阅读说明：本技术 铜冶炼过程铅锌定向分配调控方法 (Directional lead-zinc distribution regulating method in copper smelting process ) 是由 王亲猛 王松松 郭学益 田庆华 田苗 于 2020-05-08 设计创作，主要内容包括：本发明公开了一种铜冶炼过程铅锌定向分配调控方法,包括以下步骤：将混合铜精矿加入熔炼炉,鼓入含氧气体进行富氧熔炼,得到铜锍、熔炼渣及烟气；定向分配调控方法包括以下路线中的至少一种：路线A：控制所述混合铜精矿中Cu、Fe、S的质量百分比分别为25-27％、18-23％、27-30％；路线B：控制所述混合铜精矿的加入速率和控制富氧浓度为73-80％以使氧矿比为161-165Nm<Sup>3</Sup>/t。本发明通过生产过程优化调控及改进炼铜装置,使铅、锌在熔炼过程中优先被氧化为PbO、ZnO入渣,实现向熔炼渣中定向富集。(The invention discloses a directional distribution regulation and control method for lead and zinc in a copper smelting process, which comprises the following steps: adding the mixed copper concentrate into a smelting furnace, and blowing oxygen-containing gas for oxygen-enriched smelting to obtain copper matte, smelting slag and flue gas; the directional distribution regulation method comprises at least one of the following routes: route a: controlling the mass percentages of Cu, Fe and S in the mixed copper concentrate to be 25-27%, 18-23% and 27-30% respectively; route B: controlling the addition rate of the mixed copper concentrate and controlling the oxygen-enriched concentration to 73-80% so that the oxygen-ore ratio is 161-165Nm 3 T is calculated. According to the invention, the production process is optimized, regulated and controlled, and the copper smelting device is improved, so that lead and zinc are preferentially oxidized into PbO and ZnO to enter the slag in the smelting process, and directional enrichment in the smelting slag is realized.)

1. A method for regulating and controlling directional distribution of lead and zinc in a copper smelting process comprises the following steps: adding the mixed copper concentrate into a smelting furnace, and blowing oxygen-containing gas for oxygen-enriched smelting to obtain copper matte, smelting slag and flue gas; the method is characterized in that the directional distribution regulation and control method comprises at least one of the following routes:

route a: controlling the mass percentages of Cu, Fe and S in the mixed copper concentrate to be 25-27%, 18-23% and 27-30% respectively;

route B: controlling the addition rate of the mixed copper concentrate and controlling the oxygen-enriched concentration to 73-80% so that the oxygen-ore ratio is 161-165Nm³/t。

2. The method for regulating and controlling directional distribution of lead and zinc in the copper smelting process according to claim 1, wherein in the route B, the copper matte grade in the oxygen-enriched smelting process is 71-75%.

3. The directional distribution and control method for lead and zinc in the copper smelting process as claimed in claim 1, wherein in the route B, the smelting temperature in the oxygen-enriched smelting process is 1493-1573K.

4. The method for regulating and controlling directional distribution of lead and zinc in the copper smelting process according to claim 1, wherein the method for regulating and controlling directional distribution comprises a route A and a route B at the same time.

5. The method for regulating and controlling the directional distribution of lead and zinc in the copper smelting process according to any one of claims 1 to 4, wherein a flux quartz is added in the oxygen-enriched smelting process, and the addition amount of the quartz is controlled on the basis of controlling the iron-silicon ratio to be 1.5-1.9.

6. The directional lead-zinc distribution and regulation method in the copper smelting process according to any one of claims 1 to 4, characterized in that the smelting furnace comprises a furnace body (6), the furnace body (6) is provided with a charging port (1), a slag tap (9), a copper matte tap (7), a flue port (5) and a plurality of first oxygen lances (81), the charging port (1) is arranged at the upper part of the furnace body (6), the first oxygen lances (81) are arranged at the lower part of the furnace body (6), the first oxygen lances (81) are arranged below the charging port (1), the directional lead-zinc distribution and regulation method is characterized in that a baffle system is fixedly arranged in an inner cavity of the furnace body (6) and comprises a first high temperature resistant baffle (31) and a second high temperature resistant baffle (32), a flue gas channel is arranged between the upper end of the first high temperature resistant baffle (31) and the top of the inner cavity of the furnace body (6), a flue gas channel is arranged between the lower end of the second high-temperature resistant baffle (32) and the liquid level of the molten pool, and the baffle system is arranged between the feed inlet (1) and the flue opening (5).

7. The directional distribution and control method for lead and zinc in the copper smelting process according to claim 6, characterized in that a second oxygen lance (82) for supplementing oxygen into the furnace body (6) is arranged at one end of the furnace body (6) close to the charging opening (1).

8. The method for regulating and controlling the directional distribution of lead and zinc in the copper smelting process according to claim 6, wherein the first high temperature resistant baffle (31) is arranged between the charging opening (1) and a second high temperature resistant baffle (32), and the second high temperature resistant baffle (32) is arranged between the flue opening (5) and the first high temperature resistant baffle (31).

9. The method for regulating and controlling the directional distribution of lead and zinc in the copper smelting process according to claim 8, characterized in that the first oxygen lance (81) and the charging opening (1) are positioned on the same side of the second high temperature resistant baffle (32), and at least one first oxygen lance (81) is arranged between the first high temperature resistant baffle (31) and the second high temperature resistant baffle (32).

10. The directional distribution and regulation method for lead and zinc in the copper smelting process according to claim 6, characterized in that the lower end of the first high temperature resistant baffle (31) extends into the liquid level of the molten pool, and the upper end of the second high temperature resistant baffle (32) is hermetically arranged at the upper part of the inner cavity of the furnace body (6).

Technical Field

The invention belongs to the field of pyrometallurgy, and particularly relates to a copper smelting method.

Background

Along with the gradual depletion of high-quality mineral resources, low-grade multi-metal associated primary resources, electronic wastes and other complex secondary resources are becoming main processing raw materials. Lead and zinc in low-grade multi-metal associated primary resources mainly exist in the forms of sulfate, oxide and sulfide, and lead in complex secondary resources such as electronic waste and the like mainly comes from lead-containing soldering tin. The low-grade multi-metal associated primary resource and the electronic waste are usually matched with other copper concentrates to form smelting raw materials, and the matched raw materials are usually called mixed copper concentrates.

In the process of smelting the mixed copper concentrate, lead and zinc respectively enter three phases of copper matte, smelting slag and flue gas in different forms due to different physical and chemical properties of lead and zinc. Lead mainly enters copper matte in the form of Pb and PbS, enters smelting slag in the form of PbO, and volatilizes into flue gas in the form of PbS; zinc mainly enters copper matte in the form of ZnS, enters smelting slag in the form of ZnO, and volatilizes into flue gas in the form of Zn and ZnS. Lead and zinc entering the copper matte can reduce the quality of the copper matte and increase the pressure of subsequent copper matte blowing, fire refining and electrolytic refining; lead and zinc in the flue gas can cause serious coking at the flue port, which affects normal production, and lead and zinc heavy metals are dissipated in workshops along with the flue gas, which seriously harms the production environment and the health of workers.

The reports about the directional regulation and control of lead and zinc in the smelting process of the mixed copper concentrate to reduce the lead and zinc entering copper matte and flue gas are few in the prior art, and the method is a problem worthy of deep research.

Disclosure of Invention

The technical problem to be solved by the invention is to overcome the defects and shortcomings mentioned in the background technology, and provide a method for regulating and controlling directional distribution of lead and zinc in the copper smelting process, which can realize directional enrichment of lead and zinc elements in smelting slag, improve the quality of copper matte products, reduce the content of lead and zinc elements in flue gas, improve the quality of products, reduce coking at flue ports and reduce harm to environment and workers. In order to solve the technical problems, the technical scheme provided by the invention is as follows:

a method for regulating and controlling directional distribution of lead and zinc in a copper smelting process comprises the following steps: adding the mixed copper concentrate into a smelting furnace, and blowing oxygen-containing gas for oxygen-enriched smelting to obtain copper matte, smelting slag and flue gas; the directional distribution regulation method comprises at least one of the following routes:

route a: controlling the mass percentages of Cu, Fe and S in the mixed copper concentrate to be 25-27%, 18-23% and 27-30% respectively;

route B: the addition rate of the bulk copper concentrate was controlled and the oxygen enrichment concentration was controlled to 73-80% so that the oxygen ore ratio (the ratio of the oxygen blow-in volume to the amount of bulk copper concentrate added in a unit hour, which can be controlled by changing the concentrate addition rate and the oxygen blow-in rate) was 161 and 165Nm³T; the oxygen-rich concentration means the mass percentage of oxygen in the blown oxygen-containing gas to the total gas. In the production, the oxygen-enriched concentration is controlled by matching the proportion of air (oxygen concentration is 21%) and pure oxygen (oxygen concentration is 98%).

In the method for regulating and controlling directional distribution of lead and zinc in the copper smelting process, preferably, in the route B, the copper matte grade is controlled to be 71-75% in the oxygen-enriched smelting process. The copper matte grade can be realized by changing the concentrate components, the concentrate adding speed and the oxygen blowing speed.

In the method for regulating and controlling directional distribution of lead and zinc in the copper smelting process, preferably, in the route B, the smelting temperature in the oxygen-enriched smelting process is 1493-.

In the method for regulating and controlling directional distribution of lead and zinc in the copper smelting process, preferably, the method for regulating and controlling directional distribution simultaneously comprises a route A and a route B. The route A and the route B act simultaneously, so that the oxygen potential is improved, the smelting temperature is reached, lead and zinc are added into slag, and directional distribution regulation and control of lead and zinc are realized.

In the method for regulating and controlling the directional distribution of lead and zinc in the copper smelting process, preferably, flux quartz is added in the oxygen-enriched smelting process, and the adding amount of the quartz is subject to the control of the iron-silicon ratio to be 1.5-1.9. Copper concentrates contain a large amount of iron and it is desirable to separate copper and iron during copper smelting because copper tends to bind sulfur and iron to bind oxygen, i.e., iron is more easily oxidized than copper, so oxygen is bubbled to oxidize the iron in the concentrate to ferrous oxide, but ferrous oxide is miscible with copper matte, requiring the addition of stonesEnglish (the main component is SiO)₂) The iron oxide reacts with the ferrous oxide to generate smelting slag, so that the ferrous oxide can be separated from the copper matte, namely, part of iron is separated from copper. The iron-silicon ratio can be controlled by changing the concentrate components and the addition amount of the fusing agent. Further reducing the iron-silicon ratio to lead PbO, ZnO and SiO₂Slagging and removing are carried out, the activity of PbO and ZnO in slag is reduced, the directional enrichment of lead and zinc in the slag is facilitated, but the iron-silicon ratio is reduced, so that the slag quantity is increased, and the treatment capacity of a slag dressing workshop is increased.

In the method for regulating and controlling directional distribution of lead and zinc in the copper smelting process, preferably, the mixed copper concentrate contains lead and zinc, the mass percent of the lead is 0.01-5%, and the mass percent of the zinc is 0.01-10%.

The principle of the invention is as follows: the activity coefficients of Pb, PbS and ZnS in the copper matte are reduced along with the rise of the smelting temperature, namely, the rise of the temperature is not beneficial to the enrichment of lead and zinc in the copper matte; partial pressures of PbS, Zn and ZnS in the flue gas are increased along with temperature rise, namely, the higher smelting temperature is beneficial to lead and zinc to be volatilized to enter the flue gas; along with the increase of smelting oxygen potential, Pb, PbS and ZnS in copper matte and PbS, Zn and ZnS in smoke are easily oxidized into PbO and ZnO to enter slag, namely, the oxygen potential is improved, and the enrichment of lead and zinc in the slag is facilitated; SiO in the slag along with the reduction of the iron-silicon ratio₂The content is increased, so that PbO and ZnO are easy to react with SiO₂Combined with PbO. SiO₂、2ZnO·SiO₂The form of the lead-free slag is fixed in the slag, namely, the iron-silicon ratio is reduced, and the lead and the zinc are favorably enriched in the slag.

In the invention, the mixed copper concentrate is prepared by matching concentrates from various countries/various mineral plants, the concentrates of various countries/various mineral plants are usually composed of main metals such As Cu, Fe, S and the like and impurity elements such As As, Sb, Bi and the like, only the contents are different, and the components of the final mixed copper concentrate can be regulated and controlled by adjusting the matching proportion of various concentrates according to production requirements. Because the copper smelting process is a process of oxidizing and removing elements such as iron, sulfur and the like; under the condition that other parameters are not changed, the oxygen amount blown into the smelting furnace is not changed, so that the Cu content in the concentrate is increased, the Fe and S contents are correspondingly reduced, namely, less substances consuming oxygen are consumed, and the oxygen potential is increased; in the smelting process, a large amount of heat is taken away by flue gas, and S is reducedThe content of the additive reduces the amount of flue gas, reduces the heat quantity taken away by the flue gas, and increases the smelting temperature. The increase of the oxygen potential and the smelting temperature is beneficial to lead and zinc entering the smelting slag. And similarly, the influence of the contents of Fe and S is reduced, and the oxygen potential and the smelting temperature are also favorably improved. But the content of Cu is not excessive, the content of Cu is excessive, the reduction of Fe and S in the concentrate leads to the increase of oxygen potential, and Fe is oxidized into FeO and then further oxidized into Fe₃O₄，Fe₃O₄The smelting slag is a high-melting-point substance, so that the viscosity of the liquid smelting slag is increased, the separation of the matte and the smelting slag by using density difference is not facilitated, the loss of copper in the smelting slag is large, and the improvement of the yield of copper is not facilitated.

In the invention, the oxygen ore ratio and the oxygen-enriched concentration in the route B are more beneficial to improving the oxygen potential and the smelting temperature, the requirement of the application is met, and lead and zinc are easy to enter smelting slag to ensure normal smelting. But further improving the oxygen ore ratio and the oxygen-enriched concentration can increase the heat load of the furnace body, reduce the service life of the furnace body, increase the loss of copper in slag and reduce the direct yield of valuable metals.

In the method for regulating and controlling directional distribution of lead and zinc in the copper smelting process, preferably, the smelting furnace comprises a furnace body, wherein a feed inlet, a slag tap, a copper matte tap, a flue port and a plurality of first oxygen lances are arranged on the furnace body, the feed inlet is arranged on the upper part of the furnace body, the first oxygen lances are arranged on the lower part of the furnace body, the first oxygen lances are arranged below the feed inlet, a baffle system is fixedly arranged in an inner cavity of the furnace body, the baffle system comprises a first high-temperature-resistant baffle and a second high-temperature-resistant baffle, a flue gas channel is arranged between the upper end of the first high-temperature-resistant baffle and the top of the inner cavity of the furnace body, a flue gas channel is arranged between the lower end of the second high-temperature-resistant baffle and the liquid level of a molten pool, and.

In the method for regulating and controlling directional distribution of lead and zinc in the copper smelting process, preferably, a second oxygen lance for supplementing oxygen into the furnace body is arranged at one end of the furnace body, which is close to the charging opening. The second oxygen gun may further provide an oxygen potential within the region of strong oxygen potential.

In the method for regulating and controlling directional distribution of lead and zinc in the copper smelting process, preferably, the first high-temperature-resistant baffle is arranged between the feeding opening and the second high-temperature-resistant baffle, and the second high-temperature-resistant baffle is arranged between the flue opening and the first high-temperature-resistant baffle. The arrangement mode is favorable for improving the oxygen potential between the first high-temperature-resistant baffle and the second high-temperature-resistant baffle.

In the method for regulating and controlling the directional distribution of lead and zinc in the copper smelting process, preferably, the first oxygen lance and the charging opening are positioned on the same side of the second high-temperature-resistant baffle, and at least one first oxygen lance is arranged between the first high-temperature-resistant baffle and the second high-temperature-resistant baffle. The first oxygen lance and the charging opening are positioned on the same side of the second high-temperature-resistant baffle, so that the formed strong oxygen potential area is more obvious, and the effect is more obvious. The oxygen gun is arranged between the first high-temperature-resistant baffle and the second high-temperature-resistant baffle and mainly used for increasing oxygen potential between the first high-temperature-resistant baffle and the second high-temperature-resistant baffle as much as possible.

In the method for regulating and controlling directional distribution of lead and zinc in the copper smelting process, preferably, the lower end of the first high-temperature-resistant baffle plate extends below the liquid level of a molten pool, and the upper end of the second high-temperature-resistant baffle plate is hermetically arranged at the upper part of the inner cavity of the furnace body. In order to ensure the flow of the flue gas, the flue gas channel is not smaller than 1/4 of the upper space of the liquid level of the molten pool. The arrangement mode can ensure that the flue gas channel is in an S-shaped flowing mode at the upper part of the inner cavity of the furnace body, and the retention time of the flue gas in the strong oxygen potential area is longer.

In the method for regulating and controlling directional distribution of lead and zinc in the copper smelting process, preferably, the wall of the furnace body comprises a shell and a refractory material layer, the shell is arranged on the outer surface of the refractory material layer, and the first high-temperature-resistant baffle and the second high-temperature-resistant baffle are embedded in the refractory material layer.

In the method for regulating and controlling the directional distribution of lead and zinc in the copper smelting process, in order to further extend the retention time of the flue gas in a strong oxygen potential area, more high-temperature-resistant baffles can be additionally arranged on the basis of the first high-temperature-resistant baffle and the second high-temperature-resistant baffle, a second oxygen gun can be additionally arranged between the high-temperature-resistant baffles, and the specific operation mode can be further optimized and selected according to the shape of the inner cavity of the furnace body, the smelting requirement and the like.

The baffle plate system can form a strong oxygen potential area on one side of the charging opening and increase the residence time of the flue gas generated in the smelting process in the strong oxygen potential area. The upper hearth of the smelting furnace is separated by arranging the baffle system on the upper part of the furnace body of the copper smelting furnace, and oxygen-enriched air is continuously blown into one side close to an oxygen lance, so that oxygen passes through a molten pool and is blocked by the baffle system, and a high-temperature area with strong oxygen potential is formed in the area; lead and zinc elements in the concentrate are preferentially oxidized into PbO and ZnO in the area and enter the slag, and part of the lead and zinc elements enter the flue gas by PbS, Zn and ZnS; the flue gas is blocked by the baffle system, the residence time in the area is increased, which is beneficial to further oxidizing PbS, Zn and ZnS into PbO and ZnO to enter the slag, thus realizing the directional distribution of lead and zinc elements into the slag.

According to the invention, through the route A and the route B and the specific smelting furnace, a plurality of factors are cooperated together, so that the directional distribution regulation and control of lead and zinc are more favorable, and lead and zinc can enter smelting slag more favorably.

Compared with the prior art, the invention has the advantages that: according to the invention, through optimization and regulation of the production process (such as raw material component proportion and optimization of smelting process parameters) and improvement of a copper smelting device (improvement of a smelting furnace), a strong oxygen potential area is formed in the furnace, the smelting temperature and the oxygen potential in the copper smelting process are improved, lead and zinc are preferentially oxidized into PbO and ZnO slag in the smelting process, directional enrichment in the smelting slag is realized (the proportion of lead and zinc in the smelting slag is improved, and the proportion of lead and zinc in copper matte is reduced), and the open circuit is realized from the production system along with the smelting slag, so that lead and zinc entering the copper matte and lead and zinc entering smoke are reduced, the influence of lead and zinc on production and environment is reduced, a foundation is laid for clean and efficient extraction of subsequent lead and zinc, and the comprehensive recovery rate of resources is improved.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

Fig. 1 is a schematic view of the structure of the melting furnace of the present invention.

FIG. 2 is a cross-sectional view taken along the line A-A in FIG. 1.

