CN111457735A - Integrated pyrometallurgical furnace and method for treating zinc leaching residues - Google Patents
Integrated pyrometallurgical furnace and method for treating zinc leaching residues Download PDFInfo
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- CN111457735A CN111457735A CN202010294658.3A CN202010294658A CN111457735A CN 111457735 A CN111457735 A CN 111457735A CN 202010294658 A CN202010294658 A CN 202010294658A CN 111457735 A CN111457735 A CN 111457735A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B19/00—Combinations of furnaces of kinds not covered by a single preceding main group
- F27B19/02—Combinations of furnaces of kinds not covered by a single preceding main group combined in one structure
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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
- C22B13/025—Recovery from waste materials
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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
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D11/00—Arrangement of elements for electric heating in or on furnaces
- F27D11/08—Heating by electric discharge, e.g. arc discharge
- F27D11/10—Disposition of electrodes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
- F27D17/004—Systems for reclaiming waste heat
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
- F27D17/008—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases cleaning gases
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D3/00—Charging; Discharging; Manipulation of charge
- F27D3/16—Introducing a fluid jet or current into the charge
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D99/00—Subject matter not provided for in other groups of this subclass
- F27D99/0001—Heating elements or systems
- F27D99/0033—Heating elements or systems using burners
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D3/00—Charging; Discharging; Manipulation of charge
- F27D3/16—Introducing a fluid jet or current into the charge
- F27D2003/162—Introducing a fluid jet or current into the charge the fluid being an oxidant or a fuel
- F27D2003/163—Introducing a fluid jet or current into the charge the fluid being an oxidant or a fuel the fluid being an oxidant
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D3/00—Charging; Discharging; Manipulation of charge
- F27D3/16—Introducing a fluid jet or current into the charge
- F27D2003/168—Introducing a fluid jet or current into the charge through a lance
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27M—INDEXING SCHEME RELATING TO ASPECTS OF THE CHARGES OR FURNACES, KILNS, OVENS OR RETORTS
- F27M2003/00—Type of treatment of the charge
- F27M2003/13—Smelting
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27M—INDEXING SCHEME RELATING TO ASPECTS OF THE CHARGES OR FURNACES, KILNS, OVENS OR RETORTS
- F27M2003/00—Type of treatment of the charge
- F27M2003/16—Treatment involving a chemical reaction
- F27M2003/165—Reduction
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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Abstract
The invention discloses an integrated pyrometallurgical furnace and a method for treating zinc leaching residues, wherein the integrated pyrometallurgical furnace comprises a smelting furnace body, a smelting zone and an electric heating reduction zone are defined in the smelting furnace body, a partition wall is arranged between the smelting zone and the electric heating reduction zone, and the smelting zone is communicated with the bottom of the electric heating reduction zone; the smelting zone is provided with a material inlet, an oxygen-containing gas spray gun and a smelting flue gas outlet, and the electric heating reduction zone is provided with an electrode, a reducing agent spray gun, a zinc-containing steam outlet, a slag discharge port and a metal melt outlet. Therefore, the integrated pyrometallurgical furnace can realize short-flow and low-energy-consumption treatment of zinc leaching residues, and valuable metals such as lead, iron, silver, indium, germanium and the like are comprehensively recovered, and the zinc element has higher direct yield.
Description
Technical Field
The invention belongs to the field of metallurgy, and particularly relates to an integrated pyrometallurgical furnace and a method for treating zinc leaching residues.
Background
Zinc is an important basic metal raw material in national economic construction. From the market demand, the demand of zinc in our country market has increased greatly in the past 10 years. In order to meet the requirement of national economic construction, China needs to import a large amount of zinc concentrate every year, the import level of the zinc concentrate in China will reach about 200 ten thousand tons in the future, and the zinc concentrate is continuously increased. But the level of producing the regenerated zinc by treating and utilizing secondary zinc-containing materials such as zinc leaching residues and the like in China is lower, and the market potential is huge.
The zinc leaching residue is solid waste residue generated in the zinc hydrometallurgy process, has complex components and contains various valuable metals such as zinc, lead, copper, indium, silver and the like. However, because the content of the valuable metal elements is low, the method is limited by the current economy and technology, and the valuable metal elements are difficult to fully recycle, thereby causing a large amount of zinc leaching residues to be stockpiled. The zinc leaching residues belong to hazardous wastes, the disposal of the zinc leaching residues must strictly execute the hazardous waste storage pollution control standard (GB 18597-2001), the disposal cost is high, and the enterprise burden is greatly increased.
