EP0276032A1 - Instant smelting process for sulfidic ores - Google Patents
Instant smelting process for sulfidic ores Download PDFInfo
- Publication number
- EP0276032A1 EP0276032A1 EP88200025A EP88200025A EP0276032A1 EP 0276032 A1 EP0276032 A1 EP 0276032A1 EP 88200025 A EP88200025 A EP 88200025A EP 88200025 A EP88200025 A EP 88200025A EP 0276032 A1 EP0276032 A1 EP 0276032A1
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- European Patent Office
- Prior art keywords
- zone
- slag
- reduction zone
- oxidation
- reduction
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
- C22B23/025—Obtaining nickel or cobalt by dry processes with formation of a matte or by matte refining or converting into nickel or cobalt, e.g. by the Oxford process
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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
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
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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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/003—Bath smelting or converting
- C22B15/0036—Bath smelting or converting in reverberatory furnaces
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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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/003—Bath smelting or converting
- C22B15/0041—Bath smelting or converting in converters
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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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0052—Reduction smelting or converting
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
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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
Definitions
- the invention relates to a process for the continuous direct melting of materials containing sulfidic non-ferrous metals.
- roasting, reduction and melting take place simultaneously in one reactor. Either the metal or a stone is created.
- a melt consisting of a slag phase and a phase rich in non-ferrous metals is located in an oblong lying reactor.
- the reactor contains an oxidation zone and a reduction zone with nozzles that blow oxygen-containing gases into the melt.
- the feed is charged to the weld pool and oxidized by the oxygen blown in.
- the generated non-ferrous metal oxide-rich slag flows into the reduction zone, where carbon-containing reducing agents are blown into the melt.
- the reduced metal then flows into the oxidation zone in the non-ferrous metal-rich phase.
- the non-ferrous metal-poor slag phase is drawn off at the end of the reduction zone and the non-ferrous metal-rich phase at the beginning of the oxidation zone. If no metal is to be produced, but a stone, a sulfur-containing substance, eg SO2, is introduced into the melt in the reduction zone. The exhaust will end up deducted from the reduction zone. Before the tapping, the slag can be blown off by blowing in carbon-containing material, non-ferrous metals such as zinc and lead being volatilized, removed in the exhaust gas from the reactor and then separated from the exhaust gas.
- CA-PS 893 624 discloses a direct method for melting lead sulfides, in which a gradual oxidation of the lead sulfides to molten lead takes place in the oxidation zone.
- the slag which is already relatively low in lead, is blown in the reduction zone by blowing in hydrocarbons, the zinc content being largely volatilized and removed from the reactor with the exhaust gas.
- the metallic lead is tapped from a central zone of the reactor between the oxidation zone and the reduction zone. The exhaust gas is drawn off at about the end of the oxidation zone.
- the SO2-containing gas is withdrawn from the oxidation zone separately from the SO2-free gas from the reduction zone.
- the partition does not allow the gas to be drawn from one zone through the other zone. As a result, it is not possible to repair or inspect the gas exhaust or downstream units in a zone without cooling this zone.
- the partition also prevents the slag from flowing out of the oxidation zone into the reduction zone if the passage under the partition is obstructed.
- the partition also prevents the transfer of volatilized metals from the adjacent part of one zone to the other zone.
- the invention has for its object in this method of direct melting of sulfidic materials a largely separate withdrawal of the exhaust gases from the oxidation zone and the reduction zone with the possibility of a gas-side connection of the adjacent parts of the oxidation and reduction zone and the emergency drainage of the slag from the oxidation zone and to allow smoke gases to be extracted from one zone through the other zone.
- the oxidation zone can be operated so that only one slag phase is formed, which contains the entire non-ferrous metal content in the form of oxides. It can also be operated in such a way that a slag phase and a phase rich in non-ferrous metals are formed. The slag then contains only part of the non-ferrous metal content in oxidic form.
- the non-ferrous metal-rich phase can consist of metal, such as lead, or stone, such as copper stone. Oxygen-enriched air or technically pure oxygen are used as the oxygen-containing gases.
- the reducing agents used in the reduction zone can be solid, gaseous or liquid.
- the non-ferrous metal-rich phase formed in the reduction zone can be in vapor form, such as zinc and lead vapor, or it can also be molten, such as metallic lead, copper or copper stone.
- a vaporous phase can also be present in addition to a molten phase.
- the molten non-ferrous metal-rich phase can be drawn off at any point in the oxidation zone from the beginning to the end or at the beginning of the reduction zone.
- the slag is withdrawn at the end of the reduction zone.
- the oxygen-containing gases and the reducing agents are preferably blown into the melt in a known manner through nozzles with several concentric tubes from below, a coolant being blown into the melt to protect the nozzles against erosion.
- the exhaust gases are suctioned out of the two zones in general at the beginning of the oxidation zone and at the end of the reduction zone, but in principle can also take place at other points. If, for metallurgical reasons, a gas-side connection of the adjacent parts of the two zones is to take place, the zero point of the differential pressure is shifted accordingly. In this way, for example, a non-ferrous metal that is reduced and volatilized at a higher oxidation potential can be separated from a non-ferrous metal that is reduced and volatilized at a lower oxidation potential.
- the slag at the beginning of the reduction zone can initially be selectively reduced to lead, a part of the lead content of the slag being obtained in vapor form and being drawn into the oxidation zone by means of a corresponding vacuum control.
- the slag can then be reduced to zinc in the reduction zone, the zinc being produced in vapor form and being sucked off separately from the reduction zone with a minimum lead content.
