CN1871366A - Method and apparatus for reducing metal-oxygen compounds - Google Patents
Method and apparatus for reducing metal-oxygen compounds Download PDFInfo
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- CN1871366A CN1871366A CNA2004800311109A CN200480031110A CN1871366A CN 1871366 A CN1871366 A CN 1871366A CN A2004800311109 A CNA2004800311109 A CN A2004800311109A CN 200480031110 A CN200480031110 A CN 200480031110A CN 1871366 A CN1871366 A CN 1871366A
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Abstract
The present invention relates to a method of reducing a metal-oxygen compound wherein carbon acts as a reducing agent, comprising in a first reaction stage, passing CO gas into a reaction chamber containing said metal-oxygen compound, under conditions such that CO is converted to solid carbon and carbon dioxide thereby introducing the solid carbon so formed to said metal-oxygen compound, and in a second reaction stage, causing said carbon, which is introduced to the metal-oxygen compound in said first reaction stage, to reduce said metal-oxygen compound, wherein there is present, at least in said second reaction stage, a first promoter material effective to promote the reduction of said metal-oxygen compound, the first promoter material comprising a first promoter metal and/or a compound of a first promoter metal. The invention also relates to an apparatus for carrying out the reduction of a metaloxygen compound wherein carbon acts as a reducing agent.
Description
Technical field
The present invention relates to adopt the method for carbon as the reducing metal-oxygen compounds of the reductive agent of reducing metal-oxygen compounds.The present invention also relates to adopt the equipment of carbon as the reducing metal-oxygen compounds of the reductive agent of reducing metal-oxygen compounds.
Background technology
The compound of metal-oxygen comprises that the reduction of the oxide compound of various metal oxides such as iron is carried out in large-scale reduction furnace.For the reduction of iron-oxygen compound, since century, adopted blast furnace more than one as the major equipment for preparing the pig iron by iron ore always.The main reductive agent in the described blast furnace and the source of chemical energy are coke.Coke is to be prepared from by the roasting coal under anaerobic environment, and purpose is to remove volatile hydrocarbon polymer, makes coke have the required key property of blast furnace steady running.
Because many volatile hydrocarbons are harmful, therefore, consider the burnt existing problems of system from environmental.And, be not that all types of coals all are fit to system Jiao.In addition, the demand of making burnt byproduct is reduced.
Therefore, reduce the principal focal point that coke ratio in the blast furnace and total fuel ratio have become R﹠D work in recent years.And, developed the new technology of avoiding described blast furnace method, for example the direct-reduced iron ore.
Directly reduction comprises that described reductive agent can be solid state reduction agent or gaseous reducing agent by adopting the reductive agent reducing iron ore to prepare iron.The solid state reduction agent can be the coal of virtually any size, rather than coke.The example of gaseous reducing agent is Sweet natural gas and carbon monoxide.Be used for high and low the strictly regulating of harmful element content of iron per-cent that must meet the demands of direct reductive ore.
The direct-reduced iron ore can be produced solid-state direct reductive iron product, perhaps, under high service temperature or use smelting apparatus simultaneously, can prepare liquid product.
The product of direct method of reducing can be delivered to second reactor, carry out melting and optional further refining, perhaps cool off and stores wait until after use.
At present, the starting material that will be used as the ore preparatory stage from the dust and the sludge circulation of comprehensive steel mill.The waste material of these so-called " chip (fines) " may comprise iron containing compounds, as the oxide compound of iron.But, owing in these chips, have high-load metal such as zinc, gathering of these elements, and need the amount of these metals be limited in the blast furnace to sending into, therefore, often have to adopt alternate manner to recycle or handle these waste materials, the result has additionally increased cost or environmental pressure.
A kind of method of known reducing iron ore is based on the direct reaction of coal in rotary kiln and iron ore stone or bead.Another kind of currently known methods is based on reducing composite pellets in rotary hearth furnace, the ferruginous oxide compound of described composite pellets bag and from for example carbon of coal, coke or charcoal.The discharge gas that reduction reaction produces can secondary combustion in stove, and the part heat of this processing requirement is provided.Another currently known methods is included in direct-reduced iron ore fine powder in the fluidized-bed reactor.
A main drawback of these known method of reducing is that they must implement at high temperature.For example, the working temperature of rotary hearth furnace method is about 1250 ℃.If these methods are to use coal, then another shortcoming is to produce a large amount of carbon monoxide, hydrogen and complicated and deleterious hydrocarbon polymer.Must avoid needing to remove or discharge these hydrocarbon condensation that the gas secondary combustion must prevent the metal reoxidation simultaneously.In addition, because working temperature is high and calorific loss takes place, and produces a large amount of carbon monoxide thereupon, therefore, directly the energy efficiency of method of reducing is generally very low, causes the rate of consumption of carbon very high.The working temperature height also can cause forming a large amount of deleterious oxynitrides (NOx gas).In addition, owing to have sulphur in the coal, so, must handle the sulphur content problem of higher based on the direct reduction technique that uses coal.
GB-A-1471544 has described a kind of method of direct-reduced iron ore, in this method, the oxide compound of iron such as magnetite are given birth to the nuclear agent with iron(ic) chloride mix, and, coal also with the activator mix of same iron(ic) chloride form.With these two kinds of mixture thorough mixing together, form the ball piece.The ball piece is adopted cold nitrogen purge, then, it slowly is heated to 1050 ℃, keep in cold nitrogen, cooling off in 30 minutes by heated nitrogen.Reaction by carbon and oxide compound at first forms CO
2Activator promotes carbon to CO
2Reduction, form CO.Give birth to nuclear agent (iron that comes from iron(ic) chloride), help CO to adsorb, thereby quicken the reduction of CO oxide compound at oxide surface.
