阅读说明：本技术 一种粗铅火法精炼除铜剂、制备方法及应用 (Fire refining decoppering agent for lead bullion, preparation method and application ) 是由 柯朋 张祖涛 霍成立 杨文明 王旬 刘超 庞杰 黄仙 于 2020-12-10 设计创作，主要内容包括：本发明公开了一种粗铅火法精炼除铜剂、制备方法及应用,除铜剂,按质量分数计包括：硫铁矿50-70％,硫磺10-30％,硅酸盐水泥1％-20％,铁粉5％-20％；制备方法包括：按比例称取硫铁矿、硫磺、硅酸盐水泥和铁粉,搅拌混合均匀制得除铜剂；应用包括：将除铜剂加入到粗铅熔液中,充分搅拌反应,形成漂浮在铅液中的除铜渣,去除粗铅熔液中的铜杂质。本发明的除铜剂可有效去除粗铅液中的杂质铜,降低除铜渣中的含铅量,提高铅直收率；同时,该除铜剂加入铅液中基本不产生SO-2,减少对环境的污染。(The invention discloses a copper removing agent for fire refining of lead bullion, a preparation method and application thereof, wherein the copper removing agent comprises the following components in percentage by mass: 50-70% of pyrite, 10-30% of sulfur, 1-20% of Portland cement and 5-20% of iron powder; the preparation method comprises the following steps: weighing pyrite, sulfur, portland cement and iron powder according to a proportion, and uniformly stirring and mixing to prepare a copper removing agent; the application comprises the following steps: adding the copper removing agent into the crude lead solution, fully stirring for reaction to form copper removing slag floating in the lead solution, and removing copper impurities in the crude lead solution. The copper removing agent can effectively remove impurity copper in the crude lead liquid, reduce the lead content in the copper removing slag and improve the vertical yield; meanwhile, the copper removing agent does not generate SO basically when added into the lead liquid 2 And the pollution to the environment is reduced.)

1. The copper removing agent for the fire refining of the crude lead is characterized by comprising the following components in parts by mass:

50-70% of pyrite;

10-30% of sulfur;

1% -20% of Portland cement;

5 to 20 percent of iron powder.

2. The copper remover according to claim 1, which comprises the following components in percentage by mass:

55-65% of pyrite;

15-25% of sulfur;

5 to 15 percent of Portland cement;

10 to 15 percent of iron powder.

3. The copper remover according to claim 2, which comprises the following components in percentage by mass:

60% of pyrite;

20% of sulfur;

10% of Portland cement;

10 percent of iron powder.

4. The copper removing agent according to any one of claims 1 to 3, wherein the pyrite is crushed, sieved and dried to obtain powder with the particle size of 20-50 μm and the water content of less than 0.8%.

5. The copper remover according to any of claims 1 to 3, wherein the sulphur is flake sulphur or powdered sulphur, having a moisture content of < 0.5%.

6. The copper remover according to any one of claims 1-3, wherein the portland cement comprises CaO and SiO₂And FeO for slagging in the copper removal process.

7. The copper remover according to any of claims 1 to 3, characterized in that the particle size of the iron powder is <40 μm.

8. A method for preparing the copper removing agent according to any one of claims 1 to 7, which comprises the following steps:

weighing pyrite, sulfur, portland cement and iron powder according to a proportion, and stirring and mixing uniformly to prepare the copper removing agent.

9. Use of a copper remover according to any of claims 1-7, comprising:

and adding the copper removing agent into the crude lead melt, fully stirring for reaction to form copper removing slag floating in the lead melt, and removing copper impurities in the crude lead melt.

10. The use according to claim 9,

the adding amount of the copper removing agent is 1-2 times of the mass of copper in the crude lead;

the adding temperature of the copper removing agent is 340-360 ℃;

the reaction stirring time of the copper removing agent is 30-60 min.

Technical Field

The invention relates to the technical field of lead smelting, in particular to a fire refining copper removing agent for lead bullion, a preparation method and application.

Background

The crude lead produced by smelting the primary lead and the secondary lead is prepared into an anode plate after fire refining and impurity removal, and then enters an electrolytic refining process. Firstly, removing impurity element copper in pyrometallurgical refining, wherein the traditional copper removal method comprises liquating copper removal and sulfuration copper removal; the copper is removed by melting out, namely, part of copper is removed by utilizing the fact that the solubility of copper in lead is reduced along with the reduction of temperature, the limit value of the copper is 0.06 percent, and the copper can only be used for preliminary copper removal; the copper removal by vulcanization is carried out by adding sulfur and copper to react to generate Cu₂S，Cu₂The density of S is less than that of the lead liquid, and the S floats to the slag phase on the upper layer of the lead liquid, so that the S is separated from the lead liquid.

In the copper removing process by sulfuration, because the sulfur is inflammable, the sulfur can be rapidly combusted when being added into the lead liquid to generate a large amount of SO₂Smoke pollutes the environment and reduces the utilization rate; in addition, the sulfur and the lead react to generate lead sulfide which enters a slag layer, so that the lead content in the copper-removing slag is high, and the direct yield of lead metal in the lead liquid is reduced.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a copper removing agent for fire refining of crude lead, a preparation method and application thereof, wherein the copper removing agent can effectively remove impurity copper in crude lead liquid, reduce the lead content in copper removing slag and improve the vertical yield; meanwhile, the copper removing agent does not generate SO basically when added into the lead liquid₂And the pollution to the environment is reduced.

The invention aims to provide a copper removing agent for fire refining of lead bullion, which comprises the following components in percentage by mass:

50-70% of pyrite;

10-30% of sulfur;

1% -20% of Portland cement;

5 to 20 percent of iron powder.

As a further improvement of the invention, the method comprises the following steps in percentage by mass:

55-65% of pyrite;

15-25% of sulfur;

5 to 15 percent of Portland cement;

10 to 15 percent of iron powder.

As a further improvement of the invention, the method comprises the following steps in percentage by mass:

60% of pyrite;

20% of sulfur;

10% of Portland cement;

10 percent of iron powder.

As a further improvement of the invention, the pyrite is crushed, screened and dried to obtain powder with the particle size of 20-50 μm and the water content of less than 0.8%.

As a further improvement of the invention, the sulfur is flake sulfur or powdered sulfur, and the water content is less than 0.5%.

As a further improvement of the invention, the portland cement comprises CaO and SiO₂And FeO for slagging in the copper removal process.

As a further development of the invention, the particle size of the iron powder is <40 μm.

The second purpose of the invention is to provide a preparation method of the copper removing agent, which comprises the following steps:

weighing pyrite, sulfur, portland cement and iron powder according to a proportion, and stirring and mixing uniformly to prepare the copper removing agent.

The third purpose of the invention is to provide an application of the copper removing agent, which comprises the following components:

and adding the copper removing agent into the crude lead melt, fully stirring for reaction to form copper removing slag floating in the lead melt, and removing copper impurities in the crude lead melt.

As a further improvement of the present invention,

the adding amount of the copper removing agent is 1-2 times of the mass of copper in the crude lead;

the adding temperature of the copper removing agent is 340-360 ℃;

the reaction stirring time of the copper removing agent is 30-60 min.

Compared with the prior art, the invention has the beneficial effects that:

the method utilizes the synergistic reaction of pyrite and sulfur, utilizes Portland cement for slagging and utilizes iron powder for replacement to fully reduce lead in the slag, fully removes impurity copper in the crude lead liquid, and can remove the copper content in the crude lead to be below 0.001 percent; it reduces the lead content in the decoppered slag, improves the lead yield, and avoids the generation of SO₂The flue gas pollutes the environment, improves the copper removal effect, reduces the lead loss in the copper removal process and improves the economic benefit.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

The invention is described in further detail below:

the invention provides a copper removing agent for fire refining of lead bullion, which comprises the following components in percentage by mass:

50-70% of pyrite;

10-30% of sulfur;

1% -20% of Portland cement;

5 to 20 percent of iron powder.

