CN101545054B - Method for recovering nickel, copper and cobalt from a nickel, copper and cobalt smelting waste slag - Google Patents
Method for recovering nickel, copper and cobalt from a nickel, copper and cobalt smelting waste slag Download PDFInfo
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- CN101545054B CN101545054B CN2009101172127A CN200910117212A CN101545054B CN 101545054 B CN101545054 B CN 101545054B CN 2009101172127 A CN2009101172127 A CN 2009101172127A CN 200910117212 A CN200910117212 A CN 200910117212A CN 101545054 B CN101545054 B CN 101545054B
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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
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Abstract
The present invention relates to a method for recovering nickel, copper and cobalt from a nickel, copper and cobalt smelting waste slag, including the steps as follows: a. heating the nickel, copper and cobalt slag to a molten state or fetching the nickel, copper and cobalt slag of the molten state to place in a thermal slag ladle directly; b. holding the nickel, copper and cobalt slag in the molten state by heat insulation, at the same time infusing oxygen or air into the nickel, copper and cobalt slag to react to generate solid residue to purify; c. shaking the thermal slag ladle for 30 to 40 minutes, then standing for 8 to 12 minutes; d. removing the solid residue; e. pouring out a precious metal layer of 4-6% of the total weight of the nickel, copper and cobalt smelting waste slag from the nickel, copper and cobalt smelting waste slag of the molten state, and then cooling; f. crushing and rubbing again, then a nickel, copper and cobalt concentrative powder will be obtained througha floatation process. By means of the method of the invention, it is capable of recovering the nickel, copper, cobalt and the like from the nickel, copper and cobalt smelting waste slag with high efficiency, so as to reuse the bulk industry solid wastes resource.
Description
Technical field
The present invention relates to a kind of method that from nickel, copper, cobalt smelting waste slag, reclaims nickel, copper, cobalt.
Background technology
Nickel, copper, cobalt smelting waste slag are nickel, copper, cobalt is smelted the smelting waste slag of discharging in the production, is a kind of industrial solid castoff.Along with the development of producing, solid waste increases year by year, the nickel of enormous amount, copper, cobalt smelting waste slag are stored up in the open in smelting enterprise periphery slag field, except that minute quantity water supply mud factory makes additive (replacement iron ore), all the other overwhelming majority do not obtain utilizing, and have caused the serious environmental issue to enterprise's periphery ecotope, human settlement.
Measuring and calculating contains a large amount of irony elements and silicon-dioxide in nickel, copper, the cobalt smelting waste slag by analysis, contains metallic elements such as minor amount of nickel, copper, cobalt, lead, zinc in addition.With the about 1,600,000 tons waste of certain super-huge smelting enterprise is example, and wherein metal, nonmetal theoretical storage are: 620,000 tons of iron content, 4917 tons in nickel, 6273 tons of copper, 1864 tons of cobalts, 337 tons in lead, 5976 tons on zinc, 590,000 tons of silicon-dioxide.This is the huge wasting of resources, shows that also nickel, copper, cobalt smelting waste slag have huge value of exploiting and utilizing simultaneously, the difficult problem yet the comprehensive utilization of nickel, copper, cobalt smelting waste slag has at present become international in fact.
Summary of the invention
The purpose of this invention is to provide a kind of method that from nickel, copper, cobalt smelting waste slag, reclaims nickel, copper, cobalt, this method can make full use of depleted nickel, copper, cobalt smelting waste slag resource, avoid the wasting of resources and the environmental influence that bring thus, with the noble metal in the lower cost recovery waste.
For achieving the above object, the technical solution used in the present invention is:
A kind of method that reclaims nickel, copper, cobalt from nickel, copper, cobalt smelting waste slag is characterized in that, comprises the steps:
A, the nickel, copper, the cobalt smelting waste slag that nickel, copper, cobalt smelting waste slag are heated to molten state or directly get molten state are positioned in the warm sludge bag;
B, insulation make nickel, copper, cobalt smelting waste slag keep molten state, thus simultaneously in nickel, copper, cobalt smelting waste slag aerating oxygen or air generate solid residue with purification and impurity removal;
C, concussion warm sludge bag 30-40 minute left standstill 8-12 minute then;
C, remove solid residue;
D, pour out the noble metal layers postcooling that molten state nickel, copper, cobalt smelting waste slag lower floor account for nickel, copper, cobalt smelting waste slag gross weight 4-6%;
E, fragmentation are ground the back again and can be obtained nickel, copper, cobalt concentrate powder by floatation process.