US-A-3979206 has described at 1000-2000 ℃, exists to adopt carbon reduction MgO under the condition of iron, cobalt, nickel, chromium or manganese.Fe powder, MgO powder and C powder are heated in vacuum oven.Reclaim the Mg steam.It is said that Fe plays catalyst action, can reduce temperature of reaction.
Summary of the invention
An object of the present invention is to provide the method and apparatus of the reducing metal-oxygen compounds that can operate at a lower temperature.
Another object of the present invention provides and can produce for example method and apparatus of the reducing metal-oxygen compounds of hydrocarbon polymer and/or NOx gas of less harmful discharge gas (off-gas).
Another purpose of the present invention provides the method and apparatus of the reducing metal-oxygen compounds of the carbon efficiencies that can improve the per unit weight reducing metal.
Another purpose of the present invention provides the efficiency that can have improvement and the method and apparatus of the low-sulfur content reducing metal-oxygen compounds of product that obtains.
Another purpose of the present invention provides and can be used to reduce the mixture of different metal-oxygen compound, obtains the method and apparatus of metal alloy.
In order to reach one or more described purposes, a kind of method that adopts carbon as the reducing metal-oxygen compounds of reductive agent is provided, it comprises: in first step of reaction, CO gas is sent into the reaction chamber of the compound of containing metal-oxygen, the condition of reaction chamber makes CO be transformed into solid carbon and carbonic acid gas, thereby formed solid carbon is incorporated in the metal-oxide compound, and, in second step of reaction, make in first step of reaction and be incorporated into carbon reduction metal-oxide compound in the metal-oxide compound, wherein, at least in second step of reaction, exist first kind can effectively promote metal-oxide compound reductive promotor (promoter) material, this first kind of promoter material comprises the compound of first kind of promoter metals and/or first kind of promoter metals.
A characteristic of the present invention is to use first kind of promoter material in second step of reaction.Be surprisingly found out that: add the rate of reduction that first kind of promoter material can greatly improve metal-oxide compound when adopting carbon as the reductive agent of reducing metal-oxygen compounds.Also find: compare with known direct method of reducing, this reduction can be carried out under the temperature that obviously reduces.For example, the working temperature that currently known methods adopted of reduced iron-oxygen compound is higher than 950 ℃.Because method of the present invention can be implemented at a lower temperature, thereby also can reduce deleterious nitrogen-oxygen compound output and the calorific loss that reduces equipment.
It should be noted that: in known method of reducing, in the method for reducing as iron-oxygen compound in the blast furnace of system iron, the metal pair reduction reaction that forms in the reduction process does not have help, because it does not play catalyzer.It is believed that this is relevant with the following fact, that is: at this class currently known methods and in this class blast furnace, the reduction reaction that does not satisfy the metal pair reduced iron-oxygen compound that forms plays the required processing condition of katalysis.
In one embodiment of the invention, form by intermediate compound (first kind of promoter material) to first kind of promoter metals of small part, described intermediate compound is selected from metallic carbide, metal hydride and metal nitride, wherein, metal in the compound is first kind of promoter metals, the optional oxygen that comprises of described compound.This intermediate compound can be added in the metal-oxide compound.Intermediate compound such as metallic carbide can form first kind of metal, thereby help the reduction reaction of metal-oxide compound.Other intermediate compound for example is metal hydride, metal nitride or comprises metallic carbide and/or the mixture of metal hydride and/or metal nitride.The another kind of example of intermediate compound is a metallic carbonyls, and metallic carbonyls can resolve into metal and carbon monoxide.Metallic carbonyls is quite expensive, is not used in usually in the production process of a large amount of metals.
Use the advantage of intermediate compound to be first kind of tiny dispersion of promoter metals of formation when intermediate compound decomposes, thereby make it can effectively promote reduction reaction.First kind of metal can (just) be formed by intermediate compound before the reduction reaction of reducing metal-oxygen compounds.If intermediate compound is wherein a metal is the metallic carbide of first kind of promoter metals, then when middle compound decomposition, first kind of promoter metals and carbon all are in tiny dispersion state, thereby make kind of the promoter metals of winning effectively to promote reduction reaction, and carbon effectively plays a role as reductive agent in reduction reaction.
As long as first kind of promoter metals exists when the metal-oxide compound should reductive take place at least, the first kind of promoter metals that then is used for metal-oxide compound reduction reaction can be added into the metal-oxide compound in any stage of described method.
Second characteristic of the present invention is that carbon monoxide contacts with the metal-oxide compound, and, react by Bu Shi (Boudouard), preferably by second kind of promoter material, form described carbon and carbonic acid gas by carbon monoxide, described second kind of promoter material for example can be second kind of promoter metals.Described carbon is called Bu Shi carbon, and it typically has crystal structure of graphite.Carbon monoxide can be pure basically carbon monoxide, but also can be the gaseous mixture that part comprises carbon monoxide.No matter when the method for reducing metal-oxygen compounds begins, still in the process of reducing metal-oxygen compounds, compound such as powdered graphite similar with Bu Shi carbon and that form is suitable can be added in the metal-oxide compound, play reductive agent for the reduction of part metals-oxygen compound at least.
Therefore, the carbon that is used as the reductive agent of reducing metal-oxygen compounds is amorphous carbon and/or crystalline carbon, preferred graphite, and reason is that the reduction rate of reduction reaction can obviously improve.Crystalline carbon or especially graphite are the carbon of preferred form.Among the present invention, carbon is powder type, can play the effect that increases point of contact number between the reactive material like this, thereby also improve speed of response.
Bu Shi carbon, decomposes carbon monoxide and produces by the Bu Shi reaction takes place in first step of reaction, and described Bu Shi reaction is:
In first step of reaction, reaction conditions makes this balance shift to reaction (1) right side, and the result forms carbon.The professional can be easy to select appropriate condition.
Surprisingly, find: this Bu Shi carbon with graphite-structure is a kind of reductive agent, it is with first kind of promoter material, first kind of promoter metals for example, at Bu Shi carbon, when first kind of promoter metals contacts with the metal-oxide compound, reducing metal-oxygen compounds very effectively.
As being addressed, preferred, at least in first reactions steps, there be second kind of promoter material, this second kind of promoter material comprises promotion CO and is transformed into the second kind of promoter metals of carbon and carbonic acid gas and/or the compound of second kind of promoter metals.The carbide that preferred second kind of promoter material is second kind of promoter metals, second kind of promoter metals, the hydride of second kind of promoter metals or the nitride of second kind of promoter metals or their combination.Preferred second kind of promoter material is powder type.
Usually, among the present invention, first kind and second kind of promoter material, particularly first kind and second kind of promoter metals have by katalysis or another kind of reaction mechanism, make each reactions of described two step of reaction function faster, more complete or that (the perhaps combination of these effects) carried out under low temperature more.
Surprisingly, also have been found that: first kind of promoter material, for example first kind of promoter metals not only helps the reduction of metal-oxide compound, but also can help forming Bu Shi carbon by the Bu Shi reaction.First kind of promoter metals can be added in the described process, but some first kind of promoter metals wherein also can form by the reduction of ongoing metal-oxide compound under the lesser temps that the Bu Shi reaction takes place.
In one embodiment of the invention, in the reduction reaction of reducing metal-oxygen compounds, the oxygen in the metal-oxide compound mainly combines with the carbon that is formed by carbon monoxide by the Bu Shi reaction.When using carbon as main reductive agent, described technology can be implemented under low temperature.Situation is like this when coal is used as main carbon source.But, if select for use Sweet natural gas as main carbon source, the hydrogen amount that is produced by Sweet natural gas (containing a large amount of hydrocarbon polymers such as methane usually) cracking can have disadvantageous effect to operational condition, thereby weakened by effective utilization of the advantage, particularly fossil oil that obtain according to the inventive method and lower enforcement temperature.
Known a spot of hydrogen can promote to form Bu Shi carbon and carbonic acid gas by the Bu Shi reaction by carbon monoxide.When using pure carbon monoxide, a small amount of hydrogen can be added in the carbon monoxide.Preferred hydrogen amount is lower than 8vol.%, more preferably less than 6vol.%.Because under the selected working conditions, hydrogen is unimportant to the reduction of metal-oxide compound.Under obviously higher temperature hydrogen reduction metal-oxide compound can take place, thereby offset the advantage according to the inventive method.
Among the present invention, typically be higher than 50% in the metal-oxide compound, preferably be higher than 70%, more preferably be higher than 80%, even more preferably be higher than 90% oxygen and in the reduction reaction of reducing metal-oxygen compounds, combine with Bu Shi carbon.If for example obtain to comprise the gaseous mixture of carbon monoxide by gasification of coal, then this gaseous mixture also comprises a spot of hydrogen.
Can add similarly and have a compound of appropriate form in the method, perhaps when initial stage for example, add producing Bu Shi carbon compound such as metallic carbide with Bu Shi carbon.If the Bu Shi carbon like this, then in the previous embodiments is the Bu Shi carbon that formed by carbon monoxide and/or similar and have the interpolation carbon of appropriate form and/or be derived from the carbon of metallic carbide with Bu Shi carbon.Owing to compare, comprise high-load carbon dioxide gas according to the gaseous reaction products of the inventive method, so carbon used effectively, thereby also reduced the consumption of fossil oil with the discharge gas in the traditional method.As a result, reducing the used carbon amount of the metal of unit weight in the method according to the invention reduces.
And, because the carbon that adopts the Bu Shi carbon be derived from carbon monoxide rather than coal form does not contain the harmful hydrocarbon polymer that closes with coal facies as the reductive agent in the inventive method according to the gaseous reaction products in the inventive method.Do not comprise sulphur compound if contain the gaseous mixture of carbon monoxide, the sulphur content of then reacting in the solid is unaffected.Comprise hydrocarbon polymer and/or sulphur compound if contain the gaseous mixture of carbon monoxide, then the gaseous reaction products according to the inventive method will comprise content lower these hydrocarbon polymers and/or sulphur compound, reason is in described method, at least the heavy constituent meeting generation cracking of hydrocarbon partial and/or be used.The compound of sulphur can for example be processed into calcium-sulphur compound by a kind of known calcium treatment process such as CaS is neutralized, and CaS can for example partly separate with metal in tornado dust collector.
In yet another embodiment of the present invention, first kind of promoter metals is identical with second kind of promoter metals, thereby reduces other amount of metal in the reduction reaction product that enters reducing metal-oxygen compounds as far as possible.In another embodiment of the present invention, the metallographic phase in first kind and/or second kind of promoter metals and the metal-oxide compound with.When a kind of metallic substance of manufacture order, the amount of other elements is remained on alap level, to prevent to be subjected to the pollution of other metals.When producing a kind of alloy, maybe advantageously use one or more metals different as first kind and/or second kind of promoter metals with metal in the metal-oxide compound.
In a preferred embodiment of the invention, the reduction reaction of metal-oxide compound is carried out in a successive processes, first and second step of reaction are carried out simultaneously, and the metal-oxide compound is transplanted on second reaction zone that second step of reaction takes place by first reaction zone that first step of reaction takes place.Therefore, in a preferred embodiment, carbon monoxide is with respect to by metal-oxide compound, the reductive agent that is used for reducing metal-oxygen compounds and first kind and/or second kind of mixture movement that promoter metals constitutes.In another preferred embodiment, the metal-oxide compound transmits in a direction, and carbon monoxide transmits in another direction.In another preferred embodiment, metal-oxide compound and carbon monoxide adverse current transmit.In addition, can send into again in the described process by near small part gaseous reaction products, thereby reduced the new CO content that will add.And, basic solid product that can near small part metal-oxide compound reduction reaction is sent in the described process again as first kind of reduction reaction and/or second kind of promoter metals, thereby has reduced the amount of first kind and/or the second kind new promoter material that will add.
Consider for reaction kinetics, preferably be lower than 650 ℃ in the working temperature of first reaction zone that the Bu Shi reaction takes place, more preferably between 300-600 ℃, also more preferably between 450-550 ℃.In a preferred embodiment of the invention, the metal-oxide compound comprises iron-oxygen compound, for example the carbonate of the oxyhydroxide of the oxide compound of iron and/or iron and/or iron.In addition, first kind and/or second kind of promoter metals can comprise iron, so that be limited in the amount of non-ferrous metal in the iron that obtains-oxygen compound reduction reaction product.Consider that for reaction kinetics carrying out reducing metal-oxygen compounds, for example the working temperature of the reaction zone of iron-oxygen compound is preferably 550-900 ℃, more preferably 650-850 ℃, also more preferably 700-775 ℃.Above-mentioned the method according to this invention can be carried out under barometric point substantially.It is evident that for the professional person: under non-barometric point, implement the method according to this invention molecular balance is moved.The present invention is also included within to be below or above and implements described method under the barometric point, and, the present invention also comprises the mode of using according to the inventive method of controlling, and makes when the pressure that Bu Shi reaction (first step of reaction) takes place reduces (second step of reaction) with the metal-oxide compound different.
Be noted that owing to the essence of Bu Shi reaction and the reason of metal-oxide compound reduction kinetics aspect, between the reaction zone of reaction zone that forms carbon by the Bu Shi reaction by carbon monoxide and main generation metal-oxide compound reduction reaction, can there be overlapping, because some Bu Shi carbon still can form at the reaction zone of generation metal-oxide compound reduction reaction and/or because some metal-oxide compound may reduce at the reaction zone that the Bu Shi reaction takes place to small part, provide the first kind of metal that is used for reduction reaction to small part thus.
Because the decision of the point of contact number between reductive agent, first kind of promoter metals and the metal-oxide compound is according to the kinetics of the inventive method reducing metal-oxygen compounds process, therefore, preferable alloy-oxygen compound or metal-oxide compound and first kind of promoter material are powder type as first kind of promoter metals.Described particles of powder size should be preferably less than 1mm, but 100 μ m or littler more preferably.Described powder or its mixture can pre-treatment become agglomerate such as bead or sinter, and there is sufficient hole in described agglomerate, can make carbon monoxide arrive metal-oxide compound or first kind of metal and metal-oxide compound in the agglomerate.Although it is just effective when first kind of promoter metals amount is very little according to the inventive method, but the amount of having found first kind of promoter metals should preferably be higher than 1 weight % of metal-oxide compound, more preferably be higher than 5 weight %, and, preferably be about 10 weight % in the initial stage that metal-oxide compound reductive technology takes place.
The present invention also relates to implement in a kind of shaft furnace such as the blast furnace reductive method.Also comprise a kind of method among the present invention, wherein, the metal-oxide compound comprises iron-oxygen compound, and the reduction reaction of iron-oxygen compound is carried out in shaft furnace such as blast furnace, to produce iron.Find: in traditional blast furnace technology, use and comprise that adding iron can cause the out-of-proportion increase of molten pig as first kind of promoter metals of reduction of iron ore reaction according to the inventive method.For example, the iron that adds powder type for example in iron ore forms mixture as first kind of promoter metals, prepares traditional bead by it, and the iron-oxygen compound that enters blast furnace technology and mixture as the iron of first kind of promoter metals can be provided.During blast furnace technology, bead falls and enters into stove, and produces Bu Shi carbon at first by CO (carbon monoxide converter) gas under proper temperature, and described CO (carbon monoxide converter) gas stems from the combustion of coke in bottom house zone.CO (carbon monoxide converter) gas is reduced into carbon dioxide and Bu Shi carbon.
Be noted that because temperature height when in traditional blast furnace technology, producing the pig iron by the oxide compound of iron, so, Bu Shi balance (equation (1)) is shifted to by carbon and carbonic acid gas and is formed carbon monoxide one side, and described carbonic acid gas is formed by coke and the oxygen that is blown into the blast furnace bottom.Therefore, iron-oxygen compound reductive position taking place can not form Bu Shi carbon in blast furnace in traditional blast furnace technology.
In the method according to the invention, it is believed that Bu Shi carbon is depositing by on iron-oxygen compound and the mixture that constitutes as the iron of first kind of promoter metals, and this composition material descends further and enters into blast furnace.Under suitable temperature, iron-oxygen compound will begin reduction, and iron-oxygen compound is reduced into iron.Finally, in addition further drop in the blast furnace after, iron will melt and prepare to adopt currently known methods by blast furnace casting.Obviously, when iron ore and first kind of promoter metals (can be iron) being had with sintered products or any other long-pending agglomerate of large contact surface joins according to the inventive method between iron ore, first kind of metal and carbon monoxide, this method also works.As result of the present invention, the carbon monoxide output of described blast furnace technology reduces, and reason is that the carbon that is derived from coke obtains more effective utilization, and for the interpolation iron catalyst, the output of blast furnace unit time molten pig has out-of-proportion increase.In other words, in the unit time, in iron ore, add after the iron of first kind of promoter metals of conduct of x%, the 100+x% of the amount of molten iron that time per unit can will can be taken out greater than time per unit by the amount of molten iron of taking out in the stove, therefore, newly form the amount of iron by increasing time per unit by iron ore, blast furnace is more effectively utilized.Obviously, the corresponding increase of the consumption of time per unit iron ore.
In any traditional equipment of direct reduction of handling metallic ore (for example can be sintered compact or bead form), can obtain the effect suitable with described method, productivity also can obtain suitable increase.Described equipment generally includes at least one metal-oxide compound reductive stove takes place, and wherein, described stove for example is selected from the stove that comprises rotary hearth furnace, rotation kiln, shaft furnace, cyclone furnaces (cyclone furnace) or discontinuous stove.Therefore, also comprise a kind of method among the present invention, in this method, the reduction reaction of metal-oxide compound is carried out in fluidized-bed, rotary hearth furnace, rotation kiln, cyclone furnaces or discontinuous stove, to obtain direct reductive metal.Also comprise a kind of method among the present invention in addition, in this method, the metal-oxide compound is iron-oxygen compound, and the reduction process of this iron-oxygen compound is carried out in fluidized-bed, rotary hearth furnace, rotation kiln, cyclone furnaces or discontinuous stove.
Also comprise a kind of method that the metal-oxide compound is reduced into the basic solid-state material that comprises metal part and non-metallic part among the present invention, in this method, substantially solid-state material is handled, so that for example gangue or slag separate with metal part and non-metallic part.This separating step can for example carry out in tornado dust collector (cyclone).
Also comprise a kind of method among the present invention, in this method, divide compression with metal part, to reduce its porosity.Also metal partly can be rolled into slab, square billet, bloom, bar, stocking or band.This method can be saved a step that starts from ore, ends at slab in the production process, thereby can significantly reduce cost and energy consumption.Also metal partly can be squeezed into profiled material, stocking or bar, perhaps form near the net shape product.These products do not require, perhaps only require limited final processing.
Also can be with metal partly as the starting material in the smelting operation of for example using electric arc furnace, perhaps when metal part is divided into iron, as steelmaking process, in for example alkaline oxygen converter steelmaking technology or Siemens Martin process for making to the starting material of the surrogate of small part waste material.
Be noted that the metal in preferable alloy-oxygen compound is iron, copper, cobalt, nickel, ruthenium, rhodium, palladium, platinum or iridium.Be noted that for some metal, exist more than a kind of metal-oxide compound, for example oxyhydroxide of the oxide compound of copper and copper.The present invention also relates to the method that a kind of metal-oxide compound comprises the mixture of at least two kinds of metal-oxide compounds, in this method, metal difference in each metal-oxide compound, and, each metal comprises iron, copper, cobalt, nickel, ruthenium, rhodium, palladium, platinum or iridium, prepares the original product of going back that comprises at least two kinds of different metals thus.The advantage of this embodiment is directly to prepare alloy.A kind of or described first kind of promoter metals also can be different with the metal in the metal-oxide compound.
Can be by in standard gasifier, handling at least a carbon compound according to currently known methods, prepare and contain and will form the gaseous mixture of the carbon monoxide of carbon by the Bu Shi reaction, described carbon compound is selected from the one group of carbon compound that comprises coke, coal, charcoal, oil, plastics, Sweet natural gas, paper, biomass, Tar sands, is subjected to the strong carbon containing energy that pollutes.By suitable pre-treatment and/or aftertreatment can with undesirable element for example sulphur from gaseous mixture, remove.Standard gasifier can be equipped the device of control by harmful or undesirable byproduct output of carbon compound gasification generation.
The present invention also relates to a kind of carbon that adopts as the compound reductive device of reductive agent with metal-oxygen, this device comprises: the fs reaction chamber that is fit to hold the solid-state material of metal-oxide compound, be used to import the inlet that leads to the fs reaction chamber of metal-oxide compound, the subordinate phase reaction chamber, be used for after fs reaction chamber reaction, solid-state material being delivered to from the fs reaction chamber e Foerderanlage of subordinate phase reaction chamber, be used for CO gas is transferred to by the subordinate phase reaction chamber device of fs reaction chamber, and be used for the discharge that solid-state substantially reactor product is discharged from the subordinate phase reaction chamber is exported.
Thereby for example, employed reactor comprises first reaction zone and second reaction zone.At first reaction zone, enter the mouth near the metal-oxide compound, by selection operation parameter such as temperature and pressure, reaction forms carbon by carbon monoxide by Bu Shi, at second reaction zone, near being derived from the basic solid-state material outlet of metal-oxide compound reductive,, the metal-oxide compound is reduced by selection operation parameter such as temperature and pressure.Preferably under similar operation pressure, the temperature of first reaction zone is lower than second reaction zone.
Be noted that preferably and add first kind and/or second kind of promoter material in the described method initial stage.Can add first kind and/or second kind of metal in the later or earlier stage of described method by noted earlier obviously choosing wantonly as can be known also, thereby need a selectable extra inlet.In addition, not only in described method between elementary period, and carry out in the process in described method, can in the metal-oxide compound, add similar and have the compound of appropriate form to Bu Shi carbon, as powdered graphite, in the reduction reaction of metal-oxide compound, play the reductive agent effect, therefore, the one or more extra carbon inlets of optionally require.
Preferred described equipment comprises the device that produces the hot CO gas wait to send into the subordinate phase reaction chamber.
In according to another embodiment of the invention, described equipment comprises that also near small part gaseous reaction products sends into the device of described technological process again.And described equipment can comprise that also near small part is derived from the device that the basic solid-state material of metal-oxide compound reductive is sent into described technological process again.
In another embodiment, described each reaction zone can physical sepn appearing at each in reactor separately, thereby can select work parameter such as temperature and pressure more independently.
In another embodiment, described equipment comprises fluidized-bed, and this fluidized-bed provides at least one in the described first and second elementary reaction chambers.In another embodiment, described equipment comprises the stove that is selected from rotary hearth furnace, rotation kiln, shaft furnace, cyclone furnaces, continuous or discontinuous stove.
In a preferred embodiment, described equipment substantially in a tubular form, more preferably shape substantially axisymmetricly.
Description of drawings
Now explain specific embodiments of the present invention by following non-limiting example and with reference to schematic figures, in the described accompanying drawing:
Fig. 1 has schematically shown the equipment of the present invention of implementing.
Fig. 2 has schematically shown another embodiment of implementing equipment of the present invention.
Fig. 3 has schematically shown another embodiment of the enforcement present device with separate reaction zones.
Preferred embodiment is described
Among Fig. 1, carry out in the equipment that is implemented in reducing metal-oxygen compounds of the present invention, wherein, described equipment comprises reactor 1, the inlet 2 of metal-oxide compound, the inlet of first kind and/or second kind of promoter material (herein being the form of first kind and/or second kind metal) is (not shown, unless first kind and/or second kind of metal and metal-oxide compound add together, in this case, the inlet of first kind and/or second kind metal also is an inlet 2), the inlet 3 that comprises the gaseous mixture of carbon monoxide, heating unit (not shown) to the heating of reactor different piece, the outlet 4 of gaseous reaction products and the outlet 5 that is derived from the basic solid-state material of metal-oxide compound reductive.
Shown in Fig. 2 is another embodiment of the invention, wherein, described equipment comprises reactor 1, the inlet 2 of metal-oxide compound, the inlet of first kind and/or second kind of promoter material (herein being the form of first kind and/or second kind metal) is (not shown, unless first kind and/or second kind of metal and metal-oxide compound add together, in this case, the inlet of first kind and/or second kind metal also is an inlet 2), the inlet 3 that comprises the gaseous mixture of carbon monoxide, to the heating of reactor different piece or refrigerative heating or refrigerating unit (not shown), the outlet 4 of gaseous reaction products and the outlet 5 that is derived from the basic solid-state material of metal-oxide compound reductive, the e Foerderanlage 6 of conveying solid substance reactant, the device 7 that near small part gaseous reaction products is sent into described technological process again by outlet 4, and near small part is derived from the device 8 that the basic solid-state material of metal-oxide compound reductive is introduced again.
Shown in Fig. 3 is another embodiment of the present invention, wherein, described reactor comprises that main generation produces the first reactor part 9 of carbon by the Bu Shi reaction, the main metal-oxide compound reductive second reactor part 10 that takes place, be used for solid reactant is sent to by the first reactor part 9 transport unit 11 of the second reactor part 10, the gaseous mixture that is used for comprising carbon monoxide is sent to the transport unit 11 of the first reactor part 9 by the second reactor part 10, the inlet 2 of metal-oxide compound, the inlet of first kind and/or second kind of promoter material (herein being the form of first kind and/or second kind metal) is (not shown, unless first kind and/or second kind of metal add with the metal-oxide compound, in this case, the inlet of first kind and/or second kind metal also is an inlet 2), the inlet 3 that comprises the gaseous mixture of carbon monoxide, to the heating of reactor different piece or refrigerative heating or refrigerating unit (not shown), the outlet 4 of gaseous reaction products and the outlet 5 that is derived from the basic solid-state material of metal-oxide compound reductive.This embodiment also can be equipped with near small part gaseous reaction products is sent into described technological process again by outlet 4 device, and near small part is derived from the basic solid-state material of metal-oxide compound reductive is introduced described technological process again by catalyst inlet as first kind and/or second kind of metal device, but above-mentioned these are not shown in Figure 3.
In above-mentioned all three embodiments, can there be one or more optional inlets, be used in the described method initial stage and/or introduce similar during carrying out and have the compound of appropriate form, for example powdered graphite to Bu Shi carbon.
Provide embodiment now, to explain and example explanation the present invention.What embodiment 1 and 2 illustrated is the effect that only obtains in the present invention's second step of reaction.
Embodiment 1
In a thermogravimetric analyzer, to by as the ferriferous oxide of metal-oxide compound, heat as the carbon of the reductive agent of reducing metal-oxygen compounds and as the uniform mixture that the iron of first kind and second kind metal constitutes.The carbon amount is selected, made it be enough to and ferriferous oxide can be reduced into metallic iron fully.The minimizing of mixture quality has directly shown the reduction of metal-oxide compound.When reducing fully, prospective quality be reduced to about 12-15%.These measuring results show: when using crystalline carbon powder such as kish, synthetic graphite, elektrographite or Bu Shi carbon, under 650-850 ℃, the oxide compound of iron is realized reduction fully.Confirmed that powdery coal, gac or powdery coke effect are relatively poor because ferriferous oxide be lower than under 900 ℃ can not or only part be reduced into iron.Confirm: the specific activity crystalline carbon of amorphous carbon reducing iron oxides such as graphite active low, but active high than powdery coal, gac or powdery coke.
In the reactor that comprises stainless steel tube and stove, the e Foerderanlage of forcing machine formula screw rod as solid reactant is installed.Will be by ferriferous oxide, similar and have the carbon of suitable form and send in the described pipe as the mixture that the iron powder of first kind of metal constitutes with Bu Shi carbon, and be heated to 650-850 ℃.Ferriferous oxide is reduced into iron very soon.
Embodiment 3 (embodiments of the invention)
In the reactor according to Fig. 2, stainless steel tube constitutes this reactor, and the e Foerderanlage 6 of forcing machine formula screw rod as solid reactant is installed.Arrow is represented the delivery direction of solid reactant.By the mixture that constitutes as the ferriferous oxide of metal-oxide compound with as the iron powder of first kind of metal by sending at the inlet 2 of described Guan Yiduan and being sent to the steel pipe the other end by forcing machine formula screw rod 6.The hot gas mixture that will comprise carbon monoxide with reflux type 3 is incorporated in the reactor by entering the mouth, and so also is provided at the heat that is used for reduction reaction in the reactor.Temperature at gaseous mixture ingress reactant is about 900 ℃, is about 550 ℃ in the temperature of gaseous mixture exit solid reactant.At the cold junction of reactor, in first reaction zone,, form Bu Shi carbon by carbon monoxide by the Bu Shi reaction by playing the metallic iron relevant with catalyzer.The carbonic acid gas that is produced leaves this technological process as the part gaseous reaction products by exporting 4.The Bu Shi carbon laydown on solid reactant, and with solid reactant together by forcing machine formula screw conveyer to second reaction zone.At described second reaction zone, ferriferous oxide is obtained the mixture of metallic iron and carbon monoxide and carbonic acid gas by the Bu Shi carbon reduction.The basic solid iron of part can 2 be sent into described technical process by for example entering the mouth by device 8 again as first kind of metal, and the portion gas reaction product can 3 be sent into by for example entering the mouth again by device 7.
Certainly, should be appreciated that to the invention is not restricted to above-mentioned embodiment and embodiment, and should be included in claim and the specification sheets scope and the interior any He all embodiments of disclosed herein the present invention spirit scope.
Claims (26)
1. the method for a reducing metal-oxygen compounds, wherein adopt carbon as reductive agent, described method comprises: in first step of reaction, CO gas is sent into the reaction chamber that contains described metal-oxide compound, the condition of its reaction chamber makes CO be transformed into solid carbon and carbonic acid gas, thereby formed solid carbon is incorporated in the metal-oxide compound, and, in second step of reaction, be used in described first step of reaction and be incorporated into the described metal-oxide compound of described carbon reduction in the metal-oxide compound, wherein, at least in described second step of reaction, existence can effectively promote first kind of promoter material of described metal-oxide compound reductive, and this first kind of promoter material comprises the compound of first kind of promoter metals and/or first kind of promoter metals.
2. according to the method for claim 1, wherein, described method is carried out continuously, described first and described second step of reaction carry out simultaneously, described metal-oxide compound is shifted into second reaction zone that described second step of reaction takes place by first reaction zone that described first step of reaction takes place.
3. according to the method for claim 2, wherein, use the CO gas that forms in second step of reaction in described first step of reaction.
4. according to any one the method in the aforementioned claim, wherein, described second step of reaction is carried out under than the higher temperature of described first step of reaction.
5. according to any one the method in the aforementioned claim, wherein, described first kind of promoter material is described first kind of promoter metals or first kind of promoter metals carbide, first kind of promoter metals hydride or first kind of promoter metals nitride or their combination.
6. according to any one the method in the aforementioned claim, wherein, described first kind of promoter material is powder type.
7. according to any one the method in the aforementioned claim, wherein, the metallographic phase in described first kind of promoter metals and the described metal-oxide compound with.
8. according to any one the method in the aforementioned claim, wherein, at least in described first step of reaction, have second kind of promoter material, this second kind of promoter material comprises promotion CO and is transformed into the second kind of promoter metals of carbon and carbonic acid gas and/or the compound of second kind of promoter metals.
