. Condensation of the hydrocarbons that requires off-gas removal or post-combustion should be avoided while preventing metal reoxidation. In addition, due to the high operating temperatures and consequent heat losses, the energy efficiency of direct reduction is generally poor, resulting in higher carbon consumption. In addition, due to the high operating temperature, dangerous nitrogen-oxygen compounds (NOx-gases) are formed in large quantities, or ammonia-type compounds are formed in large quantities under a reducing atmosphere. In addition, direct reduction techniques based on the direct use of coal have to deal with large amounts of sulfur because of the presence of sulfur in the coal.

US 3,788,835 discloses an iron ore reduction process in which most of the reduction is carried out with a gas reducing agent such as methane, which is separated into hydrogen and CO at high temperatures. Reduction of iron ore by gas reducing agent is carried out until metallization is obtained about 85 to 90%. While the ore is reduced in the zone where most metallization is obtained, carbon is deposited on the ore. After the degree of metallization is obtained up to about 85-90%, the deposited carbon is subsequently reacted with any remaining oxide in a separate separate inert stage to increase the metallization by 0.5-2.5%.

EP 1 568 793 discloses a method for reducing a metal-oxygen compound in a reduction reaction, in which carbon is used to reduce the metal-oxygen compound in which the metal acts as a catalyst for the reduction reaction. EP 1 568 793 discloses a reactor type which implements a method comprising an extruder type screw as a vehicle for solid reactants.

It is an object of the present invention to provide a method and apparatus for directly reducing metal-containing materials using solid carbon as the reducing agent.

It is also an object of the present invention to provide a method for reducing metal-oxygen compounds that can be operated at relatively low temperatures to increase energy efficiency and / or produce dangerous off-gases such as hydrocarbons and / or NOx-gases in small amounts and To provide a device.

It is also an object of the present invention to provide a method and apparatus for reducing metal-oxygen compounds, which can increase carbon efficiency per reduced metal weight unit.

In order to achieve one or more of the above objects, a method is provided for reducing a metal-containing material to a reduction product, the method comprising the following steps, wherein the substantially solid-solid reaction between the incomplete reduction portion of the reduction product and the solid carbon The following final reduction product is further reduced in the final stage reactor to increase the degree of metallization:

Providing a gaseous phase comprising gaseous CO by gasifying the carbon-containing compound using an oxygen containing gas flow;

Providing a metal containing material to the reaction chamber of a fluidized bed reactor;

Providing said gaseous CO to a reaction chamber of a fluidized bed reactor and converting said gaseous CO into solid carbon and gaseous carbon dioxide to precipitate solid carbon onto the metal-containing material and / or the reducing product;

Using the metal-containing material and / or the reducing product as a promoter to reduce some or all of the metal-containing material to the reducing product by means of solid carbon to convert gaseous CO to solid carbon and gaseous carbon dioxide; And

Draining the final reduction product from the reaction chamber.

The solid carbon is called Boudouard-carbon and typically has a crystal structure of graphite with a very high surface to volume ratio. For clarity, it should be understood that any other form of carbonaceous compound, such as coal or charcoal, is not solid carbon in the context of this description, despite the very high carbon content of such solid compounds. The CO may be fairly pure CO but may also be part of a gas mixture comprising CO. Solid carbon is generated by the separation of carbon monoxide by the following budoa reaction:

The reaction, which is an equilibrium reaction, moves to the right under suitable conditions such as temperature and pressure to form carbon. In addition, it was found that the metal-containing material or reduction product also promoted the formation of solid carbon by the boudoa reaction. In the context of the present invention, the reduced product is not a product having a defined degree of reduction, but expresses any reduced state between the reduced state of the metal-containing material having a reduced degree of zero and the reduced state of the final reduced product having a desired degree of reduction. It is important to be used. This means that reduction products of different degrees of reduction coexist during the process according to the invention. Thus, the degree of reduction of the final reduction product is the average reduction of the various fractions of the reduction products that make up the final reduction product. In the case of reducing iron ore (as a non-limiting example) as a metal-containing starting material, the degree of metallization of the reduction product is between the number of iron atoms in the iron-carbide and the metal iron relative to the total number of iron atoms in the reduction product. It is prescribed as a ratio. The ratio between metal iron and iron carbide depends on the process conditions of the reaction chamber.

It is believed that the reduction of metal-containing materials may be related to the presence of meta-stable carbides. Solid carbon or budoa-carbon may be reacted with the metal-containing material to yield metastable carbides which finally separate into carbon dioxide and the metal of the metal-containing material. Thus, in the context of the present invention, solid carbon includes buoa carbon and metastable metal-carbide. This process is shown schematically in Scheme 2 and simplified:

It is contemplated that such suitable conditions may be selected within the capabilities of those skilled in the art as far as the selection of suitable conditions in the reaction chamber is concerned. Small amounts of hydrogen are known to promote the formation of solid-carbon and carbon dioxide from CO by the boudoa reaction. Thus a small amount of hydrogen can be added to the CO when pure CO is used. In the present invention, at least 50%, preferably at least 70%, more preferably at least 80%, even more preferably at least 90% of the oxygen of the metal-oxygen compound is deposited after the final reduction in the final stage reactor. Binds to carbon. Such gas mixtures may also comprise hydrogen if a gas mixture comprising CO is produced, for example, by gasifying coal.

Preferably, the amount of hydrogen is at most 40% by volume, preferably at most 30% by volume, when technically pure oxygen is used as the oxygen containing gas flow in the gasifier, and the oxygen content in the gasifier. When air is used as the gas flow, the volume is preferably 8% by volume or less, more preferably 6% by volume or less. Hydrogen does not play an important role in the reduction of metal-oxygen compounds due to the selected operating conditions.

Preferably, the entire process of gasification, reduction and final reduction is carried out at super-atmospheric pressure. The inventors have found that an overpressure of at least 3 bar (g) and preferably about 5 bar (g) is preferred. Due to the pressure drop during the process, the pressure of the gasifier can be operated at 8 bar (g) to obtain an overpressure of 5 bar (g) at the FB. This allows the use of smaller reaction vessels and can have a beneficial effect on the process conditions in the vessels. It is also possible to operate the gasification and reduction reactions at ultra-atmospheric pressures and to carry out the final reduction at much lower pressures, preferably sub-atmospheric pressures, but as a result of this a very large final stage reactor, It is therefore important to realize that more capital and execution costs are needed.

It should be noted that in the process according to the invention it is essential to transfer the carbon formed from the gaseous CO in the reaction chamber to the reaction chamber in gaseous form and convert it to solid carbon in the reaction chamber by a budoa-reaction. Accordingly, the present invention preferably precipitates on a reduction product or metal-containing material which is converted into a gaseous state as a carbon oxide and is formed in the reaction chamber by reduction of the metal-containing material, optionally in the form of a carbide of the metal of the metal-containing material. Or do not add carbon in solid form to the reaction chamber, except that it precipitates on carbon that has already been precipitated by the Budoa-reaction. It should be appreciated that no reducing product may yet exist during the start of the reaction. It will only be present after some reduction of the metal-containing material. Previously reduced reduction products may also be added to help start the process quickly.