- Several oxidation and reduction zones can also be arranged side by side. If a stone, such as copper stone, is produced as the non-ferrous metal-rich phase, then a sulfide or SO2 with another reducing agent is used as the reducing agent in the reduction zone.
- the reactor can be rotated about its axis so that the nozzles can be rotated out of the melt.
- a preferred embodiment is that the cross section of the gas space in the reactor is constricted at the boundary between the oxidation zone and the reduction zone.
- the term "constricted” is intended to encompass any narrowing of the cross section of the gas space which leaves an opening in the gas space above the surface of the melt open.
- the opening can be arranged in the middle of the cross section or laterally. Generally only one opening is provided, but in principle several openings can also be provided.
- the constriction preferably consists of a wall with a gas passage opening, the wall being immersed in the melt and leaving an underflow free for the melt. The restriction of the position of the zero point of the differential pressure can be carried out particularly well by the constriction.
- a preferred embodiment consists in that the gas passage opening of the constriction lies closely above the surface of the slag bath. This causes the slag to overflow from the oxidation zone into the reduction zone as soon as there is a disturbance in the slag flow under the constriction. This soon overflow prevents a noticeably increased static pressure due to a higher slag layer from occurring in the oxidation zone.
- a preferred embodiment consists in that a dam with a passage opening for the slag is attached in the slag bath at the boundary between the oxidation zone and the reduction zone.
- the dam preferably consists of a partition wall which has an opening at the bottom or in the middle of a slot.
- the dam is expedient formed as a unit with the partition in the gas space. The dam facilitates the metallurgical work in the oxidation and reduction zone.
- a preferred embodiment is that a passage opening for the non-ferrous metal-rich phase and the slag is provided in the dam.
- a common opening for the metal phase and the slag phase has the advantage that the metal phase melting at a lower temperature always keeps the opening open and thus also enables the flow of slag through the opening.
- the primary metal phase generated in the oxidation zone can be subtracted together with a secondary metal phase generated in the reduction zone.
- a preferred embodiment consists in that at least part of the reduction zone of the reactor is designed with a smaller diameter than the oxidation zone. This ensures good flow of the slag from the oxidation zone into the reduction zone and the molten non-ferrous metal-rich phase from the reduction zone into the oxidation zone without the thickness of the refractory lining having to be different in the two zones.
- the beginning of the reduction zone is still in the final part of the part of the reactor with a larger diameter when a dam is arranged in the slag bath because this always results in a metal bath in the underflow opening of the dam.
- a preferred embodiment consists in that the size of the gas passage opening of the constriction has a gas velocity when sucking in smoke gases below 15 m / sec, preferably 4 to 8 m / sec. If a repair or an inspection has to be carried out on one of the two gas fume cupboards or downstream units, the melt is kept liquid by heating and the resulting flue gases are discharged through the other gas fume cupboard, so that emptying of the reactor and cooling of the lining is not necessary. With this gas velocity, keeping warm is very possible.
- a wall (3) with gas passage opening (4) is arranged as a constriction in the gas space at the boundary between oxidation zone (1) and reduction zone (2).
- the wall (3) also serves as a dam (5) in the slag layer (6).
- the lower edge of the gas passage opening (4) is just above the surface of the slag layer (6).
- the dam (5) has a passage opening (7) on the bottom, the upper edge of which lies in the slag layer (6), so that the slag can flow through the passage opening (7).
- the batch is charged onto the melt via a plurality of charging points (8).
- Oxygen (9) is blown in from below.
- a slag phase (6) with a high proportion of non-ferrous metal oxide and a primary non-ferrous metal-rich phase (10) are formed.
- the slag phase (6) flows through the passage opening (7) into the reduction zone (2).
- oxygen and reducing agent (11) are blown in from below, the non-ferrous metal oxide content of the slag is reduced and a liquid secondary non-ferrous metal-rich phase (12) is formed, which flows in the direction of the oxidation zone (1).
- the primary (10) and secondary (11) non-ferrous metal-rich phases are subtracted together at (13).
- a second non-ferrous metal-rich phase can be formed in the form of volatilized non-ferrous metals, which is drawn off with the SO2-free exhaust gas (14).
- the non-ferrous metal slag is removed at (15).
- the SO2-containing exhaust gas from the oxidation zone (1) is drawn off at (16).
- the advantages of the invention are that, despite the separate withdrawal of the gases from the oxidation zone and reduction zone, a gas-side connection of the adjacent parts of the two zones is possible and, if necessary, vaporized metals can be transferred from the adjacent part of one zone to the other zone. This keeps the process flexible.
- flue gases from one zone can be led through the other zone. This makes it possible to repair or inspect the gas outlet of one of the two zones or downstream units without cooling the masonry and the melt.
- the slag from the oxidation zone can always flow into the reduction zone even in the event of faults.
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- Mechanical Engineering (AREA)
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- Organic Chemistry (AREA)
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Abstract
Description
Die Erfindung betrifft ein Verfahren zum kontinuierlichen direkten Schmelzen von sulfidische NE-Metalle enthaltenden Materialien.The invention relates to a process for the continuous direct melting of materials containing sulfidic non-ferrous metals.
Beim direkten Schmelzen von sulfidische NE-Metalle enthaltenden Materialien, wie Konzentrate oder Erze von Blei, Kupfer, Zink, Nickel, Kobalt oder deren Mischungen, erfolgen Röstung, Reduktion und Einschmelzen gleichzeitig in einem Reaktor. Dabei wird entweder das Metall oder ein Stein erzeugt.In the direct melting of materials containing sulfidic non-ferrous metals, such as concentrates or ores of lead, copper, zinc, nickel, cobalt or their mixtures, roasting, reduction and melting take place simultaneously in one reactor. Either the metal or a stone is created.