Wherein behind step b, also to be incubated and make nickel, copper, cobalt smelting waste slag keep molten state, thereby in nickel, copper, cobalt smelting waste slag, feed chlorine simultaneously and generate solid residue with purification and impurity removal, the consumption of chlorine is nickel per ton, copper, cobalt smelting waste slag 0.1-0.25 cubic meter, aeration time is 5-10 minute, or feeding chlorine meets the requirements until foreign matter content in nickel, copper, cobalt smelting waste slag.
Wherein the consumption of aerating oxygen is nickel per ton, copper, cobalt smelting waste slag 0.4-1 cubic meter in step b, and aeration time is 5-10 minute, or aerating oxygen meets the requirements until foreign matter content in nickel, copper, cobalt smelting waste slag.
Wherein the consumption of bubbling air is nickel per ton, copper, cobalt smelting waste slag 2-5 cubic meter in step b, and aeration time is 5-10 minute, or bubbling air meets the requirements until foreign matter content in nickel, copper, cobalt smelting waste slag.
Wherein use graphitized carbon cellulosic material gas duct to stretch in this warm sludge bag with ventilation.
Wherein the nickel of molten state, copper, cobalt smelting waste slag are meant that nickel, copper, cobalt smelting waste slag temperature are at 1150-1300 ℃.
Wherein among the step e to broken, grind identical with the processing requirement of flotation with conventional nickel minerals or copper mine.
Wherein refrigerating work procedure is to pour noble metal layers at least one mould slowly cooling in the steps d.
Through repeatedly experimental results show that, the nickel that adopts the inventive method to obtain, copper, the noble metal layers weight of cobalt smelting waste slag lower floor accounts for the 4-6% of waste gross weight, but the nickel of enrichment wherein, cobalt, copper accounts for and remains nickel in the waste, cobalt, the 60-83% of copper gross weight, at enriching quantity is 60% o'clock, nickel content 0.12% becomes 1.2% from waste, copper content 0.25% becomes 2.5% from waste, cobalt contents 0.16% becomes 1.6% from waste, thereby make by flotation process and select nickel, copper, cobalt concentrate becomes possibility, and it is 83% o'clock at enriching quantity, nickel, copper, cobalt contents becomes 1.66% respectively, 3.46%, 2.21%, considerably beyond the minimum requirements of flotation process ore dressing.Adopt efficiently element such as the nickel in comprehensive recovery nickel, copper, the cobalt smelting waste slag, cobalt, copper of method of the present invention, reached the purpose of large industrial solid castoff recycling.
Embodiment
The inventive method to the principle of nickel, copper, cobalt smelting waste slag purification and impurity removal is:
Utilize furnace outer refining technology, high pressure oxygen, high pressure chlorine successively are blown into respectively in the nickel, copper, cobalt smelting waste slag of molten state, quantitatively it is carried out purification and impurity removal handles in batches, detrimental impurity (as aluminum oxide, magnesium oxide, calcium oxide, sulfide etc.) in the waste is fully reacted, promote to generate the less new compound of proportion by even, slight level concussion simultaneously, new compound floats on nickel, copper, above the cobalt smelting waste slag and separate out, and noble metal enrichments such as nickel, copper, cobalt are deposited on lower floor, are beneficial to recovery.
Reaction equation is
FeS+3Fe
3O
4+ 5SiO
2+ 5O
2=5 (2FeOSiO
2)+SO
2↑ (under the high temperature fused state)
2Ca+O
2=2CaO (under the high temperature fused state)
2Mg+O
2=2MgO (under the high temperature fused state)
4Al+3O
2=2Al
2O
3(under the high temperature fused state)
2K+Cl
2=2KCl (under the high temperature fused state)
2Na+Cl
2=2NaCl (under the high temperature fused state)
Below for producing low nickel matte, hot waste is the chemical component table of the electric furnace warm sludge composition representative value of ferronickel slag:
Electric furnace warm sludge composition (%) in three months
Embodiment 1:
A, nickel, copper, cobalt smelting waste slag be heated to 1150 ℃ molten state;
B, insulation make nickel, copper, cobalt smelting waste slag remain on molten state, graphitized carbon cellulosic material gas duct is stretched into aerating oxygen in this warm sludge bag (high pressure oxygen) simultaneously thus generate solid residue with purification and impurity removal, the consumption of oxygen is 0.4 cubic metre in a nickel per ton, copper, cobalt smelting waste slag, and aeration time is 5 minutes;
C, even, slight level were shaken the warm sludge bag 30 minutes, left standstill then 8 minutes;
C, remove solid residue;
D, pour out noble metal layers slowly cooling in mould that molten state nickel, copper, cobalt smelting waste slag lower floor account for nickel, copper, cobalt smelting waste slag gross weight 4%;
E, fragmentation are ground the back again and can be obtained nickel, copper, cobalt concentrate powder by floatation process, and the processing requirement of concrete fragmentation, grinding and flotation is with identical to conventional nickel minerals or copper mine.
