CN114574707A - Slag type optimizing agent in copper smelting process and preparation method thereof - Google Patents
Slag type optimizing agent in copper smelting process and preparation method thereof Download PDFInfo
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- CN114574707A CN114574707A CN202210397823.7A CN202210397823A CN114574707A CN 114574707 A CN114574707 A CN 114574707A CN 202210397823 A CN202210397823 A CN 202210397823A CN 114574707 A CN114574707 A CN 114574707A
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- slag
- optimizing agent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/006—Pyrometallurgy working up of molten copper, e.g. refining
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- 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
Abstract
The invention discloses a slag type optimizing agent, which comprises 25-30 wt% of Al2O320 to 30 weight percent of SiO215 to 20 weight percent of Fe powder, 15 to 20 weight percent of lime and 5 to 10 weight percent of Na2CO3. The invention also provides a preparation method of the slag modifier. The slag-type optimizing agent provided by the invention has the advantages of low melting point, high melting speed, good slag fluidity, strong adsorption and inclusion capacity and the like, so that the slag-type optimizing agent has good effects of slag mixing, improvement of adsorption, entrainment and removal of impurity elements such As As, Pb and the like, the output of hazardous waste residues in the copper smelting process is reduced, the environmental pollution caused by poor stacking of the hazardous waste residues is avoided, and the treatment cost of the hazardous waste residues is reduced. And the slag modifier is convenient to use, does not increase the labor intensity of workers, and improves the impurity element removing capacity in the copper smelting process, thereby reducing the production cost.
Description
Technical Field
The invention relates to a slag type optimizing agent in a copper smelting process and a preparation method thereof, belonging to the technical field of pyrometallurgy in copper smelting.
Background
In the past, enterprises adopt high-quality copper ore raw materials to carry out smelting production of copper, the problem of overhigh content of As and Pb does not exist generally, and the impurities can be removed in an electrolytic refining section. Along with the rapid development of the copper smelting industry in China, high-grade low-impurity copper concentrates are increasingly poor, and most of copper ore resources in China are poor ores and associated ores, so that the grade is low. In recent years, As the components of copper raw materials become more complex, the content of impurities such As As, Pb and the like increases, and the quality of products cannot be ensured by conventional operation. Copper smelting enterprises face a common problem of treating high-impurity copper concentrates, and meanwhile, the output of dangerous wastes is increased, and most representative is arsenic sulfide slag. Therefore, how to efficiently regulate and control harmful impurity elements such As As, Pb and the like to enter smelting slag phase to form general solid waste slag is very important for the copper pyrometallurgical industry.
At present, the domestic copper smelting industry has no successful reference application case for removing As and Pb impurity elements in the blister copper. Therefore, the development of a slag-type optimizing agent capable of deeply and efficiently regulating and controlling harmful impurity elements such As As, Pb and the like to enter a smelting slag phase becomes a technical problem to be solved.
Disclosure of Invention
The invention solves the technical problem of a slag type optimizing agent in the copper smelting process and a preparation method thereof, and the slag type optimizing agent has good effects of slag regulation and entrainment removal of harmful impurity elements such As As, Pb and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a slag type optimizing agent in a copper smelting process comprises the following raw materials in percentage by mass:
25%-30wt% Al2O3，
20%30wt% SiO2，
15 to 20 weight percent of Fe powder,
15 to 20 weight percent of lime,
5%-10wt% Na2CO3。
preferably, the Al is calculated by mass percent2O3The purity of the adopted raw materials is more than 99 percent, and the granularity is not more than 2 mm;
preferably, the SiO is calculated by mass percentage2The purity of the adopted raw materials is more than 90 percent, and the granularity is not more than 2 mm;
preferably, the purity content of the raw materials adopted by the Fe powder is more than 99 percent, and the particle size is not more than 2mm in percentage by mass;
preferably, the purity content of the raw materials adopted by the lime is more than 90% and the granularity is not more than 2mm in percentage by mass;
preferably, the Na is calculated by mass percentage2CO3The purity of the adopted raw materials is more than 98 percent, and the granularity is not more than 1.5 mm.
The granularity of each component of the slag-type optimizing agent influences the reaction rate and the reaction sufficiency degree, and finally influences the effect of the slag-type optimizing agent. The thinner the slag type optimizing agent is, the larger the specific surface area and the specific surface energy of the slag type optimizing agent are, so that the improvement of the reaction rate is facilitated, the reaction can be carried out more fully within a certain time, the utilization rate of the slag type optimizing agent is higher, a better slag type optimizing effect is achieved, and the As and Pb impurity removal effect is better.