Preferably, the paint comprises the following components in percentage by mass:

55-65% of pyrite;

15-25% of sulfur;

5 to 15 percent of Portland cement;

10 to 15 percent of iron powder.

Further preferably, the paint comprises the following components in percentage by mass:

60% of pyrite;

20% of sulfur;

10% of Portland cement;

10 percent of iron powder.

In the copper removing agent, the pyrite of the invention is crushed, screened and dried to obtain powder with the particle size of 20-50 mu m and the water content of less than 0.8%; according to the invention, the pyrite is subjected to crushing, screening and drying treatment, so that the specific surface area of the pyrite is increased, and the reaction rate of the pyrite and the impurity copper in the lead liquid is increased.

In the copper removing agent, the sulfur is flaky sulfur or powdery sulfur, and the water content is less than 0.5 percent; so as to increase the specific surface area of the sulfur and improve the reaction rate of the sulfur and the impurity copper in the lead liquid.

In the copper remover, the Portland cement of the invention comprises CaO and SiO₂And FeO, the portland cement mainly plays a slagging role in the copper removal process, and the portland cement can reduce the density and viscosity of the copper removal slag generated in the copper removal process, so that the copper removal slag is fully separated from lead liquid, the metal lead in the copper removal slag is effectively reduced, and the vertical yield is improved.

In the above copper remover, the particle size of the iron powder of the present invention is <40 μm; so as to increase the specific surface area of the iron powder and improve the reaction rate of the iron powder and the copper removal reaction process.

Based on the formula of the copper remover, the preparation method of the copper remover comprises the following steps:

weighing pyrite, sulfur, portland cement and iron powder according to a proportion, and stirring and mixing uniformly to prepare the copper removing agent.

Based on the formula of the copper remover, the application of the copper remover comprises the following steps:

adding a copper removing agent into the crude lead solution, fully stirring for reaction to form copper removing slag floating in the lead solution, and removing copper impurities in the crude lead solution; wherein the content of the first and second substances,

the adding amount of the copper removing agent is 1-2 times of the mass of copper in the crude lead; furthermore, when the copper concentration in the crude lead is higher, the addition times can be increased, so that the copper removal effect is ensured, and unnecessary waste is not caused excessively;

the adding temperature of the copper removing agent is 340-360 ℃, and the reaction temperature is close to the melting point of the crude lead, so that the solubility of copper in the crude lead can be reduced;

the reaction stirring time of the copper removing agent is 30-60min, and the copper removing agent is fully reacted by fully stirring, so that the copper removing efficiency is improved.

The reaction principle of the copper removing agent for removing impurity copper in the crude lead solution is as follows:

1) the main component of the pyrite of the invention is FeS₂During the reaction, FeS₂Firstly, heating to decompose the mixture into FeS and elemental S; since S and Cu have a higher affinity than S and Fe, FeS reacts with Cu to form Cu₂S due to Cu₂Low density of S in lead liquid, Cu₂S can enter a slag layer to be separated from lead liquid; the generated simple substance S firstly reacts with Pb to produce PbS, and PbS reacts with Cu to generate Cu₂S，Cu₂S enters a slag layer to be separated from the lead liquid, and the main reactions involved are as follows:

2FeS₂→2FeS+2S

FeS+2Cu→Cu₂S+Fe

S+Pb→PbS

PbS+2Cu→Cu₂S+Pb

2) the sulfur of the invention can further react with copper in the crude lead solution to fully remove the copper in the crude lead, the sulfur firstly contacts with the lead to react to generate PbS because the lead is taken as a main metal, and the affinity of S and Cu is greater than that of S and Pb, and the PbS further reacts with Cu to generate Cu₂S，Cu₂S floats upwards to a slag layer and is separated from lead liquid, and the related main reactions are as follows:

S+Pb→PbS

PbS+2Cu→Cu₂S+Pb

3) the main components of the Portland cement of the invention are CaO and SiO₂FeO mainly plays a role in slagging in the copper removal process, and portland cement can reduce the density and viscosity of the copper removal slag generated in the copper removal process, so that the copper removal slag is fully separated from lead liquid, the metal lead in the copper removal slag is effectively reduced, and the vertical yield is improved.