Embodiment 2:
A, nickel, copper, cobalt smelting waste slag be heated to 1300 ℃ molten state;
B, insulation make nickel, copper, cobalt smelting waste slag remain on molten state, graphitized carbon cellulosic material gas duct is stretched into aerating oxygen in this warm sludge bag (high pressure oxygen) simultaneously thus generate solid residue with purification and impurity removal, the consumption of oxygen is 1 cubic metre in a nickel per ton, copper, cobalt smelting waste slag, and aeration time is 10 minutes;
C, even, slight level were shaken the warm sludge bag 40 minutes, left standstill then 12 minutes;
C, remove solid residue;
D, pour out noble metal layers slowly cooling in mould that molten state nickel, copper, cobalt smelting waste slag lower floor account for nickel, copper, cobalt smelting waste slag gross weight 6%;
E, fragmentation are ground the back again and can be obtained nickel, copper, cobalt concentrate powder by floatation process, and the processing requirement of concrete fragmentation, grinding and flotation is with identical to conventional nickel minerals or copper mine.
Embodiment 3:
A, nickel, copper, cobalt smelting waste slag be heated to 1200 ℃ molten state;
B, insulation make nickel, copper, cobalt smelting waste slag remain on molten state, graphitized carbon cellulosic material gas duct is stretched into aerating oxygen in this warm sludge bag (high pressure oxygen) simultaneously thus generate solid residue with purification and impurity removal, the consumption of oxygen is 0.8 cubic metre in a nickel per ton, copper, cobalt smelting waste slag, and aeration time is 7 minutes;
C, even, slight level were shaken the warm sludge bag 35 minutes, left standstill then 10 minutes;
C, remove solid residue;
D, pour out noble metal layers slowly cooling in mould that molten state nickel, copper, cobalt smelting waste slag lower floor account for nickel, copper, cobalt smelting waste slag gross weight 5%;
E, fragmentation are ground the back again and can be obtained nickel, copper, cobalt concentrate powder by floatation process, and the processing requirement of concrete fragmentation, grinding and flotation is with identical to conventional nickel minerals or copper mine.
Embodiment 4:
A, nickel, copper, cobalt smelting waste slag be heated to 1150 ℃ molten state;
B, insulation make nickel, copper, cobalt smelting waste slag remain on molten state, graphitized carbon cellulosic material gas duct is stretched into bubbling air (high-pressure air) in this warm sludge bag simultaneously thus generate solid residue with purification and impurity removal, the consumption of air is 2 cubic metres in a nickel per ton, copper, cobalt smelting waste slag, and aeration time is 5 minutes;
C, even, slight level were shaken the warm sludge bag 30 minutes, left standstill then 8 minutes;
C, remove solid residue;
D, pour out noble metal layers slowly cooling in mould that molten state nickel, copper, cobalt smelting waste slag lower floor account for nickel, copper, cobalt smelting waste slag gross weight 4%;
E, fragmentation are ground the back again and can be obtained nickel, copper, cobalt concentrate powder by floatation process, and the processing requirement of concrete fragmentation, grinding and flotation is with identical to conventional nickel minerals or copper mine.
Embodiment 5:
A, nickel, copper, cobalt smelting waste slag be heated to 1300 ℃ molten state;
B, insulation make nickel, copper, cobalt smelting waste slag remain on molten state, graphitized carbon cellulosic material gas duct is stretched into bubbling air (high-pressure air) in this warm sludge bag simultaneously thus generate solid residue with purification and impurity removal, the consumption of air is 5 cubic metres in a nickel per ton, copper, cobalt smelting waste slag, and aeration time is 10 minutes;
C, even, slight level were shaken the warm sludge bag 40 minutes, left standstill then 12 minutes;
C, remove solid residue;
D, pour out noble metal layers slowly cooling in mould that molten state nickel, copper, cobalt smelting waste slag lower floor account for nickel, copper, cobalt smelting waste slag gross weight 6%;
E, fragmentation are ground the back again and can be obtained nickel, copper, cobalt concentrate powder by floatation process, and the processing requirement of concrete fragmentation, grinding and flotation is with identical to conventional nickel minerals or copper mine.
