CN104313328A - Method for smelting and recovering lead and gold from reduction and sulfur fixation molten pool based on refractory gold ores and lead-containing residue raw materials - Google Patents

Abstract

The invention discloses a method for recovering lead and gold by smelting refractory gold ore and lead-containing waste slag raw materials to reduce sulfur-fixing molten pool. The method comprises refractory gold ore, lead-containing material, iron-containing sulfur-fixing agent and flux powder After mixing, granulate and dry to obtain pellets; after the obtained pellets are mixed with carbon reducing agent, they are added to an oxygen bottom-blown furnace, and oxygen-enriched air is introduced for smelting to obtain smelting slag, rough lead, iron matte and flue gas ; Gold and lead are mainly recovered from crude lead, the gold recovery rate is greater than 99%, and the lead recovery rate is greater than 95%; the smelting slag is used as high-silicon ingredients for cement or construction; the flue gas is emptied after recovering valuable metals; After boiling roasting, the iron slag is recovered, and the sulfur dioxide tail gas is used for acid production, thereby realizing the comprehensive recovery and utilization of resources; the method is simple in operation and low in cost, and satisfies industrial production.

Description

Method for recovering lead and gold based on refractory gold ore and lead-containing waste slag raw materials reduction and solidification molten pool smelting

technical field

The invention relates to a method for recovering lead and gold based on refractory gold ore and lead-containing waste slag raw materials reduction and sulfur-fixing molten pool smelting, which belongs to the technical field of gold ore smelting.

Background technique

At present, when refining complex and difficult gold concentrates containing arsenic, carbon, copper, and fine particles, the extraction methods used at home and abroad mainly include: boiling oxidation roasting method, pressure leaching pre-oxidation, bacterial pre-oxidation, etc. Oxidative cyanidation gold extraction method, etc. However, the above methods have problems such as large pollution, high cost requirements, long processing period and low adaptability to raw ore, and only focus on gold recovery, while seldom considering other valuable metals commonly found in gold mines . Therefore, it has become an inevitable trend to develop a high-efficiency and clean process for recovering gold from refractory gold mines and comprehensively recovering valuable metals therein.

my country is the world's largest lead producer, and also the world's largest lead-acid battery producer. It produces more than 2 million tons of waste lead-acid battery cement every year, which is the main source of low-sulfur lead-containing secondary materials. A small part is combined with lead sulfide concentrate to enter the lead smelting system, and most of them adopt the wet desulfurization conversion-reduction smelting process. In this process, wet desulfurization consumes a large amount of reagents and produces a large amount of waste water, and reduction smelting is an intermittent operation. High energy consumption, High cost and other serious problems. Other lead secondary materials include a variety of refractory lead secondary materials produced in the process of non-ferrous metals and ferromanganese metallurgy, such as lead soot, lead mud, lead sulfate slag, waste battery smelting slag, etc. Lead soot includes secondary lead smelting soot, blast furnace lead smelting soot, copper converter soot, lead matte treatment soot, lead-containing soot recovered from manganese plants, and lead-containing soot recovered from steel plants; lead sludge includes sludge generated from lead-containing wastewater treatment , Acid sludge collected by spraying and trapping of acid tail gas, sludge collected from rainwater and circulating water in lead factories; slag, zinc smelter high pressure oxygen leaching slag sulfur tailings. Most of these lead secondary materials are smelted by reverberatory furnaces or sintering-blast furnaces, which also have serious problems such as heavy pollution and high energy consumption.

Contents of the invention

In view of the deficiencies in the prior art for the treatment of refractory gold ore and low-sulfur lead-containing secondary materials, the purpose of the present invention is to provide a method based on refractory gold ore and lead-containing waste slag raw materials that can be effectively recovered through simple smelting technology The method of gold and lead, the method is simple in operation and low in cost, realizes comprehensive recycling of valuable resources, and satisfies industrial production.