The formation of solid carbon from carbon monoxide is an exothermic reaction under reaction chamber conditions. The energy released by the exothermic reaction can advantageously be used for the reduction reaction in the reaction chamber of the metal containing material with solid carbon to produce a reduction product.

The use of a fluidized bed is important because of the high heat and mass transfer coefficients obtainable here by the high surface area to volume ratio of the particles. In the process according to the invention the reactants can be brought into close proximity to one another and are also highly reactive and the formation of one of the reactants, ie solid carbon, is an exothermic reaction in which fluid bed conditions are optimal for the reduction of metal-containing material particles. It is certain that metal-containing materials must have a specific morphology for fluidization. The maximum particle size of the metal-containing material that can be accommodated depends on the fluid bed design and operating parameters.

The method according to the invention has the advantage that the solid carbon required for the reduction of the metal containing material is formed in situ by exothermic reaction in a highly reactive form. This prevents the introduction of solid carbon containing materials such as less reactive, even disturbing properties, or solid carbon containing materials such as ash that no longer aid in reduction into the reaction chamber. This disturbing property may itself indicate contamination of the reduction product with sulfur, which may, for example, disturb the reduction reaction of the metal-containing material with solid carbon or disturb the formation of solid carbon. There is no risk for deposits and mass formation since the metal-containing material is provided to the reaction chamber of the fluidized bed and solid carbon precipitates from the gaseous carbon monoxide on the metal-containing material or reducing product, preferably in the reaction chamber.

In embodiments of the invention the degree of reduction of the final reduction product after withdrawing from the reaction chamber of the fluidized bed reactor is at least 50%. This amount provides a good starting point for reduction in the final stage reactor.

In one embodiment the reduction in the final stage reactor is carried out in a non-inert atmosphere. The non-inert atmosphere is important for making the desired reaction conditions for the final reduction product further reduced in the final stage reactor to the desired reduction or metallization degree at the end of the process. In one embodiment a hot gas flow comprising gaseous CO is fed to the final stage reactor. It has been found that introducing a hot gas flow comprising, for example, a gaseous CO derived from a gasifier, or a recycle process gas, yields suitable reaction conditions in the final stage reactor. In one embodiment oxygen and / or CO / CO ₂ containing gas is fed to the final stage reactor, preferably the CO / CO ₂ containing gas is fresh syngas, and / or is a recycle process gas, and And / or the oxygen containing gas is air or industrial pure oxygen. The final-stage reactor is fed with the reduction product from the final CFB together with the fresh synthesis gas or with the recycle process gas comprising air or industrial pure oxygen and CO injected into the final-stage reactor. The reaction in the final-stage reactor is exothermic and the heat released as a result of oxygen injection, which is preferably injected into the bottom of the final-stage reactor, promotes the conditions to reach the desired degree of reduction or metallization at the end of the process. .

In embodiments of the present invention the fluidized bed is of rapid fluidization or pneumatic conveying or toroidal fluidized bed reactor type. This type of fluidized bed reactor enables rapid fluidized bed formation that provides sufficient high reaction rates in gasification and residence time of solids to complete the reaction.

In one embodiment of the present invention the metal-containing material and gaseous CO are continuously or batchwise provided to the reaction chamber of a fluidized bed reactor to produce a reduction product continuously, and the final reduction product is continuously or batched in the reaction chamber. The method is carried out as a continuous process which can be discharged in a manner. In this embodiment the exothermic properties of solid carbon formation can be optimally used and the process can be carried out in the most economical way. In view of the unit mass per unit time of the reduction product, the capacity of the reactor is one of the parameters that can ensure optimal process efficiency and thereby process efficiency. The final reduction product released from the reaction chamber is in solid form and, as a result, the degree of reduction is higher than the degree of reduction of the metal-containing material provided to the reaction chamber as a feed material. It should be appreciated that the final reduction product can later be used as a metal-containing material in the process to further increase the degree of reduction. In the latter case, the degree of reduction is measured with respect to the degree of reduction of the metal-containing material prior to the first reduction process, which is generally assumed to be zero. The 50% reduction degree in the reduction product indicates that 50% oxygen in the metal-containing material was removed from the metal-containing material. 50% of the metallization means that 50% of the metal atoms originally present in the metal-containing material are in metal form and / or metal-carbide. The other 50% is still more or less oxidized. More specifically, a reduction of 50% may mean that the degree of metallization is still zero if all of the MeO ₂ (eg) has been reduced to MeO. It should be noted that the advantages of the present invention are fully utilized when the degree of reduction of the metal-containing starting material is 0%, but the preliminary reduction in which the degree of reduction of the metal-containing starting material can be, for example, higher than zero. It will be clear even if it is higher due to manipulation. In the case of iron ore, 100% Fe ₂ O ₃ will have a degree of reduction of 0%. Preferably the initial reduction degree of the metal-containing material is 25% or less, preferably 15 or less, more preferably 5% or less, and most preferably 0%.

In a preferred embodiment the degree of reduction of the final reduction product after withdrawing from the reaction chamber of the fluidized bed reactor is at least 50%, preferably at least 60%, more preferably at least 70%. The optimum degree of reduction must be such that the reduction is complete, i.e. at least 90 or 95% or higher, and in fact complete reduction or complete metallization can be achieved technically in a fluidized bed reactor. And not the most economical process. In addition, the tendency of adhesion of the reduced particles increases with increasing degree of metallization. The degree of reduction of the final reduction product is somewhat lower, at least 50%, preferably at least 60%, more preferably at least 70%, and the final stage substantially reduces the degree of complete reduction to 90 or 95 in the dedicated process stage of the final stage reactor. It confirmed that it was desirable to aim at the% or more.

In a preferred embodiment of the invention the metal-containing material is an iron-compound, preferably iron ore. The inventors can advantageously carry out the process according to the invention using iron-compounds, preferably iron ores, as metal-containing materials, which have advantageous temperature ranges and iron-compounds, preferably forming solid carbon from gaseous CO. Found that the advantageous temperature range for reducing iron ore to metal iron is at least partially consistent. This results in a very economical process for producing a final reduction product, or substantially metal iron, with a high degree of reduction or degree of metallization.

In embodiments of the invention the maximum temperature of the reaction chamber, preferably the maximum temperature of the reaction chamber when using an iron-compound as the metal-containing material, is 875 ° C., preferably 845 ° C., more preferably 825 ° C. and more. More preferably 800 ° C or 790 ° C. It has been found that even at this low temperature in the reaction chamber, reduction of the metal containing material by solid carbon can be effected to produce a reduction product. The exothermic reaction of the solid carbon formation can maintain a wide range of reactions, and low temperatures prevent the formation of dangerous nitrogen-oxygen compounds (NOx-gases), with favorable results limiting energy losses due to high process temperatures. . Another advantage of low operating temperatures is that the solubility of various elements in the metal can be reduced to obtain metals with high purity. It was confirmed that no significant reduction was observed at the reaction chamber temperature below 400 ° C. At about 450 ° C. or higher, for example 500 ° C., the reduction rate is significantly increased. It was found that a suitable minimum temperature of the reaction chamber was 640 ° C, preferably 690 ° C. However, although no significant reduction was observed at temperatures below 500 ° C., the presence of a reducing product or metal-containing material formed by the reduction of the metal-containing material, optionally through the metal carbide form of the metal-containing material or to Carbon deposition occurs very easily at temperatures between 400 and 500 ° C., as it promotes precipitation of solid carbon from gaseous CO over the carbon that has already been precipitated. The equilibrium state of the boudoa-reaction will move to the left (CO-side) at high temperatures, and this shift is prominent above 600 ° C. Above this temperature it was confirmed that carbon was deposited if solid carbon was already present.