9. according to the method for aforementioned claim 8, wherein, described second kind of promoter material carbide that is described second kind of promoter metals or second kind of promoter metals, hydride or the nitride of second kind of promoter metals or their combination of second kind of promoter metals.
10. according to the method for aforementioned claim 9, wherein, described second kind of promoter material is powder type.
11. according to any one the method among the aforementioned claim 1-10, wherein, described metal-oxide compound is the agglomerate that is formed by powder.
12. according to any one the method among the aforementioned claim 1-11, wherein, described metal-oxide compound and described first kind of promoter material and as the agglomerate form that its powder forms of all serving as reasons of second kind of promoter material as described in existing.
13. according to any one the method in the aforementioned claim, wherein, the metal in the described metal-oxide compound is Fe, Cu, Co, Ni, Ru, Rh, Pd, Pt or Ir.
14. according to any one the method in the aforementioned claim, wherein, described first step of reaction is carried out being lower than under 650 ℃.
15. according to any one the method in the aforementioned claim, wherein, described metal-oxide compound comprises iron-oxygen compound, for example ferriferous oxide and/or iron hydroxide and/or iron carbonate.
16. according to any one the method in the aforementioned claim, wherein, described first kind of promoter metals and be iron as second kind of promoter metals as described in existing.
17. according to the method for aforementioned claim 15 or 16, wherein, described second step of reaction is carried out at 550-900 ℃.
18. according to any one the method in the aforementioned claim, wherein, described metal-oxide compound comprises the mixture of at least two kinds of metal-oxide compounds, wherein, the metal in the described metal-oxide compound is different, and, each described metal comprises Fe, Cu, Co, Ni, Ru, Rh, Pd, Pt or Ir.
19. according to any one the method in the aforementioned claim, described method is carried out in shaft furnace, blast furnace, fluidized-bed, rotary hearth furnace, rotation kiln, cyclone furnaces or discontinuous stove.
20. according to any one the method in the aforementioned claim, wherein, producing substantially in second step of reaction be solid-state reaction product, and, wherein, be admitted to described first step of reaction by the described reaction product of part of described second step of reaction generation.
21., wherein, extract gaseous reaction products and send into described technological process again according to any one the method in the aforementioned claim.
22. the equipment of a reducing metal-oxygen compounds, wherein adopt carbon as reductive agent, this equipment comprises: the fs reaction chamber that is suitable for holding the solid-state material of metal-oxide compound, be used to import the inlet of described fs reaction chamber of leading to of described metal-oxide compound, the subordinate phase reaction chamber, be used for after described fs reaction chamber reaction, solid-state material being delivered to from described fs reaction chamber the e Foerderanlage of described subordinate phase reaction chamber, be used for CO gas is delivered to by described subordinate phase reaction chamber the device of described fs reaction chamber, and the discharge that is used for discharging from described subordinate phase reaction chamber for solid-state reaction product substantially exports.
23., have and be used for outlet that gaseous reaction products discharges from described fs reaction chamber and the device that is used for gaseous reaction products is sent into again described subordinate phase reaction chamber according to the equipment of aforementioned claim 22.
24., have the device that is used for the basic solid reaction products of being discharged by described discharge outlet is sent into again described fs reaction chamber according to the equipment of aforementioned claim 22 or 23.
25., comprise the device that produces the hot CO gas of waiting to send into described subordinate phase reaction chamber according to aforementioned claim 22,23 or 24 equipment.
26. any one the equipment according among the aforementioned claim 22-25 comprises the fluidized-bed reactor that fs reaction chamber and/or subordinate phase reaction chamber are provided.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03078074.6 | 2003-10-03 | ||
| EP03078074 | 2003-10-03 | ||
| EP04075552.2 | 2004-02-23 | ||
| EP04075552A EP1568793A1 (en) | 2004-02-23 | 2004-02-23 | Method and apparatus for reducing metal-oxygen compounds |
| PCT/EP2004/011345 WO2005033347A1 (en) | 2003-10-03 | 2004-10-01 | Method and apparatus for reducing metal-oxygen compounds |
Publications (2)
| Publication Number | Publication Date |
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| CN1871366A true CN1871366A (en) | 2006-11-29 |
| CN1871366B CN1871366B (en) | 2011-06-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004800311109A Expired - Fee Related CN1871366B (en) | 2003-10-03 | 2004-10-01 | Method and apparatus for reducing metal-oxygen compounds |
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| Country | Link |
|---|---|
| CN (1) | CN1871366B (en) |
| UA (1) | UA81360C2 (en) |
| ZA (1) | ZA200602724B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113718117A (en) * | 2020-05-26 | 2021-11-30 | 山西华清能创环境科技有限公司 | Method for preparing inorganic fiber and nickel-iron alloy and inorganic fiber |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2979396A (en) * | 1957-05-31 | 1961-04-11 | Crucible Steel Co America | Method to catalyze the reduction of ores |
| GB1471544A (en) * | 1974-10-25 | 1977-04-27 | British Steel Corp | Direct reduction of metallic ores |
-
2004
- 2004-10-01 ZA ZA200602724A patent/ZA200602724B/en unknown
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| CN113718117A (en) * | 2020-05-26 | 2021-11-30 | 山西华清能创环境科技有限公司 | Method for preparing inorganic fiber and nickel-iron alloy and inorganic fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1871366B (en) | 2011-06-29 |
| ZA200602724B (en) | 2007-09-26 |
| UA81360C2 (en) | 2007-12-25 |
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