The present invention provides a method for reclaiming lead and gold based on refractory gold ore and lead-containing waste slag raw materials reduction sulfur fixation molten pool smelting recovery lead and gold, the method includes the following steps:

Step 1: Granulation

After mixing refractory gold ore, lead-containing material, iron-containing sulfur fixative and flux powder, granulate and dry to obtain pellets; among them, the mass of lead-containing material is 30-60% of the mass of refractory gold ore, and the iron-containing The amount of sulfur-fixing agent added is 1.0-2.0 times the theoretical molar amount required for all iron in the iron-sulfur-fixing agent to be converted into iron sulfide, and the amount of flux added makes the composition of the pellets meet the molar ratio of _SiO2 to FeO of 0.8-1.2:1 , the molar ratio of _SiO2 to CaO is 1～2:1; the lead-containing material is one or the several kinds; the iron-containing sulfur-fixing agent is iron oxide ore and/or pyrite slag; the flux is river sand and/or limestone;

Step 2: Smelting

After the pellets obtained in Step 1 are mixed with the carbon reducing agent, they are added to an oxygen bottom-blown furnace, and oxygen-enriched air is introduced, and smelted at a high temperature of 900-1300°C to obtain smelting slag, rough lead, iron matte and flue gas; among them, The intake of oxygen-enriched air is 100-200Nm ^per ton of pellets; the volume content of oxygen in the oxygen-enriched air is 30-95%; the mass of the carbon reducing agent is 8-15% of the mass of the pellets;

Step 3: Electrolysis

The crude lead obtained in step 2 is electrolytically refined to obtain refined lead and gold-containing anode slime.

The method for recovering lead and gold based on refractory gold ore and lead-containing waste slag raw materials reduction sulfur-fixing molten pool smelting and recovery of lead and gold also includes the following preferred schemes:

In the preferred solution, the particle size of the refractory gold ore is 0.02-1mm.

In a preferred solution, the particle size of the lead-containing material is 0.02-10mm.

In a preferred solution, the particle size of the flux is 1-20 mm.

In a preferred scheme, the particle size of the carbon reducing agent is 5-25mm.

In a preferred solution, the carbon reducing agent is pulverized coal and/or coking coal.

In a preferred solution, the mass percentage of moisture in the pellets is 2-10%, and the particle size of the pellets is 6-30 mm.

In a preferred solution, the melting temperature is 1100-1300°C.

In a preferred scheme, the smelting time is 30 to 120 minutes.

In the preferred scheme, the iron matte obtained in step 2 is boiled and roasted to obtain iron slag and sulfur dioxide flue gas, and the iron slag is used as an iron-containing sulfur fixation agent to return to the step 1 process, and the sulfur dioxide tail gas enters the acid system to prepare sulfuric acid.

In the preferred scheme, the flue gas obtained in step 2 is emptied after dust removal to recover valuable metals.

In the preferred solution, the smelting slag obtained in step 2 is used as a high-silicon ingredient for cement or construction.

The inventive point of the present invention: After a large amount of research by the inventor, it is found that complex and difficult-to-handle gold ore containing arsenic, carbon, copper, and fine particle wrapping and lead-containing waste slag raw materials are subjected to an iron-containing sulfur-fixing agent and subjected to an appropriate temperature. The reduction smelting under the environment can effectively dissociate impurities such as lead and gold from other metals, and finally obtain a lead-gold alloy. A large number of studies show: refractory gold ore, lead-containing material and iron-containing sulfur fixative, etc., under the reaction conditions of the present invention, carry out the following series of reactions: (1) iron oxide is reduced to ferrous oxide or metallic iron: Fe ₂ O ₃ +CO=2FeO+CO ₂ , Fe ₂ O ₃ +3CO=2Fe+CO ₂ , (2) reduction and decomposition of lead sulfate in lead waste residue: PbSO ₄ +4CO=PbS+4CO ₂ , (3) sulfur fixation The FeS produced by the reaction forms iron matte: FeS ₂ +FeO+CO=2FeS+CO ₂ , 2FeS ₂ =2FeS+S ₂ , FeO+0.5S ₂ +CO=FeS+CO ₂ , 4FeAsS+3O ₂ =4FeS+2As ₂ O ₃ , PbSO ₄ +FeO+CO=Pb+FeS+CO ₂ , PbS+FeO+CO=Pb+FeS+CO ₂ , (4) reduction reaction of lead oxide: PbO+CO=Pb+CO ₂ , PbO ₂ + 2CO = Pb + 2CO ₂ . Through the smelting process of the present invention, most of the gold enters the crude lead, and the refined lead and gold-rich anode slime are obtained after the crude lead is electrolytically refined, and valuable elements such as gold are recovered from the anode slime; iron and sulfur form iron matte, A small part of gold and other metals enter the iron matte. After the iron matte is boiled and roasted, the iron slag returns to the smelting process to recycle iron and recover gold, while the tail gas is high sulfur dioxide gas. After recovering heat energy through the waste heat boiler, acid is produced through the acid system; The smelting slag is used as a high-silicon ingredient in cement or construction. The technical scheme of the invention realizes the co-recovery of valuable metals in refractory gold ore and lead waste residue, so that resources can be fully utilized.

Compared with the prior art, the beneficial effects of the present invention are: 1. The process is simple, the cost is low, and large-scale industrial production is possible. 2. The gold recovery rate is greater than 99%, and the lead recovery rate is greater than 95%. The smelting slag is used as a high-silicon ingredient in cement or construction; the flue gas is emptied after recovering valuable metals; after the iron matte is calcined, the iron slag is recovered, and the tail gas is rich in Sulfur dioxide is used to make acid, realizing the comprehensive recycling of resources, which is environmentally friendly and economical.

Description of drawings

[Fig. 1] is a process flow diagram of the present invention.

Detailed ways

The following examples are intended to further illustrate the content of the present invention, but not to limit the protection scope of the present invention.

Example 1

Gold ore with high sulfur content (with a particle size range of 0.08-0.5mm), lead sulfide concentrate (with a particle size range of 0.05-5mm), iron oxide ore (with a particle size range of 0.08-5mm) and limestone (with a particle size range of 2~15mm) powders are mixed, granulated and dried until the moisture content is about 8%, and the pellets with a particle size of about 20mm are obtained; the main components of the pellets are Pb21.01%, _SiO2 11.86%, FeO11 .67%, CaO5.27%, S10.63%, Au10g/t. Gained pellets are mixed with coking coal (the quality is 14% of the pellet mass, and the particle diameter is 10-20 mm), then they are added to the oxygen bottom-blown furnace, and the oxygen volume percentage is fed at a rate of 180 Nm ^per ton of pellets. 35% oxygen-enriched air, smelting at a high temperature of 1200-1300°C for 50 minutes to obtain smelting slag, crude lead, iron matte and flue gas; the crude lead alloy contains 135g/t of gold, and the rate of gold into the alloy is 99.2%, through electrolytic refining The anode slime containing lead and gold is obtained, the comprehensive recovery rate of gold is 99.8%, the recovery rate of lead reaches 84.75%, and the recovery rate is 98.64%. The flue gas product is collected through dust removal and dust containing metal oxides such as zinc, and the concentration of SO ₂ is less than 400ppm, which meets the requirement of direct emptying and achieves the effect of sulfur fixation. After the iron matte is roasted by high-temperature boiling, the mass percentage concentration of _SO2 in the obtained sulfur dioxide tail gas is greater than 18%, and the acid production process is directly used to produce acid. The smelting slag is a high-silicon product and is used as a construction raw material.

Example 2

Gold ore with high carbon content (with a particle size range of 0.1-1mm), hydrometallurgy slag (with a particle size range of 0.1-10mm), iron oxide ore (with a particle size range of 1-10mm) and limestone (with a particle size range of 2-15mm) powders are mixed, granulated and dried until the moisture content is about 10%, and the pellets with a particle size of about 15mm are obtained; the main components of the pellets are Pb15.8%, _SiO2 20.96%, FeO20.09%, CaO10.44%, S20.3%, Au14g/t. Gained pellets are mixed with coking coal (the quality is 12% of the pellet mass, and the particle diameter is 15-25 mm), and then they are added to the oxygen bottom-blown furnace, and the oxygen volume percentage is fed at a rate of 150 Nm ^per ton of pellets. 60% oxygen-enriched air, smelting at a high temperature of 1150-1250°C for 80 minutes to obtain smelting slag, crude lead, iron matte and flue gas; the crude lead alloy contains 157g/t of gold, and the rate of gold into the alloy is 99%, through electrolytic refining The anode slime containing lead and gold is obtained, the comprehensive gold recovery rate is 99.2%, the lead recovery rate reaches 80.62%, and the recovery rate is 98.6%. The flue gas product is collected through dust removal and dust containing metal oxides such as zinc, and the concentration of SO ₂ is less than 400ppm, which meets the requirement of direct emptying and achieves the effect of sulfur fixation. After the iron matte is roasted by high-temperature boiling, the mass percentage concentration of _SO2 in the obtained sulfur dioxide tail gas is greater than 18%, and the acid production process is directly used to produce acid. The smelting slag is a high-silicon product and is used as a construction raw material.

Example 3

The arsenic-containing gold ore (with a particle size range of 0.05-1 mm), lead-acid battery mud (with a particle size range of 1-10 mm), pyrite slag (with a particle size range of 1-10 mm) and river sand (with a particle size of range of 5 to 15mm) powders are mixed, granulated and dried until the moisture content is about 6%, to obtain pellets with a particle size of about 15mm; the main components of the prepared pellets are Pb18.30%, Zn13%, SiO ₂ 19.23%, FeO21.93%, CaO10.83%, S20.12%, As2%, Au15g/t. Gained pellets are mixed with coking coal (the quality is 10% of the pellet mass, and the particle diameter is 10-25 mm), then they are added to the bottom-blown oxygen furnace, and the oxygen volume percentage is fed at a rate of 180 Nm ^per ton of pellets. 80% oxygen-enriched air, smelting at a high temperature of 1100-1200°C for 50 minutes to obtain smelting slag, crude lead, iron matte and flue gas; the crude lead alloy contains 163g/t of gold, and the rate of gold into the alloy is 99.3%, through electrolytic refining The anode slime containing lead and gold is obtained, the comprehensive recovery rate of gold is 99.5%, the recovery rate of lead reaches 79.98%, and the recovery rate is 98.4%. The flue gas product is collected through dust removal and dust containing metal oxides such as zinc, and the concentration of SO ₂ is less than 400ppm, which meets the requirement of direct emptying and achieves the effect of sulfur fixation. After the iron matte is roasted by high-temperature boiling, the mass percentage concentration of _SO2 in the obtained sulfur dioxide tail gas is greater than 18%, and the acid production process is directly used to produce acid. Smelting slag is a high-silicon product and is used as cement raw material.

Claims (9)

1. reduce based on difficult-treating gold mine and lead containing sludge raw material and consolidate the method that lead and gold are reclaimed in sulfur melting bath melting, it is characterized in that, comprise the following steps:

Step one: granulation

After difficult-treating gold mine, lead-containing material, iron content sulphur-fixing agent and flux powder being mixed, granulation, drying, obtain pellet; Wherein, the quality of lead-containing material is 30 ~ 60% of difficult-treating gold mine quality, and the add-on of iron content sulphur-fixing agent all changes into 1.0 ~ 2.0 times of theoretical molar amount needed for iron sulphide for iron in iron sulphur-fixing agent, and the add-on of flux makes pellet composition meet SiO ₂be 0.8 ~ 1.2:1, SiO with the mol ratio of FeO ₂be 1 ~ 2:1 with the mol ratio of CaO; Described lead-containing material is one or more in concentrate of lead sulfide ore, From Zinc Hydrometallurgy Residue, leaded wet type copper smelting slag, lead acid cell mud; Described iron content sulphur-fixing agent is iron oxide ore and/or pyrite cinder; Described flux is river sand and/or Wingdale;

Step 2: melting

After step one gained pellet mixes with charcoal reductive agent, join in oxygen bottom blown furnace, pass into oxygen-rich air, melting under 900 ~ 1300 DEG C of high temperature, obtain smelting slag, lead bullion, iron sulfonium and flue gas; Wherein, the intake of oxygen-rich air is 100 ~ 200Nm ³pellet per ton; In described oxygen-rich air, oxygen volume content is 30 ~ 95%; Described charcoal reductive agent quality is 8 ~ 15% of pellet mass;

Step 3: electrolysis

Step 2 gained lead bullion, by electrorefining, obtains lead bullion and the anode sludge containing gold.

2. the method for claim 1, is characterized in that, described difficult-treating gold mine granularity is 0.02 ~ 1mm; Described lead-containing material granularity is 0.02 ~ 10mm; Described flux granularity is 1 ~ 20mm.

3. the method for claim 1, is characterized in that, described charcoal reductive agent granularity is 5 ~ 25mm.

4. method as claimed in claim 3, it is characterized in that, described charcoal reductive agent is fine coal and/or coking coal.

5. the method for claim 1, is characterized in that, in described pellet, biodiversity percentage composition is 2 ~ 10%, and pellet particle diameter is 6 ~ 30mm.

6. the method for claim 1, is characterized in that, smelting temperature is 1100 ~ 1300 DEG C.

7. the method for claim 1, is characterized in that, described smelting time is 30 ~ 120 minutes.

8. the method as described in any one of claim 1 ~ 7, it is characterized in that, step 2 gained iron sulfonium obtains scum and sulfur dioxide flue gas after fluidized bed roasting, and scum returns step one process as iron content sulphur-fixing agent, and SO 2 tail gas body enters acid making system and prepares sulfuric acid.

9. the method for claim 1, is characterized in that, step 2 gained flue gas reclaims after valuable metal emptying through dedusting.