CN113999996B

CN113999996B - Method for preparing anode plate by complex copper-containing material through fire refining

Info

Publication number: CN113999996B
Application number: CN202111131690.0A
Authority: CN
Inventors: 刘亮强; 程贵桃; 王强; 罗波
Original assignee: Jiangxi Copper Qingyuan Co ltd; Jiangxi Copper Technology Research Institute Co ltd
Current assignee: Jiangxi Copper Qingyuan Co ltd; Jiangxi Copper Technology Research Institute Co ltd
Priority date: 2021-09-26
Filing date: 2021-09-26
Publication date: 2022-03-29
Anticipated expiration: 2041-09-26
Also published as: CN113999996A

Abstract

The invention relates to a fire metallurgy process in the field of nonferrous metallurgy, in particular to a method for preparing an anode plate by complex copper-containing material fire refining, which comprises the following steps: detecting the contents of copper and iron in the complex copper-containing material; preparing a slagging agent according to the detection result, adding the complex copper-containing material and the slagging agent into a reaction furnace, heating to a preset temperature, and introducing compressed air or oxygen-enriched air to stir for carrying out oxidation reaction; and (4) preserving heat for a certain time after the oxidation is finished, then slagging off, and casting the copper liquid into an anode plate after the reduction. The invention has the beneficial effects that: the invention adopts the composite slagging agent to oxidize and slagging, improves the good fluidity and low viscosity of the slag, and simultaneously ensures that copper in the slag is further settled, the slag amount is 90-95 percent of the original slag amount, the slag contains copper bottom, and the invention has the advantages of high direct copper yield, short process flow and low production cost.

Description

Method for preparing anode plate by complex copper-containing material through fire refining

Technical Field

The invention relates to a fire metallurgy process in the field of nonferrous metallurgy, in particular to a method for preparing an anode plate by complex copper-containing material fire refining.

Background

Copper is an important basic metal, and is widely applied to the fields of electric power, communication, building, military industry, transportation and the like due to excellent mechanical, heat conduction, electric conduction and corrosion resistance. With the economic development, China has become the largest copper producing and consuming countries, and the annual production of refined copper is close to 1000 million tons.

The production of refined copper partly originates from the naturally developed copper ore and partly from the secondary copper resources for recovery. The traditional copper smelting mainly uses copper ores as raw materials to produce, the copper ores are subjected to mineral separation to obtain copper concentrate, most of the copper ores exist in the form of sulfides, and sulfur in the part has larger heat, so the copper concentrate is sent to a pyrometallurgical smelting furnace, a mixture mainly containing copper, iron and sulfur, namely copper and sulfur, is obtained by adding a slag former in a high-temperature environment, the copper and sulfur are further sent to a converter to be subjected to oxidation converting, and the slag former is added in the high-temperature environment to remove the iron and the sulfur, so that the blister copper is obtained. The copper content of the crude copper is over 98 percent, the crude copper is sent to a fire refining furnace, a small amount of impurities are further removed through oxidation reduction, an anode plate containing over 99 percent of copper is obtained, and the anode plate obtains the final product of electrolytic refined copper through electrolysis.

With the increase of the cumulative consumption of copper, a process for preparing refined copper by secondary resource re-smelting of copper gradually appears in the market, because the grade difference of the secondary resource of copper is large, the recycling of the secondary resource of copper also appears in a division cooperation manner, part of enterprises only process raw materials with low copper-containing grade, usually contain less than 60% of copper, prepare intermediate products with high copper-containing grade for sale, usually contain 85-99% of copper in the part of intermediate products, only recover high-grade copper-containing materials in part of enterprises, usually contain more than 85% of copper in the part of copper-containing materials, and prepare crude copper, anode plates, electrolytic copper and the like for further sale.

For more than 85% of copper-containing materials, most of the current enterprises adopt a fire refining furnace (such as an anode furnace tilting furnace) to carry out fire refining to prepare the anode plate. Compared with the traditional mineral crude copper raw material, the copper content is more than 98%, the raw material to be processed by the current fire refining furnace is more complex, and the source, the impurity type and the impurity content of impurities are greatly fluctuated, so that higher requirements are provided for the impurity removal process of the current fire refining furnace.