The preparation method of the slag type optimizing agent in the scheme comprises the following steps:
mixing Al2O3、SiO2Fe powder, lime and Na2CO3Proportionally adding the raw materials into a mixer to be mixed to obtain mixed raw materials, namely the slag-type optimizing agent;
preferably, the Al is2O3、SiO2Fe powder, lime and Na2CO3Dry mixing is carried out for 30 min;
preferably, the particle size of the slag-type optimizing agent obtained by mixing is not more than 5 mm.
Has the advantages that: the slag type optimizing agent of the inventionForm an Al2O3-SiO2The FeO-CaO based smelting slag has the advantages of low melting point, high melting speed, good slag fluidity, strong adsorption and inclusion capacity and the like, so that the slag has good effects of slag regulation, improvement of adsorption and entrainment removal of impurity elements such As As, Pb and the like when being used As a slag type optimizing agent, the output of hazardous waste residues in the copper smelting process is reduced, the environmental pollution caused by poor stacking of the hazardous waste residues is avoided, and the treatment cost of the hazardous waste residues is reduced.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The invention discloses a slag type optimizing agent, which comprises:
25%-30wt% Al2O3，
20%-30wt% SiO2，
15 to 20 weight percent of Fe powder,
15 to 20 weight percent of lime,
5%-10wt% Na2CO3。
the invention provides a slag type optimizing agent, which comprises: which comprises Al2O3、SiO2Fe powder, lime and Na2CO3(ii) a The application provides a slag form optimizing agent has advantages such As the melting point is low, melting speed is fast, the slag mobility is good, the adsorption inclusion ability is strong, consequently it has good accent sediment, improves the effect of impurity element's such As As, Pb absorption smuggle with the desorption As the slag form optimizing agent, has reduced the output of dangerous waste residue among the copper smelting process, avoids the environmental pollution that dangerous waste residue pile up badly to cause, has reduced the treatment cost of dangerous waste residue simultaneously. And the slag modifier is convenient to use, does not increase the labor intensity of workers, and improves the impurity element removing capacity in the copper smelting process, thereby reducing the production cost.
In the present invention, the Al2O3Metallurgical grade alpha-Al well known to those skilled in the art2O3The source thereof is not particularly limited in the present invention, but the Al is used for securing the performance and effect of the slag type optimizing agent2O3The content of the compound is more than 99 percent, and the granularity is 0-2 mm; al (Al)2O3Al acts to improve the adsorption capacity of the slag2O3The mass percentage of the mixed slag type optimizing agent is 25 to 30 weight percent;
in the present invention, the SiO2The source of the silica sand, which is well known to those skilled in the art, is not particularly limited in the present invention, but the SiO is used in order to ensure the performance and effect of the slag type optimizer2The content of (A) is more than 90%, and the granularity is 0-2 mm; SiO 22SiO plays a role in improving the viscosity and the fluidity of the slag2The mass percentage of the mixed slag type optimizing agent is 20-30 wt%;
in the invention, the Fe powder is industrial-grade iron powder well known to those skilled in the art, the source of the Fe powder is not particularly limited, but in order to ensure the performance and the effect of the slag-type optimizing agent, the Fe content in the Fe powder is more than 99%, and the particle size is 0-2 mm; the Fe powder plays a role in accelerating the melting speed, and the mass percent of the Fe powder added into the slag type optimizing agent is 15-20 wt%;
in the invention, the lime is industrial lime well known to those skilled in the art, the source of the lime is not particularly limited, but in order to ensure the performance and effect of the slag type optimizing agent, the lime content is more than 90%, and the particle size is 0-2 mm; lime plays a role in adjusting alkalinity; the mass percentage of lime added into the slag type optimizing agent is 15-20 wt%;
in the present invention, the Na is2CO3Technical grade Na well known to those skilled in the art2CO3The source thereof is not particularly limited in the present invention, but in order to secure the performance and effect of the slag type optimizer2CO3The content is more than 98 percent, and the granularity is 0-1.5 mm; na (Na)2CO3The functions of adjusting the alkalinity and improving the fluidity of the slag are achieved; na (Na)2CO3The mass percentage of the mixed slag type optimizing agent is 5 to 10 weight percent;
the invention also provides a preparation method of the slag type optimizing agent, which comprises the following steps:
the invention also provides a preparation method of the slag type optimizing agent, which comprises the following steps:
mixing Al2O3、SiO2Fe powder, lime and Na2CO3Proportionally adding the raw materials into a mixer to be mixed to obtain mixed raw materials, namely the slag-type optimizing agent;
in the preparation process of the slag modifier, in order to ensure that the raw materials are fully mixed, the invention preferably prepares the mixed raw materials according to the following scheme:
firstly, Al is added2O3And SiO2Dry mixing for 5min, adding Fe powder, dry mixing for 5min, adding lime, dry mixing for 5min, and adding Na2CO3Dry mixing for 15 min; the materials are ensured to be uniformly mixed;
and (3) obtaining a mixed raw material, namely a slag type optimizing agent with the granularity of 0-5 mm, bagging, sealing, warehousing and piling for later use.
In order to facilitate further understanding of the present invention, the following examples are provided to illustrate the slag form optimizing agent and the preparation method thereof, and the scope of the present invention is not limited by the following examples.
Example 1
Will account for 25wt% of Al in the raw material2O3And 25wt% SiO2Firstly carrying out dry mixing for 5min, then adding 20wt% of Fe powder for dry mixing for 5min, then adding 20wt% of lime for dry mixing for 5min, and finally adding 10wt% of Na2CO3Dry mixing for 15 min; the materials are ensured to be uniformly mixed; al in the raw material2O3The granularity is not more than 2 mm; SiO 22The granularity is not more than 2 mm; the granularity of Fe is not more than 2 mm; the lime granularity is not more than 2 mm; na (Na)2CO3The grain size is not more than 1.5 mm.
And (3) obtaining a mixed raw material, namely a slag type optimizing agent with the granularity of 0-5 mm, bagging, sealing, warehousing and piling for later use.
When the slag form optimizing agent prepared in the embodiment is used in copper pyrometallurgy, the content of impurity elements in slag is removed before and after slag form optimization is compared, as shown in Table 1
Example 2
30wt% of Al in the raw material2O3And 28wt% SiO2Firstly carrying out dry mixing for 5min, then adding 18wt% of Fe powder, dry mixing for 5min, then adding 16wt% of lime, dry mixing for 5min, and finally adding 8wt% of Na2CO3Dry-mixing for 15 min; the uniform mixing of the materials is ensured; al in the raw material2O3The content of the compound is more than 99 percent, and the granularity is 0-2 mm; SiO 22The content of (A) is more than 90%, and the granularity is 0-2 mm; the Fe content in the Fe powder is more than 99%, and the particle size is 0-2 mm; the lime content is more than 90%, and the granularity is 0-2 mm; na (Na)2CO3The content is more than 98 percent, and the granularity is 0-1.5 mm.
And (3) obtaining a mixed raw material, namely a slag type optimizing agent with the granularity of 0-5 mm, bagging, sealing, warehousing and piling for later use.
When the slag form optimizing agent prepared in the embodiment is used in copper pyrometallurgy, the content of impurity elements in slag is removed before and after slag form optimization is compared, as shown in Table 2
Example 3
Will account for 28wt% of Al in the raw material2O3And 30wt% SiO2Firstly carrying out dry mixing for 5min, adding 18wt% of Fe powder, dry mixing for 5min, adding 18wt% of lime, dry mixing for 5min, and finally adding 6wt% of Na2CO3Dry mixing for 15 min; the materials are ensured to be uniformly mixed; al in the raw material2O3The content of the compound is more than 99 percent, and the granularity is 0-2 mm; SiO 22The content of (A) is more than 90%, and the granularity is 0-2 mm; the Fe content in the Fe powder is more than 99%, and the particle size is 0-2 mm; the lime content is more than 90%, and the granularity is 0-2 mm; na (Na)2CO3The content is more than 98 percent, and the granularity is 0-1.5 mm.
And (3) obtaining a mixed raw material, namely a slag type optimizing agent with the granularity of 0-5 mm, bagging, sealing, warehousing and piling for later use.
When the slag form optimizing agent prepared in the embodiment is used in copper pyrometallurgy, the content of impurity elements in slag is removed before and after slag form optimization is compared, as shown in Table 3
Comparative experiment
Al2O3The main effect of the Al in the slag-type optimizing agent is to improve the adsorption capacity of high slag, and thermodynamic calculation and phase diagram analysis show that Al is in the smelting process2O3Can form AlAsO with As in the material4Phase, thereby increasing the slag rate of As; further, Al2O3The specific surface area of the slag is large, and the slag adsorption capacity can be increased to a certain extent when the slag is added into a smelting process.
