EP0222452A1 - Process for reducing the oxidation level of metallic oxides - Google Patents
Process for reducing the oxidation level of metallic oxides Download PDFInfo
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- EP0222452A1 EP0222452A1 EP86201942A EP86201942A EP0222452A1 EP 0222452 A1 EP0222452 A1 EP 0222452A1 EP 86201942 A EP86201942 A EP 86201942A EP 86201942 A EP86201942 A EP 86201942A EP 0222452 A1 EP0222452 A1 EP 0222452A1
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- carbon
- fluidized bed
- metal oxides
- calcination
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/09—Reaction techniques
- Y10S423/16—Fluidization
Definitions
- the invention relates to a method for reducing higher metal oxides to lower metal oxides by means of carbon-containing reducing agents.
- ores that contain metals - such as Fe, Ni, Mn - in the form of higher oxides must be subjected to a reducing treatment so that these metals are in the form of lower oxides.
- Such ores are processed in such a way that they are pre-reduced as far as possible to the FeO stage and then only as much metallic iron is produced in a melting process by further reduction as is permissible for the desired ferroalloy .
- the remaining iron oxide is slagged.
- the pre-reduction is carried out on an industrial scale in rotary kilns using coal as a reducing agent.
- the problem of the pre-reduction in the rotary kiln lies in the constant adherence to an exact pre-reduction of the iron oxides, the discharge material being allowed to contain only as much excess, solid carbon as is permissible for the further reduction in the melting process.
- the pre-reduction is not carried out up to the FeO stage.
- the pre-reduction takes place only up to a considerably higher degree of oxidation.
- a larger reduction work in the melt flow which mostly takes place in electric furnaces, is necessary, which makes the overall process more expensive.
- the adjustment of the further reduction in the melt flow is difficult since the degree of oxidation and carbon content of the discharge of the rotary kiln often fluctuate, even in the case of small furnaces.
- Another case concerns the reduction of ores which contain higher manganese oxides and whose manganese content is to be reduced to low manganese oxides.
- the invention has for its object the reduction of higher metal oxides to lower metal oxides as far as possible to be carried out continuously and constantly to the desired oxidation level and either to set as little as possible or to set a constant, small excess of carbon in the reduced discharge material.
- the grain size of the solids is in the range of less than 3 mm.
- the calcination can take place in a stationary fluidized bed, a circulating fluidized bed or another process in which the solids are suspended in a gas stream.
- the raw materials can be dried in the calcination before use. Drying can take place with the waste heat from the calcination. As a result, the water is evaporated without the consumption of carbon, the water vapor does not have to be heated to the considerably higher temperature in the calcination, and the waste heat is used in a favorable manner. After drying, further heating can be carried out before charging into the calcination, a certain amount of precalculation being able to occur.
- a stationary fluidized bed is to be understood as a fluidized bed in which a dense phase is separated from the dust space above by a clear density jump, and a defined boundary layer exists between these two distribution states.
- the amount of the oxygen-containing gases introduced as fluidizing gas into the stationary fluidized bed is such that the carbon-containing reducing agent is either virtually completely gasified or to a desired excess shot of carbon is gasified in the discharge material.
- the oxygen-containing gases generally consist of air.
- a preferred embodiment consists in that the calcination according to (a) takes place in a circulating fluidized bed which is passed from the fluidized bed reactor suspension into a separator, at least a partial flow of the separated solids is returned to the fluidized bed reactor, and the exhaust gas for drying and preheating the solids containing higher metal oxides are passed into suspension heat exchangers.
- the circulating fluidized bed system consists of a fluidized bed reactor, a separator and a return line for solids from the separator to the fluidized bed reactor.
- the fluidized bed in the fluidized bed reactor has - in contrast to the stationary fluidized bed, in which a dense phase is separated from the gas space above by a clear density jump - distribution states without a defined boundary layer. A leap in density between the dense phase and the dust space above it does not exist; however, the solids concentration within the reactor decreases continuously from bottom to top.
- the solids discharged from the fluidized bed reactor with the gases are returned to the fluidized bed reactor to form a circulating fluidized bed in such a way that the hourly solids circulation is at least five times the solids weight in the reactor shaft.
- a quantity of solids corresponding to the entry is withdrawn from the system of the circulating fluidized bed and passed into the stationary fluidized bed.
- the circulating fluidized bed results in a high throughput during calcination, a high burnout of the fuel and, due to the multi-stage combustion, a low content of CO and NO x in the exhaust gas.
- a preferred embodiment is that the exhaust gas from the stationary fluidized bed according to (d) before the introduction is passed into the calcination by a separator, and the separated solid is returned to the stationary fluidized bed.
- the dust separator expediently consists of a cyclone. This largely avoids the circulation of solids between the reduction stage and the oxidation stage.
- a preferred embodiment is that the reduction according to (b) is carried out with the addition of solid, carbon-containing reducing agents.
- the addition of solid fuels results in a better distribution in the fluidized bed and the desired amount of excess carbon in the discharge material can be adjusted very precisely and evenly.
- One embodiment consists of the use of iron-nickel ores and the addition of carbon-containing reducing agent in the stationary fluidized bed in accordance with (c) such that it is used to reduce the higher iron oxides, for example to the FeO stage, to reduce the nickel oxides, is sufficient to set the reduction temperature and there is a maximum of 2% by weight of excess carbon in the discharge material, and the discharge material is further processed in the melt flow to produce an amount of metallic iron corresponding to the desired iron-nickel alloy and slagging of the remaining iron content.