Embodiment 6:
A, nickel, copper, cobalt smelting waste slag be heated to 1200 ℃ molten state;
B, insulation make nickel, copper, cobalt smelting waste slag remain on molten state, graphitized carbon cellulosic material gas duct is stretched into bubbling air (high-pressure air) in this warm sludge bag simultaneously thus generate solid residue with purification and impurity removal, the consumption of air is 3 cubic metres in a nickel per ton, copper, cobalt smelting waste slag, and aeration time is 7 minutes;
C, even, slight level were shaken the warm sludge bag 35 minutes, left standstill then 10 minutes;
C, remove solid residue;
D, pour out noble metal layers slowly cooling in mould that molten state nickel, copper, cobalt smelting waste slag lower floor account for nickel, copper, cobalt smelting waste slag gross weight 5%;
E, fragmentation are ground the back again and can be obtained nickel, copper, cobalt concentrate powder by floatation process, and the processing requirement of concrete fragmentation, grinding and flotation is with identical to conventional nickel minerals or copper mine.
Embodiment 7:
A, nickel, copper, cobalt smelting waste slag be heated to 1200 ℃ molten state;
B, insulation make nickel, copper, cobalt smelting waste slag remain on molten state, graphitized carbon cellulosic material gas duct is stretched into aerating oxygen in this warm sludge bag (high pressure oxygen) simultaneously thus generate solid residue with purification and impurity removal, the consumption of oxygen is 0.8 cubic metre in a nickel per ton, copper, cobalt smelting waste slag, and aeration time is 7 minutes;
C, insulation make nickel, copper, cobalt smelting waste slag keep molten state, while feeds chlorine (high pressure chlorine) thereby generates solid residue with purification and impurity removal in nickel, copper, cobalt smelting waste slag, the consumption of chlorine is 0.2 cubic metre in a nickel per ton, copper, cobalt smelting waste slag, and aeration time is 8 minutes;
D, even, slight level were shaken the warm sludge bag 35 minutes, left standstill then 10 minutes;
E, remove solid residue;
F, pour out noble metal layers slowly cooling in mould that molten state nickel, copper, cobalt smelting waste slag lower floor account for nickel, copper, cobalt smelting waste slag gross weight 5%;
G, fragmentation are ground the back again and can be obtained nickel, copper, cobalt concentrate powder by floatation process, and the processing requirement of concrete fragmentation, grinding and flotation is with identical to conventional nickel minerals or copper mine.
Embodiment 8:
A, nickel, copper, cobalt smelting waste slag be heated to 1250 ℃ molten state;
B, insulation make nickel, copper, cobalt smelting waste slag remain on molten state, graphitized carbon cellulosic material gas duct is stretched into bubbling air (high-pressure air) in this warm sludge bag simultaneously thus generate solid residue with purification and impurity removal, meet the requirements until foreign matter content;
C, insulation make nickel, copper, cobalt smelting waste slag keep molten state, thereby in nickel, copper, cobalt smelting waste slag, feed chlorine simultaneously and generate solid residue with purification and impurity removal, the consumption of chlorine is 0.2 cubic metre in a nickel per ton, copper, cobalt smelting waste slag, aeration time is 8 minutes, meets the requirements until foreign matter content;
D, even, slight level were shaken the warm sludge bag 32 minutes, left standstill then 9 minutes;
E, remove solid residue;
F, pour out noble metal layers slowly cooling in mould that molten state nickel, copper, cobalt smelting waste slag lower floor account for nickel, copper, cobalt smelting waste slag gross weight 5%;
G, fragmentation are ground the back again and can be obtained nickel, copper, cobalt concentrate powder by floatation process, and the processing requirement of concrete fragmentation, grinding and flotation is with identical to conventional nickel minerals or copper mine.
Claims (6)
1. a method that reclaims nickel, copper, cobalt from nickel, copper, cobalt smelting waste slag is characterized in that, comprises the steps:
A, the nickel, copper, the cobalt smelting waste slag that nickel, copper, cobalt smelting waste slag are heated to molten state or directly get molten state are positioned in the warm sludge bag;
B, insulation make nickel, copper, cobalt smelting waste slag keep molten state, thus simultaneously in nickel, copper, cobalt smelting waste slag aerating oxygen or air generate solid residue with purification and impurity removal; Also to be incubated then and make nickel, copper, cobalt smelting waste slag keep molten state, thereby in nickel, copper, cobalt smelting waste slag, feed chlorine simultaneously and generate solid residue with purification and impurity removal, the consumption of chlorine is nickel per ton, copper, cobalt smelting waste slag 0.1-0.25 cubic meter, and aeration time is 5-10 minute;
C, concussion warm sludge bag 30-40 minute left standstill 8-12 minute then;
C, remove solid residue;
D, pour out the noble metal layers postcooling that molten state nickel, copper, cobalt smelting waste slag lower floor account for nickel, copper, cobalt smelting waste slag gross weight 4-6%;
E, fragmentation are ground the back again and can be obtained nickel, copper, cobalt concentrate powder by floatation process.
