CN113005283A - Method for recovering copper in low-grade copper smelting slag - Google Patents
Method for recovering copper in low-grade copper smelting slag Download PDFInfo
- Publication number
- CN113005283A CN113005283A CN202110210166.6A CN202110210166A CN113005283A CN 113005283 A CN113005283 A CN 113005283A CN 202110210166 A CN202110210166 A CN 202110210166A CN 113005283 A CN113005283 A CN 113005283A
- Authority
- CN
- China
- Prior art keywords
- copper
- slag
- smelting slag
- grade
- boron oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- 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
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering copper in low-grade copper smelting slag; the method comprises the steps of crushing copper slag, mixing the crushed copper slag with boron oxide, and roasting and melting the mixture in an air atmosphere; the method can lead the fine-grained copper minerals in the copper slag to be agglomerated and grown into coarse-grained copper, improve the flotation effect, realize secondary recycling of the copper slag, solve the problems of fine granularity of the copper particles in the copper slag, poor quality of flotation recycled concentrate and the like, and realize recycling utilization of the copper slag.
Description
Technical Field
The invention relates to a method for recovering copper in low-grade copper smelting slag, and belongs to the technical field of resource recovery.
Background
Copper is one of the most important nonferrous metals required by normal operation of national economy, is widely applied in the fields of electricity, construction, mechanical manufacturing, national defense industry and the like, and is a nonferrous metal material with the second largest consumption in China. More than 90% of enterprises in China adopt the pyrometallurgical copper smelting process to produce refined copper, the pyrometallurgical process generates about 2000 million tons of copper smelting slag every year, wherein the copper grade is generally higher than 0.5%, even higher than some raw copper ores mined and processed in China, the copper smelting slag is undoubtedly a pair of double-edged sword, the simple stockpiling treatment method not only brings potential safety hazards to local ecological environment and generates a large amount of waste, but also if the residual value can be effectively utilized, the copper smelting slag has great utilization potential. The research on how to recycle and how to better recycle the copper resources in the copper smelting slag has important practical significance for the current stage of China.
The method for recycling the copper smelting slag comprises a pyrogenic depletion method, a flotation method and wet leaching. Compared with other methods, the flotation method has the advantages of simple process, low cost and the like. The process flow of crushing, grinding and flotation by directly using copper slag as raw ore usually has unsatisfactory effect because the copper sulfur in the copper smelting slag is in a crystalline state, and is too fine and dispersed. Particularly, for low-grade copper smelting slag, the recovery is more difficult, and based on the current situation, a process method which is efficient, energy-saving and good in effect is urgently needed for recovering copper resources in the low-grade copper smelting slag.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and aims to provide a method for recovering copper in low-grade copper smelting slag.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a method for recovering copper in low-grade copper smelting slag, which comprises the following steps:
mixing copper slag particles and boron oxide to obtain a mixture, roasting the mixture in an air atmosphere, and then slowly cooling and re-solidifying to obtain a modified product; and crushing, ball-milling and flotation separation are carried out on the modified product to obtain copper concentrate.
In the preferred scheme, the grade of the copper smelting slag is less than or equal to 0.5 percent.
The low-grade copper smelting slag is very difficult to recover, and the grade of the copper smelting slag can be greatly improved by adopting the method disclosed by the invention, so that the recovery efficiency of the low-grade copper smelting slag is greatly improved.
The main minerals in the copper slag are magnetite and fayalite, and the magnetite and the fayalite are high-melting-point substances with melting points of 1594 ℃ and 1205 ℃ respectively. Too high melting point of the mixed copper slag results in too little molten liquid phase, higher viscosity, unfavorable crystallization and higher energy consumption.
The inventor unexpectedly finds that the boron oxide serving as an additive not only can reduce the melting temperature of the copper slag, but also can greatly improve the growth efficiency of copper particles. The liquid phase system formed after the boron oxide is melted can reduce the viscosity of the copper slag, so that the copper particles of the copper slag can have a better growth environment.
