CN108728672B - Extraction method of antimony metal - Google Patents

Extraction method of antimony metal Download PDF

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CN108728672B
CN108728672B CN201810545757.7A CN201810545757A CN108728672B CN 108728672 B CN108728672 B CN 108728672B CN 201810545757 A CN201810545757 A CN 201810545757A CN 108728672 B CN108728672 B CN 108728672B
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antimony
volatilization
extraction method
smelting
slag
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CN108728672A (en
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李东波
邓卫华
陆志方
金贵忠
蒋继穆
廖光荣
尉克俭
梁俊杰
刘诚
李志强
黎敏
刘放云
茹洪顺
龚福保
杨晓华
周立坤
王忠实
邓兆磊
吴卫国
陈学刚
冯双杰
曹珂菲
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HSIKWANG SHAN TWINKLING STAR CO Ltd
China ENFI Engineering Corp
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China ENFI Engineering Corp
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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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/02—Obtaining antimony
    • 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
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/04—Heavy metals
    • 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
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/16—Dry methods smelting of sulfides or formation of mattes with volatilisation or condensation of the metal being produced
    • 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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Abstract

The invention provides a method for extracting antimony metal. The extraction method comprises extracting the extract of radix Paeoniae albaAnd (3) carrying out volatilization smelting on the antimony material, wherein the volatilization smelting is carried out in an electric heating volatilization device. The antimony-containing material is volatilized and smelted in an electric heating mode, and the whole volatilizing and smelting process does not need blast combustion fuel, SO that the smoke gas amount can be greatly reduced, and further SO in the smoke gas can be greatly improved2The concentration of (c). High concentration SO produced2The flue gas can be recovered by acid making, thereby solving the problem of low concentration SO in the traditional blast furnace volatilization process2The pollution problem caused by the failure of recovery. Meanwhile, the electric heating efficiency is high, and the molten state of the slag can be always kept when the slag type of the slag fluctuates. The method can reduce the dosage of the added flux, reduce the amount of slag, and is beneficial to improving the high volatilization rate of antimony sulfide and antimony oxide, thereby realizing the comprehensive benefits of environmental protection, energy conservation, improvement of recovery rate and the like.

Description

Extraction method of antimony metal
Technical Field
The invention relates to the field of metal smelting, in particular to an extraction method of antimony metal.
Background
Antimony smelting is divided into a pyrogenic process and a wet process. At present, the pyrometallurgical process is mainly used in the metallurgical production of antimony, and the content of the antimony reaches more than 90 percent. The basic process of most antimony smelting plants in the field at present is antimony concentrate blast furnace volatilization smelting-crude antimony trioxide reverberatory furnace reduction smelting.
The antimony blast furnace volatilization smelting process has the defects of poor environmental protection, high energy consumption, large flue gas amount and SO in the flue gas2Low content, difficult acid preparation and the like. Meanwhile, the waste slag of the blast furnace has high antimony content, which causes resource waste. The blast furnace cannot process low-grade antimony concentrate. The reduction process of the reverberatory furnace also has the defects of poor labor condition, poor environmental protection, low production efficiency, high energy consumption, low direct yield and the like.
Disclosure of Invention
The invention mainly aims to provide an extraction method of antimony metal, which aims to solve the problems of large smoke gas amount, poor environmental protection and high energy consumption in the volatilization process of the existing antimony smelting process.
In order to achieve the above object, according to the present invention, there is provided an extraction method of antimony metal, comprising a step of performing volatilization smelting on antimony-containing materials, the step of performing volatilization smelting being performed in an electrothermal volatilization device.
Further, the device adopted by the extraction method also comprises a first dust collecting device and a reduction device which are sequentially connected with the outlet end of the electrothermal volatilization device, and the extraction method comprises the following steps: volatilizing and smelting the antimony-containing material in an electric heating volatilizing device to obtain antimony-containing flue gas, wherein the antimony-containing material comprises antimony sulfide; collecting the antimony-containing flue gas in a first dust collecting device to obtain antimony oxide dust; and (4) carrying out reduction smelting on the antimony oxide dust in a reduction device to obtain the metallic antimony.