Ein solches Verfahren ist aus der US-PS 3 941 587 bekannt. In einem länglichen liegenden Reaktor befindet sich eine Schmelze aus einer Schlackenphase und einer NE-Metall-reichen Phase. Der Reaktor enthält eine Oxidationszone und eine Reduktionszone mit Düsen, die sauerstoffhaltige Gase in die Schmelze blasen. In der Oxidationszone wird die Beschickung auf das Schmelzbad chargiert und durch den eingeblasenen Sauerstoff oxidiert. Die erzeugte NE-Metalloxid-reiche Schlacke fließt in die Reduktionszone, wo kohlenstoffhaltige Reduktionsmittel in die Schmelze eingeblasen werden. Das reduzierte Metall fließt dann in der NE-Metall-reichen Phase in die Oxidationszone. Die NE-Metall-arme Schlackenphase wird am Ende der Reduktionszone und die NE-Metall-reiche Phase am Anfang der Oxidationszone abgezogen. Falls kein Metall erzeugt werden soll, sondern ein Stein, wird in der Reduktionszone ein Schwefel enthaltender Stoff, z.B. SO₂, in die Schmelze eingebracht. Das Abgas wird am Ende der Reduktionszone abgezogen. Die Schlacke kann vor dem Abstich durch das Einblasen von kohlenstoffhaltigem Material verblasen werden, wobei NE-Metalle, wie Zink und Blei, verflüchtigt werden, im Abgas aus dem Reaktor abgeführt und dann aus dem Abgas abgeschieden werden.Such a method is known from US Pat. No. 3,941,587. A melt consisting of a slag phase and a phase rich in non-ferrous metals is located in an oblong lying reactor. The reactor contains an oxidation zone and a reduction zone with nozzles that blow oxygen-containing gases into the melt. In the oxidation zone, the feed is charged to the weld pool and oxidized by the oxygen blown in. The generated non-ferrous metal oxide-rich slag flows into the reduction zone, where carbon-containing reducing agents are blown into the melt. The reduced metal then flows into the oxidation zone in the non-ferrous metal-rich phase. The non-ferrous metal-poor slag phase is drawn off at the end of the reduction zone and the non-ferrous metal-rich phase at the beginning of the oxidation zone. If no metal is to be produced, but a stone, a sulfur-containing substance, eg SO₂, is introduced into the melt in the reduction zone. The exhaust will end up deducted from the reduction zone. Before the tapping, the slag can be blown off by blowing in carbon-containing material, non-ferrous metals such as zinc and lead being volatilized, removed in the exhaust gas from the reactor and then separated from the exhaust gas.
Aus der US-PS 4 266 971 ist eine Modifikation dieses Verfahrens bekannt, bei der das Abgas im Gegenstrom zur Strömungsrichtung der Schlackenphase geführt und am Anfang der Oxidationszone abgezogen wird.A modification of this method is known from US Pat. No. 4,266,971, in which the exhaust gas is conducted in countercurrent to the direction of flow of the slag phase and is drawn off at the beginning of the oxidation zone.
Aus der CA-PS 893 624 ist ein direktes Verfahren zum Schmelzen von Bleisulfiden bekannt, bei dem eine graduelle Oxidation der Bleisulfide zu geschmolzenem Blei in der Oxidationszone erfolgt. Die bereits relativ bleiarme Schlacke wird in der Reduktionszone durch Einblasen von Kohlenwasserstoffen verblasen, wobei der Zinkgehalt weitgehend verflüchtigt und mit dem Abgas aus dem Reaktor entfernt wird. Das metallische Blei wird aus einer mittleren Zone des Reaktors zwischen Oxidationszone und Reduktionszone abgestochen. Das Abgas wird etwa am Ende der Oxidationszone abgezogen.CA-PS 893 624 discloses a direct method for melting lead sulfides, in which a gradual oxidation of the lead sulfides to molten lead takes place in the oxidation zone. The slag, which is already relatively low in lead, is blown in the reduction zone by blowing in hydrocarbons, the zinc content being largely volatilized and removed from the reactor with the exhaust gas. The metallic lead is tapped from a central zone of the reactor between the oxidation zone and the reduction zone. The exhaust gas is drawn off at about the end of the oxidation zone.
Bei diesen Verfahren werden die Abgase aus der Oxidationszone und der Reduktionszone gemeinsam abgezogen.In these processes, the exhaust gases from the oxidation zone and the reduction zone are drawn off together.