- One embodiment consists in that materials containing manganese oxides are used, and the addition of carbon-containing reducing agent in the stationary fluidized bed is dimensioned in accordance with (c) such that it is sufficient to reduce the higher manganese oxides, for example to the MnO stage, to set the reduction temperature, and There is as little excess carbon as possible in the discharge material.
- the ore 1 is charged via a screw 2 into a venturi-like suspension dryer 3. There it is suspended in the gas stream and passed via line 4 into a separator 5. The gas is cleaned in the electrostatic filter 6 and discharged as exhaust gas 7. The separated solids are fed into line 8 by screw 7a. A partial stream is fed into the calcination via line 9.
- the calcination is designed as a circulating fluidized bed and consists of the fluidized bed reactor l0, the return cyclone ll and the return line l2. Part of the solid is passed via line l3 into the preheater l4, suspended there in the gas stream and passed through line l5 into the separator l6. The separated solid is passed via line l7 into the reactor l0.
- the gas flows from the separator l6 into the suspension dryer 3. Fluidizing air l8 is introduced into the lower region of the reactor l0. At a higher point, secondary air 19 and coal 20 are introduced.
- a gas / solid suspension which fills the entire reactor 10 is formed within the fluidized bed reactor 10 and is passed at the top via line 2 1 into the recycling cyclone 11, where a separation of solid and gas takes place.
- the gas flows into the preheater l4 and the solid enters the return line l2, in which a U-shaped closure l3 is arranged, in the bottom of which a small amount of fluidizing air (not shown) is passed.
- the fluidized bed reactor l0 has a diameter of 3.7 m and a height of l6 m.
- the temperature in the reactor is 900 ° C.
- the fluidized bed reactor 24 has a diameter of 3 m and a height of 2.5 m.
- the temperature in the reactor is 900 ° C.
- Auger 2 100 t / h ore Fluidizing air l8: 20,000 Nm3 / h Secondary air l9: 22 600 Nm3 / h Coal 20: 4.26 t / h 8l, 8% C 2.6% H 5.6% O 1.5% ash 6.7% moisture H u : 7 043 kcal / kg Line 2l: 58 600 Nm3 / h 900 ° C Line 9: 60% of the solid Line l3: 40% of the solid Fluidizing air 25: 6 030 Nm3 / h Coal 26: 3.43 t / h Exhaust gas 27: 9 430 Nm3 / h 8.8% CO l7.6% CO2 6.3% H2 7.4% H2O 50.5% N2 Discharge 3l: 72.65 t / h 2l, 4% FeO 1.9% Ni
- the advantages of the invention are that, on the one hand, the calcination can be carried out in a very economical manner with the generation of a largely burnt-out, low-pollutant exhaust gas and, on the other hand, a reduced product is obtained which has a precise and uniform degree of reduction and a precisely defined and uniform content of excess Contains carbon, which content can also be practically zero.
- the iron oxides can be largely reduced to FeO and the formation of metallic iron can nevertheless be avoided.
- the carbon content in the discharge can be kept very low or only as high and absolutely uniform as is necessary for the reduction of the small amounts of metallic iron in the melting process. This enables precise metering of the amount of carbon in the electric furnace.
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Abstract
Zur Erzielung einer möglichst genauen und konstanten Reduktion und eines geringen Kohlenstoffüberschusses erfolgt die Reduktion mittels kohlenstoffhaltiger Reduktionsmittel in der Weise, daß höhere Metalloxide enthaltende Feststoffe in feinkörniger Form mit heißen Gasen von 800 bis ll00°C kalziniert werden, wobei die Feststoffe in den heißen Gasen suspendiert werden, die kalzinierten Feststoffe in einer stationären Wirbelschicht unter Zugabe von kohlenstoffhaltigen Reduktionsmitteln und sauerstoffhaltigen Gasen bei einer Temperatur im Bereich von 800 bis ll00°C zu niedrigen Metalloxiden reduziert werden, der Zusatz an kohlenstoffhaltigem Reduktionsmittel so bemessen wird, daß die Menge des zugegebenen Kohlenstoffs zur Reduktion der höheren Metalloxide zu niedrigen Metalloxiden, zur Erzeugung der Reduktionstemperatur und zur Einstellung des gewünschten Kohlenstoffgehaltes im Austragsmaterial ausreicht, das Abgas aus der stationären Wirbelschicht als Sekundärgas in die Kalzination geleitet wird und in die Kalzination Brennstoff in einer solchen Menge eingeleitet wird, daß dessen Verbrennung und die durch das Abgas eingebrachte Wärmemenge die für die Kalzination erforderliche Wärmemenge ergeben.To achieve the most accurate and constant reduction possible and a small excess of carbon, the reduction is carried out by means of carbon-containing reducing agents in such a way that solids containing higher metal oxides are calcined in fine-grained form with hot gases of 800 to ll00 ° C., the solids being suspended in the hot gases the calcined solids are reduced to low metal oxides in a stationary fluidized bed with the addition of carbon-containing reducing agents and oxygen-containing gases at a temperature in the range from 800 to ll00 ° C., the addition of carbon-containing reducing agent is measured so that the amount of carbon added to the Reduction of the higher metal oxides to low metal oxides, to generate the reduction temperature and to set the desired carbon content in the discharge material is sufficient, the exhaust gas from the stationary fluidized bed as secondary gas into the calcination et is and fuel is introduced into the calcination in such an amount that its combustion and the amount of heat introduced by the exhaust gas result in the amount of heat required for the calcination.
Description
Die Erfindung betrifft ein Verfahren zur Reduktion von höheren Metalloxiden zu niedrigen Metalloxiden mittels kohlenstoffhaltiger Reduktionsmittel.The invention relates to a method for reducing higher metal oxides to lower metal oxides by means of carbon-containing reducing agents.
In manchen Fällen müssen Erze, die Metalle - wie Fe, Ni, Mn - in Form höherer Oxide enthalten, einer reduzierenden Behandlung unterworfen werden, damit diese Metalle in Form niedriger Oxide vorliegen.In some cases, ores that contain metals - such as Fe, Ni, Mn - in the form of higher oxides must be subjected to a reducing treatment so that these metals are in the form of lower oxides.
Dies ist insbesondere der Fall bei Verfahren zur Herstellung von Eisen-Nickel-Legierungen aus Eisen-Nickel-Erzen.This is particularly the case with processes for the production of iron-nickel alloys from iron-nickel ores.
Zur Versorgung der Industrie mit Nickel, insbesondere in Form seiner Legierung mit Eisen, müssen in zunehmendem Maße ärmere, z.B. lateritische, Erze eingesetzt werden. Diese weisen jedoch meist ein Fe/Ni-Verhältnis auf, das bei vollständiger Reduktion beider Metalle und schmelzflüssiger Abtrennung der Erzgangart als Schlacke zu einer nicht marktfähigen, weil zu Ni-armen Ferrolegierung führen würde.To supply the industry with nickel, especially in the form of its alloy with iron, increasingly poorer, e.g. lateritic, ores are used. However, these usually have an Fe / Ni ratio, which would lead to a non-marketable, because Ni-poor ferro-alloy would result in a complete reduction of both metals and a molten separation of the vein type as slag.
Während z.B. bei einem Erz mit 30 % Fe und 2 % Ni ein Fe/Ni-Verhältnis von l5/l vorliegt, weisen handelsübliche Ferrolegierungen solche Verhältnisse von höchstens 4/l auf, d.h. ihr Nickelgehalt beträgt mindestens 20 %.For example, while an ore with 30% Fe and 2% Ni has an Fe / Ni ratio of 15 / l, commercially available ferro alloys have such ratios of at most 4 / l, ie their nickel content is at least 20%.
Aus diesem Grunde werden solche Erze deshalb in der Weise verarbeitet, daß sie durch eine Vorreduktion möglichst bis zum FeO-Stadium vorreduziert werden und dann in einem Schmelz-prozeß nur so viel metallisches Eisen durch weitere Reduktion erzeugt wird, wie für die gewünschte Ferrolegierung zulässig ist. Das restliche Eisenoxid wird verschlackt. Die Vorreduktion erfolgt großtechnisch in Drehrohröfen unter Einsatz von Kohle als Reduktionsmittel. Das Problem der Vorreduktion im Drehrohrofen liegt in der konstanten Einhaltung einer genauen Vorreduktion der Eisenoxide, wobei das Austragsmaterial nur so viel überschüssigen, festen Kohlenstoff enthalten darf, wie für die weitere Reduktion im Schmelzprozeß zulässig ist. Da im Drehrohrofen bei der Vorreduktion relativ starke Schwankungen im Reduktionsgrad auftreten, die Bildung von metallischem Eisen aber vermieden werden soll, wird die Vorreduktion nicht bis zum FeO-Stadium durchgeführt. Aus Sicherheitsgründen erfolgt die Vorreduktion nur bis zu einem beträchtlich höheren Oxidationsgrad. Dadurch wird aber eine größere Reduktionsarbeit im Schmelzfluß, die meistens in Elektroöfen erfolgt, notwendig, wodurch das Gesamtverfahren teurer wird. Außerdem ist die Einstellung der weiteren Reduktion im Schmelzfluß schwierig, da der Oxidationsgrad und Kohlenstoffgehalt des Austrages des Drehrohrofens, selbst bei kleinen Öfen, oft schwankt.For this reason, such ores are processed in such a way that they are pre-reduced as far as possible to the FeO stage and then only as much metallic iron is produced in a melting process by further reduction as is permissible for the desired ferroalloy . The remaining iron oxide is slagged. The pre-reduction is carried out on an industrial scale in rotary kilns using coal as a reducing agent. The problem of the pre-reduction in the rotary kiln lies in the constant adherence to an exact pre-reduction of the iron oxides, the discharge material being allowed to contain only as much excess, solid carbon as is permissible for the further reduction in the melting process. Since relatively large fluctuations in the degree of reduction occur in the rotary kiln during the pre-reduction, but the formation of metallic iron should be avoided, the pre-reduction is not carried out up to the FeO stage. For safety reasons, the pre-reduction takes place only up to a considerably higher degree of oxidation. As a result, however, a larger reduction work in the melt flow, which mostly takes place in electric furnaces, is necessary, which makes the overall process more expensive. In addition, the adjustment of the further reduction in the melt flow is difficult since the degree of oxidation and carbon content of the discharge of the rotary kiln often fluctuate, even in the case of small furnaces.