In one embodiment of the present invention the promoter for conversion of gaseous CO to solid carbon and gaseous carbon dioxide also acts as an accelerator of the reduction of the metal containing material. Such promoters may be used to catalyze the formation of solid carbon from gaseous carbon monoxide, and / or the reduction of metal-containing materials by catalyst or another reaction mechanism, more rapidly, more completely, or at lower temperatures (or in combination with all of the above conditions). ) Has the function to execute.

The process according to the invention is an economical process for producing metal cobalt, nickel or alloys thereof from nickel-compounds, preferably nickel-ores, cobalt-compounds, preferably cobalt-ores, which are metal-containing materials. It should be noted that it is suitable for the phosphorus process.

In one embodiment of the invention the metal-containing material or in particular the iron-compound or iron ore is provided in the form of a fine compound or ore, preferably a crystal size of the compound or ore from 0.1 to 5000 μm. Suitable maximum grain size is 200 μm, preferably 100 μm. Preferably the crystal size is at least 5 μm, preferably at most 50 μm, and more preferably 5 to 50 μm. The use of this type of ore is advantageous because, from an economic point of view, fine ore is generally cheaper than agglomerated iron, and this fine ore is also suitable for fluidized bed processing.

The solubility of various elements, such as, for example, carbon in the ferrite form of iron is strongly reduced with temperature, and for carbon is about 0.02% at 720 ° C., so the final reduction product obtained in the iron form is a very small amount of possible undesirable elements. It contains.

According to one embodiment of the invention the metal-containing material is a mixture of two or more compounds from the group of compounds comprising nickel-compounds such as nickel-ores, cobalt-compounds such as cobalt-ores, iron-compounds such as iron ores to be. The (final) reduction product obtained after complete reduction of the metal-containing material using a mixture of these compounds is the respective metal mixture, thus providing an economical and simple method for producing an alloy.

In one embodiment of the invention solid carbon is precipitated on the reduction product and / or on the metal-containing material in the form of carbon nano-tubes. The inventors have found a surprising fact that solid carbon formed from gaseous CO has a carbon nano-tube form. Reduction products as carbon formation promoters and / or substrates using the process according to the invention as an alternative for reducing the metal-containing material particles to produce metals as reducing products by appropriately designing the reaction chamber and appropriately selecting process parameters. And / or solid carbon in the form of carbon nano-tubes may be produced by using metal-containing materials and continuing solid carbon formation from gaseous CO. In subsequent processes the solid carbon may be separated from the substrate. The substrate can then be reused in the process, and the nano-tubes can be used for a variety of purposes.

In one embodiment of the invention the gaseous CO provided to the reaction chamber of a fluidized bed reactor is prepared by gasifying a carbon-containing compound using an oxygen containing gas flow, preferably the gas flow is a hot gas flow. Preferably the oxygen containing gas flow is industrial pure oxygen, for example the oxygen content is at least 85%, preferably at least 90%, more preferably at least 95%. The advantage of using oxygen over air is that the reactor can be made smaller and the process more energy efficient, because the air contains 80% of inert nitrogen which needs to be heated and cooled. The gaseous CO to be supplied to the reaction chamber using separate gasification steps can remove undesirable components such as volatile hydrocarbons or sulfur compounds that are present in the carbon-containing compound or are formed by gasifying the carbon-containing compound. The gasification step can be carried out in a standard gasifier, but most ashes are removed as slag because the operating temperature of the entrained flow gasifier is above the ash fusion temperature, so it is recommended to use a gasifier gasifier. desirable. It is evident that the way in which the gasifier operates depends on the actual amount of gaseous CO in the gas leaving the gasifier (ie gasifier off-gas or 'synthetic gas'). Syngas may include, for example, various concentrations of CO, CO ₂ , H ₂ , H ₂ O, and N ₂ . The amount of gaseous CO in the gasifier off-gas also depends on the nature of the gas supplied to the gasifier for gasification of coal. If pure oxygen is used, the level of CO in off-gas is higher than with air. Preferably the amount of gaseous CO in the gasifier off-gas is at least 10% (vol%). The equilibrium CO / CO ₂ in the gasifier off-gas is at least 2, preferably at least 5, more preferably at least 10. CO / H ₂ should be at least 1, preferably at least 3. The carbon-containing compound may be coke, coal, charcoal, oils, polymers, natural gas, paper, biomass, tar sands or heavily contaminated carbon-containing energy sources. The process according to the invention contributes to the effective use of waste or uneconomical carbon-sources. It should be noted that the temperature of the gasifier off-gas can be very high, for example, from 1300 to 1600 ° C, or about 1500 ° C. The gasifier off-gas must be cooled to make it suitable for introduction into the fluidized bed reactor to reduce the metal-containing starting material. The gasifier off-gas is preferably cooled by mixing with a cooler recycle process gas or fresh fresh syngas or by cooling in a heat exchanger. The gas phase obtained has a temperature of about 800 ° C. and is fed to FB where the gas phase enters the reduction process. It will be apparent that the gaseous composition may change as a result of mixing with the recycle gas as the recycle process gas is a gas phase that can be washed and CO ₂ -washed after being released from the FB after interacting with the metal-containing starting material in the FB. will be.

In one embodiment of the invention off-gas exits the reaction chamber and some or all of the remaining gas CO and / or CO from the off-gas to reintroduce the remaining gas CO and CO ₂ into the gasifier reaction chamber. Remove ₂ The CO ₂ can be used as a source for providing CO by a reverse boudoir reaction by reacting with carbon of a carbon-containing compound in a gasifier. It is also possible to reuse CO-compounds from off-gases. This means that the CO must be able to be separated from the off-gas, for example using a separating means such as a scrubber. The recycle CO-gas may be reintroduced into the fluidized bed reaction chamber after passing through the gasifier or heat exchanger, or directly to the gasifier or heat exchanger.

Instead of recirculating the carbon in the off-gas, the hot off-gas from the reaction chamber is fed through the heat exchange unit to reheat the oxygen-containing gas flow prior to entering the gasifier, thereby reducing the oxygen-containing gas flow entering the gasifier. Thermal energy may be used to reheat, and / or burn off-gas to recycle any remaining thermal energy and / or remaining chemical energy still present in the off-gas.