In the experimental process, the inventor also tried that a large amount of other oxides, even the same low-melting point oxides, can not achieve the effect of improving the recovery rate of the copper smelting slag and even can reduce the effect.
In the preferred scheme, the copper slag particles are obtained by crushing or ball-milling copper smelting slag and then sieving the crushed copper smelting slag by a 100-mesh sieve.
Preferably, the addition amount of the boron oxide is less than or equal to 15 percent.
In the present invention, the added amount of boron oxide means the mass fraction of boron oxide in the mixture.
More preferably, the addition amount of the boron oxide is 3 to 15%.
More preferably, the addition amount of the boron oxide is 9 to 12%.
The inventor finds that the recovery rate of copper in the copper smelting slag can be greatly improved by controlling the addition amount of boron oxide within the preferable range, and the excessive addition amount can increase the impurity amount, increase the content of amorphous glass in a melt and inhibit the precipitation and growth of crystals; the addition amount is too small, the viscosity and the fluidity of the melt during melting cannot be remarkably changed, and the recovery rate improving effect is limited.
In a preferable scheme, the roasting temperature is 1000-1300 ℃, the roasting temperature is preferably 1150 ℃, and the roasting time is 0.5-4 h.
In the preferable scheme, the slow cooling rate is 1-8 ℃/min, and preferably 1-3 ℃/min.
In the invention, the slow cooling speed needs to be effectively controlled, the copper mineral particles can be aggregated and grown only by adopting slow cooling, and if the cooling speed of the copper smelting slag is too high, high-melting-point substances in the slag are quickly separated out, the viscosity of the slag is quickly increased, so that the copper mineral particles cannot be aggregated and grown, and are complicated and continuous with other components.
In a preferred scheme, the modified product is crushed, sieved by a 100-mesh sieve and then ball-milled for 1-6 min.
In a preferable scheme, the collecting agent used for flotation separation is butyl xanthate, and the using amount of the collecting agent is 100 g/t-500 g/t.
Principles and advantages
According to the technical scheme, boron oxide is used as an additive in the slow cooling-recondensing process of the copper slag, the growth environment of copper-containing particles in the copper slag is improved by utilizing the properties of the boron oxide, such as melt viscosity, surface tension and melting point, so that the particle size of the copper particles is greatly increased, the flotation efficiency is improved, the direct heat preservation and slow cooling of the copper slag in an air atmosphere can be realized, fine copper particles are condensed and coagulated to grow coarse copper particles, and the efficient separation and recovery of copper minerals can be realized.
The invention has the beneficial effects that:
1. according to the technical scheme, the copper particles in the copper slag are subjected to slow cooling-recondensation, so that fine copper particles grow into coarse particles, the copper minerals are recovered by flotation, and the flotation recovery rate and grade of the copper slag are obviously improved.
2. According to the technical scheme, the boron oxide is used as the additive, so that the melting temperature of the copper slag can be reduced, and the growth efficiency of copper particles can be greatly improved. The liquid phase system formed after the boron oxide is melted can reduce the viscosity of the copper slag, so that the copper particles of the copper slag can have a better growth environment.
3. The technical scheme of the invention can obviously improve the flotation effect of the copper slag and greatly improve the secondary resource utilization of the copper slag.
4. The technical scheme of the invention has the advantages of energy conservation, high efficiency, short flow and the like, can efficiently recover associated valuable resources in the copper slag, and is favorable for popularization and application.
Drawings
FIG. 1 is a process flow diagram of the process of the present invention;
FIG. 2 is an XRD comparison chart before and after modification of copper dross in example 1 and comparative example 2; compare the blank group with the other additive groups: compared with the blank group, the addition of zinc oxide and aluminum oxide can enhance the peak intensity of high-melting-point substances such as fayalite and magnetite, while boron oxide can weaken the main peak intensity and has more impurity peaks. The addition of the boron oxide can obviously change the crystal structure of the raw slag, reduce the melting point and viscosity of the molten copper slag, promote the aggregation of copper particles during temperature reduction to grow up, and reduce the aggregation of high-melting-point substances.