Ein solches Verfahren ist beschrieben im TMS-AIME Paper Selection, Paper No. A 74-40, Seiten l-23.Such a process is described in TMS-AIME Paper Selection, Paper No. A 74-40, pages l-23.
Ein weiterer Fall betrifft die Reduktion von Erzen, die höhere Manganoxide enthalten und deren Mangangehalt zu niedrigen Manganoxiden reduziert werden soll.Another case concerns the reduction of ores which contain higher manganese oxides and whose manganese content is to be reduced to low manganese oxides.
Der Erfindung liegt die Aufgabe zugrunde, die Reduktion von höheren Metalloxiden zu niedrigen Metalloxiden möglichst weit gehend und konstant zur gewünschten Oxidationsstufe durchzuführen und entweder möglichst wenig oder einen konstanten, geringen Überschuß an Kohlenstoff im reduzierten Austragsmaterial einzustellen.The invention has for its object the reduction of higher metal oxides to lower metal oxides as far as possible to be carried out continuously and constantly to the desired oxidation level and either to set as little as possible or to set a constant, small excess of carbon in the reduced discharge material.
Die Lösung dieser Aufgabe erfolgt erfindungsgemäß dadurch, daß
- a) höhere Metalloxide enthaltende Feststoffe in feinkörniger Form mit heißen Gasen von 800 bis ll00°C kalziniert werden, wobei die Feststoffe in den heißen Gasen suspenddiert werden,
- b) die kalzinierten Feststoffe in einer stationären Wirbelschicht unter Zugabe von kohlenstoffhaltigen Reduktionsmitteln und sauerstoffhaltigen Gasen bei einer Temperatur im Bereich von 800 bis ll00°C zu niedrigen Metalloxiden reduziert werden,
- c) der Zusatz an kohlenstoffhaltigem Reduktionsmittel in (b) so bemessen wird, daß die Menge des zugegebenen Kohlenstoffs zur Reduktion der höheren Metalloxide zu niedrigen Metalloxiden, zur Erzeugung der Reduktionstemperatur und zur Einstellung des gewünschten Kohlenstoffgehaltes im Austragsmaterial ausreicht,
- d) das Abgas aus der stationären Wirbelschicht gemäß (b) als Sekundärgas in die Kalzination gemäß (a) geleitet wird und
- e) in die Kalzination gemäß (a) Brennstoff in einer solchen Menge eingeleitet wird, daß dessen Verbrennung und die durch das Abgas gemäß (d) eingebrachte Wärmemenge die für die Kalzination erforderliche Wärmemenge ergeben.
- a) solids containing higher metal oxides are calcined in fine-grained form with hot gases of 800 to ll00 ° C., the solids being suspended in the hot gases,
- b) the calcined solids are reduced to low metal oxides in a stationary fluidized bed with the addition of carbon-containing reducing agents and oxygen-containing gases at a temperature in the range from 800 to ll00 ° C.,
- c) the addition of carbon-containing reducing agent in (b) is such that the amount of carbon added is sufficient to reduce the higher metal oxides to lower metal oxides, to generate the reduction temperature and to set the desired carbon content in the discharge material,
- d) the exhaust gas from the stationary fluidized bed according to (b) is passed as secondary gas into the calcination according to (a) and
- e) fuel is introduced into the calcination according to (a) in such an amount that its combustion and the amount of heat introduced by the exhaust gas according to (d) result in the amount of heat required for the calcination.
Die Korngröße der Feststoffe liegt im Bereich kleiner 3 mm.The grain size of the solids is in the range of less than 3 mm.
In der Kalzination werden Kristallwasser ausgetrieben, Karbonate unter Entwicklung von CO₂ zerlegt und eventuell vorhandene Feuchtigkeit verdampft. Die Kalzination erfolgt unter oxidierenden Bedingungen. Die heißen Gase können durch Verbrennung von festen, flüssigen oder gasförmigen Brennstoffen erzeugt werden.In the calcination, crystal water is expelled, carbonates are broken down with the development of CO₂ and any moisture that may be present is evaporated. The calcination takes place under oxidizing conditions. The hot gases can be generated by burning solid, liquid or gaseous fuels.
Die Kalzination kann in einer stationären Wirbelschicht, einer zirkulierenden Wirbelschicht oder einem anderen Verfahren erfolgen, bei dem die Feststoffe in einem Gasstrom suspendiert sind. Die Rohstoffe können vor dem Einsatz in die Kalzination getrocknet werden. Die Trocknung kann mit der Abwärme der Kalzination erfolgen. Dadurch erfolgt die Wasserverdampfung ohne Verbrauch an Kohlenstoff, der Wasserdampf muß nicht auf die beträchtlich höhere Temperatur in der Kalzination erhitzt werden, und die Abwärme wird in günstiger Weise ausgenutzt. Nach der Trocknung kann eine weitere Aufheizung vor der Chargierung in die Kalzination erfolgen, wobei bereits eine gewisse Vorkalzination eintreten kann.The calcination can take place in a stationary fluidized bed, a circulating fluidized bed or another process in which the solids are suspended in a gas stream. The raw materials can be dried in the calcination before use. Drying can take place with the waste heat from the calcination. As a result, the water is evaporated without the consumption of carbon, the water vapor does not have to be heated to the considerably higher temperature in the calcination, and the waste heat is used in a favorable manner. After drying, further heating can be carried out before charging into the calcination, a certain amount of precalculation being able to occur.
