Method for comprehensive recovery of multiple elements from complex gold concentrates

Abstract

The present application belongs to the field of metallurgy, and relates to a method for comprehensively recovering multiple elements from complex gold concentrate, comprising the following steps: S1. bottom blowing smelting of complex gold concentrate and auxiliary material I in a bottom blowing furnace under oxygen-rich air atmosphere to obtain copper matte, bottom slag and flue gas; S2. top blowing converting of the copper matte and auxiliary material II in a top blowing furnace under air atmosphere to obtain crude copper, flue gas and converting slag; S3. refining of the crude copper with a carbonate under air atmosphere, and reduction under inert atmosphere by passing in methane gas after the reaction is completed to obtain copper anode plate; in step S1, the coking inhibitor composed of di-aluminum oxide, calcium oxide, sodium carbonate, ammonium molybdate, sodium borate and cerium dioxide is sprayed in the rising flue of the bottom blowing furnace during the bottom blowing smelting process, which can effectively reduce the occurrence of coking and improve the production start-up rate of complex gold concentrate recovery.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of metallurgy, and particularly relates to a method for comprehensive recovery of multiple elements in complex gold concentrate. BACKGROUND

[0002] With the continuous rise of global gold demand, the pace of development and utilization of gold concentrate resources has also accelerated; with the gradual reduction of high-quality gold concentrate reserves, complex gold concentrate resources have become a key part of the gold sources of many countries. Although the development and refining technology of these complex gold concentrates are more stringent, they have contributed significantly to gold production and ensured the sustainability of gold supply.

[0003] When processing complex gold concentrates, a serious challenge is faced. These ores usually contain a large amount of harmful substances such as arsenic, antimony and bismuth, which will have a series of negative effects on smelting in the process of enriching gold by using pyrometallurgical technology. A large amount of coking will be produced in the updraft and waste heat boiler during the smelting process, which will destroy the normal combustion conditions, and in severe cases, it will even block the furnace outlet, causing forced shutdown and the need for regular cleaning; and because the raw materials contain arsenic and antimony, in the process of quenching and collecting arsenic, due to the similar properties of arsenic and antimony, antimony in the flue gas will be precipitated in the form of antimony trioxide together with arsenic trioxide during the cooling process, resulting in the presence of antimony trioxide impurities in the arsenic trioxide collected from the flue gas.

[0004] In the prior art, to deal with or inhibit the formation of coking, a coking inhibitor is usually added, but different raw materials, different types and contents of impurities result in that there is no fixed coking inhibitor that can be used. CN 119826567 A discloses a coking inhibitor and a preparation method thereof, the coking inhibitor comprising: a reducing agent, a sulfur-containing substance, a silicon-containing substance and a calcium-containing substance, wherein the valence of sulfur in the sulfur-containing substance is negative two or zero; the use of this coking inhibitor can reduce the melting point of the coking body, promote the melting of the coking body, and is conducive to inhibiting the occurrence of coking phenomenon. However, the coking inhibitor can only convert high-melting-point compounds in the coking body into low-melting-point compounds by reduction and sulfidation, and then combine the silicon-containing substance, the calcium-containing substance and the low-melting-point compounds by slagging to promote the melting of the coking body, which has limited coking inhibition effect, and the coking inhibitor is not suitable for coking bodies with complex composition and content. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a method for comprehensive recovery of multiple elements in complex gold concentrate; the coking inhibitor is sprayed during the process of smelting and recovering valuable elements in complex gold concentrate, which can reduce the occurrence of coking and improve the production start-up rate.

[0006] The specific technical solution is as follows:

[0007] A method for comprehensive multi-element recovery of complex gold concentrate, comprising the following steps:

[0008] S1. bottom blowing smelting of the complex gold concentrate and auxiliary material I in an oxygen-rich air atmosphere in a bottom blowing furnace to obtain copper matte, bottom slag and flue gas; the auxiliary material I is quartzite and limestone;

[0009] S2. top blowing converting of the copper matte and auxiliary material II in an air atmosphere in a top blowing furnace to obtain crude copper, flue gas and converting slag; the auxiliary material II is limestone;

[0010] S3. refining of the crude copper with a carbonate in an air atmosphere, and after the reaction is completed, reduction in an inert atmosphere by passing in methane gas to obtain copper anode plates;

[0011] In step S1, a coking inhibitor is sprayed in the rising flue of the bottom blowing furnace during the bottom blowing smelting process; the coking inhibitor is composed of di aluminum trioxide, calcium oxide, sodium carbonate, ammonium molybdate, sodium borate, and cerium dioxide.

[0012] Specifically, the complex gold concentrate contains gold concentrate, silver concentrate and copper concentrate, and can also contain one or both of chalcopyrite and pyrite; wherein the copper concentrate contains CuS, Fe3O4, FeS2 and CuFeS2, the chalcopyrite contains CuFeS2, the pyrite contains FeS2, and the gold concentrate and silver concentrate contain FeS2, CuFeS2 and SiO2.

[0013] More specifically, the main components in the complex gold concentrate have the following contents: Au content of 15-100 g / t, Ag content of 100-500 g / t, Cu content of 9.0wt%-25wt%, As content of ≤5.0wt%, Sb content of ≤4.0wt%, Bi content of ≤3.0wt%, S content of 20wt%-35wt%, Fe content of 20wt%-35wt%, Te content of ≤1.0wt%, Pd content of 0.02-5 g / t, and Pt content of 0.02-5 g / t.

[0014] Complex gold concentrate due to the mineral composition is more diverse, containing a large number of metal and non-metal impurity components, in the high temperature bottom blowing smelting process, the low melting point of these impurities (such as lead, zinc, etc.) first reach the melting point and liquefaction, these molten state of matter will flow with the flue gas and rise; in the rising to the inner wall surface of the flue and waste heat boiler, these liquid state of matter will gradually adhere to the deposition, at the same time, also can absorb the fine solid particles carried by the flue gas, with the passage of time, this kind of adhesion deposition phenomenon continues to accumulate, eventually form a dense aggregate, this gradually accumulated in the inner wall of smelting equipment to form solid deposits of process, in the metallurgical process is collectively referred to as coking phenomenon. Coking not only reduces the heat transfer efficiency, but also affects the normal flow of flue gas, adversely affect the normal operation of smelting equipment; especially in the internal flue, easy to form a relatively thick coking body, these coking body will destroy the normal combustion condition, serious even can block the furnace outlet, resulting in forced shutdown. Because of different raw material composition, the coking inhibitor used is different, the coking inhibitor of the present application makes the coking material from low melting point, high viscosity, dense hard harmful substances, into high melting point, good fluidity, loose porous easy to remove material, so as to achieve the dual purpose of high efficiency inhibition and convenient cleaning.

[0015] Further, in step S1, the coking inhibitor consists of 30-40 parts of aluminum oxide, 20-30 parts of calcium oxide, 10-20 parts of sodium carbonate, 10-20 parts of ammonium molybdate, 5-10 parts of sodium borate and 1-3 parts of cerium dioxide by mass fraction.

[0016] Among them, aluminum oxide as a high melting point of amphoteric oxide, is the skeleton material of building high melting point phase, which reacts with zinc ferrite to generate zinc aluminate spinel, with FeO to generate iron aluminate spinel, with CaO to generate calcium aluminate, these high melting point phase forms a solid, non-stick "skeleton", which wraps, divides and isolates the low melting point coking components (such as PbO), significantly improves the softening temperature and hardness of the whole coking material, and makes its structure brittle, easy to be mechanically removed.

[0017] Calcium oxide as a strong alkaline oxide is the most critical component for fixing arsenic, which reacts with arsenate at high temperature to generate extremely stable calcium arsenate, converts the active form of arsenic into inert and stable form, and fixes it in the slag, and cooperates with aluminum oxide to generate high melting point calcium aluminate, providing structural support for the whole system.

[0018] Sodium carbonate decomposes into sodium oxide Na2O (strong base) and CO2 at high temperature, and sodium oxide reacts with sulfide (PbS, CuS, Cu2S, etc.) to generate sodium sulfate, which can significantly reduce the high temperature viscosity of the whole system, improve the fluidity of the molten slag, and make the formed coking material more easily washed away by the gas flow of flue gas.

[0019] Ammonium molybdate decomposes into molybdenum trioxide and ammonia gas at high temperature, and the molybdenum trioxide will be embedded into the growing coking crystal structure, destroying its dense and continuous structure, so that the coking changes from hard and dense, firmly attached to loose, porous, fragile state, and this "crumbly" coking is more easily removed by gas flow impact or mechanical decoking.

[0020] Sodium borate has a low melting point (about 740 DEG C), and at this temperature, it will melt to form a borate glass liquid phase, and the molten borate glass liquid phase has good fluidity, can wet and spread on the un-melted coking particles and refractory material surface, forming a physical barrier to isolate the contact between the coking particles, and the contact between the coking and the reaction atmosphere (such as flue gas), which can inhibit the further adsorption of coking; at the same time, sodium borate and sodium carbonate can further reduce the viscosity of the system.

[0021] Cerium dioxide plays a role in inhibiting catalysis and dispersion. Metals such as Cu and Fe and their compounds are catalysts for coking reactions, and cerium dioxide strongly adsorbs on these catalytically active sites through its unique electronic effect, like a "seal" to block the contact between reactants and active sites, thereby inhibiting the activity of these catalysts and making them inactive; and cerium dioxide particles can adhere to the surface of coking particles to prevent their aggregation and growth, thereby playing a dispersion role.

[0022] In the process of complex gold concentrate bottom blowing smelting, the coking inhibitor is sprayed in the rising flue of the bottom blowing furnace, so that the coking changes from low-melting-point, high-viscosity, dense and hard harmful substances to high-melting-point, good-fluidity, loose and porous easily-removed substances, thereby achieving the dual purposes of efficient inhibition of coking and convenient cleaning, reducing the generation of coking in the rising flue of the bottom blowing furnace, and prolonging the cleaning interval of the coking generated in the waste heat boiler along with the flue gas from 20-25 days to 45-50 days; the cleaning time is reduced from 6-12 hours to 4-8 hours each time, reducing the labor intensity and improving the production efficiency.

[0023] In the process of complex gold concentrate bottom blowing smelting, the coking inhibitor is sprayed in the rising flue of the bottom blowing furnace, so that the coking changes from low-melting-point, high-viscosity, dense and hard harmful substances to high-melting-point, good-fluidity, loose and porous easily-removed substances, thereby achieving the dual purposes of efficient inhibition of coking and convenient cleaning, reducing the generation of coking in the rising flue of the bottom blowing furnace, and prolonging the cleaning interval of the coking generated in the waste heat boiler along with the flue gas from 20-25 days to 45-50 days; the cleaning time is reduced from 6-12 hours to 4-8 hours each time, reducing the labor intensity and improving the production efficiency.

[0024] Further, in step S1, the total amount of the coking inhibitor is 0.01wt%-0.05wt% of the total amount of the complex gold concentrate.

[0025] Further, in step S1, the coking inhibitor has a particle size of no more than 74 μm.

[0026] Preferably, in step S1, the temperature of the bottom-blown smelting is 1150-1250°C, and the mass ratio of S / Cu in the complex gold concentrate is ≥1.3; during the bottom-blown smelting, continuous feeding is adopted, and the bottom slag is discharged once every 25-35 min, and the copper matte is discharged once every 1.3-1.6 h.

[0027] Preferably, in step S1, the amounts of the auxiliary materials quartzite and limestone are respectively calculated based on SiO2 and CaO in the bottom slag, the mass ratio of Fe / SiO2 in the bottom slag is (1.2-2.0):1, and the mass ratio of CaO / SiO2 in the bottom slag is (0.12-0.16):1; the quartzite is used for slagging, and the CaO generated by the reaction of the limestone is used to adjust the viscosity and fluidity of the bottom slag.

[0028] Preferably, in step S1, the oxygen volume fraction of the oxygen-enriched air is 70%-85%.

[0029] In step S1, the bottom slag is returned to a slag separation system to recover copper concentrate and iron concentrate, and the copper concentrate can be returned to step S1 for bottom-blown smelting.

[0030] In step S1, the flue gas is sequentially returned to a waste heat recovery system, an electric dust removal system, an arsenic recovery system, and a sulfuric acid recovery system.

[0031] Preferably, the arsenic recovery system recovers the crude arsenic trioxide solid by a quenching arsenic recovery method.

[0032] In the quenching arsenic recovery process, because arsenic and antimony have similar properties, antimony in the flue gas is precipitated in the form of antimony trioxide together with arsenic trioxide during the cooling process, so that the arsenic trioxide collected from the flue gas contains antimony trioxide impurities. The present application takes advantage of the characteristics that arsenic trioxide is difficult to dissolve in saturated arsenic trioxide dilute hydrochloric acid solution, while antimony trioxide is soluble in the solution and generates soluble chlorides, and performs acid leaching (saturated arsenic trioxide dilute hydrochloric acid solution) on the antimony-containing arsenic trioxide, effectively removing the antimony impurities, and obtaining arsenic trioxide with a purity of more than 99.5%. The main reaction is:

[0033] Sb2O3+6HCl→2SbCl3+3H2O.

[0034] Specifically, the saturated arsenic trioxide aqueous solution and the crude arsenic trioxide are mixed according to a liquid-solid mass ratio of (4-8):1, then 12 mol / L analytical pure hydrochloric acid is added, and stirring reaction is carried out at 5-25°C for 4-8 h, and then filtration and drying are carried out to obtain refined arsenic trioxide with a purity of more than 99.5%; preferably, the molar ratio of the hydrochloric acid to the total amount of antimony in the crude arsenic trioxide is (5-20):1.

[0035] Further, in step S2, the top-blown converting temperature is 1150-1250 DEG C, and in the top-blown converting process, the feeding is carried out once every 1.3-1.6 hours, the converting slag is discharged once every 3.5-4.5 hours, and the blister copper is discharged once every 7.5-8.5 hours.

[0036] Preferably, in step S2, the amount of the auxiliary material limestone is calculated based on CaO in the converting slag, and the mass ratio of CaO / Fe2O3 in the converting slag is (0.8-1.0):1; the CaO generated by the reaction of the limestone is used for slagging.

[0037] In step S2, the flue gas is returned to the waste heat recovery system, the electric dust removal system and the sulfuric acid recovery system in sequence to recover the boiler ash, the electric dust removal ash and the sulfuric acid; the boiler ash can be returned to step S1 for bottom-blown smelting, and the electric dust removal ash is sent to the dust recovery system to obtain arsenic-iron alloy.

[0038] In step S2, the converting slag is returned to the slag separation system to recover copper concentrate and iron concentrate powder, and the copper concentrate can be returned to step S1 for bottom-blown smelting.

[0039] Preferably, in step S3, the carbonate is sodium carbonate or potassium carbonate.

[0040] Preferably, in step S3, the mass ratio of the carbonate to the total amount of arsenic and antimony in the blister copper is (1.5-5):1, the refining temperature is 1150-1200 DEG C, and the refining time is 4-6 hours; the molar ratio of methane to the total amount of copper in the blister copper is (1-2):4, the reduction temperature is 1200-1300 DEG C, and the reduction time is 2-4 hours.

[0041] Further, in step S3, after the refining is completed, slag can be obtained by slagging, and the slag can be returned to step S2 for top-blown converting.

[0042] Further, the copper anode plate in step S3 is electrolyzed to obtain cathode copper and copper anode slime, and the copper anode slime is returned to the dilute valuable metal recovery system to recover valuable metals such as gold, silver, tellurium, bismuth, palladium, platinum and diantimony trioxide.

[0043] Compared with the prior art, the present application has the following beneficial effects:

[0044] In the process of smelting and recovering valuable elements from the complex gold concentrate, the coking inhibitor composed of diaspore, calcium oxide, sodium carbonate, ammonium molybdate, sodium borate and cerium dioxide is sprayed, which can effectively reduce the occurrence of coking and improve the production start-up rate of smelting and recovering valuable elements from the complex gold concentrate. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 It is a process flow chart of the method for comprehensive recovery of multiple elements from the complex gold concentrate in the specific embodiment. DETAILED DESCRIPTION

[0046] The embodiments of the present application will be further described in conjunction with the drawings and examples. The following examples are used to illustrate the present application but should not be used to limit the scope of the present application. The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, etc. used in the following examples can be obtained from commercial channels unless otherwise specified.

[0047] Example 1

[0048] A method for comprehensive recovery of multiple elements from complex gold concentrate, wherein,

[0049] The complex gold concentrate contains chalcopyrite, pyrite, gold concentrate, silver concentrate and copper concentrate; the main contents of the complex gold concentrate are: Au content of 15.21 g / t, Ag content of 101.24 g / t, Cu content of 24.58 wt%, S content of 34.25 wt%, Fe content of 20.58 wt%, As content of 0.25 wt%, Sb content of 0.14 wt%, Bi content of 0.57 wt%, Te content of 0.14 wt%, Pd content of 0.02 g / t, and Pt content of 0.02 g / t; wherein, the mass ratio of S / Cu in the complex gold concentrate is 1.39.

[0050] The method steps are as follows:

[0051] S1 complex gold concentrate, quartz and limestone mixed by belt continuous delivery to the bottom of the blast furnace, continuously through the bottom of the lance to the drum into the oxygen volume fraction of 85% oxygen-enriched air, at 1150 DEG C under continuous bottom blowing smelting, in the bottom of the blast furnace in the rising flue injection particle size of not more than 74 μm of coking inhibitor, the coking inhibitor, according to the mass fraction of 30 parts of alumina, 20 parts of calcium oxide, 10 parts of sodium carbonate, 10 parts of ammonium molybdate, 5 parts of sodium borate, 1 part of cerium dioxide, the total amount of coking inhibitor injection is 0.05wt% of the total amount of complex gold concentrate, every 25 min from the slag tapping hole bottom slag once, the bottom slag can be automatically discharged from the slag tapping hole, every 1.3 h from the copper tapping hole ice copper once, the copper can be automatically discharged from the copper tapping hole; the X-ray fluorescence spectrometer is used to detect the total Si, Ca element content in the bottom slag, and the total Si, Ca element content in the bottom slag is converted into SiO2, CaO mass, the mass ratio of Fe / SiO2 in the bottom slag is 1.2:1, and the mass ratio of CaO / SiO2 in the bottom slag is 0.12:1; the flue gas obtained in the bottom blowing smelting process is returned to the waste heat recovery system, i.e. waste heat boiler, electric dust removal system, i.e. electric dust collector, arsenic recovery system and sulfuric acid recovery system in turn to recover boiler ash, electric dust removal ash, crude arsenic trioxide and sulfuric acid, the boiler ash is sent to the bottom of the blast furnace for bottom blowing smelting, the electric dust removal ash is sent to the dust recovery system to recover arsenic iron alloy, the steam obtained in the waste heat recovery system, i.e. waste heat boiler, can be used for power generation by using its waste heat; the bottom slag returns to the slag separation system to recover copper concentrate and iron concentrate, the copper concentrate can be sent to the bottom of the blast furnace for bottom blowing smelting; the arsenic recovery system recovers crude arsenic trioxide solid by quenching, then mixes the saturated arsenic trioxide aqueous solution with the crude arsenic trioxide according to the liquid-solid mass ratio of 4:1, then adds 12 mol / L hydrochloric acid, the molar ratio of hydrochloric acid to total antimony in crude arsenic trioxide is 5:1, 25 DEG C stirring reaction for 6 h, after filtration and drying, the purity of the refined arsenic trioxide is 99.58%;

[0052] S2: The matte and limestone obtained in step S1 are mixed and fed directly into the top-blown furnace via a chute. Feeding occurs every 1.3 hours, while air is continuously blown into the furnace through the top spray gun. Top-blown smelting is carried out at 1150℃. Smelting slag is discharged from the slag discharge port every 3.5 hours, and the smelting slag flows out automatically from the slag discharge port. Crude copper is discharged from the copper discharge port every 7.5 hours, and the crude copper flows out automatically from the copper discharge port. X-ray fluorescence spectrometry is used to detect the total Ca and Fe element content in the smelting slag, and these are converted into the mass of CaO and Fe2O3. The mass ratio of CaO / Fe2O3 is 0.9:1. The flue gas obtained during the top-blown smelting process is sequentially returned to the waste heat recovery system (waste heat boiler), the electrostatic precipitator system (electrostatic precipitator), and the sulfuric acid recovery system to recover boiler ash, electrostatic precipitator ash, and sulfuric acid. The boiler ash is sent to the bottom-blown furnace for bottom-blown smelting, and the electrostatic precipitator ash is sent to the flue gas recovery system to recover ferroarsenic alloy. The steam obtained in the waste heat recovery system can be used for power generation using waste heat. The smelting slag is returned to the slag beneficiation system to recover copper concentrate and iron concentrate. The copper concentrate can be sent to the bottom-blown furnace for bottom-blown smelting.

[0053] S3. The crude copper obtained in step S2 is transferred to the anode furnace. Sodium carbonate is added at a mass ratio of 1.5:1 to the total mass of arsenic and antimony in the crude copper. Air is continuously blown in, and the refining is carried out at 1150℃ for 4 hours. After the refining is completed, slag is obtained by skimming and returned to step S2 for top blowing refining. After the reaction is completed, methane gas is introduced at a molar ratio of 1:4 to copper in the crude copper. The refining is carried out at 1200℃ in a nitrogen atmosphere for 4 hours. Finally, copper anode plates are obtained by casting. The copper anode plates are sent to the electrolysis system for electrolysis to obtain cathode copper and copper anode mud. The copper anode mud is returned to the rare and precious metals recovery system to recover gold ingots, silver ingots, tellurium ingots, bismuth ingots, sponge palladium, sponge platinum, and antimony trioxide.

[0054] Example 2

[0055] A comprehensive method for multi-element recovery from complex gold concentrates, in which...

[0056] The complex gold concentrate contains chalcopyrite, pyrite, gold concentrate, silver concentrate, and copper concentrate. The main contents of the complex gold concentrate are: Au 99.84 g / t, Ag 499.21 g / t, Cu 9.21 wt%, S 20.47 wt%, Fe 34.27 wt%, As 4.81 wt%, Sb 3.87 wt%, Bi 2.54 wt%, Te 0.94 wt%, Pd 4.85 g / t, and Pt 4.97 g / t. The S / Cu mass ratio in the complex gold concentrate is 2.22.

[0057] The steps are as follows:

[0058] S1 complex gold concentrate, quartz and limestone mixed by belt continuous delivery to the bottom of the blast furnace, continuous through the bottom of the lance to the drum into the oxygen volume fraction of 70% oxygen-enriched air, at 1250 ℃ under continuous bottom blowing smelting, in the process of bottom blowing smelting, the ascending flue of the bottom blowing furnace is sprayed with a coking inhibitor with a particle size of not more than 74 μm, the coking inhibitor is composed of 35 parts of aluminum oxide, 25 parts of calcium oxide, 15 parts of sodium carbonate, 20 parts of ammonium molybdate, 10 parts of sodium borate, 3 parts of cerium dioxide, according to mass fraction, the total amount of coking inhibitor is 0.03wt% of the total amount of complex gold concentrate, the bottom slag is discharged from the slag outlet every 35 min, the bottom slag can automatically flow out from the slag outlet, the copper is discharged from the copper outlet every 1.6h, the copper can automatically flow out from the copper outlet; the total Si and Ca content in the bottom slag is detected by X-ray fluorescence spectrometer, and the mass of SiO2 and CaO is converted, the mass ratio of Fe / SiO2 in the bottom slag is 2.0:1, and the mass ratio of CaO / SiO2 in the bottom slag is 0.16:1; the flue gas obtained in the process of bottom blowing smelting is returned to the waste heat recovery system, i.e. waste heat boiler, electric dust removal system, i.e. electric dust collector, arsenic recovery system and sulfuric acid recovery system to recover boiler ash, electric dust removal ash, crude arsenic trioxide and sulfuric acid, and the boiler ash is sent to the bottom blowing furnace for bottom blowing smelting, the electric dust removal ash is sent to the dust recovery system to recover arsenic iron alloy, and the steam obtained in the waste heat recovery system, i.e. waste heat boiler, can be used for power generation; the bottom slag returns to the slag separation system to recover copper concentrate and iron concentrate, the copper concentrate can be sent to the bottom blowing furnace for bottom blowing smelting; the arsenic recovery system recovers crude arsenic trioxide solid by quenching, then mixes the saturated arsenic trioxide aqueous solution with the crude arsenic trioxide according to the liquid-solid mass ratio of 8:1, then adds hydrochloric acid with a concentration of 12 mol / L, the molar ratio of hydrochloric acid to total antimony in crude arsenic trioxide is 20:1, stirs at 5 ℃ for 8h, filters and dries to obtain pure arsenic trioxide with a purity of 99.61%;

[0059] S2 the copper matte and limestone obtained in step S1 are mixed and directly flowed into the top-blown furnace through a chute, the feeding is carried out once every 1.6 h, and air is continuously blown into the furnace through the top lance, top-blown converting is carried out at 1250℃, the converting slag is discharged from the slag discharge port once every 4.5 h, the converting slag can automatically flow out from the slag discharge port, the blister copper is discharged from the blister copper discharge port once every 8.5 h, and the blister copper can automatically flow out from the blister copper discharge port; the total Ca and Fe element contents in the converting slag are detected by an X-ray fluorescence spectrometer, and the contents are converted into the mass of CaO and Fe2O3, and the mass ratio of CaO / Fe2O3 in the converting slag is 0.8:1; the flue gas obtained in the top-blown converting process is returned to the waste heat recovery system, i.e., a waste heat boiler, an electric dust removal system, i.e., an electric dust collector, and a sulfuric acid recovery system to recover boiler ash, electric dust removal ash and sulfuric acid, and the boiler ash is sent to the bottom-blown furnace for bottom-blown smelting, the electric dust removal ash is sent to a dust recovery system to obtain arsenic-iron alloy, and the steam obtained in the waste heat recovery system can be used to generate power by using the remaining heat; the converting slag is returned to a slag separation system to recover copper concentrate and iron concentrate powder, and the copper concentrate can be sent to the bottom-blown furnace for bottom-blown smelting;

[0060] S3 the blister copper obtained in step S2 is transferred to the anode furnace, sodium carbonate is added according to the mass ratio of sodium carbonate to the total amount of arsenic and antimony in the blister copper being 5:1, air is continuously blown in, refining is carried out at 1200℃ for 6 h, and then slag is obtained by skimming, and the slag is returned to step S2 for top-blown converting; after the reaction is completed, methane gas is introduced according to the molar ratio of methane to copper in the blister copper being 2:4, reduction is carried out in a nitrogen atmosphere at 1250℃ for 2 h, and finally copper anode plates are obtained by casting; the copper anode plates are sent to an electrolysis system to obtain cathode copper and copper anode sludge, and the copper anode sludge is returned to a rare and precious recovery system to obtain gold ingots, silver ingots, tellurium ingots, bismuth ingots, sponge palladium, sponge platinum and diantimony trioxide.

[0061] Example 3

[0062] A method for comprehensive recovery of multiple elements from a complex gold concentrate, wherein,

[0063] The complex gold concentrate contains chalcopyrite, pyrite, gold concentrate, silver concentrate and copper concentrate; the main contents of the complex gold concentrate are as follows: Au content 60.21 g / t, Ag content 280.14 g / t, Cu content 14.21 wt%, S content 26.57 wt%, Fe content 29.32 wt%, As content 2.31 wt%, Sb content 1.58 wt%, Bi content 1.74 wt%, Te content 0.54 wt%, Pd content 1.21 g / t and Pt content 1.09 g / t; wherein, the mass ratio of S / Cu in the complex gold concentrate is 1.87.