FIG. 3 is an XRD contrast before and after modification of copper dross in comparative example 1; compared with the blank group, after the boron oxide crystal is added, the intensity of the impurity peak in the copper slag is slightly enhanced, but the intensity of the diffraction peak of the main mineral is not obviously changed, which shows that the boron oxide has lower improvement effect on the high-grade copper slag.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are provided for illustration only and are not intended to be limiting.
Example 1
In the embodiment 1, the smelting copper slag is used as a raw material, and the chemical components are shown in table 1:
TABLE 1 chemical composition analysis of copper slag
A method for recovering copper in low-grade copper smelting slag comprises the following specific steps:
(1) crushing the copper slag, and then sieving the crushed copper slag by a 6mm vibrating screen to obtain copper slag particles;
(2) uniformly mixing the copper slag particles obtained in the step (1) with boron oxide to obtain a mixture; wherein the adding amount of boron oxide is respectively 0%, 3%, 6%, 9%, 12% and 15%;
(3) roasting and melting the mixture obtained in the step (2) in an air atmosphere; obtaining a modified product after slow cooling and recondensing; the roasting temperature is 1300 ℃, the heat preservation time is 2h, and the slow cooling rate is 2 ℃/min.
(4) And (4) crushing and vibrating the modified product obtained in the step (3), sieving the modified product with a 100-mesh sieve, then carrying out ball milling for 3min, and carrying out flotation separation, wherein a collecting agent used for flotation separation is butyl xanthate, the using amount of the collecting agent is 300g/t, and the obtained product is copper concentrate. The copper concentrate recovery is shown in table 2.
TABLE 2 influence of boron oxide addition on copper slag flotation
As can be seen from Table 2, when the addition amount of boron oxide is 9%, the grade of the copper concentrate is 3.27%, the recovery rate is 51.23%, and compared with the method without adding boron oxide, the grade is improved by 2.46 times, and the recovery rate is improved by 1.59 times; when the addition amount of boron oxide is 12%, the grade of the copper concentrate is 3.85%, the recovery rate is 49.67%, and compared with the method without adding boron oxide, the grade is improved by 2.89 times, and the recovery rate is improved by 1.53 times.
Example 2
Other conditions of example 2 were the same as in example 1, the amount of boron oxide added was 0, and the firing temperatures were 1150, 1120, 1250, 1300, and 1350 ℃.
TABLE 3 influence of the addition amount of roasting temperature on copper slag flotation
As can be seen from Table 3, in the range of 1150-plus-1350 ℃ of roasting temperature, the recovery rate of 1150 ℃ and the grade of copper concentrate are both optimal, and in the range of 1300 ℃, the recovery rate and the grade of copper concentrate are both better, but when the temperature reaches 1350 ℃, the grade of copper concentrate and the recovery rate are greatly reduced, and the grade of copper concentrate after flotation is reduced from 2.04% to 1.04%; the recovery rate also decreased from 40.48% to 21.38%.
Comparative example 1:
the chemical components of the copper slag of comparative example 1 are shown in Table 4:
TABLE 4 chemical composition analysis of copper slag
A method for recovering copper in low-grade copper smelting slag comprises the following specific steps:
(1) crushing and ball-milling the copper slag, and sieving the copper slag by a 100mm sieve to obtain copper slag particles;
(2) uniformly mixing the copper slag particles obtained in the step (1) with boron oxide to obtain a mixture; wherein the adding amount of boron oxide is respectively 0%, 3%, 6%, 9%, 12% and 15%;
(3) roasting and melting the mixture obtained in the step (2) in an air atmosphere; obtaining a modified product B after slow cooling and recondensation; the roasting temperature is 1300 ℃, the heat preservation time is 2h, and the slow cooling rate is 2 ℃/min.
(4) And (4) crushing and vibromilling the modified product obtained in the step (3), sieving the product with a 100-mesh sieve, then carrying out ball milling for 4min, and carrying out flotation separation to obtain the product of copper concentrate. The copper concentrate recovery is shown in table 4.