Aus der GB-PS 1 351 999 ist ein Verfahren zur Gewinnung von Metallen in hoher Reinheit bekannt, dessen Schritte entweder in separaten Reaktoren durchgeführt werden, die schmelzseitig miteinander verbunden sind, oder in einem länglichen Reaktor, dessen Gasraum über der Schmelze durch Trennwände in verschiedene Zonen geteilt wird, aus denen die Abgase getrennt abgezogen werden. Bei der Verarbeitung von sulfidischen Erzen werden die SO₂-haltigen Gase der oxidierenden Einschmelzzone getrennt von den Gasen der weiteren Behandlungszone abgezogen.From GB-
Aus der DE-OS 36 11 159 ist es bekannt, insbesondere Zinksulfidkonzentrate in einem liegenden Reaktor zu verarbeiten, dessen Gasraum zwischen Oxidationszone und Reduktionszone durch eine Trennwand unterteilt ist. Das Abgas aus der Oxidationszone wird am Anfang der Oxidationszone und das Abgas aus der Reduktionszone wird aus dem ersten Teil der Reduktionszone abgezogen. In der Oxidationszone wird ein Schlackenbad erzeugt, das den Metallinhalt der Charge als Metalloxide enthält. Die Schlacke fließt dann unter der Trennwand her in die Reduktionszone, wo Kohle in das Schlackenbad eingeführt und die Metalloxide reduziert werden. Zink und Blei werden verdampft und aus dem Abgas abgeschieden.From DE-OS 36 11 159 it is known to process zinc sulfide concentrates in particular in a horizontal reactor, the gas space of which is divided between the oxidation zone and the reduction zone by a partition. The exhaust gas from the oxidation zone is withdrawn at the beginning of the oxidation zone and the exhaust gas from the reduction zone is withdrawn from the first part of the reduction zone. A slag bath is generated in the oxidation zone, which contains the metal content of the batch as metal oxides. The slag then flows under the partition into the reduction zone, where coal is introduced into the slag bath and the metal oxides are reduced. Zinc and lead are evaporated and separated from the exhaust gas.
Bei den beiden letzten Verfahren wird das SO₂-haltige Gas aus der Oxidationszone getrennt von dem SO₂-freien Gas aus der Reduktionszone abgezogen. Die Trennwand erlaubt aber keinen Abzug des Gases aus einer Zone durch die andere Zone. Dadurch ist eine Reparatur oder Inspektion des Gasabzuges oder nachgeschalteter Aggregate einer Zone ohne Abkühlung dieser Zone nicht möglich. Außerdem verhindert die Trennwand auch einen Abfluß der Schlacke aus der Oxidationszone in die Reduktionszone, wenn der Durchtritt unter der Trennwand gestört ist. Die Trennwand verhindert außerdem die Überführung verflüchtigter Metalle aus dem benachbarten Teil der einen Zone in die andere Zone.In the last two processes, the SO₂-containing gas is withdrawn from the oxidation zone separately from the SO₂-free gas from the reduction zone. The partition does not allow the gas to be drawn from one zone through the other zone. As a result, it is not possible to repair or inspect the gas exhaust or downstream units in a zone without cooling this zone. In addition, the partition also prevents the slag from flowing out of the oxidation zone into the reduction zone if the passage under the partition is obstructed. The partition also prevents the transfer of volatilized metals from the adjacent part of one zone to the other zone.
Der Erfindung liegt die Aufgabe zugrunde, bei diesem Verfahren des direkten Schmelzens von sulfidischen Materialien einen weitgehend getrennten Abzug der Abgase aus der Oxidationszone und der Reduktionszone mit der Möglichkeit einer gasseitigen Verbindung der benachbarten Teile der Oxidations- und Reduktionszone sowie des Notabflusses der Schlacke aus der Oxidationszone und des Abzuges von Rauchgasen aus einer Zone durch die andere Zone zu ermöglichen.The invention has for its object in this method of direct melting of sulfidic materials a largely separate withdrawal of the exhaust gases from the oxidation zone and the reduction zone with the possibility of a gas-side connection of the adjacent parts of the oxidation and reduction zone and the emergency drainage of the slag from the oxidation zone and to allow smoke gases to be extracted from one zone through the other zone.
Die Lösung dieser Aufgabe erfolgt erfindungsgemäß dadurch, daß
- a) das Schmelzen in einem Reaktor mit nebeneinander liegender Oxidationszone und Reduktionszone erfolgt,
- b) das Schlackenbad beider Zonen miteinander in Verbindung steht,
- c) die Materialien in der Oxidationszone auf das Schlackenbad chargiert werden und in das Schlackenbad sauerstoffhaltige Gase eingeblasen werden,
- d) eine Schlacke mit hohem Gehalt an NE-Metalloxiden aus der Oxidationszone in die Reduktionszone geleitet wird,
- e) in der Reduktionszone Reduktionsmittel und sauerstoffhaltige Gase in die Schlacke in solchen Mengen eingeblasen werden, daß die NE-Metalloxide weitestgehend reduziert werden und eine NE-Metall-reiche Phase gebildet wird,
- f) eine NE-Metall-arme Schlacke aus der Reduktionszone abgezogen wird,
- g) die Gase aus der Oxidationszone und aus der Reduktionszone separat abgesaugt werden,
- h) die Unterdrücke in den Absaugleitungen aus der Oxidationszone und aus der Reduktionszone so eingestellt werden, daß etwa an der Grenze zwischen Oxidationszone und Reduktionszone der Differenzdruck Null herrscht.
- a) the melting takes place in a reactor with an adjacent oxidation zone and reduction zone,
- b) the slag bath of both zones is connected to one another,
- c) the materials in the oxidation zone are charged onto the slag bath and oxygen-containing gases are blown into the slag bath,
- d) a slag with a high content of non-ferrous metal oxides is passed from the oxidation zone into the reduction zone,
- e) reducing agents and oxygen-containing gases are blown into the slag in such quantities in the reduction zone that the non-ferrous metal oxides are largely reduced and a non-ferrous metal-rich phase is formed,
- f) a non-ferrous metal-poor slag is withdrawn from the reduction zone,
- g) the gases are extracted separately from the oxidation zone and from the reduction zone,
- h) the negative pressures in the suction lines from the oxidation zone and from the reduction zone are set such that the differential pressure is zero at about the boundary between the oxidation zone and the reduction zone.