In a preferred embodiment the reduction of the metal-containing material by solid carbon is carried out in a circulating fluidized bed (CFB) reactor, where the reactor has a riser part and a return leg, the metal-containing material and gas CO is supplied to the vertical tube member of the CFB, and the gas stream containing gas CO actually moves the metal-containing material upwards through the vertical tube member of the CFB, and converting the gas CO into solid carbon and gaseous carbon dioxide is a metal. Some or all of this is done while the containing material and gaseous CO are moving substantially upwards.

CFB is used to allow the reactant to circulate through the reaction chamber, the reaction chamber being equipped with a return leg and a vertical tube member of the CFB, and the conversion of gaseous CO to solid carbon and gaseous carbon dioxide is partially or fully metal-containing. And gas CO occur substantially while moving upwards, and reduction of the metal-containing material is known to be carried out in a substantially more or less stagnant phase in the return leg before being reintroduced into the riser member. Thus in embodiments of the present invention the reduced product and the metal containing material obtained by the reduction of the metal containing material and the solid carbon are discharged to the return leg of the CFB, and the metal containing material and the reducing product and the solid carbon are substantially reduced through the return leg of the CFB. And the reduction of the reduction product and the metal-containing material by the solid carbon is preferably carried out in part or in whole preferably at substantially the return leg of the CFB. Since the reduction of the metal-containing material by solid carbon is a solid-solid reaction, the reaction rate is lower than in the gas-solid reaction of solid carbon formation from gas CO. The difference in residence time in the riser member and the return leg is due to this different reaction rate.

The residence time of the metal-containing particles in the CFB is chosen to be of many cycles, depending on the degree of reduction or metallization desired. CFB may be provided with separation means such as cyclones to separate solid portions, such as metal-containing materials, reduction products obtained from the reduction of metal-containing materials, and solid carbon from the upward movement of the gas stream, Gas and carbon dioxide. The separation is preferably carried out in close proximity to the upper side of the riser member of the CFB, preferably by one or more cyclones.

The process according to the invention can be carried out as a batch process withdrawing from the reaction chamber as the final reducing product when the reduction product reaches the desired degree of reduction or metallization. This final reduction product may be provided in subsequent processes for further reduction or metallization.

In one embodiment of the present invention the reduction of the metal-containing material is carried out in a plurality of fluidized bed reactors (ie two or more), releasing the final reduction product of the preceding fluidized bed reactor (i) to reduce the degree of reduction or metallization. Pass through to subsequent fluid bed reactor (i + 1) for further reduction to be higher. The temperature in the (i + 1) fluidized bed reactor is preferably higher than in the i fluidized bed reactor. In this embodiment the process conditions and the FB-design can be optimized to obtain the individual degree of reduction or metallization of the final reduction product. The preceding fluidized bed reactors or reactors can also be optimized for solid carbon production and subsequent reactors or reactors can be designed in such a way that they can be optimized to achieve the desired reduction or metallization of the metal-containing material.

In a preferred embodiment the gaseous phase released from the subsequent fluidized bed is discharged into the preceding fluidized bed reactor for further processing. The gas phase can be obtained in a counterflow-process to more economically obtain heat and gaseous CO-gas present in the gas. The gas phase with the highest concentration of CO is thus introduced into a fluidized bed reactor containing the reduced product with the highest degree of reduction or metallization. Thus, the above embodiment is characterized in that the gas phase and the metal-containing particles are totally flowed back in the fluidized bed reactor even though the gas phase and the metal-containing particles flow in the same direction but not in the reverse direction.

In one embodiment of the present invention, the final reduction product is further reduced to allow 90% of the final reduction product in the final stage reactor by a substantially solid-solid reaction between the incompletely reduced portion of the reduction product and the remaining solid carbon. Above, preferably at least 95%, more preferably at least 98%, the degree of reduction or metallization is higher, with the final stage reactor being preferably a rotary kiln, a rotary hearth furnace or a fluidized bed reactor. The amount of deposited solid carbon suitable for obtaining the final reduction in the final-stage reactor with a directly reduced metal, such as DRI, and the degree of initiation reduction in an economical way of reduction or metallization is preferably 25% or less, preferably 15 It has now been found that a process with four, preferably three subsequent fluid beds is suitable for reducing the metal-containing starting material which is more preferably 5% or less, and most preferably 0%.

In this embodiment the metal containing material is reduced almost completely to the individual metal. It has been found that it is advantageous to carry out the final reduction in a final-stage reactor to at least 90%, preferably at least 95%, more preferably at least 98%, to a higher degree of reduction or metallization. Ideally the degree of metallization may be higher, ie at least 99% or at least 99.5%. Further reduction in rotary kilns, rotary furnaces or another fluidized bed reactor has proven advantageous. It is also possible to obtain higher degrees of metallization by dissolving the reduction product.

The final reduction product provided by the process according to the invention has a large surface area as a direct result of the process. If an iron-oxygen compound or iron ore is used as the metal-containing material, the intermediate and / or final reduction product will include metal iron or strongly reduced iron-oxygen compounds. In the process according to the invention iron is obtained with very small amounts of contaminants and very large surface areas. This makes the reduction product very suitable for the sponge iron process (SIP) for hydrogen production. The sponge iron process is a well known technique for producing hydrogen. This involves reoxidizing iron or reduced iron-oxides with steam to form magnetite and hydrogen. The hydrogen produced is of high purity grade and meets the requirements of fuel cell precious metal catalysts. The process is therefore very advantageous for the production and purification of hydrogen for use in hot and cold fuel cells. Of course, the hydrogen can also be used for other purposes.

The final reduction product in the form of iron with a large surface area or in the form of a strongly reduced iron-oxygen compound, as provided by the process according to the invention, is used as the fuel of a vehicle, which for example powers a fuel cell. And is oxidized with steam to form hydrogen suitable for the vehicle or usable for operating the engine or device. Hydrogen, which can be produced using the final reduction product in the form of iron or strongly reduced iron-oxygen compounds produced by the process according to the invention, is more economical than, for example, from natural gas and also produces less carbon dioxide. do.

The final reduction product can be subjected to a separation treatment to separate the metal parts from non-metal parts such as gangue or slag. The separation treatment may include, for example, techniques such as gravimetric treatment, particle size treatment or magnetic treatment.

The final reduction product may be further compressed into a solid product, or preferably rolled into a rolled product, preferably by briquetting. The briquettes or rolled products can be used for melting operations. The rolled product may be used as feed material in further rolling operations or may be used for its own use to provide a rolled product with the desired properties for direct use.