Der aus der Kalzination abgezogene Feststoff wird in einer stationären (klassischen) Wirbelschicht vorreduziert. Unter einer stationären Wirbelschicht ist eine Wirbelschicht zu verstehen, bei der eine dichte Phase durch einen deutlichen Dichtesprung von dem darüber befindlichen Staubraum getrennt ist, und eine definierte Grenzschicht zwischen diesen beiden Verteilungszuständen vorliegt.The solid withdrawn from the calcination is pre-reduced in a stationary (classic) fluidized bed. A stationary fluidized bed is to be understood as a fluidized bed in which a dense phase is separated from the dust space above by a clear density jump, and a defined boundary layer exists between these two distribution states.
Die Menge der als Fluidisierungsgas in die stationäre Wirbelschicht geleiteten sauerstoffhaltigen Gase wird so bemessen, daß das kohlenstoffhaltige Reduktionsmittel entweder praktisch vollständig vergast wird oder bis auf einen gewünschten Über schuß an Kohlenstoff im Austragsmaterial vergast wird. Die sauerstoffhaltigen Gase bestehen im allgemeinen aus Luft.The amount of the oxygen-containing gases introduced as fluidizing gas into the stationary fluidized bed is such that the carbon-containing reducing agent is either virtually completely gasified or to a desired excess shot of carbon is gasified in the discharge material. The oxygen-containing gases generally consist of air.
Eine vorzugsweise Ausgestaltung besteht darin, daß die Kalzination gemäß (a) in einer zirkulierenden Wirbelschicht erfolgt, die aus dem Wirbelschichtreaktor ausgetragene Suspension in einen Abscheider geleitet wird, mindesten ein Teilstrom der abgeschiedenen Feststoffe in den Wirbelschichtreaktor zurückgeleitet wird, und das Abgas zur Trocknung und Vorwärmung der höhere Metalloxide enthaltenden Feststoffe in Suspensions-Wärmeaustauscher geleitet wird. Das System der zirkulierenden Wirbelschicht besteht aus einem Wirbelschichtreaktor, einem Abscheider und einer Rückführleitung für Feststoffe vom Abscheider in den Wirbelschichtreaktor. Die Wirbelschicht im Wirbelschichtreaktor weist - im Gegensatz zur stationären Wirbelschicht, bei der eine dichte Phase durch einen deutlichen Dichtesprung von dem darüber befindlichen Gasraum getrennt ist - Verteilungszustände ohne definierte Grenzschicht auf. Ein Dichtesprung zwischen dichter Phase und darüber befindlichem Staubraum ist nicht existent; jedoch nimmt innerhalb des Reaktors die Feststoffkonzentration von unten nach oben ständig ab. Bei der Definition der Betriebsbedingungen über die Kennzahlen von Froude und Archimedes ergeben sich die Bereiche:
Es bedeuten:
u die relataive Gasgeschwindigkeit in m/sec.
Ar die Archimedes-Zahl
Fr die Froude-Zahl
dk den Durchmesser des kugelförmigen Teilchens in m
ν die kinematische Zähigkeit in m²/sec.
g die Gravitationskonstante in m/sec.²It means:
u the relative gas velocity in m / sec.
Ar is the Archimedes number
For the Froude number
d k is the diameter of the spherical particle in m
ν the kinematic toughness in m² / sec.
g is the gravitational constant in m / sec.²
Die mit den Gasen aus dem Wirbelschichtreaktor ausgetragenen Feststoffe werden derart zur Ausbildung einer zirkulierenden Wirbelschicht in den Wirbelschichtreaktor zurückgeleitet, daß der stündliche Feststoffumlauf mindestens das Fünffache des im Reaktorschacht befindlichen Feststoffgewichtes ausmacht. Eine dem Eintrag entsprechende Menge an Feststoffen wird aus dem System der zirkulierenden Wirbelschicht abgezogen und in die stationäre Wirbelschicht geleitet. Die zirkulierende Wirbelschicht ergibt eine hohe Durchsatzleistung bei der Kalzination, einen hohen Ausbrand des Brennstoffes und durch die mehrstufige Verbrennung einen geringen Gehalt an CO und NOx im Abgas.The solids discharged from the fluidized bed reactor with the gases are returned to the fluidized bed reactor to form a circulating fluidized bed in such a way that the hourly solids circulation is at least five times the solids weight in the reactor shaft. A quantity of solids corresponding to the entry is withdrawn from the system of the circulating fluidized bed and passed into the stationary fluidized bed. The circulating fluidized bed results in a high throughput during calcination, a high burnout of the fuel and, due to the multi-stage combustion, a low content of CO and NO x in the exhaust gas.
Eine vorzugsweise Ausgestaltung besteht darin, daß das Abgas aus der stationären Wirbelschicht gemäß (d) vor der Einleitung in die Kalzination durch einen Abscheider geleitet wird, und der abgeschiedene Feststoff in die stationäre Wirbelschicht zurückgeleitet wird. Der Staubabscheider besteht zweckmäßigerweise aus einem Zyklon. Dadurch wird eine Kreislaufführung von Feststoffen zwischen der Reduktionsstufe und der Oxidationsstufe weitgehend vermieden.A preferred embodiment is that the exhaust gas from the stationary fluidized bed according to (d) before the introduction is passed into the calcination by a separator, and the separated solid is returned to the stationary fluidized bed. The dust separator expediently consists of a cyclone. This largely avoids the circulation of solids between the reduction stage and the oxidation stage.
