CN110055418B - Smelting system and smelting method for realizing continuous multi-section comprehensive recovery of lead anode mud - Google Patents

Smelting system and smelting method for realizing continuous multi-section comprehensive recovery of lead anode mud Download PDF

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CN110055418B
CN110055418B CN201910212375.7A CN201910212375A CN110055418B CN 110055418 B CN110055418 B CN 110055418B CN 201910212375 A CN201910212375 A CN 201910212375A CN 110055418 B CN110055418 B CN 110055418B
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spray gun
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CN110055418A (en
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徐瑞东
何云龙
王军丽
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Kunming University of Science and Technology
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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
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • C22B11/021—Recovery of noble metals from waste materials
    • 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
    • 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/04—Obtaining arsenic
    • 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
    • C22B30/06—Obtaining bismuth
    • 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
    • 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

Abstract

The invention discloses a smelting system and a smelting method for realizing continuous multi-section comprehensive recovery of lead anode slime, belonging to the technical field of comprehensive recovery of non-ferrous metal secondary resources; aiming at the problems that the lead anode slime is rich in valuable elements such as arsenic, antimony, bismuth, lead, gold, silver and the like, and efficient separation of arsenic, antimony, bismuth and the like is difficult to realize in one step in reduction smelting, through three-section non-isothermal continuous heating, arsenic trioxide is recycled in the first heating section, antimony trioxide is recycled in the second heating section, and a metal alloy is produced while gold and silver are enriched in the third heating section, so that the aim of simultaneously recycling multiple valuable elements in one device is fulfilled; the equipment system and the method have the advantages of simple operation, accurate temperature control, strong adaptability of raw materials, synchronous and efficient recovery of various valuable elements, continuous production process, suitability for large-scale industrial production and the like.

Description

Smelting system and smelting method for realizing continuous multi-section comprehensive recovery of lead anode mud
Technical Field
The invention relates to a smelting system and a smelting method for realizing continuous multi-section comprehensive recovery of lead anode slime, belonging to the technical field of pyrogenic comprehensive recovery of secondary resources of color metals.
Background
With the increasing exhaustion of non-ferrous metal resources and the continuous improvement of environmental protection consciousness, the search for efficient and environment-friendly non-ferrous metal secondary resource comprehensive recovery process and equipment becomes a difficult problem which needs to be solved urgently by researchers at home and abroad. The lead anode slime is hopeful to be used as an important resource for recycling valuable metals such as gold and silver because of being rich in valuable metals such as antimony, bismuth, gold, silver and the like, and becomes a hot spot of metallurgical research in various countries at present. Among a plurality of lead anode slime treatment processes, the application of the traditional pyrogenic process is the most extensive, and how to obtain valuable metals in the lead anode slime in a low-cost and short-flow manner becomes an important factor directly influencing the comprehensive recovery economic benefit of the lead anode slime pyrogenic process. How to efficiently and comprehensively recover valuable elements in the lead anode slime, and the production of high-quality noble metal alloy meeting the electrolysis requirement is a core link of the pyrogenic process anode slime treatment process, so that an efficient and low-cost comprehensive recovery and utilization technology of the lead anode slime has important significance for the development of the pyrogenic process treatment process of the lead anode slime.
At present, the treatment method of lead anode slime can be mainly divided into two types, one type is a hydrometallurgy technology, and mainly comprises a chloride salt leaching method, a fluosilicic acid leaching method, a ferric trichloride leaching method, a potential control chlorination method, a chlorination-dry distillation method, a sodium hydroxide normal pressure leaching method, a sodium hydroxide pressure leaching method and the like. The other type is a vacuum treatment technology, and scientific research experiments and active progress have been carried out on the vacuum treatment technology of the lead anode slime by units such as Kunming technology university, China and south university. The other technology is a traditional pyrometallurgical process, the traditional process of pyrometallurgical smelting-oxidative refining-electrolytic process is generally adopted for lead anode slime at home and abroad, although the process flow is slightly different along with the difference of raw material components, the basic idea is as follows, the core content of the technology is that the anode slime is mixed with auxiliary materials such as soda, fluorite, coke and the like to carry out reduction smelting and enrichment of gold and silver under a weak reducing atmosphere, so that precious lead with the grade of the gold and silver of 20-30% is obtained, the precious lead is further subjected to oxidative refining to remove antimony, arsenic and bismuth, slag is oxidized to recover tellurium, and a gold-silver alloy plate meeting the electrolysis requirement is obtained through fusion casting. Electrolytic silver powder and electrolytic anode mud are obtained by electrolytic refining of the alloy plate, silver ingots with the grade of more than 99.99% are produced by washing, drying and ingot casting of the electrolytic silver powder, and gold ingots with the grade of more than 99.99% are produced by immersing and boiling the electrolytic anode mud in nitric acid, separating gold by chlorination, extracting, reducing gold, washing and drying. The traditional pyrogenic process of the lead anode slime is greatly developed in dust collection and dust collection technologies through continuous efforts of metallurgy workers, and an oxygen-enriched bottom blowing technology, a molten pool smelting technology, a bottom blowing and top blowing converter technology and the like are introduced into production and application, so that the pyrogenic process comprehensive recovery of the lead anode slime achieves great effects. However, the processes are complex, the requirements on equipment and refractory materials are high, the technology introduction cost is high, and domestic enterprises adopt few processes. At present, the technological research of the anode treatment by the pyrometallurgical method mainly focuses on the improvement of smelting equipment and a technological route, the traditional pyrometallurgical method is the main treatment flow of the lead anode slime, and the lead anode slime is widely applied nationwide, and has the main advantages that: strong adaptability to raw materials, high chemical reaction speed, simple equipment, large processing capacity, reliable equipment, convenient operation, easy implementation, convenient management and the like.