[0064] The method steps are as follows:

[0065] S1 complex gold concentrate, quartz and limestone mixed by belt continuous delivery to the bottom of the blast furnace, continuous through the bottom of the lance to the drum into the oxygen volume fraction of 78.25% oxygen-enriched air, at 1200 ℃ under continuous bottom blowing smelting, bottom blowing smelting process, in the bottom of the furnace flue spray particle size of not more than 74 μm of coking inhibitor, the coking inhibitor, according to the mass fraction of 40 parts of aluminum oxide, 30 parts of calcium oxide, 20 parts of sodium carbonate, 15 parts of ammonium molybdate, 7 parts of sodium borate, 2 parts of cerium dioxide, the total amount of coking inhibitor is 0.01wt% of the total amount of complex gold concentrate, every 30 min from the slag tapping hole bottom slag once, the bottom slag can be automatically discharged from the slag tapping hole, every 1.5h from the copper tapping hole ice copper once, the copper can be automatically discharged from the copper tapping hole; the total Si, Ca element content in the bottom slag is detected by X-ray fluorescence spectrometer, and the mass of SiO2 and CaO is converted, the mass ratio of Fe / SiO2 in the bottom slag is 1.6:1, and the mass ratio of CaO / SiO2 in the bottom slag is 0.14:1; the flue gas obtained in the bottom blowing smelting process is returned to the waste heat recovery system, i.e. waste heat boiler, electric dust removal system, i.e. electric dust collector, arsenic recovery system and sulfuric acid recovery system to recover boiler ash, electric dust removal ash, coarse arsenic trioxide and sulfuric acid, and the boiler ash is sent to the bottom blowing furnace for bottom blowing smelting, the electric dust removal ash is sent to the dust recovery system to recover arsenic iron alloy, and the steam obtained in the waste heat recovery system, i.e. waste heat boiler, can be used for power generation; the bottom slag returns to the slag separation system to recover copper concentrate and iron concentrate, and the copper concentrate can be sent to the bottom blowing furnace for bottom blowing smelting; the arsenic recovery system recovers coarse arsenic trioxide solid by quenching, then mixes the saturated arsenic trioxide aqueous solution with the coarse arsenic trioxide according to the liquid-solid mass ratio of 6:1, then adds 12 mol / L hydrochloric acid, the molar ratio of hydrochloric acid to total antimony in coarse arsenic trioxide is 10:1, and the stirring reaction is carried out at 15 ℃ for 4h, and then the pure arsenic trioxide with a purity of 99.64% is obtained by filtration and drying;

[0066] S2 the copper matte and limestone obtained in step S1 are mixed and directly flowed into the top-blown furnace through a chute, the feeding is carried out once every 1.5 h, and air is continuously blown into the furnace through the top lance, top-blown converting is carried out at 1200℃, the converting slag is discharged from the slag tapping hole once every 4.0 h, the converting slag can automatically flow out from the slag tapping hole, the blister copper is discharged from the blister tapping hole once every 8 h, and the blister copper can automatically flow out from the blister tapping hole; the total Ca and Fe element contents in the converting slag are detected by an X-ray fluorescence spectrometer, and the contents are converted into the mass of CaO and Fe2O3, and the mass ratio of CaO / Fe2O3 in the converting slag is 1:1; the flue gas obtained in the top-blown converting process is sequentially returned to a waste heat recovery system, i.e., a waste heat boiler, an electric dust removal system, i.e., an electric dust collector, and a sulfuric acid recovery system to recover boiler ash, electric dust removal ash, and sulfuric acid, and the boiler ash is sent to the bottom-blown furnace for bottom-blown smelting, the electric dust removal ash is sent to a dust recovery system to obtain arsenic-iron alloy, and the steam obtained in the waste heat recovery system can be used to generate power by using the remaining heat; the converting slag is returned to a slag separation system to recover copper concentrate and iron concentrate powder, and the copper concentrate can be sent to the bottom-blown furnace for bottom-blown smelting;

[0067] S3 the blister copper obtained in step S2 is transferred to the anode furnace, sodium carbonate is added according to the mass ratio of sodium carbonate to the total amount of arsenic and antimony in the blister copper of 2.5:1, air is continuously blown in, and refining is carried out at 1175℃ for 5 h, after the reaction is completed, the slag is obtained by slagging, and the slag is returned to step S2 for top-blown converting; after the reaction is completed, methane gas is introduced according to the molar ratio of methane to copper in the blister copper of 1.5:4, reduction is carried out in a nitrogen atmosphere at 1300℃ for 3 h, and finally the copper anode plate is obtained by casting; the copper anode plate is sent to an electrolysis system to obtain cathode copper and copper anode sludge, and the copper anode sludge is returned to a rare and precious recovery system to obtain gold ingot, silver ingot, tellurium ingot, bismuth ingot, sponge palladium, sponge platinum, and diantimony trioxide.

