CN116179868A - A method, device and application of lead-zinc smelting and rare precious metal recovery - Google Patents

Abstract

The invention provides a method for coordinating lead-zinc smelting with rare precious metal recovery, comprising the steps of: S1, providing a lead-zinc oxide melt and a lead-zinc oxide mixture; S2, driving the lead-zinc oxide by a reaction-promoting gas The melt, the lead-zinc oxide mixture and the electronic scrap are reacted in the reduction furnace to obtain slag, alloy and zinc-containing fume; and the composition and content of the alloy are controlled to trap rare and precious metals in the In the above alloy, wherein, the alloy contains 50-80% of Pb, 10-40% of Cu, 3-20% of Sb, and 1-15% of Sn. The invention can realize the directional capture of rare and precious metals by controlling the composition of the alloy.

Description

A method, device and application of lead-zinc smelting and rare precious metal recovery

technical field

The invention belongs to the field of rare and precious metal extraction, and in particular relates to a method, device and application of lead-zinc smelting and rare and precious metal recovery.

Background technique

Rare and precious metals in nature are generally associated with natural ores such as metal sulfide ore and oxide ore, but the content is low. Generally, they are distributed in the smoke and dust along with the smelting of the main metal in the ore through methods such as "ore mining-ore concentration-enrichment-metallurgical extraction-refining recovery" , slag and crude metal. According to the different properties of rare and precious metals, most of the rare and precious metals are enriched in crude metals during the smelting process and are separated and recovered in the refining process. However, it is inevitable that some rare and precious metals will enter the slag and smoke during the smelting process, resulting in difficulties in the recovery of rare and precious metals. drain.

With the popularization and application of electronic equipment such as communication in modern life, a considerable part of rare and precious metals are used to produce electronic components, circuit boards, etc., such as gold, silver, platinum, palladium, rhodium, etc., to increase the performance and stability of electronic equipment . With the update and iteration of technology, the obsolete period and service cycle of electronic equipment are continuously shortened. More and more waste electronic equipment is scrapped and awaits recycling. The content of rare and precious metals such as gold and silver is much higher than that in natural ores. The recovery of valuable (rare and precious) metals such as copper, tin, gold, and silver from urban minerals such as waste electronic components and circuit boards has attracted more and more attention from the state and enterprises. Rare and precious metals in urban minerals mostly exist in the state of individual metals or alloys, which are most suitable for direct melting and recycling in the pyrometallurgical process.

In the prior art, the fire method is often used to recover rare and precious metals. For example, in the flash smelting of copper sulfide concentrate and the smelting process of oxygen-enriched molten pool, a certain proportion of waste circuit boards are used to synergize in the matte phase (Cu ₂ S-FeS melt). Valuable metals such as copper and tin are pre-enriched, and then recovered in the subsequent reduction blowing process. However, metal copper, tin, etc. in the circuit board will be oxidized into a metal state in a strong oxidizing atmosphere, and part of it will enter the slag, causing losses; at the same time, matte has limited ability to capture rare and precious metals such as gold and silver.

Another example: during the smelting process of lead concentrate, rare and precious metals such as gold and silver associated in the concentrate are captured in the crude lead, and pure lead metal has limited ability to capture rare and precious metals such as gold, silver, platinum and palladium, and it is impossible to achieve efficient collaborative capture , and at this stage, the slag type of lead smelting furnace has a high solubility for rare and precious metals such as silver, which affects the further improvement of the recovery rate of rare and precious metals.

In view of this, it is necessary to provide a method, device and application of lead-zinc smelting in conjunction with recovery of rare and precious metals, so as to solve or at least alleviate the above-mentioned technical defects of the prior art that have low ability to capture rare and precious metals.

Contents of the invention

The main purpose of the present invention is to provide a method, device and application of lead-zinc smelting and recovery of rare and precious metals, aiming to solve the technical problem of the above-mentioned prior art with low capture capacity of rare and precious metals.

In order to achieve the above object, the present invention provides a method for coordinating lead-zinc smelting to recover rare and precious metals, comprising steps:

S1, providing lead-rich zinc oxide melt and lead-zinc oxide mixture;

S2, driving the lead-rich zinc oxide melt, the lead-zinc oxide mixture and electronic waste to react in a reduction furnace by a reaction-promoting gas to obtain slag, alloy and zinc-containing flue gas;

And control the content of Pb, Cu, Sb, Sn in the alloy, so as to trap rare and precious metals into the alloy; wherein, in terms of mass fraction, control the alloy to contain 50-80% of Pb, 10-80% of Cu 40%, Sb 3-20%, Sn 1-15%.