The treatment and disposal of the leaching slag of the zinc hydrometallurgy is always a difficult problem in the non-ferrous smelting process, the slag produced by different process flows has different components and different properties, and the treatment methods are different. At present, the comprehensive recovery method of zinc leaching residues mainly comprises a fire method and a wet method. The pyrogenic process mainly comprises a rotary kiln process, a top blowing furnace process, a fuming furnace process and the like, wherein zinc leaching residues are treated by the rotary kiln, the process is simple to operate, the technology is relatively mature, but the problems of high energy consumption, low silver recovery rate and the like exist; the fuming furnace has the defects of high energy consumption, low bed energy rate, high investment and the like when used for treating the cold material of the leaching slag; the technology for treating the leached slag by the top blowing furnace is over-high in introduction cost and large in construction investment, and is only used by individual enterprises at present. The wet process is still in the laboratory research stage at present, and cannot be applied in a large scale, waste acid or waste alkali liquor can be generated in the zinc leaching residue wet process (acid liquor or alkali liquor) treatment process, and leaching agent (acid or alkali) can be remained in the finally formed residue after treatment, so that gangue components in the residue are changed into secondary residue, and the secondary residue can not be utilized and can cause secondary pollution.
In conclusion, how to comprehensively and efficiently treat and utilize the zinc leaching residues and recover zinc and other valuable metals in the zinc leaching residues has important value and strategic significance for reducing enterprise burden, improving enterprise benefits, increasing zinc yield in China, reducing external dependence of concentrate in China, improving industrial treatment level of solid hazardous wastes in China and the like.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide an integrated pyrometallurgical furnace and a method for treating zinc leaching residues, by adopting the integrated pyrometallurgical furnace, short-flow and low-energy-consumption treatment of the zinc leaching residues can be realized, valuable metals such as lead, iron, silver, indium, germanium and the like are comprehensively recovered, and the zinc element has higher direct yield.
In one aspect of the invention, an integrated pyrometallurgical furnace is provided. According to an embodiment of the invention, the smelting furnace comprises:
the smelting furnace comprises a smelting furnace body, wherein a smelting area and an electric heating reduction area are defined in the smelting furnace body, a partition wall is arranged between the smelting area and the electric heating reduction area, and the bottom of the smelting area is communicated with the bottom of the electric heating reduction area;
a material inlet arranged at the top of the smelting zone;
the oxygen-containing gas spray gun is arranged on the side wall of the smelting zone;
a smelting flue gas outlet, wherein the smelting flue gas outlet is arranged in the smelting zone;
the electrode extends into the electrothermal reduction zone from the top of the electrothermal reduction zone;
the reducing agent spray gun is arranged in the electric heating reduction area;
the zinc-containing steam outlet is arranged in the electrothermal reduction area;
the slag discharging port is arranged at the bottom of the electric heating reduction zone;
and the metal melt outlet is arranged at the bottom of the electric heating reduction zone.
According to the integrated pyrometallurgical furnace provided by the embodiment of the invention, the partition wall is arranged in the smelting furnace body, the partition wall divides the interior of the smelting furnace body into the smelting zone and the electrothermal reduction zone, the smelting zone is communicated with the bottom of the electrothermal reduction zone, the oxygen-containing gas spray gun is arranged in the smelting zone, the weak reduction atmosphere in the smelting zone is controlled, the electrode, the reducing agent spray gun and the zinc-containing steam outlet are arranged in the electrothermal reduction zone, the mixture obtained by mixing zinc leaching residues, zinc-containing oxide ore and flux is supplied to the smelting zone in the integrated pyrometallurgical furnace, the mixture is subjected to desulfurization reaction, the mixture is melted and partially reduced, F, Cl and As in the mixture can be opened to a part of flue gas in the melting stage to obtain sulfur-containing smelting flue gas, and SiO in the mixture is opened to a part of2And the slag is formed, and the formed molten high-zinc slag directly enters an electrothermal reduction area to be reduced to obtain zinc-containing steam and a metal melt containing iron and lead. Therefore, the high-efficiency side-blown smelting furnace and the electrothermal reduction furnace are integrally designed, so that the occupied area is small, the configuration height difference is reduced, the construction investment of the smelting furnace and a factory building is reduced, the operation of discharging and adding the melt is reduced, the production operation rate is improved, and the consumption of operators and corresponding tools can be reduced; smelting and reduction are completed in one furnace, and the electric heating reduction zone can also maintain a certain temperature by using the high temperature of the smelting zone, so that the consumption of electric energy during the independent reduction operation is reduced; in addition, the melting bath can be used for smelting and reducing simultaneously, and the melt is stored in the furnaceThe method has relatively large amount, can increase the liquid storage time, is beneficial to improving the single-furnace processing capacity and improving the recovery rate of zinc, and can also recover lead, iron, indium, germanium and the like and ensure higher recovery rate. Specifically, the zinc leaching slag processing capacity of the single integrated pyrometallurgical furnace meets various scales such as 1-30 ten thousand tons.
In addition, the integrated pyrometallurgical furnace according to the above-described embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the smelting zone is a shaft furnace.