FIG. 3 is a cross-sectional view taken along plane B-B of FIG. 1.

Fig. 4 is a schematic view of the smelting process of the present invention.

Illustration of the drawings:

1. a feed inlet; 2. a housing; 31. a first high temperature resistant baffle; 32. a second high temperature resistant baffle; 4. a layer of refractory material; 5. a flue opening; 6. a furnace body; 7. discharging a copper matte port; 81. a first oxygen lance; 82. a second oxygen lance; 9. a slag tap.

Detailed Description

In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.

Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.

Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.

The concrete structure of the copper smelting furnace provided with the baffle plate system mentioned in the following embodiment is as follows: as shown in fig. 1-3, the smelting furnace includes a furnace body 6, a charging hole 1 is arranged on the furnace body 6, a slag tap 9, a copper matte tap 7, a flue port 5 and a plurality of first oxygen lances 81, the charging hole 1 is arranged on the upper part of the furnace body 6, the first oxygen lances 81 are arranged on the lower part of the furnace body 6, the first oxygen lances 81 are arranged below the charging hole 1, a baffle system is fixedly arranged in the inner cavity of the furnace body 6, the baffle system includes a first high temperature resistant baffle 31 and a second high temperature resistant baffle 32, a flue gas channel is arranged between the upper end of the first high temperature resistant baffle 31 and the top of the inner cavity of the furnace body 6, a flue gas channel is arranged between the lower end of the second high temperature resistant baffle 32 and the liquid level of the molten.

Further, a second oxygen gun 82 for supplying oxygen into the furnace body 6 is arranged at one end of the furnace body 6 close to the charging hole 1.

Further, a first high temperature resistant baffle 31 is arranged between the charging opening 1 and a second high temperature resistant baffle 32, and the second high temperature resistant baffle 32 is arranged between the flue opening 5 and the first high temperature resistant baffle 31.

Further, the first oxygen gun 81 and the charging port 1 are located on the same side of the second high temperature resistant baffle 32, and at least one first oxygen gun 81 is arranged between the first high temperature resistant baffle 31 and the second high temperature resistant baffle 32.

Furthermore, the lower end of the first high temperature resistant baffle 31 extends into the liquid level of the molten pool, and the upper end of the second high temperature resistant baffle 32 is hermetically arranged at the upper part of the inner cavity of the furnace body 6. The flue gas passage is not smaller than 1/4 (both the above ranges) of the upper space of the liquid level of the molten pool.

Further, the wall of furnace body 6 includes casing 2 and refractory material layer 4, and 4 surfaces on refractory material layer are located to casing 2, and high temperature resistant baffle 3 is inlayed and is located in refractory material layer 4.

The copper smelting furnace without the baffle system mentioned in the following examples or comparative examples is compared with the copper smelting furnace with the baffle system, only in that the baffle system is not used, and the rest of the structure is the same.

The process of smelting the mixed copper concentrate by using the copper smelting furnace with the baffle plate system comprises the following steps: and adding the mixed copper concentrate into a smelting furnace, and blowing oxygen-containing gas for oxygen-enriched smelting to obtain copper matte, smelting slag and flue gas. The schematic view of the smelting process is shown in fig. 4, and the direction of the arrow in fig. 4 indicates the flow direction of the flue gas.

Comparative example 1:

taking a copper smelting process of a certain bottom-blowing smelting plant in China as an example, the components and process parameters of materials (namely mixed copper concentrate, the same below) before entering a furnace are shown in tables 1 and 2, a copper smelting furnace without a baffle plate system is used for production, and the content and the distribution ratio of lead and zinc elements in copper matte, smelting slag and flue gas are shown in table 3.

Table 1: composition of charged material

Table 2: operating parameters of the process

Table 3: three-phase content and proportion of lead and zinc

As can be seen from Table 3, before optimization, the lead element is mainly distributed in the copper matte phase, and the distribution ratio in the smelting slag is 22.33%; the zinc element is mainly distributed in the smelting slag, but the distribution ratio in the two phases of the copper matte and the flue gas is about 40 percent. The copper content of the smelting slag at this time was 2.8%.