Further, the step S2 also includes: controlling the composition and content of the slag;

In terms of mass fraction, the slag is controlled to contain 15-50% of FeO, 10-30% of CaO, and 10-25% of _SiO2 ; 1.0 to 1.8.

Further, the method of obtaining the lead-rich zinc oxide melt includes: placing the metal sulfide ore, non-ferrous mining waste and the first flux in the oxidation furnace, and injecting oxygen into the oxidation furnace to obtain the obtained Described lead-rich zinc oxide melt.

Further, the metal sulfide ore includes one or more of lead metal sulfide ore, zinc metal sulfide ore and lead-zinc mixed sulfide ore;

The non-ferrous mining, dressing and smelting wastes include one or more of zinc leaching slag, copper-containing electroplating sludge, galvanizing sludge, lead-zinc-copper electrolytic refining anode sludge, lead filter cake and lead-zinc smelting blast furnace yellow slag.

Further, the method for obtaining the lead-zinc oxide mixture includes: uniformly mixing the solid oxide material, the reducing agent and the second flux to obtain the lead-zinc oxide mixture;

Wherein, the solid oxide material includes zinc-containing oxide ore, lead-containing oxide ore, copper-containing oxide ore, lead-containing soot, sub-zinc oxide soot, antimony trioxide soot, lead-zinc smelting dust removal sludge, lead-zinc-copper scum , cathode zinc scum, rectification furnace zinc slag, lead-silver slag, goethite slag, steel plant zinc-containing soot, hot-dip galvanizing process dust, zinc powder replacement precious metal sludge, waste zinc-manganese batteries and zinc-silver batteries one or more.

Further, the sources of electronic waste include waste computers, mobile phone circuit boards, waste electronic components, waste CPUs, graphics cards, sound cards, memory, capacitors, precious metal connectors, waste lead glass, and waste lithium-ion batteries. various;

The reaction-promoting gas includes one or more of coal gas, methane and hydrogen.

Further, both the lead-rich zinc oxide melt and the lead-zinc oxide mixture contain Pb, Zn, Cu, Sb, Sn, Fe, SiO ₂ and CaO.

The present invention also provides an oxidation-reduction device, which is used to realize the method for synergistic recovery of rare and precious metals in lead-zinc smelting as described in any one of the above.

Further, the redox device includes an oxidation furnace and a reduction furnace;

An oxidation furnace is formed in the oxidation furnace; the oxidation furnace is provided with a first spray gun that supplies gas to the oxidation furnace; the oxidation furnace is also provided with a first flue and a first feeding part; the first Both the flue and the first feeding part are communicated with the oxidation furnace;

A reduction furnace is formed in the reduction furnace; the bottom of the reduction furnace is communicated with the bottom of the oxidation furnace, and the bottom of the reduction furnace is lower than the bottom of the oxidation furnace;

The reduction furnace is provided with a second spray gun for supplying gas into the reduction furnace, and the reduction furnace is also provided with a second flue, a second feeding part, a slag discharge port and an alloy discharge port; the second flue , The second feeding part, the slag outlet and the alloy outlet are all connected to the reduction furnace, and the position of the slag outlet is higher than that of the alloy outlet.

The present invention also provides a method for recovering rare and precious metals as described above or an application of the redox device as described above in lead-zinc smelting.

Compared with the prior art, the present invention has the following advantages:

The invention provides a new recovery system for rare and precious metals, which can realize the simultaneous recovery of metals such as lead, zinc and copper, and efficiently capture and recover the rare and precious metals. The present invention is different from copper smelting and processing circuit boards, using matte copper and metal copper to pre-enrich/trap rare and precious metals; the present invention is also different from the reduction of crude lead in lead and other molten pools to capture and recover rare and precious metals.

The present invention generates Pb-Cu-Sb-Sn and other liquid alloys by controlling the composition of the alloy and slag, and forms good trapping phases of rare and precious metals such as gold, silver, platinum and palladium, and can capture the rare and precious metals in a directional and efficient manner; by controlling the slag The content of specific components in the slag forms a slag system with low solubility of rare and precious metals, which can minimize the dissolution and inclusion loss of rare and precious metals in the slag.

In addition, according to the different forms of rare and precious metals and impurity components in different primary ores and secondary resources, the present invention chooses to add them in the oxidation furnace or reduction furnace respectively, so that the removal of toxic and harmful substances and the recovery of rare and precious metals are more scientific and efficient.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention. For those skilled in the art, other drawings can also be obtained according to the structures shown in these drawings without creative effort.

Fig. 1 is a schematic structural diagram of a redox device in an embodiment of the present invention;

Fig. 2 is the physical figure after alloy cooling in the embodiment of the present invention 1;

Fig. 3 is a SEM image of the alloy in Comparative Example 1 of the present invention after cooling.

Reference signs: 1, the first feeding part; 2, the first spray gun; 3, the first flue; 4, the slagging outlet of the oxidation furnace accident; 5, the partition wall; 6, the second feeding part; 7, the second spray gun ; 8, the second flue; 9, zinc vapor condensing device; 10, alloy outlet; 11, alloy separation device; 12, slag outlet.

The realization of the purpose of the present invention, functional characteristics and advantages will be further described with reference to the accompanying drawings in combination with the implementation modes.

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the implementation manners in the present invention, all other implementation manners obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

Moreover, the technical solutions of the various embodiments of the present invention can be combined with each other, but it must be based on the realization of those skilled in the art. When the combination of technical solutions is contradictory or cannot be realized, it should be considered as a combination of technical solutions. Does not exist, nor is it within the scope of protection required by the present invention.

When the examples give numerical ranges, it should be understood that, unless otherwise stated in the present invention, the two endpoints of each numerical range and any value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention are consistent with those skilled in the art's grasp of the prior art and the description of the present invention, and methods, equipment, and materials similar to or used in the embodiments of the present invention can also be used. Any method, apparatus and material equivalent to the prior art to practice the present invention.

The invention provides a method for coordinating the recovery of rare and precious metals in lead-zinc smelting, comprising the steps of:

S1, providing lead-zinc oxide melts and lead-zinc oxide mixtures; wherein, the various metal elements in the lead-zinc oxide melts and lead-zinc oxide mixtures are partially or substantially all in an oxidized state.

In order to achieve effective capture of rare and precious metals, Pb, Zn, Cu, Sb, Sn, Fe, SiO ₂ and CaO can be contained in both the lead-zinc oxide melt and the lead-zinc oxide mixture, so as to facilitate the removal of slag and The composition content of the alloy is controlled.

In terms of mass fraction, the lead-rich zinc oxide melt can contain 5-25% of Pb, 1-35% of Zn, 3-20% of Cu, 0.5-5% of Sb, 0.5-5% of Sn, 8-45% of Fe, SiO ₂ 12-30%, CaO 5-18%.

In terms of mass fraction, the lead-zinc oxide mixture can contain 8-35% of Pb, 10-40% of Zn, 2-15% of Cu, 0.5-10% of Sb, 0.5-8% of Sn, 4-12% of Fe, SiO ₂ 3-8%, CaO 3-12%.

The way to obtain the lead-zinc oxide melt may include or be: mixing the metal sulfide ore, non-ferrous mining waste and the first flux into agglomerates, placing them in the oxidation furnace, and blowing oxygen into the oxidation furnace to Smelting raw materials, desulfurization and impurity removal, to obtain smelted lead-zinc oxide melt and smelting flue gas discharged through the flue; the first flux can include or be one or more of quartz stone, limestone, sodium salt, etc. kind.

Among them, the oxidation furnace can be top-blown/side-blown/bottom-blown oxygen-enriched enhanced molten pool melting furnace, flash melting furnace, reverberatory furnace, etc.; the melting temperature can be 900-1300°C, and the melting time can be 0.5-2h.

By using metal sulfide ore and non-ferrous mining wastes as raw materials for the lead-zinc oxide melt, not only can the corresponding components be provided to the lead-zinc oxide melt, but also the high temperature and oxygen-enriched Conditions, oxidation, decomposition, removal of sulfur, organic matter, fluorine, chlorine and other components in the raw material, so that the lead-rich zinc oxide melt used to capture rare and precious metals is obtained during the smelting process.

It should be pointed out that metal sulfide ores usually contain one or more of various elements such as lead, zinc, copper, antimony, tin, sulfur, iron, silicon, calcium, etc.; metal sulfide ores may include or be lead metal sulfide ores One or more of zinc metal sulfide ore and lead-zinc mixed sulfide ore; although the metal sulfide ore involved in the present invention is mainly lead-zinc mineral, metal sulfide ore usually contains other metals in addition to lead-zinc Elements such as copper, antimony, tin, etc.

Non-ferrous mining, dressing and smelting wastes may include or be zinc leaching residues such as ferrosite slag in hydrometallurgy system, copper-containing electroplating sludge, galvanizing sludge, lead/zinc/copper electrolytic refining anode sludge, lead filter cake and lead-zinc smelting One or more of blast furnace yellow slag. In addition to metal elements, non-ferrous mining, dressing and smelting waste usually contains sulfur, sulfate and organic matter.

The way to obtain the lead-zinc oxide mixture may include or include: mixing the solid oxide material with a reducing agent and a second flux to form agglomerates to obtain the lead-zinc oxide mixture.

Among them, the solid oxide material may contain Zn, Pb, Cu, Sb, Sn, Fe, CaO, SiO ₂ , and each metal element therein may partially or substantially all exist in an oxidized state; the solid oxide material may include or be Zinc-containing oxide ore, lead-containing oxide ore, copper-containing oxide ore, lead-containing soot, sub-zinc oxide soot, antimony trioxide soot (antimony white), lead-zinc smelting dust removal sludge, lead-zinc-copper scum, cathode zinc float One or more of slag, rectification furnace zinc slag, lead-silver slag, goethite slag, steel plant zinc-containing soot, hot-dip galvanizing process dust, zinc powder replacement precious metal sludge, waste zinc-manganese battery and zinc-silver battery kind.

The reducing agent may include or be one or more of coke and pulverized coal; the second flux may include or be one or more of quartz stone, limestone and sodium salt.

S2, drive the lead-zinc oxide melt, the lead-zinc oxide mixture and electronic waste to react in the reduction furnace through the reaction-promoting gas to obtain slag, alloy and zinc-containing flue gas; when not cooled, neither the slag nor the alloy Liquid, and the alloy is a crude alloy.

The specific implementation process can be as follows: introducing the lead-rich zinc oxide melt (hot state) into the reduction furnace, and then adding the lead-zinc oxide mixture to the reduction furnace; after that, blowing a reaction-promoting gas into the reduction furnace; and In the early stage of blowing the reaction-promoting gas, the electronic waste is sprayed into the reduction furnace along with the reaction-promoting gas; the lead-rich zinc oxide melt can be introduced into the reduction furnace at one time or continuously. When the lead-rich zinc oxide melt is continuously introduced into the reduction furnace, after part of the lead-rich zinc oxide melt enters the reduction furnace, the lead-zinc oxide mixture can be added to the reduction furnace.

Among them, the reduction furnace can be top-blown/side-blown/bottom-blown molten pool reduction furnace, electric furnace, reverberatory reduction furnace, converter reduction furnace, blast reduction furnace, etc. The temperature of the reaction in the reduction furnace can be 1000-1400° C.; the duration of the reaction in the reduction furnace can be 1-3 hours.

It should be pointed out that the present invention needs to control the composition and content of the alloy, so as to capture the rare and precious metals into the alloy, so as to realize the directional distribution of the rare and precious metals. Furthermore, the present invention can also control the content of specific components in the slag, form a slag system with low solubility of rare and precious metals, and minimize the dissolution and inclusion loss of rare and precious metals in the slag.

The rare metal in the present invention may include or be one or more of gold, silver, platinum, palladium, indium, tungsten, molybdenum, rhenium and the like.

In the present invention, the main source of rare and precious metals can be electronic waste, and secondly, it can also come from lead-rich zinc oxide melt and lead-zinc oxide mixture. That is, the rare and precious metals can be derived from one or more of electronic scrap, lead-zinc oxide melt and lead-zinc oxide mixture.

Specifically, in addition to rare and precious metals contained in electronic waste, metal sulfide ores and non-ferrous mining and dressing wastes may also contain rare and precious metals. The rare and precious metals in metal sulfides and non-ferrous mining and dressing wastes are melted in lead-rich Zinc oxide melt, and then into the reduction furnace was trapped into the alloy. In addition, the solid oxide material can also have rare precious metals and can be trapped into the alloy in the reduction furnace. In this way, rare and precious metals can be derived from one or more of electronic waste, metal sulfide ore, non-ferrous mining and dressing waste, and solid oxide materials.

The invention can adjust the addition amount of lead-zinc oxide melt and lead-zinc oxide mixture, the addition amount of metal sulfide ore, non-ferrous mining and dressing waste and solid oxide material, and the type of reaction-promoting gas through sampling detection. One or more of the various ways to regulate the composition and content of slag and alloy, so that rare and precious metals are trapped directly in the alloy.

Specifically, in terms of mass fraction, the present invention needs to control the alloy to contain 50-80% of Pb, 10-40% of Cu, 3-20% of Sb, and 1-15% of Sn; Alloys generally also contain 3-15% (mass fraction) of Zn, forming an alloy system together with Pb, Cu, Sb, and Sn.

In terms of mass fraction, the present invention can also control the slag to contain 15-50% of FeO, 10-30% of CaO, and 10-25% of _SiO2 ; 1.0 to 1.8.

Among them, those skilled in the art should understand that FeO refers to the total iron in the slag and is calculated in the form of FeO; the calcium in the calcium-silicon mass ratio refers to the total calcium oxide content in the slag; the iron in the iron-silicon mass ratio refers to the slag The total iron content in; the silicon in the calcium-silicon mass ratio and the iron-silicon mass ratio refers to the content of silicon dioxide.

As a description of electronic waste, electronic waste is urban minerals containing one or more rare and precious metals such as copper, tin, antimony, indium, tungsten, molybdenum, gold, silver, platinum, palladium, etc., which can be used as powder in the present invention The form exists to facilitate the injection of electronic waste. Specific sources of electronic waste can include one or more of waste computers, mobile phone circuit boards, waste electronic components, waste CPUs, graphics cards, sound cards, memory, capacitors, precious metal connectors, waste lead glass, and waste lithium-ion batteries.

As a description of the reaction-promoting gas, the reaction-promoting gas has reducing properties, and may specifically include or be one or more of reducing gases such as coal gas, methane, and hydrogen; wherein, the reaction-promoting gas cannot be non-reducing gases such as air .

The reaction-promoting gas can be sprayed into the furnace through the top, bottom or side spray guns of the reduction furnace, thereby stirring the molten pool, enhancing mass transfer and heat transfer, and driving the reduction reaction to proceed rapidly.

As a supplementary description to the present invention, in the reduction furnace, the alloy is located below the slag, and the alloy (uncooled) produced in the reduction furnace can be introduced into the alloy separation device 11, and then the alloy is separated by gradient temperature control, and then refined and recovered separately. The temperature range of the rare metal and alloy separating device 11 can be 328-1100° C., and the separation and putting time can be 1-4 hours.

And, because there is volatile zinc in the zinc-containing fume, and sometimes contains volatile rare precious metals, in order to collect zinc and volatile rare precious metals, the zinc-containing fume can be collected in the zinc vapor condensing device 9, so that The volatilized zinc vapor and other volatile rare and precious metals enter the condensing device to capture and recover metal zinc and rare and precious metals. In addition, the slag produced in the reduction furnace (uncooled) can be introduced into the slag treatment furnace to further deplete the slag.

In the present invention, by controlling the composition content of the alloy and the slag, the rare and precious metals can be directionally captured into the alloy liquid, thereby realizing efficient recovery of the rare and precious metals and other metal elements. Moreover, the present invention combines lead-zinc smelting with the capture of rare and precious metals, which not only ensures the composition and content of alloys and slag, but also completes the capture of rare and precious metals in lead-zinc minerals and the smelting of lead-zinc and other minerals. and related metal collections.

In addition, in addition to electronic waste, secondary resources such as lead and zinc, such as hydrometallurgy zinc slag, copper-containing electroplating sludge, galvanized sludge, lead/zinc/copper electrolytic refining anode slime and other non-ferrous mining and dressing waste and zinc Oxidized solid materials such as powder replacement precious metal sludge, waste zinc-manganese batteries, zinc-silver batteries, etc. also contain rich rare and precious metal resources. However, there are few technical research reports on the recovery of rare and precious metals from such resources at home and abroad. Therefore, the present invention can also achieve the effect of trapping rare and precious metals in non-ferrous mining, dressing and smelting waste and solid oxide materials, so that the present invention has great comprehensive application value.

The present invention also provides an oxidation-reduction device, which is used to realize the method for coordinating lead-zinc smelting and recovery of rare and precious metals according to any of the above-mentioned embodiments, thereby facilitating the industrial application of the above-mentioned method for recovering rare and precious metals.

As an example, as shown in FIG. 1 , the redox device includes an oxidation furnace and a reduction furnace.

An oxidation hearth is formed in the oxidation furnace; the oxidation furnace is provided with a plurality of first spray guns 2 that supply gas to the oxidation furnace. The bottom of the hearth is set.

The oxidation furnace is also provided with a first flue 3 and a first charging part 1, and the first flue 3 and the first charging part 1 are all communicated with the oxidation furnace; the first flue 3 can be understood as an oxidation furnace flue, and the first The smoke inlet of the flue 3 can be communicated with the top of the oxidation furnace; the first feeding part 1 can be understood as an oxidation furnace feeding port or an oxidation furnace feeding nozzle, and the first charging part 1 can be arranged on the top of the oxidation furnace.

The oxidation furnace can also be provided with an accidental slagging outlet 4 for the oxidation furnace, and a valve body can be installed at the accidental slagging outlet 4 for the oxidation furnace, and the accidental slagging outlet 4 for the oxidation furnace can be arranged near the bottom of the oxidation furnace.

A reduction furnace is formed in the reduction furnace, the bottom of the reduction furnace and the bottom of the oxidation furnace can be directly or indirectly connected, and the bottom position of the reduction furnace is lower than the bottom position of the oxidation furnace; the reduction furnace can be set far away from the first charging part 1 to avoid The material in the oxidation furnace enters the reduction furnace too quickly.

As a specific embodiment, the reduction furnace and the oxidation furnace can be connected through a closed chute, the top of the closed chute is connected to the bottom of the oxidation furnace, the bottom of the closed chute is connected to the oxidation furnace, and an annular heating assembly can be arranged on the closed chute , to heat the melt entering the closed chute and avoid its cooling.

As another specific embodiment, a partition wall 5 may be provided between the reduction furnace and the oxidation furnace, that is, the partition wall 5 serves as the furnace wall of the reduction furnace and the oxidation furnace at the same time, so that the reduction furnace and the oxidation furnace are horizontally separated by the partition wall 5. , The partition wall 5 can be a partition wall 5 with a copper water jacket.

The bottom of the oxidation furnace extends from the end close to the reduction furnace to the bottom of the reduction furnace, forming an extension until it connects with the bottom of the reduction furnace. The vertical height of the extension can be 0-2m or 1-2m, that is, the bottom of the oxidation furnace and The bottom of the reduction furnace may have a height difference of 0-2m or 1-2m; for the convenience of description, the height of the extension section may not be included in the height of the bottom of the reduction furnace.

There is a gap between the partition wall 5 and the bottom of the reduction furnace, so that the melt in the oxidation furnace enters the reduction furnace from the bottom of the oxidation furnace, that is, the partition wall 5 and the junction (the bottom junction of the reduction furnace and the oxidation furnace) have The gap forms a melt channel for the melt to enter the reduction furnace from the oxidation furnace; the partition wall 5 can be located above the junction.

The reduction furnace is provided with a plurality of second spray guns 7 for supplying gas into the reduction furnace. The second spray guns 7 can be immersion spray guns in the melting pool of the reduction furnace, and can be arranged on the side of the reduction furnace and can be installed near the bottom of the reduction furnace.

The reduction furnace is also provided with a second flue 8, a second feeding part 6, a slag outlet 12 and an alloy outlet 10; wherein, the second flue 8, the second feeding part 6, the slag outlet 12 and the alloy outlet 10 They are all connected to the reduction furnace.

The second flue 8 can be a straight-up flue of the reduction furnace, the smoke inlet of the second flue 8 can be communicated with the top of the reduction furnace, and the smoke outlet of the second flue 8 can be communicated with the zinc vapor condensing device 9 Setting; the second charging part 6 can be a reducing furnace charging port or a reducing furnace charging nozzle, and the second charging part 6 can be arranged on the top of the reducing furnace; the position of the slag discharge port 12 can be higher than the position of the alloy discharge port 10, and the The position of the port 12 can also be higher than the position of the second spray gun 7; the alloy discharge port 10 can be communicated with the alloy separating device 11 and arranged.

The working mode of the above redox device can be:

Throw metal sulfide ore, non-ferrous mining, dressing and smelting waste and the first flux into the oxidation furnace from the first feeding part 1, and inject oxygen into the oxidation furnace through the first spray gun 2 to obtain lead-zinc oxide melt and smelting fume The smelting flue gas is discharged from the first flue 3, and the hot lead-zinc oxide melt flows into the reduction furnace from the melt channel.

Put the lead-zinc oxide mixture into the reduction furnace from the second feeding part 6, and spray reaction-promoting gas and electronic waste into the reduction furnace through the second spray gun 7; and after the electronic waste is completely sprayed into the reduction furnace, continue to reduce The reaction-promoting gas is injected into the furnace to generate alloy, slag and zinc-containing fume in the reduction furnace.

The uncooled alloy enters the alloy separating device 11 through the alloy outlet 10, the uncooled slag enters the slag treatment furnace through the slag outlet 12, and the zinc-containing flue gas enters the zinc vapor condensing device 9 through the second flue 8.

Since the above-mentioned rare and precious metal recovery method and redox device can smelt lead and zinc, and can remove impurities and capture rare and precious metals and other metals in minerals in the process of lead and zinc smelting, the present invention also provides a method as described above. The method for recovering rare and precious metals in the embodiment or the application of the redox device in any of the above embodiments in lead-zinc smelting.

The following are specific examples of the present invention:

Example 1

1. Put the metal sulfide ore, non-ferrous mining and dressing waste and the first flux into the oxidation furnace after mixing and agglomerating; the total mass of the metal sulfide ore, non-ferrous mining and dressing waste and the first flux is 500g; among them, the first flux The mass is 35g.

In this embodiment, the metal sulfide ore is lead-antimony mixed sulfide ore and copper-containing zinc sulfide ore; non-ferrous mining and dressing waste is lead electrolysis anode slime and ferrite slag; the first flux is quartz stone.

Control the reaction temperature in the oxidation furnace to 1150°C, and oxidize, desulfurize and remove impurities for 45 minutes under the condition of 80% oxygen enrichment (flow rate: 500mL/min), to obtain the smelted lead-rich zinc oxide melt.

In terms of mass fraction, the lead-rich zinc oxide melt mainly contains: Pb 24.8%, Zn 10.7%, Cu 6.4%, Sb 1.9%, Sn 0.7%, Fe 25.9%, SiO ₂ 12.1%, CaO 7.6%.

2. Put the hot lead-zinc oxide melt in the reduction furnace, then mix the solid oxide material, reducing agent, and the second flux to form a block, and then add it to the reduction furnace as a lead-zinc oxide mixture; lead-zinc oxidation The total mass of the compound mixture is 100g; wherein, the mass of the reducing agent is 12g, and the mass of the second flux is 5g.

In terms of mass fraction, the lead-zinc oxide mixture mainly contains: Pb 12%, Zn 35%, Cu 3.9%, Sb 2.6%, Sn 1.5%, Fe 8%, SiO ₂ 7%, CaO 8%.

In this embodiment, the solid oxide material is copper-containing lead oxide ore, zinc suboxide soot, lead-silver slag and antimony white; the reducing agent is pulverized coal; the second flux is quartz stone and limestone.

Use methane gas as the reaction-promoting gas, and use the reaction-promoting gas as the carrier to spray 100g of waste circuit board powder into the reduction furnace; after spraying the waste circuit board powder into the reduction furnace, continue to inject methane gas to make the reduction reaction continue Carried out, generating slag, alloy and flue gas.

Wherein, the flow rate of methane gas is 350mL/min, the temperature of the reduction reaction is 1250°C, and the duration of the reduction reaction is 1.5h.

After the reaction is completed, the slag and alloy are detected:

Calculated by mass fraction, the main components in the obtained slag are FeO 41.6%, CaO 19.1%, SiO ₂ 24.7%, Na ₂ O 2.4%, Al ₂ O ₃ 2.7%.

According to the mass fraction, the main components in the obtained alloy are Pb 72.6%, Cu 17.1%, Sb 4.2%, Sn 1.8%, Zn 3.5%.

As shown in Figure 2, in the cooled alloy, lead and copper intercalate and intermelt, and together with antimony, tin and other metals form a high-quality collector of rare and precious metals.

Through analysis and calculation, in this embodiment, the recovery rates of lead, copper, antimony, tin, gold and silver are respectively 91.6%, 90.2%, 89.3%, 91.4%, 99.1%, 98.2%; the separation rate of zinc is 92.6%. Among them, the recovery rate: the ratio of the mass of a certain metal in the alloy to its original total mass; the zinc separation rate: the ratio of the sum of the mass of zinc in the flue gas and the alloy to the original total mass of zinc, that is, it is separated from the slag The ratio of zinc in total zinc.

Comparative example 1

Compared with Example 1 in this comparative example, only the reaction-promoting gas was adjusted to air, and other conditions were kept consistent with Example 1.

In terms of mass fraction, in this comparative example, the main components of the obtained slag are FeO 38.3%, CaO 9.5%, SiO ₂ 14.4%, Zn 9.2%, Pb 2.5%; other components are basically Na ₂ O 1.4%, Al ₂ O ₃ 0.4% and other metal oxides such as lead, zinc and magnesium.

In terms of mass fraction, in this comparative example, the main components in the obtained alloy are 83.5% of Pb, 12.8% of Cu, 1.1% of Sb, 0.4% of Sn, and 2.1% of Zn.

As shown in Figure 3, in this comparative example, the alloy is mainly composed of lead and copper, and the contents of other components are reduced.

After analysis and calculation: in this comparative example, the recovery rates of lead, copper, antimony, tin, gold and silver are 85.9%, 87.4%, 70.3%, 80.6%, 86.4%, 88.3% respectively; the separation rate of zinc is 75.7%. Among them, the recovery rate: the ratio of the mass of a certain metal in the alloy to its original total mass; the zinc separation rate: the ratio of the sum of the mass of zinc in the flue gas and the alloy to the original total mass of zinc, that is, it is separated from the slag The ratio of zinc in total zinc.

Comparing Comparative Example 1 with Example 1, it can be found that the composition of slag and alloy can be regulated by adjusting the reaction-promoting gas, thereby improving the collection efficiency of rare and precious metals.