In some embodiments of the invention, the bottom of the smelting zone and the bottom of the electrothermal reduction zone are stepped down in the direction from the smelting zone to the electrothermal reduction zone. Therefore, the high zinc slag in a molten state obtained in the smelting zone can directly flow into the electrothermal reduction zone by gravity, so that the operation of discharging and adding the melt is reduced, and the production operation rate is improved.
In some embodiments of the invention, the reductant injection lance is positioned at the top and/or at the side walls of the electrically heated reduction zone.
In some embodiments of the invention, the integrated pyrometallurgical furnace includes a plurality of said oxygen-containing gas lances arranged symmetrically on a side wall of the smelting zone.
In some embodiments of the invention, the integrated pyrometallurgical furnace includes a plurality of said electrodes, said plurality of electrodes being evenly distributed in the electrically heated reduction zone. Therefore, the temperature in the electric heating reduction zone can be ensured to be uniform.
In some embodiments of the present invention, the smelting furnace further comprises: a carbonaceous fuel lance disposed in the smelting zone. Thus, the melting efficiency of the melting zone can be improved.
In yet another aspect of the invention, a method of treating zinc leach residue is provided. According to an embodiment of the invention, the method comprises:
(1) mixing zinc leaching residues, zinc-containing oxidized ore and a flux;
(2) supplying coke or coal and the mixture obtained in the step (1) to a smelting area of a smelting furnace through a material inlet, so that the mixture is smelted with oxygen-containing gas in the smelting area under a weak reducing atmosphere to obtain sulfur-containing smelting flue gas and high-zinc slag, and supplying the high-zinc slag to an electrothermal reduction area of the smelting furnace to be contacted with a reducing agent for reduction treatment so as to obtain zinc-containing steam, iron-containing lead melt and slag, wherein the smelting furnace is the integrated pyrometallurgical furnace.
According to the method for treating the zinc leaching residues, the mixture obtained by mixing the zinc leaching residues with the zinc-containing oxide ore and the flux is supplied to the smelting area in the integrated pyrometallurgical furnace, the mixture is subjected to desulfurization reaction, the mixture is melted and partially reduced, F, Cl and As in the mixture in the melting stage can be partially broken into flue gas to obtain sulfur-containing smelting flue gas, and SiO in the mixture can be partially reduced to obtain sulfur-containing smelting flue gas2And the slag is formed, and the formed molten high-zinc slag directly enters an electrothermal reduction area to be reduced to obtain zinc-containing steam and a metal melt containing iron and lead. Therefore, the pyrometallurgical furnace adopting the smelting furnace and the electrothermal reduction furnace in integrated design not only occupies small area, reduces configuration height difference, reduces construction investment of the smelting furnace and a factory building, but also reduces operation of melt discharge and addition, improves production operation rate, and can reduce consumption of operators and corresponding tools; smelting and reduction are completed in one furnace, and the electric heating reduction zone can also maintain a certain temperature by using the high temperature of the smelting zone, so that the consumption of electric energy during the independent reduction operation is reduced; in addition, the melting bath gives consideration to melting and smelting and reduction operations, the amount of the stored melt in the furnace is relatively large, the liquid storage time can be increased, the single-furnace processing capacity is favorably improved, the recovery rate of zinc is improved, and lead, iron, indium, germanium and the like can be simultaneously recovered, and the higher recovery rate is ensured.
In addition, the method for treating zinc leaching slag according to the above embodiment of the invention may also have the following additional technical features:
in some embodiments of the invention, in step (1), the zinc leach residue is a wet zinc leach residue.
In some embodiments of the invention, in step (1), the flux is a siliceous flux.
In some embodiments of the invention, in step (1), the mass ratio of the zinc leaching residue, the zinc-containing oxide ore and the flux is (30-60): (20-50): (2-10).
In some embodiments of the invention, in step (2), the temperature of the melting is 1250 to 1450 ℃.
In some embodiments of the invention, in step (2), the oxygen-containing gas has an oxygen concentration of 30% to 75% by volume.
In some embodiments of the invention, in step (2), the reductant is coke.
In some embodiments of the present invention, in the step (2), the temperature of the reduction treatment is 1250 to 1650 ℃.
In some embodiments of the invention, in step (2), the carbonaceous fuel is supplied to the smelting zone using carbonaceous fuel lances for concurrent heating. Therefore, the carbonaceous fuel is supplied to the smelting zone to supplement heat for the smelting zone, so that the smelting efficiency of the smelting zone is improved.
In some embodiments of the invention, the method further comprises: (3) and (3) recovering waste heat and removing dust of the sulfur-containing smelting flue gas, and then preparing acid. Therefore, the resource utilization of the zinc leaching residues is realized.
In some embodiments of the present invention, the above method further comprises (4) condensing the zinc-containing vapor to obtain crude zinc, crude lead, and flue gas; (5) purifying the flue gas to obtain coal gas, and supplying the coal gas to the smelting zone to be used as the carbonaceous fuel. Therefore, the resource utilization of the zinc leaching residues is realized.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic longitudinal sectional view of an integrated pyrometallurgical furnace in accordance with one embodiment of the present invention;
FIG. 2 is a longitudinal section block diagram of a smelting zone of an integrated pyrometallurgical furnace in accordance with an embodiment of the present invention;
FIG. 3 is a longitudinal sectional view of an electrothermal reduction zone of an integrated pyrometallurgical furnace in accordance with an embodiment of the present invention;
FIG. 4 is a schematic flow diagram of a method of treating zinc leach residue according to one embodiment of the present invention;
FIG. 5 is a schematic flow diagram of a method of treating zinc leach residue according to a further embodiment of the present invention;
FIG. 6 is a schematic flow diagram of a method of treating zinc leach residue according to yet another embodiment of the present invention;
fig. 7 is a schematic flow diagram of a method of treating zinc leach residue according to yet another embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the invention.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In one aspect of the invention, an integrated pyrometallurgical furnace is provided. According to an embodiment of the present invention, referring to fig. 1 to 3, the integrated pyrometallurgical furnace includes a furnace body 100, the furnace body 100 defining a smelting zone 11 and an electrothermal reduction zone 12 therein, a partition wall 13 is provided between the smelting zone 11 and the electrothermal reduction zone 12, and the smelting zone 11 and the electrothermal reduction zone 12 are communicated at the bottom. Specifically, raw materials which are not completely reacted are blocked between the smelting zone 11 and the electrothermal reduction zone 12 through a partition wall 13, meanwhile, smoke generated by the smelting zone 11 and zinc-containing steam generated by the electrothermal zone 12 are completely separated, and only the bottom of the smelting zone 11 is communicated with the bottom of the electrothermal reduction zone 12.
In accordance with an embodiment of the present invention, and with reference to FIGS. 1-2, the smelting zone 11 is provided with a material inlet 111, an oxygen-containing gas injection lance 112 and a smelt flue gas outlet 113, preferably with the material inlet 111 being provided at the top of the smelting zone and the oxygen-containing gas injection lance being provided at the top of the smelting zoneThe lances 112 are located in the side walls of the smelting zone and the smelt flue gas outlets 113 are located at the top and/or side walls of the smelting zone 11. Specifically, a mixture obtained by mixing zinc leaching residues with zinc-containing oxide ores and a flux (a siliceous flux) and coke or coal (the coke or coal accounts for 0.5-3 wt% to ensure a weak reducing atmosphere in a smelting zone) are supplied to the smelting zone 11 in the integrated pyrometallurgical furnace through a material inlet 111, oxygen-containing gas and fuel are blown to the smelting zone 11 through an oxygen-containing gas spray gun 112 to supply heat (the temperature of the smelting zone 11 is maintained at 1250-1450 ℃), the mixing ratio of the oxygen-containing gas (the volume concentration of oxygen in the oxygen-containing gas is 30-75%) and the fuel is controlled to ensure that the smelting zone 11 is in the weak reducing atmosphere, the mixture undergoes a desulfurization reaction and is melted and partially reduced, F, Cl and As in the mixture in the melting stage can be partially switched to flue gas to obtain sulfur-containing smelting flue gas, and SiO in the mixture can be partially switched to2The slag is involved in slag forming to form molten high zinc slag (the slag type of the high zinc slag is ZnO-FeO-SiO)2Type, ZnO-FeO-SiO2CaO type, ZnO-FeO-SiO2CaO-ZnO type) directly into the electrothermal reduction zone 12.
Further, the furnace type of the smelting zone 11 can be selected by those skilled in the art according to actual needs, and preferably, the smelting zone 11 is a vertical furnace body. Meanwhile, carbonaceous fuel injection lances (not shown) may be provided on the smelting zone 11 according to actual needs to inject carbonaceous fuel into the smelting zone 11 to participate in combustion for supplying heat to the smelting zone 11, and the preferred carbonaceous fuel may be at least one of natural gas, pulverized coal and high calorific value gas, and a person skilled in the art may select the specific arrangement positions of the carbonaceous fuel injection lances according to actual needs, for example, the carbonaceous fuel injection lances may be provided on the top and/or side wall of the smelting zone 11, and a plurality of oxygen-containing gas injection lances 112 may be provided on the side wall of the smelting zone 11, and the plurality of oxygen-containing gas injection lances 112 may be symmetrically arranged on the side wall of the smelting zone 11.
According to an embodiment of the present invention, referring to fig. 1 and 3, the electro-thermal reduction zone 12 is provided with an electrode 121, a reducing agent spray gun 122, a zinc-containing vapor outlet 123, a slag discharge port 124 and a metal melt outlet 125. Preferably, the electrode 121 extends into the electrothermal reduction zone 12 from the top of the electrothermal reduction zone 12, and the reducing agent spray gun 122 is arranged on the top and/or the side wall of the electrothermal reduction zone 12; the zinc-containing steam outlet 123 is arranged at the top of the electrothermal reduction zone 12; the slag discharge port 124 is arranged at the bottom of the electric heating reduction zone 12; the molten metal outlet 125 is arranged at the bottom of the electrothermal reduction zone 12. Specifically, the temperature of the electrothermal reduction region 12 is maintained at 1250-1650 ℃ under the heating of the electrode 121, and a reducing agent (coke) is injected into the electrothermal reduction zone 12 through a reducing agent injection lance 122, meanwhile, molten high-zinc slag formed in the smelting zone 11 directly enters the electrothermal reduction zone 12 to be in contact with a reducing agent for reduction, most of indium, germanium and the like in the high-zinc slag are enriched along with zinc vapor to obtain zinc-containing vapor, the zinc-containing steam is discharged from a zinc-containing steam outlet 123 arranged in the electric heating reduction zone and then enters a condensing system to produce crude zinc, meanwhile, iron, lead and the like in the high zinc slag can be reduced in an electrothermal reduction area to obtain a metal melt containing iron and lead, and the residual slag (the slag contains 0.1 to 0.5 weight percent of zinc) is discharged from a slag discharge port 124 positioned at the bottom of the electric heating reduction area 12, and is sold to building material enterprises for producing building materials such as cement and the like after being crushed, and the iron-lead containing metal melt is discharged from a metal melt outlet 125 provided at the bottom of the electrically heated reduction zone 12. It should be noted that, the 12 slag discharge port 124 and the metal melt outlet 125 of the electrothermal reduction zone of the present application may be the same port or two separate ports, and those skilled in the art can set them according to actual needs, and are not described herein again.
Furthermore, in the direction from the smelting zone 11 to the electrothermal reduction zone 12, the bottom of the smelting zone 11 and the bottom of the electrothermal reduction zone 12 are gradually reduced in a step manner, so that the molten high-zinc slag obtained in the smelting zone can directly flow into the electrothermal reduction zone by gravity, the operation of discharging and adding the melt is reduced, and the production operation rate is improved. Meanwhile, the furnace bottom step height between the smelting zone 11 and the electrothermal heat exchange zone 12 can be set by a person skilled in the art according to actual needs. In addition, a plurality of electrodes 121 are disposed on the electrothermal reduction region 12, and the plurality of electrodes 121 are uniformly distributed on the electrothermal reduction region 12. Therefore, the temperature in the electric heating reduction zone can be ensured to be uniform. And the electric heating reduction zone 12 is designed with a good furnace body sealing structure according to the process characteristics of zinc volatilization, and each part of the smelting zone 11 and the electric heating reduction zone 12 adopts different cooling modes according to the needs, and simultaneously adopts an integral elastic framework furnace type to ensure the service life of the furnace body.
According to the integrated pyrometallurgical furnace provided by the embodiment of the invention, the partition wall is arranged in the smelting furnace body, the partition wall divides the interior of the smelting furnace body into the smelting zone and the electrothermal reduction zone, the smelting zone is communicated with the bottom of the electrothermal reduction zone, the oxygen-containing gas spray gun is arranged in the smelting zone, the weak reduction atmosphere in the smelting zone is controlled, the electrode, the reducing agent spray gun and the zinc-containing steam outlet are arranged in the electrothermal reduction zone, the mixture obtained by mixing zinc leaching residues, zinc-containing oxide ore and flux is supplied to the smelting zone in the integrated pyrometallurgical furnace, the mixture is subjected to desulfurization reaction, the mixture is melted and partially reduced, F, Cl and As in the mixture can be opened to a part of flue gas in the melting stage to obtain sulfur-containing smelting flue gas, and SiO in the mixture is opened to a part of2And the slag is formed, and the formed molten high-zinc slag directly enters an electrothermal reduction area to be reduced to obtain zinc-containing steam and a metal melt containing iron and lead. Therefore, the high-efficiency side-blown smelting furnace and the electrothermal reduction furnace are integrally designed, so that the occupied area is small, the configuration height difference is reduced, the construction investment of the smelting furnace and a factory building is reduced, the operation of discharging and adding the melt is reduced, the production operation rate is improved, and the consumption of operators and corresponding tools can be reduced; smelting and reduction are completed in one furnace, and the electric heating reduction zone can also maintain a certain temperature by using the high temperature of the smelting zone, so that the consumption of electric energy during the independent reduction operation is reduced; in addition, the melting bath gives consideration to melting and smelting and reduction operations, the amount of the stored melt in the furnace is relatively large, the liquid storage time can be increased, the single-furnace processing capacity is favorably improved, the recovery rate of zinc is improved, and lead, iron, indium, germanium and the like can be simultaneously recovered, and the higher recovery rate is ensured. Specifically, the zinc leaching slag processing capacity of the single integrated pyrometallurgical furnace meets various scales such as 1-30 ten thousand tons.