Eine vorzugsweise Ausgestaltung besteht darin, daß die Reduktion gemäß (b) unter Zusatz von festen, kohlenstoffhaltigen Reduktionsmitteln erfolgt. Der Zusatz von festen Brennstoffen ergibt eine bessere Verteilung in der Wirbelschicht und die gewünschte Menge an überschüssigem Kohlenstoff im Austragsmaterial kann sehr genau und gleichmäßig eingestellt werden.A preferred embodiment is that the reduction according to (b) is carried out with the addition of solid, carbon-containing reducing agents. The addition of solid fuels results in a better distribution in the fluidized bed and the desired amount of excess carbon in the discharge material can be adjusted very precisely and evenly.
Eine Ausgestaltung besteht darin, daß Eisen-Nickel-Erze eingesetzt werden, und der Zusatz an kohlenstoffhaltigem Reduktionsmittel in die stationäre Wirbelschicht gemäß (c) so bemessen wird, daß er zur Reduktion der höheren Eisenoxide etwa zum FeO-Stadium, zur Reduktion der Nickeloxide, zur Einstellung der Reduktionstemperatur ausreicht und im Austragsmaterial ein Gehalt an überschüssigem Kohlenstoff von maximal 2 Gew.-% vorliegt, und das Austragsmaterial im Schmelzfluß unter Erzeugung einer der gewünschten Eisen-Nickel-Legierung entsprechenden Menge von metallischem Eisen und Verschlackung des restlichen Eisengehaltes weiterbehandelt wird.One embodiment consists of the use of iron-nickel ores and the addition of carbon-containing reducing agent in the stationary fluidized bed in accordance with (c) such that it is used to reduce the higher iron oxides, for example to the FeO stage, to reduce the nickel oxides, is sufficient to set the reduction temperature and there is a maximum of 2% by weight of excess carbon in the discharge material, and the discharge material is further processed in the melt flow to produce an amount of metallic iron corresponding to the desired iron-nickel alloy and slagging of the remaining iron content.
Eine Ausgestaltung besteht darin, daß Manganoxide enthaltende Materialien eingesetzt werden, und der Zusatz an kohlenstoffhaltigem Reduktionsmittel in die stationäre Wirbelschicht gemäß (c) so bemessen wird, daß er zur Reduktion der höheren Manganoxide etwa zum MnO-Stadium, zur Einstellung der Reduktionstemperatur ausreicht, und im Austragsmaterial möglichst wenig überschüssiger Kohlenstoff vorliegt.One embodiment consists in that materials containing manganese oxides are used, and the addition of carbon-containing reducing agent in the stationary fluidized bed is dimensioned in accordance with (c) such that it is sufficient to reduce the higher manganese oxides, for example to the MnO stage, to set the reduction temperature, and There is as little excess carbon as possible in the discharge material.
Die Erfindung wird anhand einer Figur und eines Beispiels näher erläutert.The invention is explained in more detail with reference to a figure and an example.
Das Erz l wird über eine Schnecke 2 in einen venturiartigen Suspensionstrockner 3 chargiert. Dort wird es im Gasstrom suspendiert und über Leitung 4 in einen Abscheider 5 geleitet. Das Gas wird im Elektrofilter 6 gereinigt und als Abgas 7 abgeleitet. Die abgeschiedenen Feststoffe werden von der Schnecke 7a in Leitung 8 eingespeist. Ein Teilstrom wird über Leitung 9 in die Kalzination geleitet. Die Kalzination ist als zirkulierende Wirbelschicht ausgebildet und besteht aus dem Wirbelschichtreaktor l0, dem Rückführzyklon ll und der Rückführleitung l2. Ein Teil des Feststoffes wird über Leitung l3 in den Vorwärmer l4 geleitet, dort im Gasstrom suspendiert und über Leitung l5 in den Abscheider l6 geleitet. Der abgeschiedene Feststoff wird über Leitung l7 in den Reaktor l0 geleitet. Das Gas strömt aus dem Abscheider l6 in den Suspensionstrockner 3. In den unteren Bereich des Reaktors l0 wird Fluidisierungsluft l8 eingeleitet. An einer höheren Stelle werden Sekundärluft l9 und Kohle 20 eingeleitet. Innerhalb des Wirbelschichtreaktors l0 bildet sich eine den gesamten Reaktor l0 ausfüllende Gas/Feststoff-Suspension aus, die am Kopf über Leitung 2l in den Rückführzyklon ll geleitet wird, wo eine Trennung von Feststoff und Gas erfolgt. Das Gas strömt in den Vorwärmer l4 und der Feststoff gelangt in die Rückführleitung l2, in der ein U-förmiger Verschluß l3 angeordnet ist, in dessen Boden eine kleine Menge Fluidisierungsluft (nicht dargestellt) geleitet wird. Ein Teil des kalzinierten Feststoffes gelangt aus dem Verschluß l3 über ein regelbares Ventil 22 und Leitung 23 in die stationäre Wirbelschicht 24, in der die Reduktion erfolgt. Über Leitung 25 wird Fluidisierungsluft in den unteren Teil eingeblasen, und über Leitung 26 wird Kohle eingeführt. Das staubhaltige Abgas wird über Leitung 27 in den Abscheider 28 geleitet. Die abgeschiedenen Feststoffe gelan gen über Leitung 29 wieder in die stationäre Wirbelschicht 24, während das Abgas über Leitung 30 in den Wirbelschichtreaktor l0 an einer höheren Stelle eingeleitet wird. Das reduzierte Material wird über Leitung 3l abgeleitet. Über Leitung 32 kann ebenfalls kalzinierter Feststoff in die stationäre Wirbelschicht 24 geleitet werden.The ore 1 is charged via a
Die Positionen beziehen sich auf die Figur.The positions refer to the figure.