In the traditional pyrometallurgical process, a slag former mainly containing silicon dioxide is usually adopted, the existing research focuses on the selection of a small amount of additives, a small amount of calcium oxide is added to remove phosphorus in a melt in part of steel smelting enterprises, iron is kept in the melt, and a small amount of borax and the like are added to reduce the melting point of the melt. Some copper and lead smelting enterprises use iron making technology for reference, and a small amount of calcium oxide, borax, calcium fluoride and the like can be added to improve the separation effect of metals and impurities. In the fire refining link of copper, the current research mainly uses quartz sand for slagging, and the selection of a small amount of additives is also applied to remove impurities such as arsenic, antimony and the like, but the research for thoroughly changing the slag type in the fire refining process is rarely reported.

The impurity removal process of the traditional copper pyrometallurgical refining furnace comprises the oxidation and reduction processes, quartz sand is added in the oxidation stage to serve as a slagging agent to carry out slagging and impurity removal, the adaptability of the process to complex high-grade complex copper-containing materials is low, the slagging process adopting the traditional process can cause the large amount of pyrometallurgical refining slag, the high copper content of slag and the low direct recovery rate of copper, and the copper content of slag is usually over 26%. Most copper smelting enterprises have relatively complete smelting processes, namely the fire refining front-end process, and the slag is returned to the front-end process for treatment, but the existing enterprises only have the fire refining single process and do not have the condition that the slag is returned to the front-end process, and the slag is usually directly sold at a reduced price, which brings direct economic loss to the enterprises.

The current relevant research focuses on further recycling the slag after the slag is produced in the fire refining process, the requirements of enterprises cannot be met in the aspects of process flow and equipment investment, and the report on reducing the copper content of the slag directly in the fire refining process is reported. Therefore, the process for reducing the copper content in the slag in the fire refining process is developed, so that economic loss reduction of a single enterprise with the fire refining process is more urgent and important.

Disclosure of Invention

The invention discloses a method for preparing an anode plate by a complex copper-containing material pyrogenic process, which aims to solve any of the technical problems and other potential problems in the prior art.

In order to achieve the aim, the invention adopts the technical scheme that: a method for preparing an anode plate by a pyrogenic process is suitable for a complex copper-containing material, wherein the high-grade complex copper-containing material treated by a single furnace is uniformly proportioned as far as possible, copper and iron in a single batch of furnace charge are detected, a slag former is added once or in batches based on the total iron content of the single batch of furnace charge (when the total iron content in the single batch of furnace charge is uncertain, 1/3 of the total impurity content of the single batch of furnace charge is used as a reference), oxidation and slag formation are carried out, the slag formation time is determined according to the total impurity content of the single batch of furnace charge, generally 1h-6h, heat preservation and standing are carried out after oxidation is finished, the time is different from 10 min to 200 min, and then slag removal is carried out. And carrying out reduction casting after slagging off to obtain the anode plate. Wherein the reference mass refers to 1/3 of the total iron-containing mass in the feedstock, or the total impurity mass of the feedstock.

The essence of the invention is to control the selection of slag forms in the fire refining process, and by detecting the total amount of impurities and iron in a single batch of furnace charge, proper types and dosage of slag formers are added in the oxidation stage to realize the selective regulation and control of the slag forms, so that the produced slag has low melting point, low viscosity and good fluidity, and the native copper in the slag is settled down under the fluctuation of copper liquid by continuously keeping warm and standing. These links are closely related and work together to achieve the goal of reducing the copper content of the slag of the refining furnace.

The specific technological process and technological parameters are as follows:

1 compounding ingredients

Copper-containing materials from different sources are detected in a raw material warehouse, and the copper and iron contents of a single batch of raw materials are obtained before the raw materials are fed into a furnace as far as possible. The material fed into the furnace should avoid the introduction of aluminum-containing substances as much as possible.

2 oxidizing and slagging

The raw materials of a single furnace are fed into the furnace in batches or at one time, a slagging agent is added in batches or at one time in the process, the slagging agent is a composite slagging agent of silicon dioxide and calcium oxide, wherein the calcium oxide can be replaced by calcium carbonate, calcium sulfate or a mixture of two or a mixture of calcium oxide, calcium carbonate and calcium sulfate with equal amount of substances, the ratio of the amount of the effective silicon dioxide to the amount of the effective calcium oxide in the slagging agent is 0.7-3, and 1: 1. the total iron content (mass) of a single batch of furnace charge is taken as a reference mass (when the total iron content of the single batch of furnace charge is uncertain, 1/3 of the total impurity content of the single batch of furnace charge is taken as the reference mass), the slag former is added in one time or in batches, and the ratio of the total mass of the effective calcium oxide in the slag former to the reference mass is controlled by the total amount of the slag former to be 0.2-1.6, preferably 0.8-1.0. The temperature of the furnace is raised to 1100-1300 ℃, preferably about 1200 ℃, and compressed air or oxygen-enriched air can be introduced into the furnace for stirring until the oxidation slagging is finished.

3 heat preservation standing and reduction casting

And standing the melt for 10-200 minutes after the oxidation is finished, slagging off, and casting the melt into an anode plate after the reduction of the copper liquid.

The silicon dioxide, the sand, the calcium oxide and the limestone are all industrial reagents.

The invention is suitable for processing high-grade complex copper-containing materials, and the copper content is not lower than 85 percent usually. The main impurities are calculated by weight percentage as (%): 1.0 to 10.0 percent of Fe1.0, 1.0 to 5.0 percent of Pb1.0, 1.0 to 5.0 percent of Zns, 0.1 to 3.0 percent of S, 0.1 to 2.0 percent of Sns, 0.1 to 1.0 percent of Sb0, 0.1 to 1.0 percent of Ass, and 0.1 to 5.0 percent of the rest

Compared with the traditional fire refining process, the invention has the following advantages:

1. the method has strong raw material adaptability, is suitable for treating high-grade complex copper-containing materials, and has the advantages of smaller slag amount, lower copper content in slag and high direct copper yield. The copper content of the slag of the traditional process is usually more than 26 percent, and the copper content of the slag of the traditional process is usually less than 18 percent.

2. The composite slag former replaces the traditional silicon dioxide single slag former, changes the slag form of the slag, has better removal effect on impurities such as iron, lead and zinc by utilizing the silicon dioxide, and has better slag fluidity, lower viscosity and less copper in the slag by utilizing the calcium oxide to change the slag form.

3. And by keeping the temperature and standing, the native copper in the slag is further settled, the copper content in the slag is further reduced, and the direct copper yield is increased.

4. The invention adopts the composite slagging agent of silicon dioxide and limestone to oxidize and slag, has good slag fluidity and low viscosity, further keeps the temperature and stands to further ensure that the copper in the slag is further settled, the slag amount is 90-95 percent of the original slag amount, and the slag contains copper bottom, and has the advantages of high direct copper yield, short process flow and low production cost.

5. The invention has the advantages of stable technical indexes of the process, low labor intensity, low production cost and the like.

Drawings

FIG. 1 is a block diagram of a process for preparing an anode plate from a complex copper-containing material by a pyrogenic process according to the present invention.

FIG. 2 is a graph showing the relationship between the total amount of slag formers and the copper content of slag.

Detailed Description

The technical solution of the present invention is further described with reference to the following specific embodiments.

As shown in fig. 1, the method for preparing the anode plate by the complex copper-containing material by the pyrogenic process of the invention specifically comprises the following steps:

s1) detecting the contents of copper and iron in the complex copper-containing material;

s2) preparing a slagging agent according to the detection result of S1), adding the complex copper-containing material and the slagging agent into a reaction furnace, heating to a preset temperature, and introducing compressed air or oxygen-enriched air to stir for oxidation reaction;

s3), preserving heat for a certain time after the oxidation is finished, then slagging off, and casting the anode plate after the reduction of the copper liquid.

The specific process in S2) comprises the following steps:

s2.1) adding the complex copper-containing material into a slagging agent at one time or in batches, controlling the ratio of the total mass of the effective calcium oxide in the slagging agent to the reference mass to be 0.2-1.5 by the total amount of the slagging agent, and adding the slagging agent into a reaction furnace.

S2.2) heating the furnace to 1100-1300 ℃, introducing compressed air or oxygen-enriched air into the furnace for stirring, and keeping the gas pressure at 0.15-0.25 Mpa until the oxidation slagging is finished.

The total amount of the slagging agent controls the ratio of the total mass of the effective calcium oxide in the slagging agent to the reference mass to be 0.8-1.0;

the incubation time in S3) is 10 minutes to 200 minutes.

The complex copper-containing material contains not less than 85% of copper, and the main impurities are respectively as follows by weight percent: 1.0 to 10.0% of Fe1.0 to 5.0% of Pb1.0 to 5.0% of Zns, 0.1 to 3.0% of S, 0.1 to 2.0% of Sns, 0.1 to 1.0% of Sb0.1 to 1.0% of Ass, and 0.1 to 5.0% of other unavoidable impurities.

The slagging agent is a compound slagging agent and comprises a silicon dioxide-containing material and a calcium oxide-containing material, wherein the amount ratio of effective silicon dioxide to effective calcium oxide in the slagging agent is 0.7-3: 1.

the material containing calcium oxide is one or a mixture of calcium carbonate and calcium sulfate.

The content of silicon dioxide in the silicon dioxide-containing material is not less than 70%.

An anode plate is prepared by the method.

Example 1:

the method comprises the steps of detecting that 308.25 tons of high-grade complex copper-containing materials are contained in a single furnace, detecting that 95.49 tons of copper are contained, 2.03 tons of iron are contained, 13.90 tons of total impurities are contained, and 10 tons of slag forming agents are added, wherein 4 tons of sand (the content of silica is 99.5 percent), 6 tons of limestone (the content of calcium is 39.5 percent, and corresponds to 55.3 percent of calcium oxide), 3 batches of high-grade complex copper-containing materials and slag forming agents are added, the furnace temperature is 1200 ℃, the feeding time is 16.10 hours in total, the removing effect of iron, lead and zinc impurities in the high-grade complex copper-containing materials of the silica is improved, the grade of furnace slag is improved by 12.79 percent, calcium oxide is added, the fluidity of the furnace slag is better, the viscosity is lower, compressed air is introduced in the later stage of feeding to accelerate the melting of the materials, and oxidation is carried out simultaneously, and the subsequent oxidation time is 5.2 hours. Then keeping the temperature and standing for 30 minutes, and then removing the slag. And then introducing pulverized coal for reduction for 0.7 hour, further settling the native copper in the slag by heat preservation and standing, reducing the copper content in the slag to below 18 percent, and then casting the copper liquid into an anode plate. The total amount of the obtained slag is 19.34 tons, and the grade of the slag is 12.79 percent. 294.25 tons of qualified anode plates are cast.

Example 2:

the total amount of high-grade complex copper-containing materials in a single furnace is 300.00 tons, the detected copper content is 92.50 percent, the total amount of impurities is 22.5 tons, the total amount of the slag former is 8 tons, wherein 3 tons of sand (the content of silicon dioxide is 99.5 percent), 5 tons of limestone (the content of calcium is 39.5 percent, and corresponds to 55.3 percent of calcium oxide), and the high-grade complex copper-containing materials and the slag former are added in 3 batches, the furnace temperature is 1200 ℃, and the total time of charging is 13.4 hours. Compressed air is introduced in the later stage of charging to accelerate melting of the materials and oxidize the materials simultaneously, the follow-up oxidation time is 3.6 hours, the effect of removing impurities of iron, lead and zinc in the high-grade complex copper-containing materials of silicon dioxide is improved, and calcium oxide is added to ensure that the slag has better fluidity and lower viscosity. Then keeping the temperature and standing for 30 minutes, and then removing the slag. And then introducing pulverized coal for reduction for 0.7 hour, further settling the native copper in the slag by heat preservation and standing, reducing the copper content in the slag to below 18 percent, and then casting the copper liquid into an anode plate. The total amount of the obtained slag is 22.06 tons, and the grade of the slag is improved by 14.02 percent. 274.02 tons of qualified anode plates are cast.

Example 3:

the method comprises the steps of detecting that 305.78 tons of high-grade complex copper-containing materials are contained in a single furnace, detecting that 96.45 tons of copper are contained in the high-grade complex copper-containing materials, preparing 5 tons of slag forming agents, wherein 2 tons of sand (the content of silica is 99.5 percent), 3 tons of limestone (the content of calcium is 39.5 percent, and the content of calcium oxide corresponds to 55.3 percent), adding the high-grade complex copper-containing materials and the slag forming agents in 3 batches, controlling the furnace temperature to be 1200 ℃, and consuming 14.6 hours in total. Compressed air is introduced in the later stage of charging to accelerate the melting of the materials, and oxidation is carried out simultaneously, and the subsequent oxidation time is 5.6 hours. Then keeping the temperature and standing for 30 minutes, and then removing the slag. Then introducing pulverized coal for reduction for 0.7 hour, and then casting the molten copper into an anode plate. The total amount of the obtained slag is 16.64 tons, and the grade of the slag is improved by 17.81 percent. 288.35 tons of qualified anode plates were cast, as shown in FIG. 1.

Influence of different total amount of slag formers on copper content in the slag for samples Nos. 5 to 71

Total multiple of slag forming agent	Weight of metal g	Copper grade%	Copper content of slag%	Residual concentration of As%
					1.2	457.83	98.75	13.73	0.016
1.0	457.30	98.92	13.62	0.013
					0.7	456.72	98.89	14.32	0.013
0.5	445.60	98.68	17.95	0.028
					0.3	418.60	97.83	24.3	0.034

The method for preparing the anode plate by performing fire refining on the complex copper-containing material provided by the embodiment of the application is described in detail above. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core ideas; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.

As used in the specification and claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.

It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a commodity or system that includes the element.

It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.

The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.

Claims

1. A method for preparing an anode plate by complex copper-containing material fire refining is characterized by comprising the following steps:

the complex copper-containing material contains not less than 85% of copper, and the impurities in percentage by weight are respectively: 1.0 to 10.0% of Fe1.0 to 5.0% of Pb1.0 to 5.0% of Zns, 0.1 to 3.0% of S, 0.1 to 2.0% of Sns, 0.1 to 1.0% of Sb0.1 to 1.0% of Ass, and 0.1 to 5.0% of other unavoidable impurities;

the slagging agent is a compound slagging agent and comprises a silicon dioxide-containing material and a calcium oxide-containing material, wherein the amount ratio of effective silicon dioxide to effective calcium oxide in the slagging agent is 0.7-3: 1;

2. The method as claimed in claim 1, wherein the specific process in S2) is:

s2.1) adding the complex copper-containing material into a slagging agent in one step or in batches, controlling the ratio of the total mass of effective calcium oxide in the slagging agent to the reference mass to be 0.2-1.6 by the total amount of the slagging agent, and adding the slagging agent into a reaction furnace; the reference mass refers to 1/3 of the mass of total iron contained in the raw material or the mass of total impurities in the raw material;

3. The method as claimed in claim 1, wherein the total amount of the slag former in S2) is controlled so that the ratio of the total mass of the available calcium oxide in the slag former to the reference mass is 0.8 to 1.0.

4. The method as claimed in claim 1, wherein the incubation time in S3) is 10 minutes to 200 minutes.

5. The method of claim 1, wherein the calcium oxide-containing material is one or more of calcium carbonate and calcium sulfate.

6. The method of claim 1, wherein the silica-containing material has a silica content of not less than 70%.

7. An anode plate produced by the method of any one of claims 1 to 6.