Antimony-containing material low-carbon collaborative smelting method

Abstract

The invention discloses a low-carbon collaborative smelting method for an antimony-containing material, which adopts a technical route of oxygen-enriched side-blown smelting, oxygen-enriched side-blown reduction and top-blown oxidative volatilization to treat a mixed material of antimony concentrate and high-antimony anode slime, and adopts a mode of mixed blowing of a powdery raw material and oxygen-enriched air to prepare the low-carbon collaborative smelting method for the antimony-containing material. Compared with the prior art, reaction kinetic conditions of materials and oxygen when the materials are fed into the furnace are enhanced, advanced volatilization of sulfides and generation of antimony matte are effectively restrained, chemical reaction heat is fully absorbed by melt, heat excess in the smelting process is achieved, high-proportion antimony-containing secondary materials can be treated through the part of heat, and multi-material synergistic self-heating smelting is achieved. And meanwhile, Au and Ag are collected through crude antimony metal generated through reduction, high-quality antimony bletilla and high-concentration precious metal alloy can be produced through volatilization blowing, and short-process recovery of precious metal elements is achieved. The method is a brand-new technical route for widening the application range of raw materials, reducing cost and improving efficiency in antimony smelting plants.

Description

Technical Field

[0001] The invention belongs to the field of nonferrous metal smelting, and in particular relates to a method for low-carbon coordinated smelting of antimony-containing materials. Background Art

[0002] Antimony is an important strategic metal resource, and my country ranks first in the world in terms of antimony reserves and production. Primary antimony ores are divided into two categories: sulfide ores and oxide ores, of which sulfide ores represented by stibnite are the main ones. In the past five years, the output of antimony ores has been declining year by year, and the supply of antimony resources has become increasingly tight. It is urgent to develop low-carbon synergistic smelting technology for primary minerals and antimony-containing polymetallic resources.

[0003] Fire smelting is the dominant method for smelting antimony concentrate, and the representative treatment process is Sb 2 S 3 Blast furnace volatilization smelting-reverberatory furnace reduction process. The general process of this process is to mix the antimony concentrate with the flux and granulate it into a blast furnace, and then volatilize and smelt it in a reducing atmosphere. 2 S 3 and Sb 2 O 3 The volatile vapor pressure is relatively large, most of it enters the smoke and forms antimony oxide powder, and some Sb 2 S 3 With Sb 2 O 3 The metal Sb is generated by the interaction and sinks to form a coarse antimony phase in the lower layer. 2 S 3 The antimony matte phase is located in the middle layer, and the calcium flux and SiO 2 The slag is formed by the gangue component and floats on the upper layer of the molten pool. The blast furnace volatilization antimony smelting has a history of 60 years in my country. Due to its advantages such as strong raw material adaptability, high metal recovery rate and easy operation, it is still the main process for antimony concentrate smelting. However, this process also has many disadvantages, such as the consumption of a large amount of coke in the smelting process and high cost; low oxygen concentration and large flue gas volume, resulting in low-concentration SO 2 It is difficult to recycle and the heat loss of flue gas is large. Smelting in a reducing atmosphere will cause a large amount of Sb 2 S 3 The sulfur directly evaporates and undergoes secondary oxidation in the upper flue gas. The chemical heat of the sulfur reaction fails to effectively heat the molten pool. At the same time, a large amount of antimony matte with high iron content and low antimony content is produced, which needs to be cooled and returned to the ingredients, resulting in ineffective circulation in the system.

[0004] The technical personnel in the industry have conducted a lot of research on the improvement of antimony concentrate smelting technology, and have made some progress in replacing the blast furnace process with molten pool smelting. Since molten pool smelting can use high-concentration oxygen-rich air, SO 2There is a problem of acid production, but the current molten pool smelting experiments mostly adopt a reaction mechanism similar to that of the blast furnace, that is, a volatilization smelting process route, in which Sb is enriched in the smoke under a neutral or weakly reducing atmosphere. Under this condition, the production and invalid circulation of antimony matte are still inevitable. At the same time, a certain amount of As element is usually associated with antimony concentrate, which will also be enriched in the smoke in the form of oxides during the volatilization process, which will have an adverse effect on the subsequent crude antimony preparation.