Among the above-mentioned technical solutions of the present invention, the above are only preferred embodiments of the present invention, and therefore do not limit the patent scope of the present invention. Under the technical conception of the present invention, the equivalent structural transformations made by utilizing the description of the present invention and the contents of the accompanying drawings , or directly/indirectly used in other related technical fields are included in the patent protection scope of the present invention.

Claims (10)

1. A method for lead-zinc smelting and rare precious metal recovery, characterized in that it comprises steps: S1, providing lead-rich zinc oxide melt and lead-zinc oxide mixture; S2, driving the lead-rich zinc oxide melt, the lead-zinc oxide mixture and electronic waste to react in a reduction furnace by a reaction-promoting gas to obtain slag, alloy and zinc-containing flue gas; And control the content of Pb, Cu, Sb, Sn in the alloy, so as to trap rare and precious metals into the alloy; wherein, in terms of mass fraction, control the alloy to contain 50-80% of Pb, 10-80% of Cu 40%, Sb 3-20%, Sn 1-15%. 2. The method according to claim 1, characterized in that the step S2 further comprises: controlling the composition and content of the slag; In terms of mass fraction, the slag is controlled to contain 15-50% of FeO, 10-30% of CaO, and 10-25% of _SiO2 ; 1.0 to 1.8. 3. The method of lead-zinc smelting and recovery of rare and precious metals according to claim 1, characterized in that the method of obtaining the lead-rich zinc oxide melt comprises: metal sulfide ore, non-ferrous mining and dressing waste and the first The flux is placed in an oxidation furnace, and oxygen is injected into the oxidation furnace to obtain the lead-rich zinc oxide melt. 4. The method of lead-zinc smelting and rare precious metal recovery according to claim 3, wherein the metal sulfide ore comprises one or more of lead metal sulfide ore, zinc metal sulfide ore and lead-zinc mixed sulfide ore kind; The non-ferrous mining, dressing and smelting wastes include one or more of zinc leaching slag, copper-containing electroplating sludge, galvanizing sludge, lead-zinc-copper electrolytic refining anode sludge, lead filter cake and lead-zinc smelting blast furnace yellow slag. 5. The method for lead-zinc smelting and recovery of rare and precious metals according to claim 1, characterized in that the method of obtaining the lead-zinc oxide mixture comprises: mixing the solid oxide material, reducing agent and second flux, Obtain the lead-zinc oxide mixture; Wherein, the solid oxide material includes zinc-containing oxide ore, lead-containing oxide ore, copper-containing oxide ore, lead-containing soot, sub-zinc oxide soot, antimony trioxide soot, lead-zinc smelting dust removal sludge, lead-zinc-copper scum , cathode zinc scum, rectification furnace zinc slag, lead-silver slag, goethite slag, steel plant zinc-containing soot, hot-dip galvanizing process dust, zinc powder replacement precious metal sludge, waste zinc-manganese batteries and zinc-silver batteries one or more. 6. The method of lead-zinc smelting in collaboration with rare and precious metal recovery according to claim 1, characterized in that the sources of electronic waste include waste computers, mobile phone circuit boards, waste electronic components, waste CPUs, graphics cards, sound cards, memory One or more of capacitors, precious metal connectors, waste lead glass and waste lithium-ion batteries; The reaction-promoting gas includes one or more of coal gas, methane and hydrogen. 7. The method according to any one of claims 1-6, characterized in that the lead-zinc oxide melt and the lead-zinc oxide mixture both contain Pb , Zn, Cu, Sb, Sn, Fe, SiO ₂ and CaO. 8. An oxidation-reduction device, characterized in that the oxidation-reduction device is used to realize the method for synergistic recovery of rare and precious metals in lead-zinc smelting according to any one of claims 1-7. 9. The redox device according to claim 8, comprising an oxidation furnace and a reduction furnace; An oxidation furnace is formed in the oxidation furnace; the oxidation furnace is provided with a first spray gun that supplies gas to the oxidation furnace; the oxidation furnace is also provided with a first flue and a first feeding part; the first Both the flue and the first feeding part are communicated with the oxidation furnace; A reduction furnace is formed in the reduction furnace; the bottom of the reduction furnace is communicated with the bottom of the oxidation furnace, and the bottom of the reduction furnace is lower than the bottom of the oxidation furnace; The reduction furnace is provided with a second spray gun for supplying gas into the reduction furnace, and the reduction furnace is also provided with a second flue, a second feeding part, a slag discharge port and an alloy discharge port; the second flue , The second feeding part, the slag outlet and the alloy outlet are all connected to the reduction furnace, and the position of the slag outlet is higher than that of the alloy outlet. 10. A method for recovering rare and precious metals according to any one of claims 1-7 or an application of the redox device according to any one of claims 8-9 in lead-zinc smelting.

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