Further, the top of electric heat volatilization device is provided with first charge door, and the process of smelting of volatilizing includes: adding the antimony-containing material into an electric heating volatilization device through a first feeding port for volatilization smelting to obtain antimony-containing flue gas;
preferably, the side wall of the electric heating volatilization device is further provided with a second feed inlet, the device used in the extraction method further comprises a drying device, the outlet end of the drying device is communicated with the second feed inlet, and the volatilization smelting process further comprises: after at least part of antimony-containing materials are dried by a drying device, adding the antimony-containing materials into an electric heating volatilization device through a second feeding port, and adding the rest part of antimony-containing materials into the electric heating volatilization device through a first feeding port so as to carry out volatilization smelting to obtain antimony-containing flue gas; or, after the antimony-containing material is dried by the drying device, adding the antimony-containing material into the electric heating volatilization device through the second feeding port for volatilization smelting to obtain antimony-containing flue gas;
preferably, the upper part of the side wall of the electric heating volatilization device is also provided with an air supply port, the volatilization smelting process further comprises the step of blowing oxygen or oxygen-enriched air into the electric heating volatilization device through the air supply port, and the volume fraction of the oxygen in the oxygen-enriched air is more than 21 vol%.
Further, a first injection inlet is further formed in the lower portion of the side wall of the electric heating volatilization device, the device adopted by the extraction method further comprises an oxygen supply device and a first injection device, the first injection device is communicated with the oxygen supply device through an oxygen supply pipeline, the first injection device is communicated with the first injection inlet, products of the volatilization smelting process further comprise volatilized slag, and the extraction method comprises the following steps: and injecting oxygen into the volatilized slag through the first injection inlet.
Furthermore, the temperature in the volatilization smelting process is 1200-1400 ℃, and preferably 1200-1300 ℃.
Further, the volatile slag comprises 40-65 wt% of SiO according to the weight percentage25-15 wt% of FeO, 10-25 wt% of CaO and the balance of impurities.
Furthermore, the temperature in the reduction smelting process is 1000-1200 ℃, and preferably 1100-1200 ℃.
Further, the process of reduction smelting comprises: carrying out reduction smelting on the antimony oxide dust and a reducing agent to obtain metallic antimony and reduction slag; preferably, the covering agent is added to the reaction system simultaneously during the reduction smelting.
Further, the weight ratio of the reducing agent to the antimony oxide dust is 5-10: 100; preferably, the reductant is one or more of crushed coal, pulverized coal, and crushed coke.
Further, the weight ratio of the covering agent to the antimony oxide dust is 1-3: 100; preferably, the covering agent is selected from Na2CO3、CaF2、NaOH、KAlSi3O8、NaAlSi3O8And CaAlSi3O8One or more of the group consisting of.
Further, the process of reduction smelting also comprises the following steps: adding an iron-containing flux and/or a calcium-containing flux in the reduction smelting process; preferably, the type of the reducing slag is FeO-SiO2-CaO-Na2O。
Further, the reducing slag comprises 50-65 wt% of SiO according to the weight percentage28-20 wt% of FeO, 10-25 wt% of CaO and 1-3 wt% of Na2O and the balance of impurities.
Further, the step of reduction smelting further comprises: and granulating the antimony oxide dust and adding the granulated antimony oxide dust into a reduction device.
Further, preheating the dried antimony-containing material by using the waste heat of the flue gas, wherein the temperature of the preheated material is 300-500 ℃.
By applying the technical scheme of the invention, in the extraction method of the antimony element provided by the application, the antimony-containing material is volatilized and smelted in an electric heating mode, and air blast fuel is not needed in the whole volatilization smelting process, SO that the smoke gas amount can be greatly reduced, and further the SO in the smoke gas can be greatly improved2The concentration of (c). High concentration SO produced2The flue gas can be recovered by acid making, thereby solving the problem of low concentration SO in the traditional blast furnace volatilization process2The pollution problem caused by the failure of recovery. Meanwhile, the electric heating efficiency is high, and the molten state of the slag can be always kept when the slag type of the slag fluctuates. Not only can reduce the dosage of the flux and the slag amount,and the method is also beneficial to improving the high volatilization rate of antimony sulfide and antimony oxide, thereby realizing the comprehensive benefits of environmental protection, energy conservation, improvement of recovery rate and the like.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a schematic flow diagram of an extraction process for providing antimony metal according to an exemplary embodiment of the present invention;
fig. 2 shows a schematic flow diagram of an extraction process for providing antimony metal according to a preferred embodiment of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the existing antimony smelting process has the problems of large flue gas amount, poor environmental protection and high energy consumption in the volatilization process. In order to solve the technical problem, the application provides an antimony element extraction method, which comprises a step of volatilizing and smelting antimony-containing materials, wherein the step of volatilizing and smelting is carried out in an electrothermal volatilizing device.
In the extraction method of the antimony element, the antimony-containing material is volatilized and smelted in an electric heating mode, and the whole volatilization smelting process does not need blast combustion fuel, SO that the smoke gas amount can be greatly reduced, and further SO in the smoke gas can be greatly improved2The concentration of (c). High concentration SO produced2The flue gas can be recovered by acid making, thereby solving the problem of low concentration SO in the traditional blast furnace volatilization process2The pollution problem caused by the failure of recovery. Meanwhile, the electric heating efficiency is high, and the molten state of the slag can be always kept when the slag type of the slag fluctuates. The method can reduce the dosage of the flux and the slag amount, and is beneficial to improving the high volatilization rate of antimony sulfide and antimony oxide, thereby realizingEnvironmental protection, energy saving, improvement of recovery rate and other comprehensive benefits.
In a preferred embodiment, as shown in fig. 1, the extraction method adopts an apparatus comprising a first dust collecting device and a reduction device which are connected with an outlet end of an electrothermal volatilization device in sequence, and comprises the following steps: volatilizing and smelting the antimony-containing material in an electric heating volatilizing device to obtain antimony-containing flue gas, wherein the antimony-containing material comprises antimony sulfide; collecting dust of the antimony-containing flue gas in a first dust collecting device to obtain antimony oxide dust; and (3) carrying out reduction smelting on the antimony oxide dust in a reduction device to obtain the metallic antimony.
Typically, a certain amount of antimony oxide will be present in the antimony-containing material, which may be present as a major constituent or in the form of impurities.
Due to the fact that the antimony sulfide and the antimony oxide are high in volatility, when the antimony-containing material is smelted in the electric heating volatilization device, the antimony sulfide and the antimony oxide can be volatilized into smoke. Meanwhile, the volatilized antimony sulfide is oxidized into antimony oxide in the upper space of the electrothermal volatilization device. And then conveying the antimony oxide smoke dust discharged from the electrothermal volatilization device to a first dust collection device for collection to obtain antimony oxide dust. And finally conveying the antimony oxide dust to a reduction device for reduction smelting to obtain the metal antimony.
Preferably, the electric heating volatilization device is an electric heating volatilization furnace.
It should be noted that, after the antimony-containing material is treated by the electrothermal volatilization device, the antimony-containing flue gas is obtained, and those skilled in the art can extract antimony element in the antimony-containing flue gas by using a conventional reduction method (reduction device) in the art to obtain antimony metal. Such as a reverberatory furnace, blast furnace or molten bath smelting unit.
More preferably, the reduction device is an electrothermal reduction furnace (see fig. 2 for a specific process flow chart). Compared with the existing reverberatory furnace and blast furnace, the electric heating reduction furnace is adopted for reduction, so that the heat efficiency can be greatly improved, the energy consumption is reduced, the smelting intensity is greatly improved, the reduction process is simplified, and the number of reduction devices is greatly reduced. Therefore, the problems of poor environmental protection, high energy consumption, low recovery rate and the like in the traditional reverberatory furnace reduction process can be solved.
Preferably, in the dust collection process, the antimony-containing flue gas is cooled through waste heat recovery and then enters a first dust collection device for collection, so that antimony-containing dust is obtained.
Preferably, the waste heat recovery adopts a waste heat boiler, the temperature of the flue gas at the outlet of an ascending flue of the waste heat boiler is 750-800 ℃, the antimony-containing flue gas is cooled to 300-400 ℃ after being cooled by a convection zone of the waste heat boiler, and then the antimony-containing flue gas enters a first dust removal device (preferably an electric dust removal device). And collecting the obtained antimony oxide dust by using the waste heat boiler and the first dust removal device, and conveying the antimony oxide dust to a semi-finished product warehouse for stockpiling. And the flue gas discharged from the first dust removal device is sent to an acid making system.
When the volatile slag in the electric heating volatilization device is accumulated to the preset measurement for slag discharge operation, the slag is quenched by water to form water-quenched slag.
In a preferred embodiment, the top of the electrothermal volatilization device is provided with a first feeding port, and the volatilization smelting process comprises the following steps: and adding the antimony-containing material into an electric heating volatilization device through a first feeding port for volatilization smelting to obtain antimony-containing flue gas.
With first charge door setting at the top of electric heat volatilization device, because the temperature at top is higher among the electric heat volatilization device, therefore throw off the antimony-containing material directly from first charge door, can make the antimony-containing material preheat at the in-process of whereabouts to be favorable to shortening process flow.
In a preferred embodiment, the sidewall of the electrothermal volatilization device is further provided with a second feeding port, and the device used in the extraction method further comprises a drying device, and the outlet end of the drying device is communicated with the second feeding port through a walking groove. After at least part of antimony-containing materials are dried by the drying device, adding the antimony-containing materials into an electric heating volatilization device from a second feeding port, and adding the rest antimony-containing materials into the electric heating volatilization device from a first feeding port for volatilization smelting; or after the antimony-containing material is dried by the drying device, adding the antimony-containing material into the electric heating volatilization device from the second feeding port for volatilization smelting. Preferably, a rotary kiln is selected as the drying device.
It should be noted that the drying device and the second charging opening may or may not be connected. When the two are not communicated, the material obtained after drying by the drying device can be added into the second feeding port by means of manual or external tools.
Preferably, the dried antimony-containing material is preheated by using the waste heat of the antimony-containing flue gas, and the temperature of the preheated material is 300-500 ℃. This is beneficial to reducing energy consumption and improving energy utilization rate.
Preferably, the antimony-containing material is dried after being crushed by sieving. Drying may be carried out by drying means commonly used in the art. As shown, the specific drying process is preferably: after the antimony-containing material is screened and crushed in the screening and crushing device, crushed coal, pulverized coal, diesel oil, natural gas and the like can be used as fuels, and then the antimony-containing material is dried in a rotary kiln.
In addition to drying the antimony-containing material during the drying process, a first flue gas is also generated. In order to further recover the antimony element in the first flue gas, the first flue gas is preferably conveyed to a second dust collecting device for collection, so that the smoke containing antimony oxide dust is obtained. The part of the smoke dust containing the antimony oxide dust can participate in the electro-thermal volatilization smelting process.
Preferably, the upper part of the side wall of the electric heating volatilization device is also provided with an air supply port, the volatilization smelting process further comprises the step of blowing oxygen or oxygen-enriched air into the electric heating volatilization device through the air supply port, and the volume fraction of the oxygen in the oxygen-enriched air is more than 21 vol%. The top of the electrothermal volatilization device is provided with an air supply port which can timely supplement oxygen required by the oxidation process, thereby being beneficial to improving the conversion rate of converting antimony sulfide into antimony oxide and improving the extraction rate of antimony element.
In a preferred embodiment, the lower portion of the sidewall of the electrothermal volatilization device is further provided with a first injection inlet, the extraction method adopts a device further comprising an oxygen supply device and a first injection device, the first injection device is communicated with the oxygen supply device through an oxygen supply pipeline, the first injection device is communicated with the first injection inlet, the product of the volatilization smelting process further comprises volatilized slag, and the extraction method comprises the following steps: and injecting oxygen into the volatilized slag through the first injection inlet.
Oxygen is sprayed into the volatilized slag from the first spraying inlet, so that the stirring speed of the volatilized slag is accelerated, the volatilization rate of the antimony element is further improved, and the extraction rate of the final antimony element is further improved.
In a preferred embodiment, the temperature of the volatilization smelting process is 1200-1400 ℃. The temperature of the volatilization smelting process includes, but is not limited to, the above range, and the limitation to the above range is advantageous for improving the volatilization efficiency of antimony element. Preferably 1200 to 1300 ℃.
Preferably, the volatilized slag comprises 40-65 wt% SiO25-15 wt% of FeO, 10-25 wt% of CaO and the balance of impurities. The volatile slag is limited to the composition, so that the volatilization rate of the antimony-containing flue gas can be further improved.
In a preferred embodiment, the temperature of the reduction smelting process is 1000-1200 ℃. The temperature of the reduction smelting process includes, but is not limited to, the above range, and it is preferable to limit the temperature to the above range in order to improve the reduction efficiency of antimony element. Preferably 1100 to 1200 ℃.
In a preferred embodiment, the reduction smelting process comprises the step of carrying out reduction smelting on the antimony oxide dust and a reducing agent to obtain metallic antimony and reduction slag.
Preferably, the weight ratio of the reducing agent to the antimony oxide dust is 5-10: 100. The weight ratio of the reducing agent to the antimony oxide dust includes, but is not limited to, the above range, and it is preferable to limit it to the above range to further increase the reduction rate of antimony element.
Preferably, the reductant includes, but is not limited to, one or more of crushed coal, crushed coke, natural gas and liquefied petroleum gas.
The crushed coke refers to coke blocks with the granularity of 2-30 mm, and the crushed coal refers to coal blocks with the granularity of 2-30 mm.
In a preferred embodiment, a covering agent is added to the reaction system during the reduction smelting. Because antimony oxide is easy to volatilize, the covering agent can play a shielding role, so that the volatilization loss of antimony metal can be reduced by adding the covering agent in the reduction smelting process, and the extraction rate of antimony element can be improved.
In a preferred embodiment, the weight ratio of the covering agent to the antimony oxide dust is 1 to 3: 100. The weight ratio of the covering agent to the antimony oxide dust includes, but is not limited to, the above range, and it is preferable to limit it to the above range to further reduce the volatilization loss rate of antimony oxide.
Preferably, the capping agent includes, but is not limited to, Na2CO3、CaF2、NaOH、KAlSi3O8、NaAlSi3O8And CaAlSi3O8One or more of (a).
During the reduction process, a third flue gas can be generated besides antimony metal. Preferably, the third flue gas is subjected to secondary combustion in the uptake flue, then is cooled by a waste heat recovery device (waste heat boiler), and enters a third dust removal device (electric dust removal device) for dust collection treatment, so as to further recover antimony oxide smoke dust in the flue gas.
In a preferred embodiment, the process of reduction smelting further comprises: adding an iron-containing flux and/or a calcium-containing flux in the reduction smelting process; preferably, the type of the reducing slag is FeO-SiO2-CaO-Na2And O. The above-mentioned composition of the reducing slag is limited to the above-mentioned composition, and it is advantageous to further improve the recovery rate of antimony.
In a preferred embodiment, the reduced slag comprises 50-65 wt% SiO28-20 wt% of FeO, 10-25 wt% of CaO and 1-3 wt% of Na2O and the balance of impurities. The slag form is beneficial to further reducing the melting point of the reduction slag, and is further beneficial to improving the subsequent extraction rate of the antimony element. In the actual smelting process, the slag form can be prepared by adding FeO and SiO in the reduction smelting process2And CaO and the like.
Preferably, the step of reduction smelting further includes: and granulating the antimony oxide dust and adding the granulated antimony oxide dust into a reduction device.
In the above reduction smelting process, preferably, the extracted liquid metal antimony is stored in a ladle. More preferably, after a certain amount of liquid metal antimony in the ladle is accumulated, the ladle is transferred to a ladle furnace station to be heated, arsenic and lead removal operation (refining process) is carried out when the temperature reaches the requirement, and a casting finished product is carried out after the refining process is finished.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
The compositions of the antimony-containing materials in examples 1 to 14 and comparative example 1 are shown in Table 1.
TABLE 1
Figure BDA0001673570610000061
Example 1
First, iron ore and limestone target slag types, 60 wt% SiO, were dosed according to the preferred smelt slag type by analyzing the antimony containing material charged to the furnace210 wt% FeO, 15wt% CaO.
Secondly, the material to be treated is volatilized and smelted in an electric heating volatilizing device (a first electric heating furnace) to ensure that Sb is volatilized2S3Then is converted into Sb2O3To obtain antimony oxide flue gas and volatile slag (type is FeO-SiO)2CaO, composition 60% by weight SiO210 wt% FeO, 15wt% CaO and the balance of impurities), and the temperature of the volatilization smelting is 1250 ℃.
Collecting the antimony oxide flue gas in a waste heat recovery device, cooling to 800 ℃, and then feeding into a dust collection device to obtain antimony oxide dust (powder Sb)2O3). After the end, the residual antimony content in the volatilized slag is only 0.12 wt%.
Mixing antimony oxide powder with covering agent (Na) at a weight ratio of 100:1:52CO3) And reducing and smelting the reducing agent (coke) in an electrothermal reduction device (a second electrothermal furnace) to obtain metallic antimony and reduced slag (the type is FeO-SiO)2-CaO-Na2O, composition of 52 wt% SiO2、15wt％FeO、20wt％CaO、2％Na2O and the balance of impurities), the temperature of reduction melting was 1150 ℃. After the reduction smelting is finished, the yield of the metallic antimony reaches up to 90 wt%.
Example 2
First, iron ore and limestone target slag types, 60 wt% SiO, were dosed according to the preferred smelt slag type by analyzing the antimony containing material charged to the furnace210 wt% FeO, 10 wt% CaO.
Secondly, the material to be treated is volatilized and smelted in an electric heating volatilizing device (a first electric heating furnace) to ensure that Sb is volatilized2S3Then is converted into Sb2O3Obtaining antimony oxide flue gas and volatile slag, wherein the temperature of the volatile melting is 1250 ℃.
The antimony oxide smoke is gathered in a waste heat recovery device, cooled to 800 ℃, and then enters a dust collection device to obtain antimony oxide dust (powder Sb)2O3). Meanwhile, oxygen-enriched blowing (oxygen blowing) is carried out on the volatilized slag, and after the oxygen-enriched blowing is finished, the content of the residual antimony in the volatilized slag is only 0.18 wt%.
Mixing antimony oxide powder with covering agent (Na) at a weight ratio of 100:1:52CO3) And reducing and smelting the reducing agent (coke) in an electrothermal reduction device (a second electrothermal furnace) to obtain metallic antimony and reduced slag (the type is FeO-SiO)2-CaO-Na2O, composition of 52 wt% SiO2、15wt％FeO、20wt％CaO、2％Na2O and the balance of impurities), the temperature of reduction melting was 1150 ℃. After the reduction smelting is finished, the yield of the metallic antimony reaches 91 wt%.
Example 3
The differences from example 1 are: the temperature of volatilization smelting is 1350 DEG C
Example 4
The differences from example 1 are: the temperature of the volatilization smelting is 1100 DEG C
Example 5
The differences from example 1 are: in the reduction smelting process, the weight ratio of the reducing agent to the antimony oxide dust is 3: 100.
Example 6
The differences from example 1 are: in the reduction smelting process, the weight ratio of the covering agent to the antimony oxide dust is 8: 100.
Example 7
The differences from example 1 are: in the reduction smelting process, the weight ratio of the covering agent to the antimony oxide dust is 0.5: 100.
Example 8
The differences from example 1 are: during the reduction smelting, no covering agent is added.
Example 9
The differences from example 1 are: in the reduction smelting process, the type of the reduction slag is FeO-SiO2CaO, composition of 45 wt% SiO25wt% FeO, 20wt% CaO and the balance impurities.
Example 10
The differences from example 1 are: oxygen blowing is not performed on the volatilized slag. The content of antimony in the volatilized slag was 0.22 wt%.
Example 11
The differences from example 1 are: and during the reduction smelting process, granulating the antimony oxide dust.
Example 12
The differences from example 1 are: in the volatilization smelting process, the antimony-containing material is preheated to 400 ℃, and then the volatilization smelting process is carried out.
Example 13
The differences from example 1 are: the reduction device is a reverberatory furnace.
Example 14
The differences from example 1 are: the reduction device is a molten pool smelting furnace.
Comparative example 1
And oxidizing and smelting the antimony sulfide ore and oxygen-enriched air in a blast furnace to obtain antimony-containing flue gas and molten slag, wherein the oxidizing and smelting temperature is 1250 ℃, and the content of antimony in the molten slag is 1 wt%.
And (3) carrying out reduction smelting on the antimony smoke dust in a reverberatory furnace to obtain metal antimony, wherein the reduction smelting temperature is 1150 ℃. The extraction rate of metallic antimony was 80 wt%.
The residual antimony content and the extraction rate of metallic antimony in the volatilized slag in examples 1 to 14 and comparative example 1 are shown in Table 1.
TABLE 1
Figure BDA0001673570610000081
Figure BDA0001673570610000091
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
comparing examples 1 to 10 and comparative example 1, it can be seen that the extraction method provided by the present application is advantageous to greatly increase the extraction rate of antimony.
As is clear from comparison of examples 1, 3 and 4, limiting the temperature of the volatilization melting to the preferable range in the present application is advantageous in further reducing the residual amount of antimony element in the volatilized slag and in further improving the extraction rate of antimony metal.
Comparing examples 1 and 5, it is found that limiting the weight ratio of the reducing agent to the antimony oxide dust to the range preferable in the present application is advantageous in further improving the reduction rate of antimony element and further in improving the extraction rate of antimony metal.
It is understood from comparison of examples 1 and 6 to 8 that limiting the weight ratio of the covering agent to the antimony oxide dust to the preferable range in the present application is advantageous in further reducing the residual amount of antimony element in the volatilized slag and in further improving the extraction rate of antimony metal.
Comparing examples 1 and 9, it is found that limiting the type of slag to the preferred range of the present application is advantageous in further reducing the residual amount of antimony in the reduction slag, and in turn, in improving the extraction rate of antimony metal.
Comparing examples 1 and 10, it is found that oxygen blowing of the volatilized slag is advantageous in further reducing the residual amount of antimony element in the volatilized slag, and is further advantageous in improving the extraction rate of antimony metal.
Comparing examples 1 and 11, it is found that performing reduction smelting after granulating the antimony oxide dust is advantageous in further reducing the residual amount of antimony element in the reduction slag, and in turn, in improving the extraction rate of antimony metal.
Comparing examples 1 and 12, it can be seen that the preheating and the volatilization smelting of the antimony-containing material are beneficial to further reducing the residual amount of antimony in the volatilized slag, and further beneficial to improving the extraction rate of antimony metal.
Comparing examples 1, 13 and 14, it is found that the use of the electrothermal reduction apparatus is advantageous in further improving the extraction rate of antimony metal.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (19)

1. The method for extracting the antimony metal is characterized in that the device adopted by the method further comprises an electric heating volatilization device, a first dust collecting device and a reduction device which are sequentially connected with the outlet end of the electric heating volatilization device, and the method for extracting the antimony metal comprises the following steps:
volatilizing and smelting antimony-containing materials in the electric heating volatilization device to obtain antimony-containing flue gas, wherein the antimony-containing materials comprise antimony sulfide;
collecting the antimony-containing flue gas in the first dust collecting device to obtain antimony oxide dust;
carrying out reduction smelting on the antimony oxide dust and a reducing agent in the reduction device to obtain metallic antimony and reduction slag; the upper part of the side wall of the electric heating volatilization device is provided with an air supply port, the volatilization smelting process also comprises a step of blowing oxygen or oxygen-enriched air into the electric heating volatilization device through the air supply port, and the volume fraction of the oxygen in the oxygen-enriched air is more than 21 vol%.