Es wurde ein lateritisches Ni-Erz folgender Zusammensetzung eingesetzt (bezogen auf trockenes Erz):
20 % Fe₂O₃
2 % NiO
6,8 % CaCO₃
9,9 % Hydratwasser
Feuchtigkeit l3,7 %
A lateritic Ni ore of the following composition was used (based on dry ore):
20% Fe₂O₃
2% NiO
6.8% CaCO₃
9.9% hydrate water
Humidity l3.7%
Der Wirbelschichtreaktor l0 hat einen Durchmesser von 3,7 m und eine Höhe von l6 m. Die Temperatur im Reaktor beträgt 900°C.The fluidized bed reactor l0 has a diameter of 3.7 m and a height of l6 m. The temperature in the reactor is 900 ° C.
Der Wirbelschichtreaktor 24 hat einen Durchmesser von 3 m und eine Höhe von 2,5 m. Die Temperatur im Reaktor beträgt 900°C.
Schnecke 2: l00 t/h Erz
Fluidisierungsluft l8: 20 000 Nm³/h
Sekundärluft l9: 22 600 Nm³/h
Kohle 20: 4,26 t/h
8l,8 % C
2,6 % H
5,6 % O
l,5 % Asche
6,7 % Feuchte
Hu: 7 043 kcal/kg
Leitung 2l: 58 600 Nm³/h
900°C
Leitung 9: 60 % des Feststoffes
Leitung l3: 40 % des Feststoffes
Fluidisierungsluft 25: 6 030 Nm³/h
Kohle 26: 3,43 t/h
Abgas 27: 9 430 Nm³/h
l8,8 % CO
l7,6 % CO₂
6,3 % H₂
7,4 % H₂O
50,5 % N₂
Austrag 3l: 72,65 t/h
2l,4 % FeO
l,9 % Ni
l,37 % C
Abgas 7: 82 000 Nm³/h
l3,7 % CO₂
37,8 % H₂O
46,7 % N₂
l,8 % O₂
l40°C
The
Auger 2: 100 t / h ore
Fluidizing air l8: 20,000 Nm³ / h
Secondary air l9: 22 600 Nm³ / h
Coal 20: 4.26 t / h
8l, 8% C
2.6% H
5.6% O
1.5% ash
6.7% moisture
H u : 7 043 kcal / kg
Line 2l: 58 600 Nm³ / h
900 ° C
Line 9: 60% of the solid
Line l3: 40% of the solid
Fluidizing air 25: 6 030 Nm³ / h
Coal 26: 3.43 t / h
Exhaust gas 27: 9 430 Nm³ / h
8.8% CO
l7.6% CO₂
6.3% H₂
7.4% H₂O
50.5% N₂
Discharge 3l: 72.65 t / h
2l, 4% FeO
1.9% Ni
l, 37% C
Exhaust gas 7: 82,000 Nm³ / h
l3.7% CO₂
37.8% H₂O
46.7% N₂
1.8% O₂
l40 ° C
Die Vorteile der Erfindung bestehen darin, daß einerseits die Kalzination in sehr wirtschaftlicher Weise unter Erzeugung eines weitgehend ausgebrannten, schadstoffarmen Abgases durchgeführt werden kann und andererseits ein reduziertes Produkt erhalten wird, das einen genauen und gleichmäßigen Reduktionsgrad aufweist und einen genau definierten und gleichmäßigen Gehalt an überschüssigem Kohlenstoff enthält, wobei dieser Gehalt auch praktisch Null sein kann.The advantages of the invention are that, on the one hand, the calcination can be carried out in a very economical manner with the generation of a largely burnt-out, low-pollutant exhaust gas and, on the other hand, a reduced product is obtained which has a precise and uniform degree of reduction and a precisely defined and uniform content of excess Contains carbon, which content can also be practically zero.