TABLE 5 influence of boron oxide addition on copper slag flotation
As can be seen from Table 5, when the addition amount of boron oxide is 6%, the grade of the copper concentrate is 24.89%, the recovery rate is 78.24%, and compared with the method without adding boron oxide, the grade is improved by 4.12%, and the recovery rate is improved by 3.99%; when the addition amount of boron oxide is 9%, the grade of the copper concentrate is 25.21%, the recovery rate is 71.77%, and compared with the method without adding boron oxide, the grade is improved by 4.44 Ge percentage points, and the recovery rate is slightly reduced. It can be seen that the method of the present invention also has a certain recovery effect on the recovery of copper from high-grade copper smelting slag, but the improvement range is much weaker than the improvement effect on the recovery of copper from low-grade copper smelting slag.
Comparative example 2
The other conditions are the same as the example 1, and only the copper slag particles and the alumina in the step (1) are uniformly mixed to obtain a mixture; wherein the adding amount of the aluminum oxide is 0-10 percent,
TABLE 6 influence of alumina on copper slag flotation
Table 6 shows that when the addition amount of alumina is 2%, the grade of the copper concentrate is 1.90%, the recovery rate is 38.30%, compared with the case of not adding boron oxide, the grade is improved by 0.63%, and the recovery rate is improved by 5.99%; when the addition amount of the boron oxide is 8 percent, the grade of the copper concentrate is 1.72 percent, the recovery rate is 31.56 percent, the grade is increased slightly when no aluminum oxide is added, and the recovery rate is even not as high as that when no additive is added.
Comparative example 3
The other conditions are the same as the example 1, and only the copper slag particles and the zinc oxide in the step (1) are uniformly mixed to obtain a mixture; wherein the adding amount of the zinc oxide is 0-15 percent,
TABLE 7 influence of alumina on copper slag flotation
Table 7 shows that when the addition amount of zinc oxide is 6%, the grade of copper concentrate is 1.85%, the recovery rate is 28.67%, and compared with the case of not adding zinc oxide, the grade is improved by 0.52%, and the recovery rate is reduced by 3.46%; when the addition of zinc oxide is 9%, the grade of copper concentrate is 1.24%, the recovery rate is 28.60%, and the grade and the recovery rate are reduced without adding zinc oxide. When the amount exceeds 15%, the recovery effect is continuously lowered by an excessive amount of impurities.
Claims (8)
1. A method for recovering copper in low-grade copper smelting slag is characterized by comprising the following steps: the method comprises the following steps: mixing copper slag particles and boron oxide to obtain a mixture, roasting the mixture in an air atmosphere, and then slowly cooling and re-solidifying to obtain a modified product; and crushing, ball-milling and flotation separation are carried out on the modified product to obtain copper concentrate.
2. The method of claim 1 for recovering copper from low grade copper smelting slag, characterized by: the grade of the copper smelting slag is less than or equal to 0.5 percent.
3. The method of claim 1 for recovering copper from low grade copper smelting slag, characterized by: the addition amount of the boron oxide is less than or equal to 15 percent.
4. A method of recovering copper from low grade copper smelting slag according to claim 3, characterized by: the addition amount of the boron oxide is 3-15%.
5. The method of claim 1 for recovering copper from low grade copper smelting slag, characterized by: the roasting temperature is 1000-1300 ℃, and the roasting time is 0.5-4 h.
6. The method of claim 1 for recovering copper from low grade copper smelting slag, characterized by: the slow cooling rate is 1-8 ℃/min.
7. The method of claim 1 for recovering copper from low grade copper smelting slag, characterized by: crushing the modified product, sieving with a 100-mesh sieve, and ball-milling for 1-6 min.