According to a second aspect according to the invention there is provided an apparatus for reducing a metal-containing material according to the method of the invention to a reducing product, comprising:

At least one fluidized bed reactor equipped with a reaction chamber;

An inlet for providing an oxygen containing gas, an inlet for providing a carbon-containing compound, an outlet for discharging a gaseous phase comprising gaseous CO and an optional outlet for discharging solid waste such as slag, A gasifier for producing a gas phase comprising gaseous CO by gasifying said carbon-containing compound using an oxygen containing gas flow;

A first inlet to the reaction chamber for introducing the metal containing material;

A second inlet for introducing the gas CO into the reaction chamber;

Means for forming a fluidized bed comprising said metal-containing material and gaseous CO in a reaction chamber;

Converting gaseous CO into solid carbon and gaseous carbon dioxide, precipitating the solid carbon onto the metal-containing material and / or reducing product, and reducing the metal-containing material by the solid carbon to produce a reducing product. Means for providing a suitable temperature to the chamber;

Means for directing some or all of the constituents of the fluidized bed towards the separating means separating the reducing product from the fluidized bed and optionally means for directing off-gas from the fluidized bed to the recycling means; And

A regression member for returning some or all of the reduction product separated from the gas stream to the reaction chamber and an outlet for withdrawing the residual reduction product from the reaction chamber as a final reduction product.

Fluidized bed reactors have a high surface area-to-volume ratio and high heat and mass transfer coefficients, providing a highly effective device for metal-containing materials to function as a location from which solid carbon can precipitate. The conditions of the fluidized bed are optimal for the reduction of metal-containing material particles because the reactants are made very close to one another and are highly reactive, and the formation of one of the reactants, ie, solid carbon, is exothermic. It is evident that the metal-containing material particles must also be of a constant size to allow fluidization. The maximum particle size that can be accommodated depends on the fluid bed design and operating parameters. In addition, solid carbon is preferably precipitated directly on the metal-containing material or on some or all of the reduced metal-containing material from the gaseous carbon monoxide in the reaction chamber of the fluidized bed, so there is no risk of deposits and mass formation. The inlet for providing the carbonizer to the gasifier and the inlet for providing the oxygen containing gas can be integrated into one inlet.

In a preferred embodiment the fluidized bed reactor is a circulating fluidized bed (CFB) comprising the following configuration:

A vertical tube member allowing substantial upward movement of the fluidized bed comprising the metal-containing material and gaseous CO;

A return leg and a means for directing the fluid phase components to the separation means upon reaching the top of the riser member to separate the reduced product from the fluidized bed and for directing the gaseous phase from the fluidized bed to the recirculation means. Means for facing away;

A return leg allowing substantial downward movement of said reduction product;

Means for withdrawing off-gas from the fluidized bed for further processing; And

Means for returning all or part of the reduction product from the return leg to the reaction chamber, the means also having an outlet for discharging the remaining reduction product from the reaction chamber as the final reduction product.

The residence time of the metal-containing particles in CFB with many cycles depends on the desired degree of metallization of the reduction product. The CFB is provided with separation means such as one or more cyclones to separate the solid portion of the metal containing material, the reducing product, etc., and the solid carbon is separated from the upwardly moving gas stream, and the gas stream separates gaseous CO and gaseous carbon dioxide. Include. This separation is preferably carried out close to the top of the riser member of the CFB by one or more cyclones.

In one embodiment of the invention the means for returning some or all of the reduction product in the return leg to the reaction chamber is a loop seal or a loop seal valve. An advantage of the loop seal is that it can be used to selectively allow some of the reduction process into the reaction chamber. Multiple loop seals may be used to allow some of the reduction product to be discharged as the final reduction product.

In one embodiment the apparatus according to the invention is a plurality of connected fluidized bed reactors, a means provided for conveying the final reduced product from the preceding fluidized bed to the reaction chamber of the subsequent fluidized bed reactor for further reduction to increase the degree of reduction. It is provided. In the context of the present description, the plural is understood to mean two or more. Thus, two, three, four or more connected fluidized bed reactors can be used. It is also possible to provide a means for providing a gaseous phase withdrawn from a subsequent fluidized bed for further processing in a preceding fluidized bed reactor to make a totally countercurrent gas stream. In one embodiment at a temperature higher than the temperature of the preceding fluidized bed reactor, preferably any subsequent reactor provides a means for operating the subsequent fluidized bed reactor to operate at a higher temperature than in any of the preceding fluidized bed reactors. do.

In one embodiment, CO and / or CO ₂ is re-introduced into the gasifier for use as a carbon source, used as heat to preheat the gas phase entering the apparatus, and is present in the off-gas by burning combustible components Gas remaining from the off-gas for reintroduction into a heat exchanger or gasifier or a reaction chamber of one or more fluidized bed reactors or a reaction chamber of a fluidized bed reactor to recover some or all of the thermal or chemical energy An apparatus is provided having recirculation means for separating some or all of CO and / or CO ₂ .

In one embodiment there is provided an apparatus with a final stage reactor for reducing the final reduction product for a higher degree of reduction or metallization by a substantially solid-solid reaction of the incomplete reducing portion of the reduction product with the solid carbon. Preferably, the final stage reactor is a rotary kiln, rotary furnace or fluidized bed reactor. If the amount of solid carbon removed from the fluidized bed is insufficient to achieve the desired reduction or metallization of the final reduction product after leaving the final stage reactor, add solid carbon to the reduction product before introducing the reduction product into the final stage reactor. Nevertheless, the solid carbon is preferably delivered from a fluidized bed reactor formed with the reduction product to the final stage reactor. In one embodiment the apparatus according to the invention is provided with means for separating the metal part of the final reduction product from the remaining part by gravity measurement, magnetic or particle size means.

In a preferred embodiment the device for carrying out the process according to the invention is a gasifier, preferably a gasifier of the countercurrent type, three continuous CFB-reactors, and an FB-type, preferably bubbling FB-type or rotary. A kiln type end-stage reactor. Embodiments have been described for the reduction of iron ore but the detailed description is equally valid for the reduction of other metal-containing materials that only minimally modify the process parameters. The gasifier includes industrial pure oxygen and coal powder. In a countercurrent gasifier, dry pulverized coal is gasified into technical oxygen in a co-current flow. The gasification reaction is carried out in a dense cloud of particulates. Higher temperatures and pressures can lead to higher throughput, meaning that no tar and volatile hydrocarbons, such as methane, are present in the gasifier off-gas. The countercurrent gasifier removes most of the ash, such as slag, where the operating temperature is much higher than the ash melting point. Small amounts of ash are made of very fine dry fly ash carried with gaseous CO as the final CFB. The gasifier off-gas comprising CO has a very high temperature at the gasifier outlet of about 1300 to 1600 ° C, preferably about 1400 to 1500 ° C. Optionally cold CO ₂ containing gas may be provided as a modulator to control the temperature in the gasifier. Conventionally used steam is not preferred as a regulator because it can adversely affect the CO / H ₂ ratio. The gasifier off-gas is preferably mixed with the recycle cooler process gas or cooled syngas or cooled in the heat exchange unit. The cold gasifier off-gas obtained has a temperature of about 800 ° C. and the gasifier off-gas (synthetic gas) is fed to the final CFB which enters the reduction process. Prior to introduction into the final CFB, the gasifier off-gas may be treated to remove sulfur from the gas, for example by treating with calcium to produce CaS.