Bei der Reduktion von Eisen-Nickel-Erzen können die Eisenoxide weitgehend zu FeO reduziert werden und trotzdem die Bildung von metallischem Eisen vermieden werden. Der Kohlenstoffgehalt im Austrag kann sehr gering gehalten oder nur so hoch und absolut gleichmäßig gehalten werden, wie für die Reduktion der geringen Mengen an metallischem Eisen im Schmelzprozeß erforderlich ist. Dadurch ist eine genaue Dosierung der Kohlenstoffmenge im Elektroofen möglich.When iron-nickel ores are reduced, the iron oxides can be largely reduced to FeO and the formation of metallic iron can nevertheless be avoided. The carbon content in the discharge can be kept very low or only as high and absolutely uniform as is necessary for the reduction of the small amounts of metallic iron in the melting process. This enables precise metering of the amount of carbon in the electric furnace.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3540541 | 1985-11-15 | ||
| DE19853540541 DE3540541A1 (en) | 1985-11-15 | 1985-11-15 | METHOD FOR REDUCING HIGHER METAL OXIDS TO LOW METAL OXIDS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0222452A1 true EP0222452A1 (en) | 1987-05-20 |
| EP0222452B1 EP0222452B1 (en) | 1989-04-05 |
Family
ID=6286069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86201942A Expired EP0222452B1 (en) | 1985-11-15 | 1986-11-07 | Process for reducing the oxidation level of metallic oxides |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4789580A (en) |
| EP (1) | EP0222452B1 (en) |
| AU (1) | AU588647B2 (en) |
| BR (1) | BR8605633A (en) |
| CA (1) | CA1266368A (en) |
| DE (2) | DE3540541A1 (en) |
| GR (2) | GR880300159T1 (en) |
| IN (1) | IN166635B (en) |
| NO (1) | NO169499C (en) |
| NZ (1) | NZ217937A (en) |
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| WO1989009290A1 (en) * | 1988-03-30 | 1989-10-05 | A. Ahlstrom Corporation | Method and apparatus for reduction of material containing metal oxide |
| WO1995028504A1 (en) * | 1994-04-15 | 1995-10-26 | Joint Stock Company 'kkip' | Method of extracting manganese from manganese-containing raw material |
| WO2009074170A1 (en) * | 2007-12-12 | 2009-06-18 | Outotec Oyj | Process and plant for producing char and fuel gas |
| US7854608B2 (en) | 2002-12-23 | 2010-12-21 | Outotec Oyj | Method and apparatus for heat treatment in a fluidized bed |
| CN104911332A (en) * | 2015-05-07 | 2015-09-16 | 王立臣 | Segmented vertical roasting furnace apparatus of low-grade manganese oxide ores, and use method thereof |
| EP3854894A4 (en) * | 2018-09-20 | 2022-05-18 | Sumitomo Metal Mining Co., Ltd. | Method for smelting oxide ore |
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| ZA946071B (en) * | 1993-08-30 | 1995-03-16 | Mintek | The production of ferronickel from nickel containing laterite |
| CH689633A5 (en) * | 1995-01-10 | 1999-07-30 | Von Roll Umwelttechnik Ag | Process for cooling and cleaning of flue gases. |
| BR0010031A (en) | 1999-01-12 | 2002-01-15 | Falconbridge Ltd | Methods for the reduction of materials containing iron oxide and nickel laterite in a reactor |
| DE10101157A1 (en) * | 2001-01-12 | 2002-07-18 | Mg Technologies Ag | Process for producing a mixture of iron ore and smoldering coke |
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| DE10260734B4 (en) * | 2002-12-23 | 2005-05-04 | Outokumpu Oyj | Process and plant for the production of carbon coke |
| DE10260731B4 (en) * | 2002-12-23 | 2005-04-14 | Outokumpu Oyj | Process and plant for the heat treatment of iron oxide-containing solids |
| DE10260739B3 (en) * | 2002-12-23 | 2004-09-16 | Outokumpu Oy | Process and plant for producing metal oxide from metal compounds |
| DE10260738A1 (en) * | 2002-12-23 | 2004-07-15 | Outokumpu Oyj | Process and plant for conveying fine-grained solids |
| DE102004042430A1 (en) * | 2004-08-31 | 2006-03-16 | Outokumpu Oyj | Fluidized bed reactor for the thermal treatment of vortex substances in a microwave-heated fluidized bed |
| CN102851490B (en) * | 2012-08-30 | 2014-04-16 | 北京矿冶研究总院 | Method for preparing high-quality calcine by fluidized reduction roasting of nickel oxide ore |
| RU2721249C1 (en) * | 2019-11-29 | 2020-05-18 | Валентин Николаевич Терехов | Composition of charge for melting of carbon-free iron |
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| WO1989009290A1 (en) * | 1988-03-30 | 1989-10-05 | A. Ahlstrom Corporation | Method and apparatus for reduction of material containing metal oxide |
| WO1995028504A1 (en) * | 1994-04-15 | 1995-10-26 | Joint Stock Company 'kkip' | Method of extracting manganese from manganese-containing raw material |
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| CN104911332B (en) * | 2015-05-07 | 2017-04-05 | 王立臣 | A kind of Low grade manganese ore segmentation vertical roasting stove device and its using method |
| EP3854894A4 (en) * | 2018-09-20 | 2022-05-18 | Sumitomo Metal Mining Co., Ltd. | Method for smelting oxide ore |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1266368A (en) | 1990-03-06 |
| AU6513486A (en) | 1987-05-21 |
| NO864490L (en) | 1987-05-18 |
| BR8605633A (en) | 1987-08-18 |
| US4789580A (en) | 1988-12-06 |
| NO169499C (en) | 1992-07-01 |
| IN166635B (en) | 1990-06-30 |
| NO169499B (en) | 1992-03-23 |
| NO864490D0 (en) | 1986-11-11 |
| GR880300159T1 (en) | 1989-03-08 |
| DE3662700D1 (en) | 1989-05-11 |
| AU588647B2 (en) | 1989-09-21 |
| DE3540541A1 (en) | 1987-05-21 |
| EP0222452B1 (en) | 1989-04-05 |
| NZ217937A (en) | 1989-07-27 |
| GR3000079T3 (en) | 1990-10-31 |
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