[0068] Comparative Example 1

[0069] The specific steps are as in Example 1, except that in step S1, no coking inhibitor is sprayed during the bottom-blown smelting.

[0070] Comparative Example 2

[0071] The specific steps are as in Example 2, except that in step S1, no coking inhibitor is sprayed during the bottom-blown smelting.

[0072] Since Examples 1-3 spray the coking inhibitor in the uptake of the bottom-blown furnace, the coking flowing with the flue gas is mainly deposited in the subsequent waste heat recovery system, i.e., the waste heat boiler, at this time, the coking to be cleaned is the coking of the waste heat boiler. When the steam produced by the waste heat boiler per hour in the bottom-blown smelting process is reduced by 5%, the coking in the waste heat boiler is cleaned; the cleaning period and the coking cleaning time of the waste heat boiler of the bottom-blown furnace in Examples 1-3 and Comparative Examples 1-2 are shown in Table 1; the coking component content in the waste heat boiler of Examples 1-3 is shown in Table 2.

[0073] Table 1: Period of cleaning coking and time of cleaning coking

[0074]

[0075] Table 2: Content table of coking components

[0076]

[0077] As shown in Table 1, compared with Comparative Examples 1-2, the coking of the waste heat boiler of the bottom-blown furnace is prolonged from original 20-25 days of cleaning once to 45-50 days of cleaning once; the cleaning time is reduced from original 6-12 h to 4-8 h each time, which shows that the coking inhibitor has better effect on inhibiting coking of the flue gas generated by the oxygen-enriched bottom-blown smelting of the complex gold concentrate; the content of the coking components in the waste heat boiler of Examples 1-3 is shown in Table 2, and the coking mainly contains Cu, Fe, S, Pb, Zn, As and the like.

[0078] The above description is merely preferred embodiments of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for the comprehensive recovery of multiple elements from complex gold concentrates, characterised in that, It comprises the following steps: S1. Complex gold concentrate and auxiliary material I are subjected to bottom blowing smelting in a bottom blowing furnace under an oxygen-rich air atmosphere to obtain copper matte, bottom slag and flue gas; the auxiliary material I is quartzite and limestone; S2. The copper matte and auxiliary material II are subjected to top blowing converting in a top blowing furnace under an air atmosphere to obtain crude copper, flue gas and converting slag; the auxiliary material II is limestone; S3. The crude copper is subjected to refining with a carbonate under an air atmosphere, and after the reaction is completed, methane gas is introduced to perform reduction under an inert atmosphere to obtain copper anode plates; In step S1, the coking inhibitor is sprayed in the ascending flue of the bottom blowing furnace during the bottom blowing smelting process; the coking inhibitor is composed of aluminum oxide, calcium oxide, sodium carbonate, ammonium molybdate, sodium borate and cerium dioxide; the coking inhibitor is composed of 30-40 parts of aluminum oxide, 20-30 parts of calcium oxide, 10-20 parts of sodium carbonate, 10-20 parts of ammonium molybdate, 5-10 parts of sodium borate and 1-3 parts of cerium dioxide in terms of mass fraction.

2. The method of claim 1, wherein, In step S1, the total amount of the coking inhibitor is 0.01wt%-0.05wt% of the total amount of the complex gold concentrate.

3. The method of claim 1, wherein, In step S1, the particle size of the coking inhibitor is not greater than 74μm.

4. The method of claim 1, wherein, In step S1, the flue gas is returned to a waste heat recovery system, an electric dust removal system, an arsenic recovery system and a sulfuric acid recovery system in sequence.

5. The method of claim 4, wherein, The arsenic recovery system recovers crude arsenic trioxide by quenching.

6. The method of claim 5, wherein, The crude arsenic trioxide is mixed with a saturated arsenic trioxide aqueous solution, then hydrochloric acid is added, and refined arsenic trioxide is obtained after the reaction is completed.

7. The method of claim 6, wherein, The solid mass ratio of the saturated arsenic trioxide aqueous solution to the crude arsenic trioxide mixed solution is (4-8):

1.

8. The method of claim 6, wherein, The molar ratio of the hydrochloric acid to the total amount of antimony in the crude arsenic trioxide is (5-20):1.

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