The iron-compound or iron ore is preferably provided in the form of fine compounds or ores having a crystal size of 5 to 200 μm. This material enters the apparatus of the first CFB as it is provided as CFB in countercurrent to the gasifier off-gas. The temperature of this first CFB is the lowest and is optimal for the purpose of depositing solid carbon on the compound or ore. The temperature of the first CFB is adjusted to 350 to 600 ° C., preferably 400 to 500 ° C. to produce solid carbon (budoa carbon and / or iron-carbide). Reduction of iron ore, in particular hematite to magnetite, is already initiated at this low temperature and iron-carbide (Fe _x C) begins to form. Iron compounds and / or reduction products thereof serve as catalysts for the formation of solid carbon at these low temperatures. The conditions of the return leg of the CFB enable the following scheme:

When leaving the final CFB (first for solid phase and last for gas phase), the reduction product reaches a desired degree of reduction of at least 50%, preferably at least 60%, more preferably at least 70%. And / or loading sufficient solid carbon to obtain a final reduction of the DRI of the final stage reactor at a degree of metallization or reduction of at least 90%, preferably at least 95%, more preferably at least 98%. Thus it is possible to select a process parameter in which iron ore does not reach the desired reduction of 50% when leaving the final CFB but instead is loaded with sufficient solid carbon to obtain a final reduction of the DRI to a degree of reduction of 90% or more or metallization. In this case the CFB-reactor is used to produce the solid carbon required to reduce the iron ore rather than to reduce the iron ore, which reduction is then carried out in a final stage reactor.

과 거의 동일하다는 것을 확인하였다. 실시양태를 3 CFB로 기재하였지만 2, 4, 5 또는 그 이상의 CFB의 사용도 또한 가능하다는 것을 알아야 한다. 본 발명자들은 3 또는 4 CFB를 사용하면 금속함유 개시 재료 상에 탄소의 피착을 위한 저온 CFB, 탄소를 추가로 피착시키기 위한 중간 온도 CFB 및 금속함유 개시 재료를 소망 정도의 환원 또는 금속화 및 피착 고체 탄소의 양으로 완전하게 환원시키기 위한 최종 '높은' 온도 CFB의 결합이 양호하게 되어 최종-단계 반응기로의 도입에 양호한 환원 생성물을 제공한다는 것을 확인하였다.The final-stage reactor is fed with reduction products in the final CFB together with air or industrial pure oxygen injected into the final-stage reactor, and the recycle process gas or fresh syngas containing CO. The reaction of the final-stage reactor is exothermic and the heat released as a result of the oxygen injection, which is preferred by bottom-injection in the final-stage reactor, promotes the conditions under which the abovementioned final reduction reaction is possible. Since the last-stage reactor is a fluidized bed, the occurrence of local hot spots is prevented and the risk of clogging of the process by coagulation of fine particles is minimized. The risk of clogging can be further reduced if necessary by adding an additive to the fluid phase, such as described in US 3,615,352. The temperature of the final-stage reactor is preferably between 680 and 850 ° C, for example about 750 ° C ± 20 ° C. Most of the reduction reactions in the final-stage reactors are believed to be pure solid-solid reactions, not gas-solid reactions. Gases are primarily present to help create conditions that enable solid-solid reactions to be performed by manipulating CO-CO ₂ -T stability diagrams for iron and its oxides. The inventors have found that the post-combustion rate of gaseous phase entering the final-stage reactor is actually the gaseous post-combustion rate released in the final-stage reactor as a result of CO evolution during final reduction.

It is confirmed that it is almost the same as. Although an embodiment is described as 3 CFB, it should be understood that the use of 2, 4, 5 or more CFBs is also possible. Using 3 or 4 CFB, the present inventors have found that a desired amount of reduced or metallized and deposited solids can be prepared by the low temperature CFB for the deposition of carbon on the metal-containing starting material, the intermediate temperature CFB for the additional deposition of carbon and the metal-containing starting material. It was found that the binding of the final 'high' temperature CFB to fully reduce the amount of carbon became good, providing a good reduction product for introduction into the final-stage reactor.

The final reduction product released in the last-stage reactor may also include gangue, slag, CaS or other undesirable materials, which can be separated from the metal phase in a magnetic sorting operation.

The final off-gas of the process that can no longer be introduced into the process may still have some chemical or thermal energy that can be used, for example, by burning it and / or using heat.

In an embodiment the device according to the invention comprises a recycling unit for recycling Zn and / or Pb and / or Cd from a Zn and / or Pb and / or Cd containing metal-containing material, the unit being ie Reducing the Zn-, Pb- and / or Cd-containing compounds to the metals Zn, Pb and / or Cd by solid carbon, and evaporating Zn, Pb and / or Cd to produce gases Zn, Pb and / or Cd Means for doing so.

In an embodiment the device comprises the following configuration:

Condensation means for condensing and / or solidifying the gases Zn, Pb and / or Cd to liquid and / or solid Zn, Pb and / or Cd; or

Oxidation means for oxidizing the gases Zn, Pb and / or Cd into zinc-oxygen compounds, lead-oxygen compounds and / or cadmium-oxygen compounds.

This embodiment enables the treatment of iron-rich waste material, for example from the steel industry. Such materials, such as iron-rich dust from steel making, can be used as metal-containing materials in the apparatus and method according to the invention. In addition to iron-oxygen compounds, these materials may also include zinc-oxygen compounds, lead-oxygen compounds or cadmium-oxygen compounds. Such compounds are recycled from metal-containing materials by reducing the iron-oxygen compounds to iron compounds. Zn, Cd or Pb are also reduced in the process of the process and become gaseous. Reduction of the zinc-oxygen compound, lead-oxygen compound or cadmium-oxygen compound can be effected by solid carbon or by direct reaction with gaseous CO or H ₂ . The Zn, Cd or Pb metal may then be condensed from the gaseous state or may be oxidized and collected as zinc-oxygen compounds, lead-oxygen compounds and / or cadmium-oxygen. In a preferred embodiment the device according to the invention is provided with a de-zincing unit, which is a metal-containing material or a reduction product or a final reduction product for reducing the Zn-containing compound to the metal Zn. Heating means and evaporate Zn to produce gas Zn or oxidize Zn to produce zinc-oxygen compounds such as ZnO or Zn (OH) ₂ . This embodiment is particularly advantageous for treating Zn-rich waste materials which are too high for use in the manufacture of conventional iron and steel, for example. The process may also be used to extract Zn-, Cd and / or Pb from the microparticles using the microparticles in conventional iron production associated with the blast furnace.

In an embodiment the device according to the invention is equipped with condensation means for condensing and / or solidifying the gas Zn to liquid and / or solid Zn.

The invention will be further illustrated by the following non-limiting drawings. 1 is a basic layout of a fluidized bed reactor. 2 is a basic layout of the overall apparatus for carrying out the method of the present invention. 3 is a basic layout of an apparatus for carrying out the method of the present invention having two or more circulating fluidized bed reactors and a final stage reactor. 4 is a basic layout of the apparatus according to FIG. 2 with a recycling unit for recycling Zn from a Zn containing metal-containing material. 5 and 6 are alternative embodiments of FIGS. 2 and 3, respectively.

In FIG. 1 the fluidized bed reactor, the circulating fluidized bed 1 in this embodiment, comprises a gas flow 3 containing a metal containing material 2 and gaseous CO. After the gas flow comprising the metal-containing material (2) and gaseous CO moves upward through the upright member of the circulating fluidized bed (1), the material is directed to the means (5) for separating gas and solid particles. do. The off-gas is derived from the means 5 as indicated by the upward pointing arrow in the means 5.

The solid portion comprising solid carbon formed from gaseous CO reacts with the metal containing material such that the metal containing material is reduced to a reducing product. The reduction product is lowered by means of a loop-silk-like means (7) via a return leg in order to return some or all of the reduction product to the reaction chamber in the circulating fluidized bed for one or more further cycles. Alternatively, some or all of the reduction product may be discharged as the final reduction product as indicated by the right arrow of the means (7).

In FIG. 2 a part of the reduction product that can be withdrawn from the means 7 is provided to the means 4. The means 4 can be a final stage reactor such as a rotary kiln, a rotary furnace or a fluidized bed reactor. Alternatively, means (4) can be one or more additional cycles comprising (1), (5), (6) and (7), wherein member (6) can be used for the return leg of the circulating fluidized bed reactor. In the schematic representation, the member 1 is a riser member and the member 5 is a separating means, such as a cyclone. This state is schematically illustrated in FIG. 3. The means 4 may also represent one or more circulating fluidized bed reactors and a final stage reactor. In Figures 2 and 3 the gas flow is schematically represented by a dot or dash arrow ('g') and the non-gas-flow is represented by a line arrow ('s'). The gaseous product separated by the means (5) can be directed to the gas cleaning unit (11), wherein the gaseous product can be discharged or the gas source from the gas cleaning unit (11) for reuse and / or preheating purposes. 12, for example, may be led to a gasifier. In FIG. 2 a gas comprising gaseous CO is produced in the gas source 12 by, for example, gasification of coal, and a hot gas flow 8 comprising gaseous CO is provided through the means 4 for a general general or overall countercurrent) to the metal-containing material and / or the reducing product. This is shown as gas flow (3). The flow of the metal-containing material and / or intermediate reduction product in the vertical tube member in the circulating fluid phase coincides with the gas flow as indicated by the thick arrows in the vacuum tube members 1 and 1a.

In FIG. 4 the apparatus of FIG. 2 is combined with a unit for recycling Zn and / or Pb and / or Cd from a Zn and / or Pb and / or Cd containing metal containing material. The final reduction product 9, which still contains Zn and / or Pb and / or Cd-containing metal-containing materials, is used to reduce zinc-oxygen compounds or lead-oxygen compounds or cadmium-oxygen compounds to metallic lead, zinc or cadmium. Which is transferred to means 13 together with a hot gas flow 8 comprising gaseous CO. The metallic lead, zinc or cadmium may then be in a gaseous state and provided to the means 15. In the means 15 the metal can be condensed from the gaseous state and can be oxidized and collected as zinc-oxygen compounds, lead-oxygen compounds and / or cadmium-oxygen.

FIG. 5 shows an alternative embodiment to that in FIG. 2, after cooling to about 800 ° C., syngas from the gasifier is introduced into the CFB. The syngas is separated from the solid particles in the means 5 and the recycle gas is cleaned in the gas scrubbing unit 11. The recycle process gas after the gas scrubbing unit can be directed to the final stage reactor 4 or gasifier 12. The recycle gas may be directed directly to the gasifier or may be used to cool the fresh syngas produced by the gasifier to about 800 ° C. The means 4 may have the same alternative meaning as shown in FIG. 2. Alternative gas flows such as those shown in FIG. 5 may be applied to the embodiments of FIG. 3 (see FIG. 6) and FIG. 4.

Claims (35)

A method of reducing a metal containing material to a reducing product, Gasifying the carbon-containing compound using an oxygen containing gas flow to provide a gas phase comprising gaseous CO; Providing a metal containing material to the reaction chamber of a fluidized bed reactor; Providing gaseous CO to a reaction chamber of a fluidized bed reactor and converting the gaseous CO into solid carbon and gaseous carbon dioxide to precipitate the solid carbon in the metal-containing material and / or the reducing product; Using the reduction product and / or metal-containing material as an accelerator to reduce some or all of the metal-containing material to the reducing product by means of solid carbon to convert gaseous CO to solid carbon and gaseous carbon dioxide; And Evacuating the final reduction product from the reaction chamber, And reducing the final reduction product further in a final stage reactor by a substantial solid-solid reaction between the incomplete reduction portion and the solid carbon in the reduction product to increase the degree of reduction or metallization. The method of claim 1, The reduction degree of the final reduction product after exiting the reaction chamber of the fluidized bed reactor is at least 50%. The method according to claim 1 or 2, The reduction reaction of the final stage reactor is carried out under a non-inert atmosphere. The method according to any one of claims 1 to 3, A reduction process characterized by feeding a hot gas flow comprising gaseous CO to the final stage reactor. The method according to any one of claims 1 to 4, Provide a CO / CO ₂ and / or oxygen containing gas to the final stage reactor, preferably the CO / CO ₂ containing gas is a new syngas and / or recycle process gas, and the oxygen containing gas is air or industrial pure water Reduction method characterized in that the oxygen. The method according to any one of claims 1 to 5, The metal-containing material and gaseous CO are continuously or batchwise provided to the reaction chamber to continuously produce the reduction product, and the final reduction product is continuously or batchwise discharged from the reaction chamber. Reduction method characterized in that. The method according to any one of claims 1 to 6, The reduction method of the final reduction product is 50% or more, preferably 60% or more, more preferably 70% or more. The method according to any one of claims 1 to 7, The maximum temperature of the reaction chamber is 875 ° C, preferably 845 ° C, more preferably 825 ° C and even more preferably 800 ° C. The method according to any one of claims 1 to 8, And a promoter for converting said gaseous CO into solid carbon and gaseous carbon dioxide also acts as a reduction promoter of said metal-containing material. The method according to any one of claims 1 to 9, The metal-containing material is an iron compound, preferably iron ore. The method of claim 10, The iron ore is provided in the form of fine ores, and the crystal size of the ore is preferably 0.1 to 5000 ㎛, more preferably 5 to 50 ㎛. The method according to any one of claims 1 to 9, The metal-containing material is a nickel compound, preferably a nickel-ore, a cobalt-compound, preferably a cobalt-ore, or a mixture thereof. The method according to any one of claims 1 to 9, The metal-containing material is a mixture of two or more compounds selected from the group consisting of nickel-compounds such as nickel ore, cobalt-compounds such as cobalt ore, iron-compounds such as iron ore. The method according to any one of claims 1 to 13, The gas CO is prepared by gasifying a carbon-containing compound using an oxygen containing gas flow, wherein the gas flow is a hot gas flow. The method according to any one of claims 1 to 14, The off-gas is discharged from the reaction chamber, a residual gas CO and / or some or all of the off for re-introduction into the residual gas CO and / or CO ₂ gasifier reaction chamber of the CO ₂ - separation from the gas Reduction method characterized in that. The method according to any one of claims 1 to 15, Off-gas is discharged from the reaction chamber, and some or all of the remaining gas CO and / or CO ₂ is separated from the off-gas to preheat the gas flow prior to entering the gasifier. . The method according to any one of claims 1 to 16, Reduction of the metal-containing material by the solid carbon is carried out in a circulating fluidized bed (CFB) reactor, the reactor having a riser part and a return leg, the metal-containing material and the A gaseous CO is provided to the upright tube member of the CFB, and a gas stream comprising the gaseous CO moves the metal-containing material substantially upwards through the upright tube member of the CFB, the solid carbon of the gaseous CO and The conversion to gaseous carbon dioxide is characterized in that some or all of the metal-containing material and gaseous CO are carried out during substantial upward movement. The method of claim 17, The metal-containing material and the reduction product obtained from the reduction of the metal-containing material and solid carbon are discharged to the return leg of the CFB, and the metal-containing material and the reducing product and solid carbon are substantially lowered through the return leg of the CFB. Moving in the direction, the reduction of the reduction product and the metal-containing material by the solid carbon is preferably carried out substantially or partly in the return leg of the CFB. The method according to any one of claims 1 to 18, The reduction metal-containing material having reached the desired degree of reduction is discharged from the reaction chamber as a final reduction product. The method according to any one of claims 1 to 19, The reduction of the metal-containing material is carried out in a plurality of fluidized bed reactors, further reducing the final reduction product of the preceding fluidized bed reactor and passing it through the subsequent fluidized bed reactor to further reduce the degree of reduction further. The method of claim 20, The gas phase exiting the subsequent fluidized bed is discharged to the preceding fluidized bed reactor for further processing. The method according to any one of claims 1 to 21, Reduction method characterized in that the fluidized bed is of high speed fluidization or pneumatic conveying type. The method according to any one of claims 1 to 22, The final reduction product is added to a degree of metallization of at least 90%, preferably at least 95%, more preferably at least 98% in the final stage reactor by a substantial solid-solid reaction between the incomplete reduction portion of the reduction product and the solid carbon. Reduction, wherein the final stage reactor is preferably a rotary kiln, a rotary hearth furnace or a fluidized bed reactor. The method according to any one of claims 1 to 23, And treating said final reduction product to separate metal parts from non-metal parts such as gangue or slag. The method according to any one of claims 1 to 24, The final reduction product is preferably further processed by briquetting the product into a compressed product or by rolling into a rolled product. The method according to any one of claims 1 to 25, The metal-containing material comprises an iron-oxygen compound and a zinc-oxygen compound, the method comprising the reduction of the iron-oxygen compound according to any one of claims 1 to 25, by solid carbon produced from gas CO. A zinc recovery step comprising reduction of a zinc-oxygen compound to zinc, vaporization of the zinc, followed by optionally condensation of the zinc from a gaseous state or re-oxidation of zinc and collection as a zinc-oxygen compound Reduction method characterized by the above-mentioned. An apparatus for reducing a metal-containing material to a reducing product according to any one of claims 1 to 26, wherein At least one fluidized bed reactor with a reaction chamber; An inlet for providing an oxygen-containing gas, an inlet for providing a carbon-containing compound, an outlet for discharging a gaseous phase comprising gaseous CO, and an optional outlet for discharging solid waste materials such as slag, A gasifier for generating a gas phase comprising gaseous CO by gasifying the carbon-containing compound using the containing gas flow; A first inlet of the reaction chamber for introducing the metal containing material; A second inlet for introducing the gas CO into the reaction chamber; Means for forming a fluidized bed comprising said gaseous CO and a metal containing material in said reaction chamber; Converting gaseous CO into solid carbon and gaseous carbon dioxide, providing a suitable temperature of the reaction chamber for precipitating solid carbon onto the metal-containing material and / or the reducing product, and converting the gas into the solid carbon to produce the reducing product. Means for reducing the metal containing material; Means for directing some or all of the constituents of the fluidized bed towards the separating means separating the reducing product from the fluidized bed and optionally means for directing off-gas from the fluidized bed to the recycling means; A regression member for returning some or all of the reduction product separated from the gas stream to the reaction chamber and an outlet for withdrawing the residual reduction product from the reaction chamber as a final reduction product; And An optional final stage reactor which further reduces the reduction product in order to obtain a higher degree of reduction by substantial solid-solid reaction of the reduction product with solid carbon, wherein the optional final stage reactor is a rotary kiln, rotary furnace or fluidized bed A reactor is preferred.). The method of claim 27, The fluidized bed reactor is a circulating fluidized bed, A riser member allowing substantial upward movement of the fluidized bed comprising said metal-containing material and gaseous CO; Means for directing the fluid phase components to the separation means upon reaching the top of the riser member to separate the reduction product from the fluidized bed, and means for directing the gas phase from the fluidized bed to the recirculation means; Means for directing to a return leg; A return leg allowing substantial downward movement of said reduction product; Means for withdrawing off-gas from the fluidized bed for further processing; A means for returning some or all of the reduction product from the return leg to the reaction chamber, the means also having an outlet for discharging the final reduction product from the reaction chamber Device. The method of claim 28, And the means for returning some or all of the reduction product from the return leg to the reaction chamber is a loop seal. The method according to any one of claims 27 to 29, Means for conveying the final reduced product from the preceding fluidized bed to the reaction chamber of the subsequent fluidized bed reactor and / or from the subsequent fluidized bed, comprising a plurality of connected fluidized bed reactors and further reducing the final reduced product to a higher degree of reduction. And a means for providing the discharged gas phase to the preceding fluidized bed reactor. The method of claim 30, Means are provided for operating a subsequent fluid bed reactor at a higher temperature than the preceding fluid bed reactor, wherein any subsequent reactor preferably operates at a higher temperature than any preceding fluid bed reactor. The method according to any one of claims 27 to 31, The apparatus is preferably an entrained flow type gasifier for providing gas CO, a plurality of connected circulating fluidized beds, preferably three, each having a reaction chamber for providing a reduction product. A final staged reactor of bubbling fluidized bed type for further reduction, wherein a continuous connection member is present between the gasifier, the circulating fluidized bed and the final staged reactor, and the pressure of the apparatus is at least 2, preferably Reducing device, characterized in that the excess pressure of 4 bar or more. The method according to any one of claims 27 to 32, A recycling unit for recycling Zn and / or Pb and / or Cd from Zn and / or Pb and / or Cd-containing metal-containing material, the unit being Zn-, Pb- and / or Cd- by solid carbon; And a heating means for reducing the containing compound to metals Zn, Pb and / or Cd and evaporating Zn, Pb and / or Cd to produce the gases Zn, Pb and / or Cd. The method of claim 33, wherein Condensation means for condensing and / or solidifying the gases Zn, Pb and / or Cd to liquid and / or solid Zn, Pb and / or Cd; or An oxidation means for oxidizing gases Zn, Pb and / or Cd into zinc-oxygen compounds, lead-oxygen compounds and / or cadmium-oxygen compounds. A method of using a reduction product, characterized in that the reduction product produced by the process according to any one of claims 6 to 26 is used in a sponge iron process for the production of hydrogen.

Images