Although the traditional fire process development of the lead anode slime is mature, the lead anode slime has a plurality of defects, such as long flow, more equipment, low direct yield of gold and silver, smoke harm, environmental pollution, bad labor conditions and the like. In addition, the traditional pyrometallurgical process has two problems: firstly, the equipment cannot realize the high-efficiency respective recovery of various valuable metals in the reduction smelting process of the lead anode slime; secondly, the precious lead produced by reduction smelting needs to be transferred to another oxidation refining furnace for treatment, so that the energy consumption, time consumption and work efficiency are low, smoke often overflows during transfer, the environmental pollution is high, and potential safety hazards also exist.
Disclosure of Invention
The invention provides a smelting system for realizing continuous multi-section comprehensive recovery of lead anode slime, aiming at the problems that the comprehensive recovery of various valuable metals is difficult, the reduction smelting and the oxidation refining are difficult to realize in one step and the like in the pyrogenic process treatment process of the lead anode slime.
The smelting system for realizing continuous multi-section comprehensive recovery of the lead anode slime realizes efficient and independent recovery of arsenic and antimony in the first two heating sections by adopting multi-section non-isothermal continuous heating in the same smelting device, and realizes one-step production of precious metal alloy suitable for electrolytic refining in the last heating section, so that multi-section continuous comprehensive recovery and utilization of valuable metals are realized.
The smelting system for realizing continuous multi-section comprehensive recovery of the lead anode slime consists of a continuous non-isothermal heating smelting furnace and 3 product recovery systems; the continuous non-isothermal heating smelting furnace is an integrated metallurgical furnace consisting of a first-stage low-temperature heating recovery furnace, a second-stage heating recovery furnace and a third-stage smelting output furnace, wherein the furnace bottoms of the first-stage low-temperature heating recovery furnace, the second-stage heating recovery furnace and the third-stage smelting output furnace are communicated in sequence and are inclined planes which are continuously reduced, the self-flowing of materials can be realized, and the self-flowing inclination angle is 20-35 degrees; the 3 product recovery systems are respectively connected with the first-stage low-temperature heating recovery furnace, the second-stage heating recovery furnace and the third-stage smelting output furnace;
the first-section low-temperature heating recovery furnace comprises a cylindrical furnace body I, an electric furnace transformer I, a storage bin I, a metering valve I, a heating electrode I, a material and compressed air spray gun I, a product outlet I and a flue stop valve I, wherein the spray gun I penetrates through the top of the cylindrical furnace body I and is arranged in the cylindrical furnace body I, the storage bin I is arranged at the top of the spray gun I and is communicated with the spray gun I, the metering valve I is arranged at the bottom of the storage bin I, more than 3 heating electrodes I are circularly arranged around the spray gun I, the product outlet I is formed in one side of the upper portion of the cylindrical furnace body I, the flue stop valve I is arranged on the product outlet I, the product outlet I is communicated with a product recovery system;
the product recovery system connected with the first-stage low-temperature heating recovery furnace comprises a condenser I, a cloth bag dust collector I and a spiral conveyor I, wherein a product outlet I is connected with the cloth bag dust collector I through the condenser I, and the spiral conveyor I is arranged at an outlet below the cloth bag dust collector I;
spray gun I is double-deck cavity's spray gun, and it includes outer tube and inner tube, and the outer tube suit is outside the inner tube, and the raw materials is carried with I intercommunication in feed bin to the inner tube, and outer tube (outer cavity) is connected with the compressed air pipeline and is used for air transportation.