Die Oxidationszone kann so betrieben werden, daß nur eine Schlackenphase entsteht, welche den gesamten NE-Metallgehalt in Form von Oxiden enthält. Sie kann auch so betrieben werden, daß eine Schlackenphase und eine NE-Metall-reiche Phase entstehen. Die Schlacke enthält dann nur einen Teil des NE-Metallgehalts in oxidischer Form. Die NE-Metall-reiche Phase kann aus Metall, wie Blei, oder Stein, wie Kupferstein, bestehen. Als sauerstoffhaltige Gase werden sauerstoffangereicherte Luft oder technisch reiner Sauerstoff verwendet. Die in die Reduktionszone eingesetzten Reduktionsmittel können fest, gasföriig oder flüssig sein. Die in der Reduktionszone gebildete NE-Metall-reiche Phase kann dampfförmig sein, wie Zink- und Bleidampf, sie kann auch schmelzflüssig sein, wie metallisches Blei, Kupfer oder Kupferstein. Es kann auch eine dampfförmige Phase neben einer schmelzflüssigen Phase vorliegen. Die schmelzflüssige NE-Metall-reiche Phase kann an jeder Stelle der Oxidationszone von deren Anfang bis zum Ende oder am Anfang der Reduktionszone abgezogen werden. Die Schlacke wird am Ende der Reduktionszone abgezogen. Das Einblasen der sauerstoffhaltigen Gase und der Reduktionsmittel in die Schmelze erfolgt vorzugsweise in bekannter Weise durch Düsen mit mehreren konzentrischen Rohren von unten, wobei zum Schutze der Düsen gegen Abbrand ein Kühlmittel mit in die Schmelze eingeblasen wird. Das Absaugen der Abgase aus den beiden Zonen erfolgt im allgemeinen am Anfang der Oxidationszone und am Ende der Reduktionszone, kann jedoch prinzipiell auch an anderen Stellen erfolgen. Wenn aus metallurgischen Gründen eine gasseitige Verbindung der nebeneinander liegenden Teile der beiden Zonen erfolgen soll, wird der Nullpunkt des Differenzdruckes entsprechend verschoben. Dadurch kann z.B. ein NE-Metall, das bei einem höheren Oxidationspotential reduziert und verflüchtigt wird, von einem NE-Metall getrennt werden, das bei einem niedrigeren Oxidationspotential reduziert und verflüchtigt wird. So kann z.B. die Schlacke am Anfang der Reduktionszone zunächst selektiv auf Blei reduziert werden, wobei ein Teil des Bleigehaltes der Schlacke in Dampfform anfällt und durch entsprechende Unterdruckregelung in die Oxidationszone gezogen wird. Anschließend kann dann die Schlacke in der Reduktionszone auf Zink reduziert werden, wobei das Zink dampfförmig anfällt und mit einem Minimum an Bleigehalt separat aus der Reduktionszone abgesaugt wird. Es können auch mehrere Oxidations- und Reduktionszonen nebeneinander angeordnet werden. Wenn als NE-Metall-reiche Phase ein Stein, wie Kupferstein, erzeugt wird, dann wird in die Reduktionszone als Reduktionsmittel ein Sulfid oder SO₂ mit einem weiteren Reduktionsmittel eingesetzt. Der Reaktor kann um seine Achse gedreht werden, so daß die Düsen aus der Schmelze herausgedreht werden können.The oxidation zone can be operated so that only one slag phase is formed, which contains the entire non-ferrous metal content in the form of oxides. It can also be operated in such a way that a slag phase and a phase rich in non-ferrous metals are formed. The slag then contains only part of the non-ferrous metal content in oxidic form. The non-ferrous metal-rich phase can consist of metal, such as lead, or stone, such as copper stone. Oxygen-enriched air or technically pure oxygen are used as the oxygen-containing gases. The reducing agents used in the reduction zone can be solid, gaseous or liquid. The non-ferrous metal-rich phase formed in the reduction zone can be in vapor form, such as zinc and lead vapor, or it can also be molten, such as metallic lead, copper or copper stone. A vaporous phase can also be present in addition to a molten phase. The molten non-ferrous metal-rich phase can be drawn off at any point in the oxidation zone from the beginning to the end or at the beginning of the reduction zone. The slag is withdrawn at the end of the reduction zone. The oxygen-containing gases and the reducing agents are preferably blown into the melt in a known manner through nozzles with several concentric tubes from below, a coolant being blown into the melt to protect the nozzles against erosion. The exhaust gases are suctioned out of the two zones in general at the beginning of the oxidation zone and at the end of the reduction zone, but in principle can also take place at other points. If, for metallurgical reasons, a gas-side connection of the adjacent parts of the two zones is to take place, the zero point of the differential pressure is shifted accordingly. In this way, for example, a non-ferrous metal that is reduced and volatilized at a higher oxidation potential can be separated from a non-ferrous metal that is reduced and volatilized at a lower oxidation potential. For example, the slag at the beginning of the reduction zone can initially be selectively reduced to lead, a part of the lead content of the slag being obtained in vapor form and being drawn into the oxidation zone by means of a corresponding vacuum control. The slag can then be reduced to zinc in the reduction zone, the zinc being produced in vapor form and being sucked off separately from the reduction zone with a minimum lead content. Several oxidation and reduction zones can also be arranged side by side. If a stone, such as copper stone, is produced as the non-ferrous metal-rich phase, then a sulfide or SO₂ with another reducing agent is used as the reducing agent in the reduction zone. The reactor can be rotated about its axis so that the nozzles can be rotated out of the melt.
Eine vorzugsweise Ausgestaltung besteht darin, daß der Querschnitt des Gasraumes im Reaktor an der Grenze zwischen Oxidationszone und Reduktionszone eingeschnürt ist. Der Ausdruck "eingeschnürt" soll jede Verengung des Querschnitts des Gasraumes erfassen, die eine Öffnung im Gasraum oberhalb der Oberfläche der Schmelze offen läßt. Die Öffnung kann in der Mitte des Querschnittes oder seitlich angeordnet sein. Im allgemeinen wird nur eine Öffnung vorgesehen, im Prinzip können jedoch auch mehrere Öffnungen vorgesehen werden. Die Einschnürung besteht vorzugsweise aus einer Wand mit einer Gasdurchtrittsöffnung, wobei die Wand in die Schmelze eintaucht und einen Untertritt für die Schmelze frei läßt. Durch die Einschnürung läßt sich die Regelung der Lage des Nullpunktes des Differenzdruckes besonders gut durchführen.A preferred embodiment is that the cross section of the gas space in the reactor is constricted at the boundary between the oxidation zone and the reduction zone. The term "constricted" is intended to encompass any narrowing of the cross section of the gas space which leaves an opening in the gas space above the surface of the melt open. The opening can be arranged in the middle of the cross section or laterally. Generally only one opening is provided, but in principle several openings can also be provided. The constriction preferably consists of a wall with a gas passage opening, the wall being immersed in the melt and leaving an underflow free for the melt. The restriction of the position of the zero point of the differential pressure can be carried out particularly well by the constriction.
Eine vorzugsweise Ausgestaltung besteht darin, daß die Gasdurchtrittsöffnung der Einschnürung dicht über der Oberfläche des Schlackenbades liegt. Dadurch wird ein baldiger Überfluß der Schlacke aus der Oxidationszone in die Reduktionszone bewirkt, wenn eine Störung des Schlackenflusses unter der Einschnürung hindurch eintritt. Durch diesen baldigen Überfluß wird verhindert, daß in der Oxidationszone ein merklich erhöhter statischer Druck infolge einer höheren Schlackenschicht eintreten kann.A preferred embodiment consists in that the gas passage opening of the constriction lies closely above the surface of the slag bath. This causes the slag to overflow from the oxidation zone into the reduction zone as soon as there is a disturbance in the slag flow under the constriction. This soon overflow prevents a noticeably increased static pressure due to a higher slag layer from occurring in the oxidation zone.
Eine vorzugsweise Ausgestaltung besteht darin, daß im Schlackenbad an der Grenze zwischen Oxidationszone und Reduktionszcne ein Damm mit Durchtrittsöffnung für die Schlacke angebracht ist. Der Damm besteht vorzugsweise aus einer Trennwand, die eine Öffnung am Boden oder in der Mitte einen Schlitz hat. Zweckmäßigerweise ist der Damm als Einheit mit der Trennwand im Gasraum ausgebildet. Durch den Damm wird die metallurgische Arbeit in der Oxidations- und Reduktionszone erleichtert.A preferred embodiment consists in that a dam with a passage opening for the slag is attached in the slag bath at the boundary between the oxidation zone and the reduction zone. The dam preferably consists of a partition wall which has an opening at the bottom or in the middle of a slot. The dam is expedient formed as a unit with the partition in the gas space. The dam facilitates the metallurgical work in the oxidation and reduction zone.
Eine vorzugsweise Ausgestaltung besteht darin, daß in dem Damm eine Durchtrittsöffnung für die NE-Metall-reiche Phase und die Schlacke angebracht ist. Eine gemeinsame Öffnung für die Metallphase und die Schlackenphase hat den Vorteil, daß die bei niedrigerer Temperatur schmelzende Metallphase immer ein Offenhalten der Öffnung bewirkt und so auch den Schlackenfluß durch die Öffnung ermöglicht. Außerdem kann die in der Oxidationszone erzeugte Primär-Metallphase mit einer in der Reduktionszone erzeugten Sekundär-Metallphase zusammen abgezogen werden.A preferred embodiment is that a passage opening for the non-ferrous metal-rich phase and the slag is provided in the dam. A common opening for the metal phase and the slag phase has the advantage that the metal phase melting at a lower temperature always keeps the opening open and thus also enables the flow of slag through the opening. In addition, the primary metal phase generated in the oxidation zone can be subtracted together with a secondary metal phase generated in the reduction zone.
Eine vorzugsweise Ausgestaltung besteht darin, daß mindestens ein Teil der Reduktionszone des Reaktors mit kleinerem Durchmesser ausgebildet ist als die Oxidationszone. Dadurch wird ein gutes Fließen der Schlacke aus der Oxidationszone in die Reduktionszone und der schmelzflüssigen NE-Metall-reichen Phase aus der Reduktionszone in die Oxidationszone erreicht, ohne daß die Dicke der feuerfesten Auskleidung in beiden Zonen unterschiedlich sein muß. Der Anfang der Reduktionszone liegt dabei noch im Schlußteil des Teiles des Reaktors mit größerem Durchmesser, wenn ein Damm im Schlackenbad angeordnet ist, weil dadurch in der Untertrittsöffnung des Dammes immer ein Metallbad steht.A preferred embodiment consists in that at least part of the reduction zone of the reactor is designed with a smaller diameter than the oxidation zone. This ensures good flow of the slag from the oxidation zone into the reduction zone and the molten non-ferrous metal-rich phase from the reduction zone into the oxidation zone without the thickness of the refractory lining having to be different in the two zones. The beginning of the reduction zone is still in the final part of the part of the reactor with a larger diameter when a dam is arranged in the slag bath because this always results in a metal bath in the underflow opening of the dam.
Eine vorzugsweise Ausgestaltung besteht darin, daß die Größe der Gasdurchtrittsöffnung der Einschnürung beim Durchsaugen von Rauchgasen eine Gasgeschwindigkeit von unter 15 m/sec, vorzugsweise 4 bis 8 m/sec, ergibt. Wenn eine Reparatur oder eine Inspektion an einem der beiden Gasabzüge oder nachgeschalteten Aggregaten erfolgen muß, wird die Schmelze durch Beheizung flüssiggehalten und die entstehenden Rauchgase durch den anderen Gasabzug abgeleitet, so daß ein Entleeren des Reaktors und Abkühlen der Auskleidung nicht erforderlich ist. Mit dieser Gasgeschwindigkeit ist ein Warmhalten sehr gut möglich.A preferred embodiment consists in that the size of the gas passage opening of the constriction has a gas velocity when sucking in smoke gases below 15 m / sec, preferably 4 to 8 m / sec. If a repair or an inspection has to be carried out on one of the two gas fume cupboards or downstream units, the melt is kept liquid by heating and the resulting flue gases are discharged through the other gas fume cupboard, so that emptying of the reactor and cooling of the lining is not necessary. With this gas velocity, keeping warm is very possible.
Die Erfindung wird anhand der Figuren näher erläutert.
- Fig. 1 ist ein Längsschnitt durch einen Reaktor mit Einschnürung.
- Fig. 2 zeigt eine Ausgestaltung der Einschnürung als Einheit mit einem Damm in der Schlackenschicht.
- Fig. 1 is a longitudinal section through a reactor with constriction.
- 2 shows an embodiment of the constriction as a unit with a dam in the slag layer.
In Fig. 1 ist an der Grenze zwischen Oxidationszone (1) und Reduktionszone (2) eine Wand (3) mit Gasdurchtrittsöffnung (4) als Einschnürung im Gasraum angeordnet. Die Wand (3) dient gleichzeitig als Damm (5) in der Schlackenschicht (6). Die Unterkante der Gasdurchtrittsöffnung (4) liegt kurz oberhalb der Oberfläche der Schlackenschicht (6). Der Damm (5) hat am Boden eine Durchtrittsöffnung (7), deren Oberkante in der Schlackenschicht (6) liegt, so daß die Schlacke durch die Durchtrittsöffnung (7) fließen kann. In der Oxidationszone (1) wird über mehrere Beschickungsstellen (8) die Charge auf die Schmelze chargiert. Von unten wird Sauerstoff (9) eingeblasen. Es werden eine Schlackenphase (6) mit hohem Anteil an NE-Metalloxid und eine primäre NE-Metall-reiche Phase (10) gebildet. Die Schlackenphase (6) fließt durch die Durchtrittsöffnung (7) in die Reduktionszone (2). Dort wird von unten Sauerstoff und Reduktionsmittel (11) eingeblasen, der NE-Metalloxidgehalt der Schlacke reduziert und eine flüssige sekundäre NE-Metall-reiche Phase (12) gebildet, die in Richtung Oxidationszone (1) fließt. Die primäre (10) und sekundäre (11) NE-Metall-reiche Phase werden gemeinsam bei (13) abgezogen. In der Reduktionszone kann eine zweite NE-Metall-reiche Phase in Form von verflüchtigten NE-Metallen gebildet werden, die mit dem SO₂-freien Abgas (14) abgezogen wird. Die NE-Metall-arme Schlacke wird bei (15) abgezogen. Das SO₂-haltige Abgas der Oxidationszone (1) wird bei (16) abgezogen.In Fig. 1, a wall (3) with gas passage opening (4) is arranged as a constriction in the gas space at the boundary between oxidation zone (1) and reduction zone (2). The wall (3) also serves as a dam (5) in the slag layer (6). The lower edge of the gas passage opening (4) is just above the surface of the slag layer (6). The dam (5) has a passage opening (7) on the bottom, the upper edge of which lies in the slag layer (6), so that the slag can flow through the passage opening (7). In the oxidation zone (1), the batch is charged onto the melt via a plurality of charging points (8). Oxygen (9) is blown in from below. A slag phase (6) with a high proportion of non-ferrous metal oxide and a primary non-ferrous metal-rich phase (10) are formed. The slag phase (6) flows through the passage opening (7) into the reduction zone (2). There, oxygen and reducing agent (11) are blown in from below, the non-ferrous metal oxide content of the slag is reduced and a liquid secondary non-ferrous metal-rich phase (12) is formed, which flows in the direction of the oxidation zone (1). The primary (10) and secondary (11) non-ferrous metal-rich phases are subtracted together at (13). In the reduction zone, a second non-ferrous metal-rich phase can be formed in the form of volatilized non-ferrous metals, which is drawn off with the SO₂-free exhaust gas (14). The non-ferrous metal slag is removed at (15). The SO₂-containing exhaust gas from the oxidation zone (1) is drawn off at (16).