[0005] Lead-antimony mixed ore is also a common antimony metal resource. At present, there is a mature molten pool smelting process to extract the Pb metal from it. The Sb element is enriched in the electrolytically refined anode mud, of which the Sb content is as high as 60% or more, and it also contains a large amount of precious metals such as Ag. At present, the common treatment process for high-antimony anode mud is to use a blast furnace to reduce it to form a precious alloy, and then use a reverberatory furnace to remove antimony to further enrich the precious metals. Since the anode mud does not contain combustible sulfur, the smelting process has high energy consumption. At the same time, the reverberatory furnace refining process has low smelting intensity and poor operating conditions. It is urgent to develop a low-carbon enhanced smelting technology to comprehensively recover Sb, Ag and other metals in the anode mud. Summary of the invention

[0006] The object of the present invention is to provide a method for low-carbon coordinated smelting of antimony-containing materials, based on the redox reaction principle of antimony sulfide concentrate and high-antimony anode mud and the melting characteristics of multi-component slag system, and using oxygen-enriched molten pool enhanced smelting process to replace the traditional blast furnace process, so as to realize the coordinated autothermal smelting of primary antimony concentrate and complex antimony-containing secondary resources and comprehensive recovery of multiple metals.

[0007] The present invention provides a method for low-carbon collaborative smelting of antimony-containing materials, comprising the following steps:

[0008] S1. The antimony concentrate and the high antimony anode mud are mixed, dried, ball-milled, and then added to a smelting furnace for smelting to obtain smelting slag, smoke 1 and flue gas 1;

[0009] S2. The smelting slag obtained in step S1 is added to a reduction furnace for reduction blowing to obtain crude antimony, reduction slag, smoke 2 and flue gas 2;

[0010] S3. Add the crude antimony obtained in step S2 into a blowing furnace for oxidative volatilization blowing to obtain precious alloys, Sb 2 O 3 Dust, slag and flue gas3.

[0011] Furthermore, in step S1, the antimony concentrate contains 30-50% Sb, 5-20% Fe, 25-35% S, ≤0.2% Pb, ≤1.5% As, and the high antimony anode mud contains 60-65% Sb, 10-13% Pb, 2-5% As, and 2-5% Ag;

[0012] The mixing ratio of the antimony concentrate and the high antimony anode mud is 1:(0.5-1); after the antimony concentrate and the high antimony anode mud are mixed, they are first dried to a moisture content of less than 0.5%, then finely ground by a ball mill to a particle size of less than 75 μm, and finally sprayed into an oxygen-enriched side-blowing molten pool smelting furnace through the inner tube of a side-blowing spray gun for smelting.

[0013] The smelting process conditions are: oxygen is blown into the outer tube of the side-blowing lance, the oxygen concentration is 30-80%, and the oxygen-to-material ratio is 280-320Nm 3 / t; at the same time, limestone flux is added to make slag, and the flux rate is 8-10%; the smelting temperature is 1100-1200℃, and the smelting time is 2-2.5h.

[0014] The smelting slag contains antimony and precious metal elements, specifically Sb45-50%, As<0.2%, Ag>1.5%, Au>100g / t, and the basic slag system of the smelting slag is Sb 2 O 4 -Fe 2 O 3 -CaO-SiO 2 Quaternary system, in which CaO / Fe 2 O 3 The mass ratio is controlled at 0.2-0.3, CaO / SiO 2 The mass ratio is controlled at 2 to 2.5; the smoke 1 includes oxides of As, Pb, and Sb; the flue gas 1 includes sulfur dioxide, and acid is produced after waste heat recovery, dust collection, and purification.

[0015] Furthermore, in step S2, the reduction furnace is a side-blown reduction smelting furnace; the process conditions of the reduction blowing are: introducing oxygen-enriched air, the oxygen concentration is 40-60%, the oxygen excess coefficient is 0.75-0.85; the coal rate is 15-18%; the atmosphere CO / (CO+CO 2 )'s volume ratio is (3-5):10; the reduction blowing temperature is 1250-1300°C, and the time is 3-4h.

[0016] The crude antimony includes simple metals Bi, Cu, Pb, Sb with weak metallic activity and precious metals such as Au, Ag, etc. The crude antimony specifically contains Sb>90%, Pb<1%, As<0.2%, Ag 3-3.5%, and Au 200-300g / t.

[0017] The reduced slag includes FeO, SiO 2 The ternary reduction slag formed by 2-nitrogen-2-ol and CaO, in which Sb < 1% and Ag < 50g / t, is discharged and sold as raw material for building materials.

[0018] The smoke 2 includes low-valent oxides of antimony, oxides of As, and oxides of Pb, and is returned to the batching after dust collection.

[0019] The flue gas 2 is discharged after being preheated, recovered, dusted and purified.

[0020] Furthermore, in step S3, the blowing furnace is a submerged top blowing furnace; the process conditions of the oxidative volatilization blowing are: oxygen-enriched air is introduced, the oxygen concentration is 21-40%, and the oxygen-to-material ratio is 130-150 Nm 3 / t; the oxidative volatilization blowing temperature is 1000-1200°C, and the blowing is stopped when the Sb content in the alloy liquid is lower than 7%.

[0021] The Sb 2 O 3 Sb in smoke 2 O 3 >99.5%; the noble alloy contains Ag>30%, Au>2000g / t; the noble alloy is sent to vacuum distillation after being released to separate the Ag and Au noble metals from Pb, Sb and Bi in the noble alloy;

[0022] The main component of the oxidized slag is Sb 2 O 3 After cooling, the process returns to step S2 for reduction smelting and recovery of Sb metal; the flue gas 3 is discharged after waste heat recovery, dust collection and purification to meet the standards.

[0023] Principle of the present invention:

[0024] In step S1, the basic slag system of the smelting slag is Sb 2 O 4 -Fe 2 O 3 -CaO-SiO 2 Quaternary system, in which CaO / Fe 2 O 3 The mass ratio is controlled at 0.2-0.3, CaO / SiO 2 The mass ratio is controlled at 2 to 2.5. Since the Sb high-valent oxides generated under the reaction conditions of this scheme are mainly enriched in the slag, the separation effect of Sb from As and Pb in the smelting stage is good, and the total content of As and Pb in the slag is less than 0.6%.

[0025] In step S2, the reducing gas and the slag are fully stirred and mixed, and the metals Bi, Cu, Pb, and Sb with relatively weak metallic activity in the slag are reduced to a single substance to form a crude antimony alloy liquid that sinks to the lower layer of the furnace, while precious metals such as Au and Ag are captured by the crude antimony.

[0026] In step S3, the reaction process fully utilizes the chemical heat of metal oxidation, and no fuel is needed. In this process, since the affinity of other metals in crude antimony with oxygen is smaller than that of Sb, a large amount of Sb is oxidized to volatile Sb 2 O 3Entering the smoke; since the metallic activity of Pb is very close to that of Sb, when the Sb content in the alloy is lower than a certain level, Pb begins to oxidize in large quantities, and PbO is easily volatilized into the smoke, reducing the quality of antimony oxide powder. Therefore, when the Sb content in the alloy liquid is lower than 7%, the blowing is stopped.

[0027] Beneficial effects of the present invention:

[0028] (1) The process of the present invention adopts a method of spraying a mixture of powdered raw materials and oxygen-enriched air, which strengthens the mixing effect of the materials with oxygen when entering the furnace, effectively inhibits the premature volatilization of sulfides, and the heat of chemical reaction is fully absorbed by the melt, thereby achieving excess heat in the smelting process. This part of the heat can be used to process a high proportion of antimony-containing secondary materials, realizing self-heating synergistic smelting;

[0029] (2) The process of the present invention strengthens the reaction kinetics of the raw materials and oxygen, and the smelting stage only produces high-antimony slag, which inhibits the generation of high-iron antimony matte in the smelting process and reduces the ineffective circulation of materials;

[0030] (3) In the process of the present invention, Sb is oxidized to a high-valent state in the smelting stage and is enriched in the slag phase. 2 O 3 Most of it enters the flue gas and is separated from Sb. The crude antimony produced by the subsequent reduction of high-antimony slag has a very low As content, ensuring that the crude antimony oxidation and blowing directly produces more than 99.5% high-quality antimony white. At the same time, the crude antimony produced in the reduction section can also be used as a collector to enrich precious metal elements such as Au and Ag. The precious alloy obtained after oxidation and blowing can be used as a raw material for extracting precious metals and sent to a mature vacuum distillation process for treatment. The extraction is easy, realizing the efficient separation of harmful elements and the short-process recovery of precious metals. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The process flow diagram of the method of the present invention is shown in FIG. DETAILED DESCRIPTION

[0032] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and meticulously below in conjunction with the accompanying drawings and preferred embodiments of the present invention, but the protection scope of the present invention is not limited to the following specific embodiments.

[0033] Unless otherwise defined, all professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0034] The oxygen-enriched side-blown molten pool smelting furnace used in the embodiment of the present invention has a rectangular furnace body with a solid charge feeding port and a flue on the top. The feeding port is used to add antimony concentrate, high-antimony anode mud mixture, flux, etc. The rear end of the flue is connected to a flue gas treatment system for waste heat recovery and smoke dust capture, and the purified flue gas enters the acid-making system. Since no metal or antimony matte is produced in the oxidation smelting process, the furnace cylinder is filled with molten slag. Therefore, several submerged side-blowing spray guns on the side wall of the furnace are arranged at the lower part of the furnace wall to ensure sufficient stirring and heat supply of the slag. The spray gun is a concentric sleeve structure, the inner layer can be blown into powdered mixed charge, and the outer layer can be blown into oxygen-enriched air of different concentrations to ensure that the charge and oxygen-enriched air are quickly mixed and oxidized to form slag when entering the molten slag layer, thereby inhibiting Sb 2 S 3 The middle and lower parts of the end wall are provided with slag outlets for normal slag discharge and furnace emptying, and are connected to the feed port of the side-blowing reduction furnace through a chute.

[0035] The side-blown reduction smelting furnace used in the embodiment of the present invention has a rectangular structure. A liquid charging port is provided on the upper part of one side end wall, and a solid charge charging port and a flue are provided on the top. The charging port is used to add flux, block fuel, etc. The rear end of the flue is connected to the flue gas treatment system for waste heat recovery and smoke dust capture. A number of submerged side-blowing lances are provided in the middle of the furnace side wall. The lances are made of multi-layer concentric sleeves and can simultaneously blow in oxygen-enriched air and pulverized coal / natural gas and other fuels. A secondary air port is provided on the upper part of the furnace side wall for igniting combustible components such as CO in the flue gas. A slag discharge port and a metal siphon port are provided on the end wall of the furnace body. The siphon port is connected to the crude antimony oxidation refining furnace through a chute.

[0036] The submerged top-blowing converting furnace used in the embodiment of the present invention has a vertical cylindrical structure as the furnace body, a liquid crude antimony feeding port is arranged at the upper part of the furnace wall, a slag port is arranged at the middle part, a noble alloy discharge port is arranged at the lower part, and a bottom emptying port is arranged. A set of top-blowing spray guns are arranged at the center of the top of the furnace, and the gun body can be raised and lowered and rotated, and can be inserted into the melt to blow oxygen-rich air for submerged oxidation converting. A flue and a solid charge feeding port are arranged on the top of the furnace, and the flue is connected to the furnace body and the waste heat boiler, and the feeding port can be used to add flux, solid fuel, etc.

[0037] Example 1

[0038] The present invention provides a method for low-carbon collaborative smelting of antimony-containing materials, and the process flow diagram thereof is as follows: Figure 1 As shown, the following steps are included:

[0039] The antimony concentrate used for smelting contains Sb 35%, Fe 19%, S 34%, Pb 0.2%, As 1%, and the high antimony anode mud contains Sb65%, Pb 11%, As 4.7%, Ag 4.5%. The two raw materials are mixed at a ratio of 1:0.5, and the mixed charge is dried to a water content of 0.3%. It is finely ground by a ball mill to a particle size of ≤75μm, and then blown into the oxygen-enriched side-blown furnace molten pool through the inner tube of the side-blowing lance. Oxygen-enriched air is blown into the side-blowing lance from the outer tube for smelting. The oxygen concentration is 30%, and the oxygen-to-material ratio is controlled at 300Nm3 / t, which can achieve self-heating smelting. At the same time, limestone flux is added from the upper feeding port to make slag, and the flux rate is 10%. The smelting temperature was maintained at 1150°C, the smelting time was 2.5h, and the high antimony smelting slag produced contained 47.90% Sb, 0.13% As, 0.43 Pb, 1.70% Ag, and 120g / t Au. The CaO / Fe2O3 mass ratio of the slag was 0.3, and the CaO / SiO2 mass ratio was 2.4. After the smelting was completed, the slag was discharged from the slag port and introduced into the reduction smelting furnace through the chute to recover Sb and rare metals.

[0040] The high antimony smelting slag produced by the smelting furnace continuously flows into the liquid charge feeding port of the reduction smelting furnace through the chute. The pulverized coal fuel is blown into the molten pool through the inner tube of the side-blowing lance, and oxygen-enriched air is blown into the molten pool through the outer tube of the side-blowing lance. The oxygen-enriched concentration is 50%, the oxygen excess coefficient is 0.85, and the coal rate is 15%. The atmosphere is maintained at CO / (CO+CO 2 ) volume ratio is 30%, and the smelting temperature is 1300℃. The crude antimony alloy produced by reduction contains Sb 91.25%, Pb 0.75%, As 0.20%, Ag 3.38%, and Au 230g / t. The crude antimony is discharged from the discharge port and introduced into the oxidation refining furnace through the chute for further treatment. The reduced slag contains Sb 0.86% and Ag 49g / t.

[0041] The crude antimony produced by the reduction furnace is introduced into the top-blowing refining furnace through a chute, and oxygen-enriched air is blown into the top-blowing lance for submerged oxidation volatilization refining. The oxygen-enriched concentration is 30%, the refining temperature is 1100℃, and the oxygen-to-material ratio is controlled at 140Nm3 / t. The reaction process can be self-heated. The dust collection system obtains high-purity Sb 2 O 3 Sb in smoke 2 O 3 99.6%, can be directly sold. The precious alloy obtained by blowing contains Ag>33.6%, Au 2320g / t, and the alloy liquid is released and sent to vacuum distillation to recover precious metals.

[0042] Example 2

[0043] The antimony concentrate used for smelting contains Sb 30%, Fe 20%, S26%, Pb 0.18%, As 1.3%, and the high antimony anode mud contains Sb 60%, Pb 13%, As 4.9%, Ag 4.9%. The two raw materials are mixed at a ratio of 1:0.9, and the mixed charge is dried to a water content of 0.5%, and finely ground to a particle size of ≤75μm by a ball mill. It is blown into the oxygen-enriched side-blown furnace molten pool through the inner tube of the side-blowing spray gun, and oxygen-enriched air is blown into the side-blowing spray gun through the outer tube for smelting. The oxygen concentration is 50%, and the oxygen-to-material ratio is controlled at 320Nm 3 / t, which can realize self-heating smelting. At the same time, limestone flux is added from the upper feeding port to make slag, and the flux rate is 9%. The smelting temperature is maintained at 1200℃, the smelting time is 2.3h, and the output high antimony smelting slag contains Sb 45.10%, As 0.18%, Pb 0.43%, Ag1.90%, Au 140g / t. Slag CaO / Fe 2 O 3 Mass ratio 0.22, CaO / SiO 2 The mass ratio is 2.1. After smelting is completed, the slag is discharged from the slag port and introduced into the reduction smelting furnace through the chute to recover Sb and rare metals.

[0044] The high antimony smelting slag produced by the smelting furnace continuously flows into the liquid charge feeding port of the reduction smelting furnace through the chute. The pulverized coal fuel is blown into the molten pool through the inner tube of the side-blowing lance, and oxygen-enriched air is blown into the molten pool through the outer tube of the side-blowing lance. The oxygen-enriched concentration is 60%, the oxygen excess coefficient is 0.8, and the coal rate is 16%. The atmosphere is maintained at CO / (CO+CO 2 ) volume ratio is 40%, and the smelting temperature is 1280℃. The crude antimony alloy produced by reduction contains Sb 90.15%, Pb 0.95%, As 0.19%, Ag 3.48%, and Au 260g / t. The crude antimony is discharged from the discharge port and introduced into the oxidation refining furnace through the chute for further treatment. The reduced slag contains Sb 0.76% and Ag 45g / t.

[0045] The crude antimony produced by the reduction furnace is introduced into the top-blown refining furnace through a chute, and oxygen-enriched air is blown into the top-blown lance for submerged oxidation volatilization refining. The oxygen-enriched concentration is 40%, the refining temperature is 1200℃, and the oxygen-to-material ratio is controlled at 140Nm 3 / t, the reaction process can be self-heating. The dust collection system obtains high-purity Sb 2 O 3 Sb in smoke 2 O 3 99.5%, can be directly sold. The precious alloy obtained by blowing contains Ag>34.5%, Au 2460g / t, and the alloy liquid is released and sent to vacuum distillation to recover precious metals.

[0046] Example 3

[0047] The antimony concentrate used for smelting contains Sb 49%, Fe 8%, S 35%, Pb 0.15%, As 1.1%, and the high antimony anode mud contains Sb 62%, Pb 12%, As 2.7%, Ag 3.5%. The two raw materials are mixed at a ratio of 1:0.6, and the mixed charge is dried to a water content of 0.3%. It is finely ground by a ball mill to a particle size of ≤75μm, and then blown into the oxygen-enriched side-blown furnace molten pool through the inner tube of the side-blowing spray gun, and oxygen-enriched air is blown into the side-blowing spray gun through the outer tube for smelting. The oxygen concentration is 75%, and the oxygen-to-material ratio is controlled at 280Nm 3 / t, which can realize self-heating smelting. At the same time, limestone flux is added from the upper feeding port to make slag, and the flux rate is 8%. The smelting temperature is maintained at 1100℃, the smelting time is 2h, and the output high antimony smelting slag contains Sb 48.90%, As 0.15%, Pb 0.5%, Ag1.50%, Au 130g / t. Slag CaO / Fe 2 O 3 Mass ratio 0.28, CaO / SiO 2 The mass ratio is 2.5. After smelting is completed, the slag is discharged from the slag port and introduced into the reduction smelting furnace through the chute to recover Sb and rare metals.

[0048] The high antimony smelting slag produced by the smelting furnace continuously flows into the liquid charge feeding port of the reduction smelting furnace through the chute. The pulverized coal fuel is blown into the molten pool through the inner tube of the side-blowing lance, and oxygen-enriched air is blown into the molten pool through the outer tube of the side-blowing lance. The oxygen-enriched concentration is 40%, the oxygen excess coefficient is 0.75, and the coal rate is 17%. The atmosphere is maintained at CO / (CO+CO 2 ) volume ratio is 50%, and the smelting temperature is 1250℃. The crude antimony alloy produced by reduction contains Sb 90.85%, Pb 0.85%, As 0.15%, Ag 3.06%, and Au 270g / t. The crude antimony is discharged from the discharge port and introduced into the oxidation refining furnace through the chute for further treatment. The reduced slag contains Sb 0.96% and Ag 47g / t.

[0049] The crude antimony produced by the reduction furnace is introduced into the top-blown refining furnace through the chute, and oxygen-enriched air is blown into the top-blown lance for submerged oxidation volatilization refining. The oxygen-enriched concentration is 25%, the refining temperature is 1050℃, and the oxygen-to-material ratio is controlled at 140Nm 3 / t, the reaction process can be self-heating. The dust collection system obtains high-purity Sb 2 O 3 Sb in smoke 2 O 3 99.55%, can be sold directly. The precious alloy obtained by blowing contains Ag>30.5%, Au 2410g / t, and the alloy liquid is released and sent to vacuum distillation to recover precious metals.

[0050] The method in the embodiment of the present invention adopts the method of mixing powdered raw materials with oxygen-enriched air and spraying them, which strengthens the mixing effect of materials with oxygen when entering the furnace, effectively inhibits the premature volatilization of sulfides and the generation of antimony matte, and the heat of chemical reaction is fully absorbed by the melt, thereby achieving excess heat in the smelting process. This part of heat can be used to process a high proportion of sulfur-free antimony materials, realizing multi-material collaborative self-heating smelting. At the same time, the crude antimony metal produced by reduction is used to capture Au and Ag, and high-quality antimony white and high-concentration precious metal alloys can be produced through volatilization and blowing, realizing the short-process recovery of precious metal elements.

[0051] Comparative Example 1

[0052] The current general treatment process for antimony concentrate is blast furnace volatilization smelting, which is relatively mature. Its process and main technical and economic indicators are reported in the textbook "Antimony Metallurgy" and related literature. First, the antimony concentrate is mixed with lime and granulated, naturally dried, and added into the furnace together with coke and flux. Then air is blown into the nozzles on both sides of the furnace body, and the materials in the furnace undergo drying, decomposition, volatilization, oxidation and slagging reactions; Sb mainly enters the flue gas in the form of antimony oxide. At the same time, the melt generated by the reaction enters the front bed for clarification and separation, forming slag, antimony matte and crude antimony respectively. The three products can be discharged separately, and the antimony matte is returned to the furnace for treatment; low-concentration SO 2 Flue gas. The flue gas SO produced by this process 2 Concentrations below 1% cannot be recycled by acid production. Coke consumption is generally 30-40% of antimony concentrate, and some companies are close to 50%, which results in high energy costs. Antimony matte production is large, usually more than 25% of antimony oxide powder, and needs to be cooled as return material, which is ineffectively circulated in the system.

[0053] The contents explained in the above embodiments should be understood as these embodiments are only used to more clearly illustrate the present invention, and are not used to limit the scope of the present invention. After reading the present invention, various equivalent forms of modifications to the present invention by those skilled in the art all fall within the scope defined by the claims attached to this application.

Claims

1. A method for low-carbon collaborative smelting of antimony-containing materials, characterized in that: The following steps are involved: S1. The antimony concentrate and high antimony anode mud are mixed, dried, ball-milled, and then added to a smelting furnace for smelting to obtain smelting slag, smoke 1 and flue gas 1; S2. The smelting slag obtained in step S1 is added to a reduction furnace for reduction blowing to obtain crude antimony, reduction slag, smoke 2 and flue gas 2; S3. Add the crude antimony obtained in step S2 into a blowing furnace for oxidative volatilization blowing to obtain precious alloy, Sb2O3 dust, oxide slag and flue gas 3.

2. The method for low-carbon coordinated smelting of antimony-containing materials according to claim 1, characterized in that: In step S1, the antimony concentrate contains Sb30-50%, Fe5-20%, S25-35%, Pb≤0.2%, As≤1.5%, and the high antimony anode mud contains Sb60-65%, Pb10-13%, As2-5%, and Ag2-5%; the mixing ratio of the antimony concentrate and the high antimony anode mud is 1:(0.5-1); after the antimony concentrate and the high antimony anode mud are mixed, they are first dried to a moisture content of less than 0.5%, then finely ground by a ball mill to a particle size of less than 75 μm, and finally sprayed into an oxygen-enriched side-blowing molten pool smelting furnace by an inner tube of a side-blowing spray gun for smelting.

3. The method for low-carbon coordinated smelting of antimony-containing materials according to claim 1, characterized in that: In step S1, the smelting process conditions are: oxygen is blown into the outer tube of the side-blowing lance, the oxygen concentration is 30-80%, and the oxygen-to-material ratio is 280-320 Nm 3 / t; at the same time, limestone flux is added to make slag, and the flux rate is 8-10%; the smelting temperature is 1100-1200℃, and the smelting time is 2-2.5h.

4. The method for low-carbon coordinated smelting of antimony-containing materials according to claim 1, characterized in that: In step S1, the smelting slag contains antimony and precious metal elements, specifically Sb45-50%, As<0.2%, Ag>1.5%, Au>100g / t, and the basic slag system of the smelting slag is Sb2O4-Fe2O3-CaO-SiO2 quaternary system, wherein the CaO / Fe2O3 mass ratio is controlled at 0.2-0.3, and the CaO / SiO2 mass ratio is controlled at 2-2.5; the smoke 1 includes oxides of As, Pb, and Sb; the flue gas 1 includes sulfur dioxide, and acid is produced after waste heat recovery, dust collection and purification.

5. The method for low-carbon coordinated smelting of antimony-containing materials according to claim 1, characterized in that: In step S2, the reduction furnace is a side-blown reduction smelting furnace; the process conditions of the reduction blowing are: introducing oxygen-enriched air, the oxygen concentration is 40-60%, the oxygen excess coefficient is 0.75-0.85; the coal rate is 15-18%; the volume ratio of CO / (CO+CO2) in the atmosphere is (3-5):10; the temperature of the reduction blowing is 1250-1300°C, and the time is 3-4h.

6. The method for low-carbon coordinated smelting of antimony-containing materials according to claim 1, characterized in that: In step S2, the crude antimony includes single metals Bi, Cu, Pb, Sb with weak metal activity and precious metals Au and Ag. The crude antimony specifically contains Sb>90%, Pb<1%, As<0.2%, Ag 3-3.5%, and Au200-300g / t.

7. The method for low-carbon coordinated smelting of antimony-containing materials according to claim 1, characterized in that: In step S2, the reduction slag includes a ternary reduction slag formed by FeO, SiO2, and CaO, wherein Sb is less than 1% and Ag is less than 50 g / t, and is discharged and sold as a raw material for building materials.

8. The method for low-carbon coordinated smelting of antimony-containing materials according to claim 1, characterized in that: In step S2, the smoke 2 includes low-valent oxides of antimony, oxides of As, and oxides of Pb, which are returned to the batching after dust collection; the smoke 2 is discharged after preheating, recovery, dust collection, and purification.

9. The method for low-carbon coordinated smelting of antimony-containing materials according to claim 1, characterized in that: In step S3, the blowing furnace is a submerged top blowing furnace; the process conditions of the oxidative volatilization blowing are: oxygen-enriched air is introduced, the oxygen concentration is 21-40%, and the oxygen-to-material ratio is 130-150 Nm 3 / t; the oxidative volatilization blowing temperature is 1000-1200°C, and the blowing is stopped when the Sb content in the alloy liquid is lower than 7%.

10. The method for low-carbon coordinated smelting of antimony-containing materials according to claim 1, characterized in that: In step S3, the Sb2O3 smoke contains Sb2O3>99.5%; the precious alloy contains Ag>30%, Au>2000g / t; the precious alloy is sent to vacuum distillation after being released to separate the Ag and Au precious metals from the Pb, Sb and Bi in the precious alloy; the main component of the oxidized slag is Sb2O3, which is returned to step S2 after cooling for reduction smelting and recovery of Sb metal; the flue gas 3 is discharged after waste heat recovery, dust collection and purification to meet the standards.

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