The second section of heating recovery furnace comprises a cylindrical furnace body II, an electric furnace transformer II, a heating electrode II, a spray gun II, a feed port and a product outlet II, wherein the feed port is formed in the top of the cylindrical furnace body II, the spray gun II penetrates through the top of the cylindrical furnace body II to be arranged in the cylindrical furnace body II, a metering valve II is arranged on the spray gun II, more than 3 heating electrodes II are circularly arranged around the spray gun II, a product outlet II is formed in one side of the upper part of the cylindrical furnace body II, a flue stop valve II is arranged on the product outlet II, the product outlet II is connected with a product recovery system, and the electric furnace transformer II is connected with the;
the product recovery system connected with the second section of heating recovery furnace comprises a condenser II, a cloth bag dust collector II and a spiral conveyor II, wherein a product outlet II is connected with the cloth bag dust collector II through the condenser II, and the spiral conveyor II is arranged at an outlet below the cloth bag dust collector II;
the third-stage smelting production furnace comprises a cylindrical furnace body III, an electric furnace transformer III, a storage bin II, a heating electrode III, a product outlet III, a metering valve III, a spray gun III, a slag outlet and a metal outlet, wherein the spray gun III is arranged in the cylindrical furnace body III through the top of the cylindrical furnace body III, the metering valve III is arranged at the joint of the storage bin II and the spray gun III, the storage bin II is arranged at the top end of the spray gun III and communicated with the spray gun III, the heating electrodes III above 3 are circularly arranged around the spray gun III, the product outlet III is formed in one side of the upper part of the cylindrical furnace body III, a flue stop valve III is arranged on the product outlet III, the product outlet III is connected with a product recovery system, the slag outlet and the metal outlet are formed in the lower.
Spray gun III is double-deck cavity's spray gun, and it includes outer tube and inner tube, and the outer tube suit is outside the inner tube, and the raw materials is carried with I intercommunication in feed bin to the inner tube, and outer tube (outer cavity) is connected with the compressed air pipeline and is used for transporting the air.
And the product recovery system connected with the third-stage smelting and producing furnace comprises a condenser III, a cloth bag dust collector III and a screw conveyor III, wherein a product outlet III is connected with the cloth bag dust collector III through the condenser III, and the screw conveyor III is arranged at an outlet below the cloth bag dust collector III.
The furnace bottom connecting section of the first section low-temperature heating recovery furnace and the second section heating recovery furnace is provided with a baffle I, the furnace bottom connecting section of the second section heating recovery furnace and the third section smelting production furnace is provided with a baffle II, and the connecting section is coated with a heat-insulating material so as to ensure the effective reaction time of materials in each heating section.
The electric furnace transformer I, the electric furnace transformer II and the electric furnace transformer III realize accurate temperature control of each heating section, the transformer is a metallurgical electric furnace transformer, the voltage regulating range designed in the constant current section of the transformer is not more than 5V, the range of the constant power section is enhanced, the accurate regulation and control of the secondary side voltage are guaranteed, and the aim of accurately controlling the smelting temperature is achieved.
The ratio of the electrode center circle diameter of the heating electrode I, the electrode center circle diameter of the heating electrode II or the electrode center circle diameter of the heating electrode III to the furnace body hearth diameter is 1: 1.2-1.6.
The invention also aims to provide a using method of the device, the method realizes three-section non-isothermal continuous heating of the lead anode in the same smelting equipment, sequentially recovers arsenic and antimony in sections, and simultaneously produces metal alloy rich in gold and silver, so that the reduction smelting and the oxidation refining of the lead anode slime are continuously carried out in the same equipment. As produced by volatilization of the first two heating zones2O3And Sb2O3The finished product recovery is realized through the product outlet, the condenser, the bag-type dust collector and the screw conveyer, and the trend of valuable elements is reasonably arranged in the third heating section of the furnace body according to the difference of the components of the anode mud and the economic benefit of the recovery, so that the noble metal alloy suitable for electrolysis is produced.