Die Vorteile der Erfindung bestehen darin, daß trotz des getrennten Abzuges der Gase aus der Oxidationszone und Reduktionszone eine gasseitige Verbindung der benachbarten Teile der beiden Zonen möglich ist und somit bei Bedarf verdampfte Metalle aus dem benachbarten Teil einer Zone an die andere Zone überführt werden können. Dadurch wird das Verfahren flexibel gehalten. Außerdem können Rauchgase aus einer Zone durch die andere Zone geführt werden. Dadurch ist eine Reparatur oder Inspektion des Gasabzuges einer der beiden Zoner oder nachgeschalteter Aggregate ohne Abkühlung des Mauerwerks und der Schmelze möglich. Weiterhin kann die Schlacke aus der Oxidationszone auch bei Störungen immer in die Reduktionszone fließen.The advantages of the invention are that, despite the separate withdrawal of the gases from the oxidation zone and reduction zone, a gas-side connection of the adjacent parts of the two zones is possible and, if necessary, vaporized metals can be transferred from the adjacent part of one zone to the other zone. This keeps the process flexible. In addition, flue gases from one zone can be led through the other zone. This makes it possible to repair or inspect the gas outlet of one of the two zones or downstream units without cooling the masonry and the melt. Furthermore, the slag from the oxidation zone can always flow into the reduction zone even in the event of faults.
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT88200025T ATE64760T1 (en) | 1987-01-23 | 1988-01-11 | DIRECT SMELTING PROCESS FOR SULPHIDE ORES. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19873701846 DE3701846A1 (en) | 1987-01-23 | 1987-01-23 | DIRECT MELTING PROCESS FOR SULFIDIC ORES |
DE3701846 | 1987-01-23 |
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EP0276032A1 true EP0276032A1 (en) | 1988-07-27 |
EP0276032B1 EP0276032B1 (en) | 1991-06-26 |
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EP88200025A Expired - Lifetime EP0276032B1 (en) | 1987-01-23 | 1988-01-11 | Instant smelting process for sulfidic ores |
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US (1) | US4895595A (en) |
EP (1) | EP0276032B1 (en) |
JP (1) | JPS63192827A (en) |
KR (1) | KR960008886B1 (en) |
AT (1) | ATE64760T1 (en) |
AU (1) | AU595418B2 (en) |
CA (1) | CA1297681C (en) |
DE (2) | DE3701846A1 (en) |
MA (1) | MA21162A1 (en) |
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ZA (1) | ZA88454B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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RU2541239C1 (en) * | 2013-07-30 | 2015-02-10 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" | Processing method of iron-containing materials in two-zone furnace |
Families Citing this family (3)
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DE4108687A1 (en) * | 1991-03-16 | 1992-11-05 | Metallgesellschaft Ag | METHOD FOR REDUCING NE-METAL OXIDES IN SLAGS |
DE69310557T2 (en) * | 1992-01-23 | 1997-09-04 | Shell Int Research | Extraction of precious metals from catalyst residues |
US5449395A (en) * | 1994-07-18 | 1995-09-12 | Kennecott Corporation | Apparatus and process for the production of fire-refined blister copper |
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CA893624A (en) * | 1969-10-27 | 1972-02-22 | J. Themelis Nickolas | Direct process for smelting of lead sulphide concentrates to lead |
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US3941587A (en) * | 1973-05-03 | 1976-03-02 | Q-S Oxygen Processes, Inc. | Metallurgical process using oxygen |
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DE3611159A1 (en) * | 1985-04-03 | 1986-10-09 | CRA Services Ltd., Melbourne, Victoria | MELTING PROCESS |
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US2769706A (en) * | 1948-06-04 | 1956-11-06 | Bolidens Gruv Ab | Smelting sulfide ores |
US4252560A (en) * | 1978-11-21 | 1981-02-24 | Vanjukov Andrei V | Pyrometallurgical method for processing heavy nonferrous metal raw materials |
-
1987
- 1987-01-23 DE DE19873701846 patent/DE3701846A1/en not_active Withdrawn
-
1988
- 1988-01-11 EP EP88200025A patent/EP0276032B1/en not_active Expired - Lifetime
- 1988-01-11 DE DE8888200025T patent/DE3863360D1/en not_active Expired - Lifetime
- 1988-01-11 AT AT88200025T patent/ATE64760T1/en not_active IP Right Cessation
- 1988-01-19 MA MA21399A patent/MA21162A1/en unknown
- 1988-01-22 US US07/146,768 patent/US4895595A/en not_active Expired - Lifetime
- 1988-01-22 ZA ZA88454A patent/ZA88454B/en unknown
- 1988-01-22 KR KR1019880000485A patent/KR960008886B1/en not_active IP Right Cessation
- 1988-01-22 AU AU10717/88A patent/AU595418B2/en not_active Expired
- 1988-01-22 MX MX010175A patent/MX167226B/en unknown
- 1988-01-22 CA CA000557206A patent/CA1297681C/en not_active Expired - Lifetime
- 1988-01-23 JP JP63013477A patent/JPS63192827A/en active Pending
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Cited By (1)
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RU2541239C1 (en) * | 2013-07-30 | 2015-02-10 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" | Processing method of iron-containing materials in two-zone furnace |
Also Published As
Publication number | Publication date |
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JPS63192827A (en) | 1988-08-10 |
MA21162A1 (en) | 1988-10-01 |
DE3863360D1 (en) | 1991-08-01 |
AU1071788A (en) | 1988-07-28 |
DE3701846A1 (en) | 1988-08-04 |
EP0276032B1 (en) | 1991-06-26 |
ATE64760T1 (en) | 1991-07-15 |
KR880009137A (en) | 1988-09-14 |
MX167226B (en) | 1993-03-10 |
AU595418B2 (en) | 1990-03-29 |
KR960008886B1 (en) | 1996-07-05 |
CA1297681C (en) | 1992-03-24 |
ZA88454B (en) | 1989-09-27 |
US4895595A (en) | 1990-01-23 |
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