4) The iron powder in the copper removing agent component can react with PbS in the slag, so that the lead content in the slag is further reduced. Excessive PbS produced by reaction in the copper removing process can enter slag, lead content in the slag is high, vertical yield is reduced, iron powder and PbS react to replace Pb in the slag, lead content in the slag is reduced, and the vertical yield is improved, wherein the involved reactions are as follows:

PbS+Fe→FeS+Pb

the design principle of the components of the copper remover is as follows:

1. the pure sulfur is added and can float on the surface to be burnt by contacting with air to generate SO₂According to the invention, the sulfur is mixed with the pyrite, the portland cement and the iron powder, the ratio of the sulfur is reduced to 10-30%, and when the copper removing agent is added into the lead liquid, the sulfur is isolated from air due to the wrapping of other substances, so that the direct contact combustion loss of the sulfur and the air is prevented, and the utilization rate of the sulfur is improved.

2. The invention adds 50% -70% of pyrite, uses pyrite as the main copper removal substance, and uses the combination of sulfur in pyrite and copper in lead liquid to remove copper, SO the pyrite is used as the main copper removal substance, on one hand, because pyrite contains about 50% of sulfur element, and does not produce SO when reacting with copper₂On the other hand, the flue gas is because the pyrite is cheap and the material source is wide.

3. According to the invention, 10-30% of sulfur is added as a supplement substance for copper removal, and the sulfur is further removed when the pyrite cannot remove the copper in the lead liquid to the required range; and the sulfur is a sulfur simple substance and is easy to react and combine with copper in the lead liquid, so that the copper removal efficiency can be further improved.

4. According to the invention, 5% -15% of portland cement is added to improve the separation effect of the copper-removing slag and the lead liquid, the slag amount is increased when the content is too high, more lead is taken away instead, and the change effect of the content is not obvious on the viscosity and density of the copper-removing slag.

5. According to the invention, 5% -20% of iron powder is added, the addition amount of the iron powder is determined according to the lead content in the slag, so that the lead reduction effect is ensured, and a small part of excessive iron powder can not be dissolved into the lead liquid to cause the standard exceeding of lead and iron content due to the incompatibility of iron and lead.

6. The density of the lead liquid is about 10.5g/cm³Much larger than other substances, yellowThe mixture of iron ore, portland cement and the like can float upwards to enter a slag layer, and as can be seen from a lead-iron binary alloy phase diagram, iron and lead are not dissolved, and iron powder floats on the upper surface layer of a lead liquid in a solid state at the temperature of 340-360 ℃. The Ca and Si of the cement in the silicate exist in oxidation state, and can not be reduced into simple substances in the lead liquid and enter the lead liquid.

7. The method takes the pyrite as a main copper removal substance and the elemental sulfur as an auxiliary substance, improves the copper removal effect, simultaneously adds a small amount of portland cement as a slagging agent, changes the surface and interfacial tension between the lead liquid and the copper removal slag, reduces the direct bonding force of the lead liquid and the copper removal slag, improves the separation effect of the lead liquid and the copper removal slag, reduces the metal lead contained in the copper removal slag, and reduces the lead metal loss caused by entrainment. And a small amount of iron powder is added, and the iron powder is used for replacing lead in the lead sulfide in the copper-removed slag, so that the lead content in the slag is further reduced. Starting from the simple substance lead and the compound lead in all directions, the lead content in the slag is reduced comprehensively, and the lead recovery rate is improved.

Example 1

The invention provides a copper removing agent for fire refining of lead bullion, which comprises the following components in percentage by mass: 50% of pyrite, 30% of sulfur, 5% of Portland cement and 15% of iron powder.