2. The extraction method as claimed in claim 1, wherein the top of the electro-thermal volatilization device is provided with a first charging port, and the volatilization smelting process comprises the following steps: and adding the antimony-containing material into the electric heating volatilization device through the first feeding port for volatilization smelting to obtain the antimony-containing flue gas.
3. The extraction method as claimed in claim 2, wherein a second feeding port is further provided on the side wall of the electrothermal volatilization device, the device used in the extraction method further comprises a drying device, and the outlet end of the drying device is communicated with the second feeding port, and the volatilization smelting process further comprises: and after at least part of the antimony-containing material is dried by the drying device, adding the antimony-containing material into the electrothermal volatilization device through the second feeding port, and adding the rest antimony-containing material into the electrothermal volatilization device through the first feeding port so as to perform volatilization smelting to obtain the antimony-containing flue gas.
4. The extraction method according to claim 2 or 3, characterized in that a first injection inlet is further arranged on the lower part of the side wall of the electrothermal volatilization device, the device adopted by the extraction method further comprises an oxygen supply device and a first injection device, the first injection device is communicated with the oxygen supply device through an oxygen supply pipeline, and the first injection device is communicated with the first injection inlet,
the product of the volatilization smelting process also comprises volatilized slag, and the extraction method comprises the following steps: and injecting oxygen into the volatilized slag through the first injection inlet.
5. The extraction method according to claim 1, wherein the temperature of the volatilization smelting process is 1200-1400 ℃.
6. The extraction method according to claim 5, wherein the temperature of the volatilization smelting process is 1200-1300 ℃.
7. The extraction method according to claim 4, wherein the volatilized slag comprises 40-65 wt% SiO by weight25-15 wt% of FeO, 10-25 wt% of CaO and the balance of impurities.
8. The extraction method according to claim 1, wherein the temperature of the reduction smelting process is 1000 to 1200 ℃.
9. The extraction method according to claim 8, wherein the temperature of the reduction smelting process is 1100-1200 ℃.
10. The extraction method according to claim 2 or 3, wherein a covering agent is simultaneously added to the reaction system during the reduction smelting.
11. The extraction method according to claim 10, wherein the weight ratio of the reducing agent to the antimony oxide dust is 5 to 10: 100.
12. The extraction process of claim 11, wherein the reducing agent is one or more of crushed coal, pulverized coal, and crushed coke.
13. The extraction method according to claim 10, wherein the weight ratio of the covering agent to the antimony oxide dust is 1 to 3: 100.
14. The extraction process according to claim 13, wherein the covering agent is selected from Na2CO3、CaF2、NaOH、KAlSi3O8、NaAlSi3O8And CaAlSi3O8One or more of (a).
15. The extraction method of claim 10, wherein the process of reduction smelting further comprises: and adding an iron-containing flux and/or a calcium-containing flux during the reduction smelting process.
16. Extraction process according to claim 15, characterized in that the reducing slag is of the type FeO-SiO2-CaO-Na2O。
17. The extraction method according to claim 15, wherein the reducing slag comprises 50-65 wt% SiO by weight percentage28-20 wt% of FeO, 10-25 wt% of CaO and 1-3 wt% of Na2O and the balance of impurities.
18. The extraction method of claim 10, wherein the step of reduction smelting further comprises: and granulating the antimony oxide dust and then adding the granulated antimony oxide dust into the reduction device.
19. The extraction method according to claim 3, wherein the dried antimony-containing material is preheated by using the waste heat of flue gas, and the temperature of the preheated material is 300-500 ℃.
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