The method comprises the following steps:
(1) lead anode mud pretreatment: crushing and drying the lead anode slime, wherein the water content of the lead anode slime is less than 2%;
(2) according to the chemical components and the treatment capacity of metals such as arsenic, antimony, bismuth, lead and the like in the lead anode mud, the carbon-oxygen ratio required by reaction recovery is obtained through metallurgical calculation, and the materials are mixed;
(3) and (3) heating at low temperature in the first section to recover arsenic in the lead anode slime: putting the metallurgical material prepared in the step (2) and compressed air into a first-stage low-temperature heating recovery furnace through a spray gun I, adjusting the furnace temperature to 450-500 ℃, and using As As the most arsenic in anode mud2O3The mixture is volatilized and recovered from a product outlet I, and other elements are left in furnace burden, and the self-flowing gradient angle is 20-35 degrees;
(4) opening the baffle I, allowing the materials to automatically flow into a second-stage heating recovery furnace for second-stage heating recovery of antimony, adjusting the furnace temperature to 700-750 ℃, and according to the specific characteristics of furnace materialsA carbonaceous reducing agent is put into the furnace body through the feeding hole to ensure that Sb is not oxidized into Sb2O5To make it with Sb2O3Volatilizing, cooling and recovering; the self-flowing slope angle is 20-35 degrees;
(5) opening a baffle II, automatically flowing the furnace burden obtained in the step (4) into a third-stage smelting production furnace, spraying a slagging agent from a spray gun III to remove bismuth if the lead content is high, spraying oxygen-enriched air from the spray gun III to perform oxidation converting to produce alloy rich in gold and silver, adding the slagging agent to remove lead and produce molten crude bismuth if the bismuth content is high, and enriching noble metals into the crude bismuth to perform electrolytic refining.
Through the steps (1) to (5), element trends can be reasonably arranged in the same equipment according to the raw material condition and the actual production of the lead anode mud, so that the efficient separation and enrichment of valuable elements such as arsenic, antimony, bismuth, gold, silver and the like are realized.
The reagent for controlling the carbon-oxygen ratio in the step (2) and the carbonaceous reducing agent in the step (4) can be anthracite, high-fixed-carbon low-ash lignite semicoke, metallurgical coke carbon and the like; the bismuth-removing slagging agent in the step (5) is a calcium-magnesium mixed reagent, so that deep bismuth removal can be realized, and the lead-removing slagging agent is silicon dioxide.
The invention has the beneficial effects that:
(1) the invention relates to a comprehensive recovery system of lead anode slime, which realizes the segmental volatilization of valuable elements at different temperature sections by continuously heating multiple ends of the lead anode slime, and can realize the comprehensive utilization of the lead anode slime;
(2) the invention relates to a continuous non-multistage recovery smelting method of lead anode slime, which is a method with low cost and simple operation, and has the advantages of easy operation, strong raw material adaptability, suitability for large-scale industrial production and the like.
Drawings
FIG. 1 is a schematic diagram of the construction of the smelting system of the present invention;
FIG. 2 is a schematic top view of the smelting system of the present invention;
FIG. 3 is a schematic view of a continuous non-isothermal heating smelting furnace;
FIG. 4 is a schematic top view of a continuous non-isothermal heating smelting furnace;
in the figure: 1-bag dust collector I; 2-condenser I; 3-an electric furnace transformer I; 4-a stock bin I; 5-heating the electrode I; 6-electric furnace transformer II; 7-heating electrode II; 8-electric furnace transformer III; 9-a storage bin II; 10-heating electrode iii; 11-condenser III; 12-bag house III; 13-screw conveyor I; 14-an outer tube; 15-baffle I; 16-an inner tube; 17-baffle II; 18-slag ladle; 19-screw conveyor iii; 20-furnace bottom; 21-condenser II; 22-bag dust collector II; 23-product outlet I; 24-product outlet II; 25-product outlet III; 26-a metering valve I; 27-a metering valve II; 28-metering valve III; 29-spray gun I; 30-spray gun II; 31-spray gun III; 32-a feeding port; 33-screw conveyor II; 34-a flue stop valve I; 35-flue stop valve II; 36-flue stop valve III; 37-a slag outlet; 38-metal outlet.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the above-described examples.
Example 1: as shown in fig. 1, 2, 3 and 4, the smelting system for realizing continuous multi-section comprehensive recovery of lead anode slime is characterized in that: consists of a continuous non-isothermal heating smelting furnace and 3 product recovery systems;
the continuous non-isothermal heating smelting furnace is an integrated metallurgical furnace consisting of a first-stage low-temperature heating recovery furnace, a second-stage heating recovery furnace and a third-stage smelting production furnace, wherein the furnace bottoms 20 of the first-stage low-temperature heating recovery furnace, the second-stage heating recovery furnace and the third-stage smelting production furnace are sequentially communicated and are inclined planes which are continuously reduced, the self-flowing of materials can be realized, and the self-flowing inclination angle is 30 degrees; the product recovery system connected with the first-stage low-temperature heating recovery furnace comprises a condenser I2, a cloth bag dust collector I1 and a spiral conveyor I13, wherein a product outlet I23 is connected with the cloth bag dust collector I1 through the condenser I2, and the spiral conveyor I13 is arranged at an outlet below the cloth bag dust collector I1; the product recovery system connected with the second section of heating recovery furnace comprises a condenser II 21, a cloth bag dust collector II 22 and a spiral conveyor II 33, wherein a product outlet II is connected with the cloth bag dust collector II 22 through the condenser II 21, and the spiral conveyor II 33 is arranged at an outlet below the cloth bag dust collector II 22; the product recovery system connected with the third-stage smelting and producing furnace comprises a condenser III 11, a bag dust collector III 12 and a screw conveyer III 19, wherein a product outlet III 25 is connected with the bag dust collector III 12 through the condenser III 11, and the screw conveyer III 19 is arranged at an outlet below the bag dust collector III 12;
the first-stage low-temperature heating recovery furnace comprises a cylindrical furnace body I, an electric furnace transformer I3, a storage bin I4, a metering valve I26, a heating electrode I5, a material and compressed air spray gun I29, a product outlet I23 and a flue stop valve I34, wherein the spray gun I29 penetrates through the top of the cylindrical furnace body I and is arranged in the cylindrical furnace body I, the storage bin I4 is arranged at the top of the spray gun I and is communicated with the spray gun I, the metering valve I26 is arranged at the bottom of the storage bin I4, 3 heating electrodes I5 are circularly arranged around the spray gun I, one side of the upper part of the cylindrical furnace body I is provided with the product outlet I23, the flue stop valve I34 is arranged on the product outlet I23, the product outlet I23 is communicated with a product recovery system; the second section of heating recovery furnace comprises a cylindrical furnace body II, an electric furnace transformer II 6, a heating electrode II 7, a spray gun II 30, a feed port 32 and a product outlet II 24, wherein the feed port 32 is formed in the top of the cylindrical furnace body II, the spray gun II 30 penetrates through the top of the cylindrical furnace body II to be arranged in the cylindrical furnace body II, a metering valve II 27 is arranged on the spray gun II, 3 heating electrodes II 7 are circularly arranged around the spray gun II, a product outlet II 24 is formed in one side of the upper part of the cylindrical furnace body II, a flue stop valve II 35 is arranged on the product outlet II 24, the product outlet II 24 is connected with a product recovery system, and the electric furnace transformer II 6 is connected with the; the third-stage smelting production furnace comprises a cylindrical furnace body III, an electric furnace transformer III 8, a storage bin II 9, a heating electrode III 10, a product outlet III 25, a metering valve III 28, a spray gun III 31, a slag outlet 37 and a metal outlet 38, wherein the spray gun III 31 is arranged in the cylindrical furnace body III through the top of the cylindrical furnace body III, the metering valve III 28 is arranged at the joint of the storage bin II 9 and the spray gun III 31, the storage bin II 9 is arranged at the top end of the spray gun III 31 and communicated with the spray gun III, 3 heating electrodes III 10 are circularly arranged around the spray gun III, the product outlet III 25 is arranged on one side of the upper part of the cylindrical furnace body III, a flue stop valve III 36 is arranged on the product outlet III 25, the product outlet III 25 is connected with a product recovery system, the slag outlet 37 and the metal outlet 38 are arranged at the lower part of; the spray gun I is a spray gun with a double-layer cavity and comprises an outer pipe 14 and an inner pipe 16, the outer pipe 14 is sleeved outside the inner pipe 16, the inner pipe 16 is communicated with the storage bin I to convey raw materials, and the outer pipe 14 (outer-layer cavity) is connected with a compressed air pipeline to convey air; the spray gun III is a spray gun with a double-layer cavity and comprises an outer pipe and an inner pipe, the outer pipe is sleeved outside the inner pipe, the inner pipe is communicated with the bin I to convey raw materials, and the outer pipe is connected with a compressed air pipeline to convey air; a baffle I15 is arranged at the connecting section of the furnace bottoms of the first section of low-temperature heating recovery furnace and the second section of heating recovery furnace, a baffle II 17 is arranged at the connecting section of the furnace bottoms of the second section of heating recovery furnace and the third section of smelting production furnace, and the connecting section is coated with heat-insulating materials;
the product outlets of all the sections have the functions of providing gaseous volatilized metal product outlets and recycling the gaseous volatilized metal product outlets through a recycling system, the product outlets can be communicated and closed through a flue stop valve, and the ratio of the electrode center circle diameter of a heating electrode I, a heating electrode II or a heating electrode III to the furnace hearth diameter of the furnace body is 1: 1.3;
the transformer of each section of the electric furnace is key equipment for ensuring the heating temperature control of each section, the design of the transformer is to expand the range of the constant power section as much as possible, the adjustable amplitude of the secondary side voltage is not more than 5V, the accurate control of the temperature can be realized, and the capacity of the transformer is sequentially increased so as to meet the heating requirement of each section of the furnace body. The storage bin is used for storing materials, each metering valve can realize accurate control of metallurgical materials, and the double-layer spray gun can realize throwing of the metallurgical materials and introduction of compressed air and optimize metallurgical dynamic conditions. A feeding port arranged on the second section of furnace top can feed metallurgical auxiliary agents into the hearth according to requirements, and product recovery is facilitated. And a slag outlet and a metal outlet are formed in the wall of the third-stage hearth and are used for slag discharge and precious metal alloy discharge, and metallurgical processes such as slagging, volatilization, melting and the like can be completed in the third-stage smelting production furnace according to process requirements. The product recovery system composed of the condenser, the bag dust collector, the screw conveyer and the like can be used for recovering products in all sections, and can effectively purify the flue gas and discharge the flue gas after reaching the standard.
The main valuable elements in the lead anode mud are As, Sb, Bi, Pb, Au and Ag. In order to comprehensively recover the valuable elements, the method can be realized according to the following smelting method: (1) conveying the metallurgical materials prepared according to the process requirements to a storage bin I4 by using a multifunctional travelling crane, and opening a metering valve I26; the first-stage low-temperature heating recovery furnace is heated by closing the baffle I15, the prepared metallurgical materials are put into the furnace, compressed air is blown in from a spray gun I29 according to the carbon-oxygen ratio of the process, the temperature is controlled according to the material quality, the temperature is controlled at 450 ℃ and the temperature is controlled at 500 ℃, the materials are fully reacted, and pure As is obtained by cooling and recovering the materials through a material recovery system2O3The white arsenic is output by a screw conveyor I13 and conveyed to a white arsenic storage area of a finished product warehouse; (2) opening the baffle I15 to enable the materials to automatically flow to the second section heating recovery furnace, adding metallurgical auxiliary agents into the second section heating recovery furnace through the feeding port 32 according to needs, introducing compressed air through the spray gun II 30, heating the furnace materials at the constant temperature of 700 ℃ and 750 ℃ through the electric furnace transformer II 6, fully reacting, and cooling and recovering Sb through the material recovery system2O3The antimony white is output by a screw conveyor II 33 and conveyed to an antimony white storage area of a finished product warehouse; (3) opening a baffle II 17 to enable the materials to automatically flow to a third section of smelting production furnace, wherein the element trend needs to be arranged according to the components of the furnace materials in the furnace body of the section: firstly, if the Pb content in the furnace burden is high, a calcium-magnesium mixed reagent can be put into the furnace burden through a spray gun III 31 to deeply remove Bi, the Bi is discharged from a furnace slag outlet 37, the furnace slag is conveyed to a slag pool through a slag bag 18 for slag sealing treatment, after the slag discharge is finished and a slag hole is blocked, compressed air is introduced through the spray gun III 31 to realize blowing smelting of precious lead rich in gold and silver, the lead is cooled and recovered through a product recovery system in a PbO form, the lead is discharged through a screw conveyor III 19 and conveyed to a lead oxide storage area of a finished product warehouse, and the produced precious metal alloy is conveyed to a casting section from the slag bag 18 for casting and then is sent to electrolytic refining; secondly, if the Bi content in the furnace charge is high, a silicon dioxide flux can be thrown into the furnace charge from a spray gun III 31 to deeply remove Pb-made lead silicate slag, the lead silicate slag is discharged from a slag discharge hole (B), the lead silicate slag is conveyed to a slag pool through a slag ladle (18) for slag sealing treatment, and after the slag discharge is finished and a slag outlet 37 is blocked, gold and silver-rich slag is produced from a metal outlet 38Conveying the produced noble metal alloy from a slag ladle 18 to a casting section for casting, then sending the alloy to electrolytic refining to obtain cathode bismuth, recovering gold and silver from anode mud, and collecting dust generated by reaction through a product recovery system and then discharging the dust up to the standard.
The smelting system and the smelting method for realizing continuous multi-section comprehensive recovery of the lead anode slime overcome the defects in the pyrogenic process treatment process of the lead anode slime, and are mainly characterized in that:
(1) the system adopts three-section continuous non-isothermal heating, the heating temperature can be accurately regulated, the multi-section continuous comprehensive recovery of valuable elements in the lead anode slime is realized in one smelting furnace, and the product recovery system is powerful and reliable;
(2) the system integrates two metallurgical processes of reduction smelting, oxidation refining and the like in the traditional pyrogenic treatment process of the lead anode slime into the same smelting furnace for completion, so that the precious metal alloy meeting the electrolysis requirement is produced in one step, the energy consumption, the overflow of flue gas and potential safety hazard in the transfer process of molten metal are eliminated, and the environmental pollution is reduced;
(3) the raw material adaptability of the system is strong, the element trend can be reasonably arranged in the last heating section, the product scheme is adjusted according to the actual situation, the valuable metals in the lead anode slime are efficiently recovered, and the pyrometallurgical process is strengthened;
(4) the equipment system and the method have the advantages of simple operation, material self-flow, continuous production process, suitability for large-scale industrial production, convenience in management and the like.
Example 2: the structure of the device of the embodiment is the same as that of the device of the embodiment 1, and is different in that the furnace bottom gradient angle of the continuous non-isothermal heating smelting furnace is 25 degrees, and the ratio of the electrode center circle diameter of the heating electrode I, the heating electrode II or the heating electrode III to the furnace body hearth diameter is 1: 1.5.

Claims (5)

1. The utility model provides a realize continuous multistage smelting system who synthesizes recovery of lead anode mud which characterized in that: consists of a continuous non-isothermal heating smelting furnace and 3 product recovery systems;
the continuous non-isothermal heating smelting furnace is an integrated metallurgical furnace consisting of a first-stage low-temperature heating recovery furnace, a second-stage heating recovery furnace and a third-stage smelting output furnace, the furnace bottoms of the first-stage low-temperature heating recovery furnace, the second-stage heating recovery furnace and the third-stage smelting output furnace are sequentially communicated and are inclined planes which are continuously reduced, and 3 product recovery systems are respectively connected with the first-stage low-temperature heating recovery furnace, the second-stage heating recovery furnace and the third-stage smelting output furnace;
wherein, the first section of low-temperature heating recovery furnace comprises a cylindrical furnace body I, an electric furnace transformer I (3), a storage bin I (4) and a metering valve I (26), the device comprises a heating electrode I (5), a material and compressed air spray gun I (29), a product outlet I (23) and a flue stop valve I (34), wherein the spray gun I (29) penetrates through the top of a cylindrical furnace body I to be arranged in the cylindrical furnace body I, a storage bin I (4) is arranged at the top of the spray gun I and is communicated with the spray gun I, a metering valve I (26) is arranged at the bottom of the storage bin I (4), more than 3 heating electrodes I (5) are circularly arranged around the spray gun I, the product outlet I (23) is formed in one side of the upper part of the cylindrical furnace body I, the flue stop valve I (34) is arranged on the product outlet I (23), the product outlet I (23) is communicated with a product recovery system, and an electric furnace transformer I (3) is connected with;
the second section of heating recovery furnace comprises a cylindrical furnace body II, an electric furnace transformer II (6), a heating electrode II (7), a spray gun II (30), a feed port (32) and a product outlet II (24), wherein the feed port (32) is formed in the top of the cylindrical furnace body II, the spray gun II (30) penetrates through the top of the cylindrical furnace body II to be arranged in the cylindrical furnace body II, a metering valve II (27) is arranged on the spray gun II, more than 3 heating electrodes II (7) are circularly arranged around the spray gun II, the product outlet II (24) is formed in one side of the upper part of the cylindrical furnace body II, a flue stop valve II (35) is arranged on the product outlet II (24), the product outlet II (24) is connected with a product recovery system, and the electric furnace transformer II (6) is connected with the;
the third-stage smelting production furnace comprises a cylindrical furnace body III, an electric furnace transformer III (8), a storage bin II (9), a heating electrode III (10), a product outlet III (25), a metering valve III (28), a spray gun III (31), a slag outlet (37) and a metal outlet (38), wherein the spray gun III (31) passes through the top of the cylindrical furnace body III to be arranged in the cylindrical furnace body III, the metering valve III (28) is arranged at the joint of the storage bin II (9) and the spray gun III (31), the storage bin II (9) is arranged at the top end of the spray gun III (31) and communicated with the spray gun III (31), more than 3 heating electrodes III (10) are circularly arranged around the spray gun III, the product outlet III (25) is formed in one side of the upper part of the cylindrical furnace body, a stop valve flue (36) is arranged on the product outlet III (25), the product outlet III (25) is connected with a product recovery system, the slag, The metal outlet (38) is connected with the heating electrode III (10) through the electric furnace transformer III (8);
the spray gun I or the spray gun III is a spray gun with a double-layer cavity and comprises an outer pipe (14) and an inner pipe (16), the outer pipe (14) is sleeved outside the inner pipe (16), the inner pipe (16) is communicated with the storage bin I or the storage bin II to convey raw materials, and the outer pipe (14) is connected with a compressed air pipeline and used for conveying air;
the smelting method of the smelting system for realizing continuous multi-section comprehensive recovery of the lead anode slime comprises the following steps:
(1) crushing and drying the lead anode slime, wherein the water content of the lead anode slime is less than 2%;
(2) according to the chemical components and the treatment capacity of the arsenic, antimony, bismuth and lead metals in the lead anode mud, the carbon-oxygen ratio required by reaction recovery is obtained through metallurgical calculation, and the materials are mixed;
(3) and (3) heating at low temperature in the first section to recover arsenic in the lead anode slime: putting the metallurgical material prepared in the step (2) and compressed air into a first-stage low-temperature heating recovery furnace through a spray gun I, adjusting the furnace temperature to 450-500 ℃, and using As As the most arsenic in anode mud2O3The mixture is volatilized and recovered from a product outlet I, and other elements are left in furnace burden, and the self-flowing gradient angle is 20-35 degrees;
(4) opening the baffle I, allowing the material to automatically flow into a second-stage heating recovery furnace for second-stage heating recovery of antimony, adjusting the furnace temperature to 700-750 ℃, and adding a carbonaceous reducing agent into the furnace body through the feeding hole according to the furnace charge characteristics to ensure that Sb is not oxidized into Sb2O5To make it with Sb2O3Volatilizing, cooling and recovering; the self-flowing slope angle is 20-35 degrees;
(5) opening a baffle II, automatically flowing the furnace burden obtained in the step (4) into a third-stage smelting production furnace, spraying a slagging agent from a spray gun III to remove bismuth if the lead content is high, spraying oxygen-enriched air from the spray gun III to perform oxidation converting to produce alloy rich in gold and silver, adding the slagging agent to remove lead and produce molten crude bismuth if the bismuth content is high, and enriching noble metals into the crude bismuth to perform electrolytic refining.
2. The smelting system for realizing continuous multi-section comprehensive recovery of lead anode slime according to claim 1, characterized in that: the product recovery system connected with the first-stage low-temperature heating recovery furnace comprises a condenser I (2), a cloth bag dust collector I (1) and a spiral conveyor I (13), wherein a product outlet I (23) is connected with the cloth bag dust collector I (1) through the condenser I (2), and the spiral conveyor I (13) is arranged at an outlet below the cloth bag dust collector I (1); the product recovery system connected with the second section of heating recovery furnace comprises a condenser II (21), a cloth bag dust collector II (22) and a spiral conveyor II (33), wherein a product outlet II is connected with the cloth bag dust collector II (22) through the condenser II (21), and the spiral conveyor II (33) is arranged at an outlet below the cloth bag dust collector II (22); and the product recovery system connected with the third-stage smelting and producing furnace comprises a condenser III (11), a cloth bag dust collector III (12) and a screw conveyor III (19), a product outlet III (25) is connected with the cloth bag dust collector III (12) through the condenser III (11), and the screw conveyor III (19) is arranged at an outlet below the cloth bag dust collector III (12).
3. The smelting system for realizing continuous multi-section comprehensive recovery of lead anode slime according to claim 1, characterized in that: a baffle I (15) is arranged at the connecting section of the furnace bottom of the first section of low-temperature heating recovery furnace and the second section of heating recovery furnace, a baffle II (17) is arranged at the connecting section of the furnace bottom of the second section of heating recovery furnace and the third section of smelting production furnace, and the connecting section is coated with a heat-insulating material.
4. The smelting system for realizing continuous multi-section comprehensive recovery of lead anode slime according to claim 1, characterized in that: the furnace bottom gradient angle of the continuous non-isothermal heating smelting furnace is 20-35 degrees.
5. The smelting system for realizing continuous multi-section comprehensive recovery of lead anode slime according to claim 1, characterized in that: the ratio of the electrode center circle diameter of the heating electrode I, the heating electrode II or the heating electrode III to the furnace body hearth diameter is 1: 1.2-1.6.
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