In yet another aspect of the invention, a method of treating zinc leach residue is provided. According to an embodiment of the invention, referring to fig. 4, the method comprises:
s100: mixing zinc leaching residue, zinc-containing oxidized ore and flux
In the step, zinc leaching residue is wet smeltingThe solid waste slag generated in the zinc process is complex in component and contains various valuable metals such as zinc, lead, copper, indium, silver and the like, and the zinc leaching slag, zinc-containing oxidized ore and flux are mixed according to the mass ratio of (30-60): (20-50): (2-10) mixing. The inventor finds that if the mass proportion of zinc leaching slag is too high or the proportion of zinc-containing oxide ore is too large, the proportion of CaO in the slagging process is increased, and the viscosity of slag is increased due to the too high content of CaO, so that the fluidity of the slag is reduced, and the energy consumption is increased; and if the mass ratio of the zinc leaching residues is too low, the production requirement cannot be met, so that the production efficiency is reduced, and the production cost is increased. Specifically, the flux is silicon flux such as quartz, zinc-containing oxide ore containing CaO and SiO2Etc. by adding the zinc-containing oxide ore, the addition amount of the siliceous flux can be reduced, and the effect of adjusting the slag form can be achieved.
S200: feeding the mixture obtained in the step S100 to a smelting zone of a smelting furnace through a material inlet, so that the mixture is smelted and reduced in the smelting zone and an electrothermal reduction zone in sequence
In the step, the mixture obtained in the step S100 and coke or coal (the ratio of the coke or coal is 0.5-3 wt% to ensure the weak reducing atmosphere of the smelting zone) are supplied to the smelting zone 11 of the integrated pyrometallurgical furnace, oxygen-containing gas and fuel are blown into the smelting zone 11 through an oxygen-containing gas spray gun 112 to supply heat (the temperature of the smelting zone 11 is maintained at 1250-1450 ℃), the mixing ratio of the oxygen-containing gas (the volume concentration of oxygen in the oxygen-containing gas is 30-75%) and the fuel is controlled, so that the smelting zone 11 is in the weak reducing atmosphere, the mixture is subjected to desulfurization reaction, the mixture is melted and partially reduced, F, Cl and As in leaching slag in the melting stage can be partially recycled to flue gas to obtain sulfur-containing smelting flue gas, and SiO in zinc leaching slag can be partially recycled to obtain sulfur-containing2The slag is involved in slag forming to form molten high zinc slag (the slag type of the high zinc slag is ZnO-FeO-SiO)2Type, ZnO-FeO-SiO2CaO type, ZnO-FeO-SiO2CaO-ZnO type) directly enters the electrothermal reduction zone 12, the electrothermal reduction zone 12 maintains the temperature at 1250-1650 ℃ under the heating of the electrode 121 (the temperature is 1250-1350 ℃, lead is reduced in the electrothermal reduction zone to obtain crude lead, most of indium and germaniumThe enrichment is obtained along with the volatilization of zinc vapor, the operation temperature is increased to about 1550-1650 ℃, pig iron generated in the furnace can be melted, the operation temperature of the electric heating reduction zone is increased, which is beneficial to the more efficient reduction and volatilization of zinc, indium, germanium and the like, a reducing agent (coke) is blown into the electric heating reduction zone 12 through a reducing agent spray gun 123, meanwhile, molten high-zinc slag formed in the smelting zone 11 directly enters the electric heating reduction zone 12 to be reduced by contacting with the reducing agent, most of indium, germanium and the like in the high-zinc slag are enriched along with the zinc vapor to obtain zinc-containing vapor, the zinc-containing vapor is discharged from a zinc-containing vapor outlet 123 arranged in the electric heating reduction zone and then enters a condensing system to produce crude zinc, meanwhile, iron, lead and the like in the high-zinc slag can be reduced in the electric heating reduction zone to obtain a metal melt containing iron and lead, and the residual slag (0.1-0.5 wt%) is discharged from a slag discharge port, the crushed water is sold to building material enterprises for producing building materials such as cement, and the metal melt containing the iron and the lead is discharged from a metal melt outlet 125 arranged at the bottom of the electric heating reduction zone 12.
Furthermore, carbonaceous fuel can be injected into the smelting zone 11 through a carbonaceous fuel spray gun arranged on the smelting zone 11 according to actual needs to participate in combustion to supplement heat for the smelting zone 11, and the preferred carbonaceous fuel can be at least one of natural gas, pulverized coal and high-calorific-value gas.
According to the method for treating the zinc leaching residues, the mixture obtained by mixing the zinc leaching residues with the zinc-containing oxide ore and the flux is supplied to the smelting area in the integrated pyrometallurgical furnace, the mixture is subjected to desulfurization reaction, the mixture is melted and partially reduced, F, Cl and As in the mixture in the melting stage can be partially broken into flue gas to obtain fluorine-chlorine-containing arsenic-sulfur smelting flue gas, and SiO in the mixture2And the slag is formed, and the formed molten high-zinc slag directly enters an electrothermal reduction area to be reduced to obtain zinc-containing steam and a metal melt containing iron and lead. Therefore, the pyrometallurgical furnace adopting the smelting furnace and the electrothermal reduction furnace in integrated design not only occupies small area, reduces configuration height difference, reduces construction investment of the smelting furnace and a workshop, but also reduces operation of melt discharge and addition, improves production operation rate, and can realize integration design of the smelting furnace and the electrothermal reduction furnaceThe consumption of operators and corresponding tools is reduced; smelting and reduction are completed in one furnace, and the electric heating reduction zone can also maintain a certain temperature by using the high temperature of the smelting zone, so that the consumption of electric energy during the independent reduction operation is reduced; in addition, the melting bath gives consideration to melting and smelting and reduction operations, the amount of the stored melt in the furnace is relatively large, the liquid storage time can be increased, the single-furnace processing capacity is favorably improved, the recovery rate of zinc is improved, and lead, iron, indium, germanium and the like can be simultaneously recovered, and the higher recovery rate is ensured.
Further, referring to fig. 5, the method for treating zinc leaching slag further comprises the following steps:
s300: the sulfur-containing smelting flue gas is subjected to waste heat recovery and dust removal and then is subjected to acid making
In this step, the sulfur-containing smelting flue gas obtained in the smelting zone 11 is subjected to waste heat recovery and dust removal, for example, a waste heat boiler can be used for waste heat recovery, electric dust removal is used in the dust removal process, so that the waste heat of the smelting flue gas can be recycled, and the sulfur trioxide gas obtained after the residual gas is subjected to fluorine, chlorine and arsenic removal enters an acid making system to make acid, so that the resource utilization of the smelting flue gas is realized. It should be noted that the defluorinated chloroarsenic process and the acid making process are conventional operations in the prior art, and are not described herein again.
Further, referring to fig. 6, the method for treating zinc leaching slag further comprises the following steps:
s400: condensing the zinc-containing vapor
In this step, the zinc-containing steam obtained in the electrothermal reduction zone 12 is condensed to obtain crude zinc, crude lead and flue gas. It should be noted that, a person skilled in the art may select specific operating conditions of the condensation process according to actual needs, as long as separation of zinc and lead can be achieved, and details are not described herein.
S500: purifying the flue gas and supplying the gas to the smelting zone
In this step, the flue gas obtained by the condensation is purified to obtain a coal gas, and the coal gas is supplied to the melting zone 11 to be used as a carbonaceous fuel. Therefore, the resource utilization of the flue gas is realized. It should be noted that, those skilled in the art can select specific operations of the flue gas purification process according to actual needs, and details are not described herein.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
Referring to FIG. 7, 55 wt% of zinc leaching slag (containing Zn: 18 wt%), 40 wt% of zinc-containing oxide ore (containing Zn: 17.8 wt%) and 5 wt% of siliceous flux quartzite are mixed, the obtained mixture is directly added from a material inlet arranged in a smelting zone of a smelting furnace, meanwhile, oxygen-enriched air (oxygen concentration of 50% in the oxygen-enriched air) and natural gas are injected from the side part of the smelting zone, the smelting zone is maintained in a weak reducing atmosphere, the temperature is kept at 1250 ℃, the zinc leaching slag is smelted, and sulfur-containing smelting flue gas and high zinc slag (the slag type of the high zinc slag is ZnO-FeO-SiO) are obtained2Type, ZnO-FeO-SiO2CaO type, ZnO-FeO-SiO2A CaO-ZnO type), discharging sulfur-containing smelting flue gas through a smelting flue gas outlet on a smelting zone, recovering waste heat of a waste heat boiler, collecting dust by an electric dust collector, removing fluorine, chlorine and arsenic, and then sending the flue gas to prepare acid; the high-zinc slag obtained in the smelting area is placed in an electrothermal reduction area through a communication channel between the smelting area and the electrothermal reduction area, and is subjected to electrothermal reduction under the heating action of a heating electrode (the temperature of the electrothermal reduction area is maintained at 1250 ℃) and the reduction action of reducing agent coke to obtain zinc-containing steam, lead-containing metal melt and slag, wherein the zinc-containing steam comprises zinc vapor, lead vapor and CO, the zinc-containing steam is condensed to obtain crude zinc, crude lead and coal gas, and the slag is sold after water quenching.