2. the method that reclaims nickel, copper, cobalt from nickel, copper, cobalt smelting waste slag as claimed in claim 1 is characterized in that: wherein the consumption of aerating oxygen is nickel per ton, copper, cobalt smelting waste slag 0.4-1 cubic meter in step b, and aeration time is 5-10 minute.
3. the method that reclaims nickel, copper, cobalt from nickel, copper, cobalt smelting waste slag as claimed in claim 1 is characterized in that: wherein the consumption of bubbling air is nickel per ton, copper, cobalt smelting waste slag 2-5 cubic meter in step b, and aeration time is 5-10 minute.
4. as any described method that from nickel, copper, cobalt smelting waste slag, reclaims nickel, copper, cobalt in the claim 1 to 3, it is characterized in that: wherein use graphitized carbon cellulosic material gas duct to stretch in this warm sludge bag with ventilation.
5. as any described method that reclaims nickel, copper, cobalt from nickel, copper, cobalt smelting waste slag in the claim 1 to 3, it is characterized in that: wherein the nickel of molten state, copper, cobalt smelting waste slag are meant that nickel, copper, cobalt smelting waste slag temperature are at 1150-1300 ℃.
6. as any described method that reclaims nickel, copper, cobalt from nickel, copper, cobalt smelting waste slag in the claim 1 to 3, it is characterized in that: wherein refrigerating work procedure is to pour noble metal layers at least one mould slowly cooling in the steps d.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101172127A CN101545054B (en) | 2009-02-09 | 2009-02-09 | Method for recovering nickel, copper and cobalt from a nickel, copper and cobalt smelting waste slag |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101172127A CN101545054B (en) | 2009-02-09 | 2009-02-09 | Method for recovering nickel, copper and cobalt from a nickel, copper and cobalt smelting waste slag |
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| CN101545054A CN101545054A (en) | 2009-09-30 |
| CN101545054B true CN101545054B (en) | 2011-07-06 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102002598B (en) * | 2010-12-22 | 2012-08-29 | 东北大学 | Method for recovering copper and cobalt from cobalt-containing copper converter slag |
| CN103834810B (en) * | 2014-03-11 | 2015-11-25 | 斯莱登（北京）化工科技有限公司 | A kind of method by copper nickel slag production of copper cobalt nickel collective concentrate |
| CN107663589A (en) * | 2017-10-10 | 2018-02-06 | 东北大学 | A kind of method by the nickeliferous mixing slag recovery valuable component with iron |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4427629A (en) * | 1982-11-23 | 1984-01-24 | Gnb Batteries Inc. | Process for metal-enrichment of lead bullion |
| CN1157858A (en) * | 1996-10-17 | 1997-08-27 | 张铁铮 | Method for producing ultra low-carbon duriron |
| CN1348999A (en) * | 2000-10-12 | 2002-05-15 | 中国科学院金属研究所 | Copper-nickel slag treating method |
| CN1603439A (en) * | 2004-11-15 | 2005-04-06 | 四川川投峨眉铁合金（集团）有限责任公司 | Production process for dry method extraction of nickel |
| CN101148701A (en) * | 2007-09-06 | 2008-03-26 | 昆明理工大学 | Method for modifying non-ferrous metal copper slag/nickel slag by using combustible matter and preparing high-grade fuel |
-
2009
- 2009-02-09 CN CN2009101172127A patent/CN101545054B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4427629A (en) * | 1982-11-23 | 1984-01-24 | Gnb Batteries Inc. | Process for metal-enrichment of lead bullion |
| CN1157858A (en) * | 1996-10-17 | 1997-08-27 | 张铁铮 | Method for producing ultra low-carbon duriron |
| CN1348999A (en) * | 2000-10-12 | 2002-05-15 | 中国科学院金属研究所 | Copper-nickel slag treating method |
| CN1603439A (en) * | 2004-11-15 | 2005-04-06 | 四川川投峨眉铁合金（集团）有限责任公司 | Production process for dry method extraction of nickel |
| CN101148701A (en) * | 2007-09-06 | 2008-03-26 | 昆明理工大学 | Method for modifying non-ferrous metal copper slag/nickel slag by using combustible matter and preparing high-grade fuel |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2003-39056A 2003.02.12 |
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