The preparation method comprises the following steps: crushing, sieving and drying the pyrite to obtain powder with the particle size of 20-50 mu m and the water content of less than 0.8 percent, and fully and uniformly mixing the powder with other raw materials according to the proportion to prepare the copper removing agent.

The application comprises the following steps: melting crude lead, sampling and testing the copper content, and calculating the total copper content in the crude lead according to the weight of the crude lead and the copper content; when the temperature of the lead liquid is 340 ℃, adding a copper removing agent with the total copper content being 1 time, stirring for 30min, sampling and testing, wherein the lead contains 0.0009 percent of Cu0 and the slag contains 52.6 percent of Pb6.

Example 2

The invention provides a crude lead fire refining copper removing agent, which comprises the following components in parts by mass: 60% of pyrite, 20% of sulfur, 10% of Portland cement and 10% of iron powder.

The preparation method comprises the following steps: crushing, sieving and drying the pyrite to obtain powder with the particle size of 20-50 mu m and the water content of less than 0.8 percent, and fully and uniformly mixing the powder with other raw materials according to the proportion to prepare the copper removing agent.

The application comprises the following steps: melting crude lead, sampling and testing the copper content, and calculating the total copper content in the crude lead according to the weight of the crude lead and the copper content; when the temperature of the lead liquid is 350 ℃, adding a copper removing agent with the total copper content being 1.5 times of that of the lead liquid, stirring for 40min, sampling and testing, wherein the lead contains 0.0007 percent of Cu0.0007 percent, and the slag contains 51.2 percent of Pb2.

Example 3

The invention provides a crude lead fire refining copper removing agent, which comprises the following components in parts by mass: 70% of pyrite, 10% of sulfur, 15% of Portland cement and 5% of iron powder.

The preparation method comprises the following steps: crushing, sieving and drying the pyrite to obtain powder with the particle size of 20-50 mu m and the water content of less than 0.8 percent, and fully and uniformly mixing the powder with other raw materials according to the proportion to prepare the copper removing agent.

The application comprises the following steps: melting crude lead, sampling and testing the copper content, and calculating the total copper content in the crude lead according to the weight of the crude lead and the copper content; when the temperature of the lead liquid is 360 ℃, adding a copper removing agent with the total copper content being 2 times of that of the lead liquid, stirring for 50min, sampling and testing, wherein the lead contains 0.0008 percent of Cu0, and the slag contains 52.1 percent of Pb.

In addition, the following embodiments are also included:

example 4

The invention provides a crude lead fire refining copper removing agent, which comprises the following components in parts by mass: 55% of pyrite, 25% of sulfur, 5% of Portland cement and 15% of iron powder.

Example 5

The invention provides a crude lead fire refining copper removing agent, which comprises the following components in parts by mass: 65% of pyrite, 15% of sulfur, 10% of Portland cement and 10% of iron powder.

Comparative example 1

Melting the crude lead, sampling and testing the copper content, and calculating the total copper content in the crude lead according to the weight of the crude lead and the copper content.

When the temperature of the lead liquid is 340 ℃, adding sulfur with the total copper content being 1 time, stirring for 30min, sampling and testing, wherein the lead contains Cu0.0035 percent, and the slag contains Pb73.5 percent.

Comparative example 2

Melting the crude lead, sampling and testing the copper content, and calculating the total copper content in the crude lead according to the weight of the crude lead and the copper content.

When the temperature of the lead liquid is 350 ℃, adding sulfur with the total copper content being 1.5 times, stirring for 40min, sampling and testing, wherein the lead contains 0.0027 percent of Cu0, and the slag contains 72.4 percent of Pb4.

Comparative example 3

Melting the crude lead, sampling and testing the copper content, and calculating the total copper content in the crude lead according to the weight of the crude lead and the copper content.

When the temperature of the lead liquid is 360 ℃, adding sulfur with the total copper content being 2 times, stirring for 50min, sampling and testing, wherein the lead contains 0.0022 percent of Cu0, and the slag contains 71.8 percent of Pb71.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.