Example 2
The difference from example 1 is that: the smelting temperature of the electric heating reduction zone is 1350 ℃.
Example 3
The difference from example 1 is that: the smelting temperature of the electrothermal reduction zone is 1550 ℃, and the lead-containing metal melt obtained in the electrothermal reduction zone contains metallic iron.
Example 4
The difference from example 3 is that: the smelting temperature of the electric heating reduction zone is 1600 ℃.
Example 5
The difference from example 3 is that: the smelting temperature of the electric heating reduction zone is 1650 ℃.
The recovery rates of zinc and iron elements in the smelting processes of zinc concentrate in examples 1 to 5 are shown in table 1.
TABLE 1
It is understood from comparative examples 2 to 5 and comparative example 1 that the limitation of the temperature of the electrically heated reduction zone within the range of the present application is advantageous in further improving the recovery rates of metallic zinc and iron.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. An integrated pyrometallurgical furnace, comprising:
the smelting furnace comprises a smelting furnace body, wherein a smelting area and an electric heating reduction area are defined in the smelting furnace body, a partition wall is arranged between the smelting area and the electric heating reduction area, and the bottom of the smelting area is communicated with the bottom of the electric heating reduction area;
a material inlet arranged at the top of the smelting zone;
the oxygen-containing gas spray gun is arranged on the side wall of the smelting zone;
a smelting flue gas outlet, wherein the smelting flue gas outlet is arranged in the smelting zone;
the electrode extends into the electrothermal reduction zone from the top of the electrothermal reduction zone;
the reducing agent spray gun is arranged in the electric heating reduction area;
the zinc-containing steam outlet is arranged in the electrothermal reduction area;
the slag discharging port is arranged at the bottom of the electric heating reduction zone;
and the metal melt outlet is arranged at the bottom of the electric heating reduction zone.
2. The integrated pyrometallurgical furnace according to claim 1, wherein the smelting zone is a shaft furnace body.
3. The integrated pyrometallurgical furnace according to claim 1, wherein the bottom of the smelting zone and the bottom of the electrically heated reduction zone are stepped down in the direction from the smelting zone to the electrically heated reduction zone.
4. The integrated pyrometallurgical furnace according to claim 1, wherein the reductant lance is provided at a top and/or a side wall of the electrically heated reduction zone;
optionally, a plurality of said oxygen-containing gas injection lances are included, the plurality of said oxygen-containing gas injection lances being symmetrically arranged on the side wall of the smelting zone;
optionally, a plurality of said electrodes are included, said plurality of electrodes being evenly distributed in said electro-thermal reduction zone.
5. The integrated pyrometallurgical furnace in accordance with any one of claims 1-4, further comprising:
a carbonaceous fuel lance disposed in the smelting zone.
6. A method of treating zinc leach residue, comprising:
(1) mixing zinc leaching residues, zinc-containing oxidized ore and a flux;
(2) feeding coke or coal and the mixture obtained in the step (1) to a smelting area of a smelting furnace through a material inlet, so that the mixture is smelted with oxygen-containing gas in the smelting area under a weak reducing atmosphere to obtain smelting flue gas and high-zinc slag, and feeding the high-zinc slag to an electrothermal reduction area of the smelting furnace to be in contact with a reducing agent for reduction treatment so as to obtain zinc-containing steam, iron-lead-containing melt and slag, wherein the smelting furnace is the integrated pyrometallurgical furnace in any one of claims 1 to 5.
7. The method according to claim 6, wherein in step (1), the zinc leaching residue is wet zinc leaching residue;
optionally, in step (1), the flux is a siliceous flux;
optionally, in the step (1), the mass ratio of the zinc leaching slag to the zinc-containing oxidized ore to the flux is (30-60): (20-50): (2-10).
8. The method according to claim 6, wherein in the step (2), the temperature of the smelting is 1250-1450 ℃;
optionally, in the step (2), the volume concentration of oxygen in the oxygen-containing gas is 30-75%;
optionally, in step (2), the reducing agent is coke;
optionally, in the step (2), the temperature of the reduction treatment is 1250-1650 ℃;
optionally, in step (2), carbonaceous fuel lances are used to supply carbonaceous fuel to the smelting zone for concurrent heating.
9. The method of claim 6, further comprising:
(3) and performing waste heat recovery and dust removal on the smelting flue gas, and then preparing acid.
10. The method of claim 8, further comprising:
(4) condensing the zinc-containing steam to obtain crude zinc, crude lead and flue gas;
(5) purifying the flue gas to obtain coal gas, and supplying the coal gas to the smelting zone to be used as the carbonaceous fuel.
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| CN112981136A (en) * | 2021-04-16 | 2021-06-18 | 中国恩菲工程技术有限公司 | One-step zinc smelting method for spraying zinc concentrate in molten pool |
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