The SiO is added during the smelting process2The viscosity and the fluidity of the smelting slag are obviously improved, and the uniform distribution and the flow of the smelting slag in the furnace are ensured, thereby ensuring the As2O3PbO can be continuously and uniformly adsorbed, and if the viscosity of the slag is low and the fluidity is poor, As is2O3PbO can quickly overflow into the flue gas and cannot be well absorbed; as was found by thermogravimetric-mass spectrometric analysis of copper concentrates2O3And PbO continuously volatilizes into the flue gas when the temperature of the PbO rises to 1600 ℃ from the furnace.
The Fe powder can improve the melting speed of the copper concentrate in the smelting process, the melting time of the material is reduced from 5min to 2min after the copper concentrate reaches the smelting temperature of over 1200 ℃ after the Fe powder is added in the smelting process, the melting time is shortened, the molten pool and the molten slag are formed quickly, As and Pb are adsorbed by the molten slag and enter the slag, and As is reduced As far As possible2O3And the PbO overflows into the flue gas. Meanwhile, the processing capacity of the furnace to the materials can be improved, and energy conservation and consumption reduction are facilitated.
Lime and Na2CO3Can adjust the alkalinity of the slag, has low price, is an alkalinity regulator commonly used in the smelting industry, but can cause the slag to agglomerate and reduce the fluidity of the slag when being excessive, but Na2CO3The addition of the lime can just make up the deficiency of the lime, and the fluidity of the slag can be increased; the smelting slag generally takes silicate As the main component, shows acidity, is not beneficial to As and Pb entering slag, lime and Na2CO3The acidity of silicate can be neutralized, the adsorption and removal capacity of the slag on As and Pb can be improved, and the results of process mineralogy analysis of the slag show that arsenic is partially present in arsenopyrite/metallic copper and arsenopyrite in the form of independent minerals, and lead is mainly present in slag in the form of galena PbS.
To sum up: al (Al)2O3、SiO2Fe powder, lime and Na2CO3The effects of the slag type optimizing agents are different and complement each other, and if any one of the effects is lacked, the effect of inhibiting As and Pb impurity elements from being entrained into slag by the slag type optimizing agents is reduced.
The above description is only a preferred embodiment of the present invention, and all the equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.
Claims (9)
1. The slag form optimizing agent in the copper smelting process is characterized by comprising the following raw materials in parts by mass:
25%-30wt% Al2O3，
20%-30wt% SiO2，
15 to 20 weight percent of Fe powder,
15 to 20 weight percent of lime,
5%-10wt% Na2CO3。
2. the slag form optimizing agent in the copper smelting process according to claim 1, wherein the Al is2O3Has a particle size of not more than 2 mm.
3. The slag type optimizing agent according to claim 1,characterized in that the SiO is2Has a particle size of not more than 2 mm.
4. The slag type optimizing agent according to claim 1, wherein the particle size of the Fe powder is not more than 2 mm.
5. The slag form optimizer of claim 1, wherein the lime has a particle size of no greater than 2 mm.
6. The slag form optimizing agent of claim 1, wherein the Na is present in an amount of, by mass percent2CO3Has a particle size of not more than 1.5 mm.
7. The method for preparing the slag-type optimizing agent in the copper smelting process according to claim 1, characterized by comprising the following steps:
mixing Al2O3、SiO2Fe powder, lime and Na2CO3Adding the mixture into a mixer to mix to obtain a mixed raw material, namely the slag type optimizing agent.
8. The method of claim 8, wherein the mixing time is 30 min.
9. The preparation method according to claim 8, wherein the particle size of the slag-type optimizing agent is not more than 5 mm.
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| CN113564381A (en) * | 2021-07-26 | 2021-10-29 | 广东飞南资源利用股份有限公司 | Synergistic copper smelting method and building material |
| CN114134352A (en) * | 2021-11-26 | 2022-03-04 | 宁波金田铜业(集团)股份有限公司 | Slag remover for scrap smelting of brass and method for smelting brass |
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2022
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Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1351999A (en) * | 1970-03-26 | 1974-05-15 | Kaiser Ind Corp | Production of metals from metalliferous materials |
| US20090217785A1 (en) * | 2005-09-01 | 2009-09-03 | Montanunversitaet Leoben | Method for separating impurities out of feed stock in copper melts |
| CN101323905A (en) * | 2007-06-15 | 2008-12-17 | 西安华英实业有限公司 | Fire metallurgy process of copper lead zinc mixing ore concentrate |
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