CN110423861B - Method for producing copper-containing steel and application of copper slag as coolant in producing copper-containing steel - Google Patents

Method for producing copper-containing steel and application of copper slag as coolant in producing copper-containing steel Download PDF

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CN110423861B
CN110423861B CN201910859811.XA CN201910859811A CN110423861B CN 110423861 B CN110423861 B CN 110423861B CN 201910859811 A CN201910859811 A CN 201910859811A CN 110423861 B CN110423861 B CN 110423861B
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copper
slag
copper slag
steel
converting
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CN110423861A (en
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高永亮
李兵
尉克俭
李东波
黎敏
郭亚光
王雪亮
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China ENFI Engineering Corp
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/30—Regulating or controlling the blowing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Materials Engineering (AREA)
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Abstract

The invention provides a method for producing copper-containing steel and application of copper slag as a coolant in producing copper-containing steel. Wherein, should include the following steps: crushing the copper slag; adding the crushed copper slag and scrap steel into a steel converter; adding lime into the steel converter for alkalinity control; wherein the copper slag comprises metallurgical slag discharged from a copper smelting furnace in a pyrometallurgical copper smelting process. By applying the technical scheme of the invention, the application process of the copper slag as the coolant in the production of copper-containing steel is simple and easy to master, the waste steel and the iron ore are replaced, the steel-making cost can be effectively reduced, no additional equipment is required, and the investment is low.

Description

Method for producing copper-containing steel and application of copper slag as coolant in producing copper-containing steel
Technical Field
The invention relates to the technical field of smelting, in particular to a method for producing copper-containing steel and application of copper slag as a coolant in producing copper-containing steel.
Background
The copper slag is the metallurgical slag discharged from a copper smelting furnace in the process of pyrometallurgy, and is a eutectic body formed by mutually melting various oxides in furnace burden and fuel. At present, copper in China is mainly produced by pyrometallurgy, and the emission amount of copper slag exceeds 1000 million tons every year according to the emission of 2.2 tons of copper slag per 1 ton of refined copper produced in the copper smelting process. In addition, the copper slag with the amount of more than 1.2 hundred million tons is piled up nationwide, and becomes a large amount of industrial solid waste generated in the metallurgical industry. Although the copper slag contains various valuable metals such as Fe, Cu, Zn, Pb, Co, Ni and the like and a small amount of precious metals such as Au, Ag and the like, most of the copper slag is piled up in a slag field and cannot be effectively utilized, so that the land is occupied, the environment is polluted, and the huge waste of resources is caused. The copper slag obtained by different smelting processes has certain differences in components, and the ranges are shown in table 1.
TABLE 1 chemical composition of slag%
TFe TCu Fe3O4 SiO2 Al2O3 CaO S Au*
29～45 0.45～3.0 1～20 25～40 ≤10 ≤10 0.6～2.8 <0.5
Unit is g/t
As can be seen from Table 1, the copper slag contains 29 to 45 percent of iron, while the average grade of all iron ores in the iron-making industry of China is only 29.1 percent, and a large amount of imported external ores are needed to be matched with the iron ores for sintering and pelletizing; at present, the mining grade of a lot of copper ores in China is only 0.2% -0.3%, and the copper content in copper slag is more than 0.5%. If the iron and the copper in the copper slag can be fully utilized, the contradiction between the supply and demand of the iron ore and the copper ore can be relieved to a certain extent. Therefore, the comprehensive utilization of the copper slag has important strategic significance and market prospect, and is an important way for the sustainable development of the current copper smelting industry. In addition, the copper slag contains a small amount of noble metals, and if the noble metals can be effectively extracted, the economic benefit can be better improved.
Iron in the copper slag was mainly ferrous silicate (2 FeO. SiO.)2) And magnetite (Fe)3O4) Is mainly in the form of iron silicate, and the copper is mainly Cu2S, CuO and Cu. Since iron in the copper slag mainly exists in the form of fayalite, it is difficult to effectively recover weak magnetic mineral fayalite by the conventional magnetic separation method. To recover iron from the copper slag, it is necessary to first ferment the 2FeO SiO in the copper slag2Conversion to Fe3O4And then recovered by a magnetic separation method. There are many methods for recovering copper in slag, mainly including pyrogenic dilution, wet extraction and mineral separation. At present, the research on the utilization technology of the copper slag mostly focuses on the utilization of copper alone or iron alone. For the extraction of metals in copper slag, the beneficiation method is widely applied, but the resource utilization rate is low; the recovery rate of pyrometallurgical metal is high, but the treatment cost is high; wet processing is potentially secondary to contamination and costly. Although the copper slag can also be used for preparing microcrystalline glass and mineral wool; used for producing cement, but this all wastes valuable iron and copper, as well as other metal resources, considerably.
According to the heat balance calculation, the heat in the converter is surplus when the converter steelmaking is carried out, and a proper amount of coolant must be added. The cooling agent used for converter steelmaking comprises scrap steel, iron ore, iron scale and the like, and the most used amount is scrap steel. Since 2010, scrap prices have exploded and are difficult to procure. In recent years, with the increasing consumption of iron ore by the steel industry, the problem of insufficient iron ore resources becomes more and more serious, so that an iron-containing resource capable of replacing scrap steel and iron ore as a coolant is urgently needed.
Disclosure of Invention
The invention aims to provide a method for producing copper-containing steel and application of copper slag as a coolant in producing copper-containing steel so as to fully utilize the copper slag.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method of producing copper-containing steel. The method comprises the following steps: crushing the copper slag; adding the crushed copper slag and scrap steel into a steel converter; adding lime into the steel converter for alkalinity control; wherein the copper slag comprises metallurgical slag discharged from a copper smelting furnace in a pyrometallurgical copper smelting process.
Further, the addition amount of lime is calculated by alkalinity R, and the calculation formula is as follows:
Figure BDA0002199387170000021
in the formula, MgO and SiO2All come from slag, omega represents the mass percentage content, and the alkalinity range is controlled to be 1.0-2.5.
Further, the method also comprises a depletion step before crushing the copper slag.
Furthermore, the granularity of the crushed copper slag is 5 mm-70 mm, and the adding amount of the crushed copper slag with the granularity of 60 mm-70 mm is controlled within 10 percent of the copper slag.
Further, the copper slag is dried before entering the furnace.
Furthermore, the adding amount of the scrap steel is 1-10% of the total charging amount.
Furthermore, the total adding amount of the copper slag accounts for 0.5 to 5 percent of the total adding amount of the molten iron and the scrap steel.
Furthermore, the adding mode of the copper slag and the lime is batch adding.
Further, the batchwise addition specifically comprises: in the early stage of converting: firstly, adding a predetermined amount of scrap steel, then adding 50-60% of the total amount of copper slag, uniformly shaking, adding molten iron, adding a slagging agent, and adopting low-lance position for slagging; in the middle stage of converting: adding copper slag in batches, and lifting the lance position by 100-200 mm to ensure that the mass fraction of FeO in the slag is 10-20%; and in the later stage of converting: copper slag is not added within 2-5 minutes before the lance is lifted, the lance position is reduced by 100-200 mm, the stirring speed is increased, the components of a molten pool are homogenized, and the temperature is raised; preferably, the temperature at the early stage of converting is controlled to be 1400-1550 ℃; controlling the temperature at 1550-1600 ℃ in the middle stage of converting; and controlling the temperature at the later stage of converting to 1600-1680 ℃.
According to another aspect of the present invention, there is provided a use of copper slag as a coolant in the production of copper-containing steel.
By applying the technical scheme of the invention, the application process of the copper slag as the coolant in the production of copper-containing steel is simple and easy to master, the waste steel and the iron ore are replaced, the steel-making cost can be effectively reduced, no additional equipment is required, and the investment is low.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
At present, copper slag (copper slag generated by copper smelting enterprises) cannot be fully utilized, so that on one hand, environmental pollution is caused, and on the other hand, precious metal resources such as iron and copper are greatly wasted. In order to make full use of the copper slag, the invention provides a series of technical schemes.
According to an exemplary embodiment of the present invention, there is provided a use of copper slag as a coolant in the production of copper-containing steel.
According to an exemplary embodiment of the present invention, a method of using a coolant for producing copper-containing steel is provided. The using method comprises the following steps: crushing the copper slag; adding the crushed copper slag and scrap steel into a steel converter; adding lime into the steel converter for alkalinity control; wherein the copper slag is metallurgical slag discharged from a copper smelting furnace in the pyrometallurgical copper smelting process.
By applying the technical scheme of the invention, the application process of the copper slag as the coolant in the production of copper-containing steel is simple and easy to master, the waste steel and the iron ore are replaced, the steel-making cost can be effectively reduced, no additional equipment is required, and the investment is low.
Preferably, the addition amount of lime is calculated as alkalinity R, and the calculation formula is as follows:
Figure BDA0002199387170000031
in the formula, MgO and SiO2All come from slag, omega represents the mass percentage content, and the alkalinity range is controlled to be 1.0-2.5. The alkalinity is mainly controlled by the adding amount of lime, and the slag forming requirement is considered, so that the method is beneficial to impurity removal.
In an exemplary embodiment of the invention, the copper slag is crushed before it is subjected to a depletion step, although in the present application, it is possible to carry out the depletion step with or without depletion. The impoverishment refers to the copper slag after partial copper is separated and extracted after the copper slag enters an electric furnace in a hot state.
Preferably, the granularity of the crushed copper slag is 5 mm-70 mm, and the adding amount of the crushed copper slag with the granularity of 60 mm-70 mm is controlled within 10 percent of the copper slag. The melting speed of the copper slag entering the furnace can be well controlled according to the standard strictly, because the copper slag is not easy to melt due to too large granularity and can not be added into the furnace due to too small granularity which can be blown away by hot gas in the furnace. The control of the proportion of large particles is mainly to prevent the waste caused by too much proportion of small particles when the small particles enter the furnace.
According to a typical embodiment of the invention, the copper slag is dried before entering the furnace, so that the occurrence of furnace spraying is prevented, and the production safety is improved.
Because of SiO in the copper slag2The content is high, therefore, the waste steel is required to be added together, and preferably, the adding amount of the waste steel is 1 to 10 percent of the total charging amount (the total amount of the added molten iron).
The total adding amount of the copper slag accounts for 0.5 to 5 percent of the total adding amount of the molten iron and the scrap steel. The copper slag contains more impurities, SiO2Too much is not suitable for the addition of high content.
The addition mode of the copper slag and the lime is batch addition, so that the temperature can be controlled not to drop too fast.
According to a typical embodiment of the invention, the batchwise addition comprises in particular:
blowing early stage (Si and Mn oxidation period): firstly, adding a predetermined amount of scrap steel, then adding 50-60% of the total amount of copper slag, uniformly shaking (for example, shaking the converter for 3-5 times), adding molten iron, adding a slag former such as lime and the like, and melting slag by adopting a lower gun position in the early stage of smelting because the copper slag is added during blowing, so that the temperature of a molten pool is rapidly increased, and the melting of the lime and the like is promoted; middle converting period (oxidation period of C): adding copper slag in batches, wherein excessive copper slag is not suitable to be added at one time, so that sudden temperature drop is avoided, and the lance position is lifted by 100-200 mm, so that the mass fraction of FeO in the slag is 10-20%; later in the blowing (while drawing carbon, ensuring that the P, S content and temperature meet the tapping temperature of steel grade): copper slag is not added within 2-5 minutes before the lance is lifted, the lance position is reduced by 100-200 mm, the stirring speed is increased, the components of a molten pool are homogenized, and the temperature is raised; preferably, the temperature at the early stage of converting is controlled to be 1400-1550 ℃; controlling the temperature at 1550-1600 ℃ in the middle stage of converting; and controlling the temperature at the later stage of converting to 1600-1680 ℃. The lance position refers to the distance from the oxygen lance nozzle to the liquid level of the molten pool, and the lance positions of different furnaces are different.
In the technical scheme of the invention, the steelmaking atmosphere is a reducing atmosphere, and CO is produced by the reaction of oxygen blown in during the steelmaking process and carbon in molten steel. The copper slag has high FeO content, is favorable for dephosphorization reaction and avoids the slag from drying.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited by the examples.
Example 1
Firstly, crushing the depleted and cooled copper slag, wherein the granularity is controlled within 5-70 mm, the grain size in the furnace is controlled within 60-70 mm, and the adding amount is controlled at 6%. The copper slag needs to be dried before entering the furnace. The adding amount of the scrap steel accounts for 2 percent of the furnace charging amount, and the total adding amount of the copper slag accounts for 0.8 percent of the total adding amount of the molten iron and the scrap steel. The lime addition is obtained by means of the alkalinity, this time 1.5. The adding mode of the copper slag and the lime is adding in batches.
In the early stage of converting: firstly adding all the scrap steel, then adding 50% of the total amount of the copper slag, shaking the converter for 3 times, adding molten iron after even shaking, and adding slag-making agents such as lime and the like. Because copper slag is added during blowing, slag melting at a lower gun position is adopted in the early stage of smelting, the gun position is reduced by 100mm compared with the normal gun position, the temperature of a molten pool is rapidly increased, lime and the like are promoted to be melted, and the temperature is controlled at 1450 ℃.
In the middle stage of converting: the residual copper slag is added in batches, so that excessive copper slag is not suitable to be added at one time, and sudden temperature drop is avoided. And (5) timely increasing the gun position in the middle period by 120mm to ensure that the mass fraction of FeO in the slag is 12%, and controlling the temperature at 1550 ℃.
And in the later stage of converting: adding copper slag is forbidden within 2 minutes before lifting the gun. And in the later stage, the gun position is reduced by 100mm, the stirring speed is enhanced, the components of a molten pool are homogenized, the temperature is increased, and the temperature is controlled at 1620 ℃. The quality of the molten steel is qualified, and the production cost of producing the copper-containing steel is reduced.
Example 2
Firstly, crushing the copper slag which is not depleted and cooled, wherein the granularity is controlled within 5-70 mm, and the adding amount of the copper slag with the granularity of 60-70 mm in the furnace is controlled at 8%. The copper slag needs to be dried before entering the furnace. The adding amount of the scrap steel accounts for 3% of the furnace charging amount, and the total adding amount of the copper slag accounts for 1% of the total adding amount of the molten iron and the scrap steel. The lime addition is obtained by means of the alkalinity, this time 1.6. The adding mode of the copper slag and the lime is adding in batches.
In the early stage of converting: firstly, adding all the scrap steel, then adding 55% of the total amount of the copper slag, shaking the converter for 4 times, adding molten iron after even shaking, and adding slag-making agents such as lime and the like. Because copper slag is added during blowing, slag melting at a lower gun position is adopted in the early stage of smelting, the gun position is reduced by 120mm compared with the normal gun position, the temperature of a molten pool is rapidly increased, lime and the like are promoted to be melted, and the temperature is controlled at 1480 ℃.
In the middle stage of converting: the residual copper slag is added in batches, so that excessive copper slag is not suitable to be added at one time, and sudden temperature drop is avoided. And (5) timely increasing the lance position in the middle period by 120mm to ensure that the mass fraction of FeO in the slag is 15%, and controlling the temperature to 1580 ℃.
And in the later stage of converting: adding copper slag is forbidden within 3 minutes before lifting the gun. And in the later stage, the gun position is reduced by 130mm, the stirring speed is increased, the components of a molten pool are homogenized, the temperature is increased, and the temperature is controlled at 1640 ℃. The quality of the molten steel is qualified, and the production cost of producing the copper-containing steel is reduced.
Example 3
Firstly, crushing the depleted and cooled copper slag, and controlling the granularity within 5-70 mm, wherein the adding amount of the charged granularity within 60-70 mm is controlled to be 9%. The copper slag needs to be dried before entering the furnace. The adding amount of the scrap steel accounts for 5% of the furnace charging amount, and the total adding amount of the copper slag accounts for 2% of the total adding amount of the molten iron and the scrap steel. The lime addition is obtained by means of alkalinity, this time alkalinity being 1.8. The adding mode of the copper slag and the lime is adding in batches.
In the early stage of converting: firstly, adding all the scrap steel, then adding 56% of the total amount of the copper slag, shaking the converter for 3 times, adding molten iron after even shaking, and adding slag-making agents such as lime and the like. Because copper slag is added during blowing, the slag is melted at a lower gun position in the early smelting period, the gun position is reduced by 150mm compared with the normal gun position, the temperature of a molten pool is rapidly increased, the melting of lime and the like is promoted, and the temperature is controlled at 1500 ℃.
In the middle stage of converting: the residual copper slag is added in batches, so that excessive copper slag is not suitable to be added at one time, and sudden temperature drop is avoided. And (5) timely increasing the lance position in the middle stage by 130mm to ensure that the mass fraction of FeO in the slag is 18%, and controlling the temperature at 1570 ℃.
And in the later stage of converting: adding copper slag is forbidden within 4 minutes before lifting the gun. And in the later stage, the gun position is reduced by 140mm, the stirring speed is enhanced, the components of a molten pool are homogenized, the temperature is increased, and the temperature is controlled at 1650 ℃. The quality of the molten steel is qualified, and the production cost of producing the copper-containing steel is reduced.
Example 4
Firstly, crushing the copper slag which is not depleted and cooled, wherein the granularity is controlled within 5-70 mm, and the adding amount of the copper slag with the granularity of 60-70 mm in the furnace is controlled at 4%. The copper slag needs to be dried before entering the furnace. The adding amount of the scrap steel accounts for 6% of the furnace charging amount, and the total adding amount of the copper slag accounts for 3% of the total adding amount of the molten iron and the scrap steel. The lime addition is obtained by means of the alkalinity, this time 1.5. The adding mode of the copper slag and the lime is adding in batches.
In the early stage of converting: firstly adding all the scrap steel, then adding 58% of the total amount of the copper slag, shaking the converter for 5 times, adding molten iron after even shaking, and adding slag-making agents such as lime and the like. Because copper slag is added during blowing, slag melting at a lower gun position is adopted in the early stage of smelting, the gun position is reduced by 170mm compared with the normal gun position, the temperature of a molten pool is rapidly increased, the melting of lime and the like is promoted, and the temperature is controlled at 1540 ℃.
In the middle stage of converting: the residual copper slag is added in batches, so that excessive addition is not suitable for one time, sudden temperature drop is avoided, and the gun position is increased by 140 mm. The lance position is timely increased in the middle period to ensure that the mass fraction of FeO in the slag is 13 percent, and the temperature is controlled to be 1590 ℃.
And in the later stage of converting: adding copper slag is forbidden within 3 minutes before lifting the gun. And the gun position is reduced at the later stage, the distance of 120mm is reduced, the stirring speed is enhanced, the components of a molten pool are homogenized, the temperature is increased, and the temperature is controlled at 1670 ℃. The quality of the molten steel is qualified, and the production cost of producing the copper-containing steel is reduced.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
1) the copper slag is used for replacing coolants such as scrap steel, iron ore and the like, so that the steel-making cost is reduced, and iron and copper resources in the slag can be effectively utilized.
2) The process is simple, the operation is easy, and other equipment is not required to be added.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by 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.

Claims (8)

1. A method of producing copper-containing steel, comprising the steps of:
crushing the copper slag;
adding the crushed copper slag and scrap steel into a steel converter for blowing;
simultaneously adding lime into the steelmaking converter for alkalinity control;
wherein the copper slag comprises metallurgical slag discharged from a copper smelting furnace in a pyrometallurgical copper smelting process;
the converting comprises an early converting stage, a middle converting stage and a later converting stage, the copper slag is added in batches, and the batch addition specifically comprises the following steps:
in the earlier stage of converting: firstly, adding a predetermined amount of scrap steel, then adding 50-60% of the total amount of copper slag, uniformly shaking, adding molten iron, adding a slagging agent, and adopting low-lance slagging;
in the middle stage of converting: adding the copper slag in batches, and lifting the lance position by 100-200 mm to ensure that the mass fraction of FeO in the slag is 10-20%;
and in the later stage of converting: the copper slag is not added within 2-5 minutes before the lance is lifted, the lance position is reduced by 100-200 mm, the stirring speed is increased, the components of a molten pool are homogenized, and the temperature is raised;
the temperature of the early stage of blowing is controlled to be 1400-1550 ℃; the temperature in the middle stage of converting is controlled to be 1550-1600 ℃; and the temperature in the later stage of converting is controlled to be 1600-1680 ℃.
2. The method according to claim 1, characterized in that the lime addition is calculated as alkalinity R, the calculation formula being as follows:
Figure 600445DEST_PATH_IMAGE002
in the formula, MgO and SiO2All come from slag, omega represents the mass percentage content, and the alkalinity range is controlled to be 1.0-2.5.
3. The method of claim 1, further comprising a step of depletion before crushing the copper slag.
4. The method according to claim 1, wherein the crushed copper slag has a particle size of 5 mm-70 mm, and the addition amount of the crushed copper slag having a particle size of 60 mm-70 mm is controlled within 10% of the crushed copper slag.
5. The method of claim 1, wherein the copper slag is dried before entering the furnace.
6. The method of claim 1, wherein the scrap steel is added in an amount of 1% to 10% of the total charge.
7. The method according to claim 1, wherein the total amount of the copper slag added is 0.5-5% of the total amount of the molten iron and the scrap steel added.
8. The method according to claim 1, characterized in that the lime is added in portions.
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Publication number Priority date Publication date Assignee Title
CN103952564A (en) * 2014-03-31 2014-07-30 中国恩菲工程技术有限公司 Copper smelting slag processing method
CN107130082A (en) * 2017-04-26 2017-09-05 湖南工业大学 A kind of method that copper is efficiently separated in high-copper iron charge
CN107881276A (en) * 2017-12-21 2018-04-06 江苏省冶金设计院有限公司 A kind of system and method that weathering steel is produced using high-temperature fusion copper ashes
CN110157972A (en) * 2019-05-23 2019-08-23 中国恩菲工程技术有限公司 The production method of copper bearing steel

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