8. The method of claim 1 for recovering copper from low grade copper smelting slag, characterized by: the collecting agent used for flotation separation is butyl xanthate, and the using amount of the collecting agent is 100 g/t-500 g/t.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110210166.6A CN113005283A (en) | 2021-02-25 | 2021-02-25 | Method for recovering copper in low-grade copper smelting slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110210166.6A CN113005283A (en) | 2021-02-25 | 2021-02-25 | Method for recovering copper in low-grade copper smelting slag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113005283A true CN113005283A (en) | 2021-06-22 |
Family
ID=76386129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110210166.6A Pending CN113005283A (en) | 2021-02-25 | 2021-02-25 | Method for recovering copper in low-grade copper smelting slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113005283A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115780075A (en) * | 2022-12-02 | 2023-03-14 | 中南大学 | Method for improving iron recovery efficiency in copper slag magnetic separation |
| CN116043023A (en) * | 2022-12-30 | 2023-05-02 | 中南大学 | Method for improving particle size of valuable component in copper smelting slag |
-
2021
- 2021-02-25 CN CN202110210166.6A patent/CN113005283A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| YUSHI: "Effect of B2O3 content on the viscosity of copper slag", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 郭正启: "熔融改性强化铜渣铜铁分离技术的研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115780075A (en) * | 2022-12-02 | 2023-03-14 | 中南大学 | Method for improving iron recovery efficiency in copper slag magnetic separation |
| CN116043023A (en) * | 2022-12-30 | 2023-05-02 | 中南大学 | Method for improving particle size of valuable component in copper smelting slag |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106676281A (en) | Process for comprehensively recycling copper and iron through ore phase restructuring of copper smelting molten slag | |
| CN113005283A (en) | Method for recovering copper in low-grade copper smelting slag | |
| CN102373329B (en) | Method for gathering nickel and iron from laterite-nickel ores | |
| CN103088208A (en) | Method for treating manganese-containing and phosphorus-containing hematite | |
| CN102199710B (en) | Method for extracting and separating nickel and molybdenum from nickel-molybdenum-containing coal gangue | |
| CN106824543A (en) | A kind of method that copper smelting slag reclaims copper | |
| CN101775485A (en) | Iron-extracting and sulfur-reducing mineral separation method by pre-separation tailing discarding of sulphur-smelting cinder and magnetizing roasting | |
| Wang et al. | Silicon recovery from silicon sawing waste by removal of SiC impurity via CaO–SiO2–Na2O slag absorption | |
| CN110106347A (en) | A kind of Copper making waste residue is applied to the processing method of sintering | |
| JP5454815B2 (en) | Method for producing hematite for iron making | |
| CN104561551B (en) | A kind of method of the valuable constituent element separation and Extraction of boron magnesium iron mineral intergrowth | |
| JP2013194283A5 (en) | ||
| CN110453079B (en) | Method for efficiently recovering silver in lead-silver slag by melting-fuming method | |
| CN114477187A (en) | Method for extracting industrial silicon from ferro-silicon-aluminum alloy | |
| CN115927876B (en) | Fire refining process for crude tin | |
| CN107723473A (en) | Comprehensive utilization method of high-arsenic-content polymetallic gold ore | |
| CN102168157B (en) | Method for reducing nickel ore by using reducing rotary kiln and producing ferronickel by rusting electric furnace | |
| CN105603178B (en) | A kind of method that the thick alloyed powder of tin iron is prepared by Iron Ore Containing Tin | |
| CN106929684B (en) | A kind of Copper making electric dilution slag recycling copper, the property-modifying additive of iron and application | |
| CN111485101B (en) | Method for recovering iron from iron-containing ore | |
| CN110117745B (en) | Method for preparing ferrophosphorus alloy by adopting middle-low grade phosphorite and copper slag | |
| CN115780075B (en) | Method for improving iron recovery efficiency in copper slag magnetic separation | |
| CN105036162A (en) | Paigeite comprehensive utilization method for separating and extracting boron, magnesium and iron | |
| CN115215300B (en) | Method for recycling elemental sulfur from high-sulfur slag | |
| CN114480864B (en) | Method for remelting, centrifugal and electroselection grading purification of aluminum-silicon-iron alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |