CN103898332A - Technology for separating copper, zinc and iron in scrap copper smelting slag leaching process - Google Patents
Technology for separating copper, zinc and iron in scrap copper smelting slag leaching process Download PDFInfo
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- CN103898332A CN103898332A CN201210587187.0A CN201210587187A CN103898332A CN 103898332 A CN103898332 A CN 103898332A CN 201210587187 A CN201210587187 A CN 201210587187A CN 103898332 A CN103898332 A CN 103898332A
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Abstract
The invention relates to a technology for separating copper, zinc and iron in a scrap copper smelting slag leaching process. The technology for separating the copper, zinc and iron in the scrap copper smelting slag leaching process comprises the following steps: (1) performing selective zinc leaching on the scrap copper smelting slag; (2) performing weak acid leaching on the selectively leached slag; (3) heating a solution after weak acid is leached and adding an oxidizing agent, so that copper zinc alloy is contained in acid leaching solution, and iron is contained in acid leaching slag; (4) extracting copper from the acid leaching solution, so that copper is separated from zinc and iron; (5) returning raffinate into the selective zinc leaching step, wherein zinc is recycled after being returned into selective leaching solution, and residual copper and iron are sedimented into the selective leaching slag by virtue of a selective leaching process. The technology for separating the copper, zinc and iron in the scrap copper smelting slag leaching process has the advantages of short technological process, low investment and operating cost, simple operation, short leaching period, high recovery rate of copper and zinc and the like, copper and zinc in scrap copper smelting slag can be environmental friendly, efficiently and quickly leached out, and copper can be separated from copper; the technology for separating the copper, zinc and iron in the scrap copper smelting slag leaching process is especially applicable to treatment on scrap copper smelting slag with high iron content and high copper zinc content.
Description
Technical field
The present invention relates to the novel process that in a kind of useless composition brass metallurgical slag leaching process, copper zinc separates with iron.
Background technology
In recent years, along with the demand of recycling economy and national environmental protection policy is strengthened, resource recovery comes into one's own day by day.In the useless composition brass cyclic regeneration process of important component part as copper resource recovery, can produce a large amount of metallurgical slags, these metallurgical slags are many employing pyrogenic attacks now, along with the demand of national energy-saving environmental protection strengthens gradually, these metallurgical slags of wet processing become the trend of development.In the process of wet processing, certainly existing the problem of deironing, and the program that is introduced separately into deironing will inevitably cause processing technological flow long, energy consumption is too high, therefore must explore new copper zinc and iron separating technology.
The main method that at present copper zinc separates with iron wet process is mainly the method for traditional deironing at present: goethite process, hematite process, ferrovanadium method, extraction process and neutralisation.These methods all need the step of independent deironing, increase the flow process of deironing, add the burden of large enterprises.In the useless composition brass metallurgical slag of wet processing, due to the specific properties of useless composition brass metallurgical slag, in its slag, be main mainly with metal oxide, in treating processes, utilize this feature after leaching, part iron to be separated, make the concentration of iron in leaching process be controlled at rational scope by rational flow process.Can in leaching process, control like this content of iron, not affect the leaching yield of copper zinc simultaneously, can reach the object separating of copper zinc and iron.
Summary of the invention
The object of this invention is to provide a kind of novel process that makes copper zinc separate with iron in useless composition brass metallurgical slag leaching process.The conditions such as the joining day of this technology utilization reasonable manner and control temperature, extraction time and oxygenant realize the high efficiency separation of copper zinc and iron, and useless composition brass metallurgical slag treatment scheme is processed in reduction.
For achieving the above object, the present invention adopts following technical scheme:
1, the technique that in useless composition brass metallurgical slag leaching process, copper zinc separates with iron, is characterized in that, it comprises the following steps:
(1) useless composition brass metallurgical slag is carried out to selectivity leaching, most of zinc enters in selective leaching fluid, and part zinc and copper iron enter during selective leaching slags tap;
(2) selective leaching is slagged tap and carried out weak acid leaching;
(3) solution after weak acid leaching is heated and adds oxygenant, and copper zinc enters acid leaching solution, and iron enters acidic leaching residue;
(4) after copper zinc separates with most of iron, acid leaching solution is carried out to copper extraction, realize separating of copper and zinc-iron;
(5) raffinate turns back in the step of selectivity leaching zinc, leaches agent as selectivity, and zinc wherein enters selective leaching fluid and is recycled, and remaining copper iron enters into selective leaching through selectivity leaching process precipitation and slags tap.
Technique as above, preferably, before the selectivity of carrying out step (1) leaches, described useless composition brass metallurgical slag first divides through 60 mesh sieves, part large granularity is separated, the little part of granularity is after metallic iron is reclaimed in magnetic separation, and metallic copper is reclaimed in gravity treatment, and the useless composition brass metallurgical slag after magnetic separation and re-selection process is as leaching raw material.
Technique as above, preferably, it is sulfuric acid, nitric acid or hydrochloric acid that described selectivity leaching and described weak acid leach leaching agent used.
Technique as above, preferably, the concentration of described sulfuric acid is 40 ~ 200g/L.
Technique as above, preferably, the concentration of described nitric acid is 50 ~ 250g/L.
Technique as above, preferably, the concentration of described hydrochloric acid is 30 ~ 200g/L.
Technique as above, preferably, controls pH 4.8～5.4 in the selectivity leaching process of step (1), extraction time 0.5～1.5h, and extraction temperature is room temperature,
Technique as above, preferably, controls pH between 2.0～2.4 in the weak acid leaching process of step (2), extraction time 1～1.5h, and extraction temperature is room temperature.
Technique as above, preferably, step (3) add temperature control temperature at 70 DEG C～90 DEG C, heating-up time 5min, adds oxygenant immediately after intensification, described oxygenant is the H that accounts for total amount of solution 2%
2o
2, and in 30min, evenly add leaching raw material, and regulate pH between 5.0～5.4, when pH does not change in 5min, leach and finish.
Technique of the present invention as above, in step (1), useless composition brass metallurgical slag is controlled extraction time and is leached acidity selectivity and leach zinc by strict, the leaching yield of copper and iron is controlled at below 0.1%, the leaching yield of zinc reaches 60% left and right, realize separating of zinc and copper iron, selective leaching fluid, through purifying recyclable zinc, does not need to introduce the step of deironing.In step (2) and (3), selective leaching is slagged tap and is leached through weak acid, leaches copper, zinc and iron wherein, and now the leaching yield of copper zinc exceedes 90%, the leaching yield of iron is 60% left and right, if now circulate by traditional mode, the accumulative speed of iron is very fast, and technique of the present invention adds oxygenant after weak acid leaches, and control other condition, can further improve the leaching yield of copper, zinc, the most of iron in leach liquor can be deposited in slag simultaneously, realize copper, zinc separates with most of iron.In step (4), leach liquor, through copper extraction process, reclaims the copper in leach liquor, and remaining zinc and small part iron are in raffinate, and this part raffinate returns to selective leaching as leaching agent and goes out operation.In step (5), selective leaching goes out operation and can not only selectivity leaches the zinc in raffinate, the iron in raffinate can be sunk to selective leaching simultaneously and go in slagging tap, in the turnover balance of the process implementation iron of circulation.
Beneficial effect of the present invention is:
The present invention proposes a kind of useless composition brass metallurgical slag New Process for Treatment of Treatment of Copper zinc-iron, according to the feature of useless composition brass metallurgical slag self, shorten the treatment scheme of processing useless composition brass metallurgical slag, make full use of useless this secondary resource of composition brass metallurgical slag, improve comprehensive utilization of resources level, reduce environmental pollution, increase economic efficiency.The present invention is particularly suitable for each useless composition brass of China and smelts recovery factory, can adapt to process the useless composition brass metallurgical slag of various scales.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Specific implementation method
Below in conjunction with concrete embodiment, the invention will be further described, refers to Fig. 1, is the schema of the useless composition brass metallurgical slag leaching process copper zinc of the present invention and iron separating technology.
(1) leach preliminary preparation
Smelt returned enterprise as example taking the large-scale useless composition brass of China.The a large amount of useless composition brass metallurgical slag of the annual generation of this enterprise, contains a large amount of copper zinc-irons in slag, its occurrence status is main mainly with oxide compound and metal alloy state.Useless composition brass metallurgical slag size-grade distribution is wide, must be through screening.The boundary of screening is 60 orders, by screening, part large grain is separated, the little part of granularity through the metallic iron of magnetic separation recovery part after, gravity treatment recovery metallic copper.Sample after magnetic separation and re-selection process operation is as leaching raw material, and wherein the content of each element is: copper 7.17%, zinc 30.43%, iron 3.82%.
(2) selectivity leaching process
Because useless composition brass metallurgical slag contains higher copper zinc content with respect to ore smelting slag, in the time that leaching, selectivity can in leaching process, realize the separation of copper, zinc.Control extraction time 1h, leaching process is strictly controlled the pH fluctuation of leaching, pH is controlled at 4.8～5.4, extraction temperature is room temperature, finally can make concentration of iron in leach liquor below 2mg/L, the concentration of copper is at 0.1g/L, and the leaching yield of zinc can approach 60%, and this part zinc solution just can be produced zinc sulfate or electrowinning zinc through simple purification.At this moment the zinc that contains most copper, iron and 40% of selective leaching in slagging tap, will continue to leach to it and process.
(3) weak acid leaching process
In order to leach remaining zinc and copper, and control the content of iron in leach liquor, weak acid leaches and will keep all the time the pH of leaching process 2.0～2.4, extraction time 1.5h, extraction temperature is room temperature, when extraction time is reached home, the leaching yield of copper, zinc exceedes 90%, the leaching yield of iron is 60% left and right, and the iron level in leach liquor is high, and can be more and more higher in the process of accumulation.In the time reaching leaching terminal, steam adds temperature control temperature 80 DEG C of left and right, adds total amount of solution 2%H after intensification
2o
2, and slowly add leaching raw material, regulate pH between 5.0～5.2, this part-time is 30min left and right, now the leaching yield of copper, zinc can exceed 95%, and iron after leaching can be with Fe (OH)
3form come back in weak acid leached mud, thereby realize separating of copper zinc and iron, the total leaching yield of weak acid extracting stage of iron can drop to below 30%.
(4) weak acid passes through after special efficacy copper extractant extracting copper after leaching, in raffinate, the content of zinc and iron is constant, this part will leach agent as selectivity and return, in the process leaching in selectivity, control leaching condition according to (2) again, iron can enter into selective leaching and slag tap, and in working cycle, in leach liquor, the concentration of iron can not exceed 10mg/L.
Can control the trend that leaches iron in flow process by this circulation, if the inlet of iron is 3.82g in working cycle, be 3.80g left and right by the iron level of walking out containing the acidic leaching residue of high ferro, in working cycle, iron has been realized balance, can realize the separation of iron without independent iron removal step, reach cost-effective object.
Claims (9)
1. the technique that in useless composition brass metallurgical slag leaching process, copper zinc separates with iron, is characterized in that, it comprises the following steps:
(1) useless composition brass metallurgical slag is carried out to selectivity leaching, most of zinc enters in selective leaching fluid, and part zinc and copper iron enter during selective leaching slags tap;
(2) selective leaching is slagged tap and carried out weak acid leaching;
(3) solution after weak acid leaching is heated and adds oxygenant, and copper zinc enters acid leaching solution, and iron enters acidic leaching residue;
(4) after copper zinc separates with most of iron, acid leaching solution is carried out to copper extraction, realize separating of copper and zinc-iron;
(5) raffinate turns back in the step of selectivity leaching zinc, leaches agent as selectivity, and zinc wherein enters selective leaching fluid and is recycled, and remaining copper iron enters into selective leaching through selectivity leaching process precipitation and slags tap.
2. technique as claimed in claim 1, it is characterized in that, before the selectivity of carrying out step (1) leaches, described useless composition brass metallurgical slag first divides through 60 mesh sieves, part large granularity is separated, the little part of granularity is after metallic iron is reclaimed in magnetic separation, and metallic copper is reclaimed in gravity treatment, and the useless composition brass metallurgical slag after magnetic separation and re-selection process is as leaching raw material.
3. technique as claimed in claim 1 or 2, is characterized in that, it is sulfuric acid, nitric acid or hydrochloric acid that described selectivity leaching and described weak acid leach leaching agent used.
4. technique as claimed in claim 3, is characterized in that, the concentration of described sulfuric acid is 40 ~ 200g/L.
5. technique as claimed in claim 3, is characterized in that, the concentration of described nitric acid is 50 ~ 250g/L.
6. technique as claimed in claim 3, is characterized in that, the concentration of described hydrochloric acid is 30 ~ 200g/L.
7. technique as claimed in claim 1 or 2, is characterized in that, in the selectivity leaching process of step (1), controls pH 4.8～5.4, extraction time 0.5～1.5h, and extraction temperature is room temperature.
8. technique as claimed in claim 1 or 2, is characterized in that, in the weak acid leaching process of step (2), controls pH between 2.0～2.4, extraction time 1～1.5h, and extraction temperature is room temperature.
9. technique as claimed in claim 1 or 2, is characterized in that, step (3) add temperature control temperature at 70 DEG C～90 DEG C, heating-up time 5min, adds oxygenant immediately after intensification, described oxygenant is the H that accounts for total amount of solution 2%
2o
2, and in 30min, evenly add leaching raw material, and regulate pH between 5.0～5.4, when pH does not change in 5min, leach and finish.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210587187.0A CN103898332B (en) | 2012-12-28 | 2012-12-28 | The technique that in copper scap metallurgical slag leaching process, copper zinc is separated with iron |
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| CN201210587187.0A CN103898332B (en) | 2012-12-28 | 2012-12-28 | The technique that in copper scap metallurgical slag leaching process, copper zinc is separated with iron |
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| CN103898332A true CN103898332A (en) | 2014-07-02 |
| CN103898332B CN103898332B (en) | 2015-08-19 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439357A (en) * | 2015-12-28 | 2016-03-30 | 中南大学 | Mine acid wastewater utilization and deep purification method |
| CN110819816A (en) * | 2019-12-26 | 2020-02-21 | 中国葛洲坝集团绿园科技有限公司 | Method for recovering zinc from scrap copper smelting slag |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900330A (en) * | 2006-06-30 | 2007-01-24 | 赤峰红烨锌冶炼有限责任公司 | Low pollution vanadium settling iron-removing wet zinc smelting method |
| CN101608258A (en) * | 2008-11-20 | 2009-12-23 | 厦门钨业股份有限公司 | Adopt cobalt-copper alloy to make the method that primary industry extracts cobalt, copper, iron |
| CN102560130A (en) * | 2010-12-15 | 2012-07-11 | 北京有色金属研究总院 | Selective leaching technology of copper and zinc in scrap copper smelting slag |
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- 2012-12-28 CN CN201210587187.0A patent/CN103898332B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900330A (en) * | 2006-06-30 | 2007-01-24 | 赤峰红烨锌冶炼有限责任公司 | Low pollution vanadium settling iron-removing wet zinc smelting method |
| CN101608258A (en) * | 2008-11-20 | 2009-12-23 | 厦门钨业股份有限公司 | Adopt cobalt-copper alloy to make the method that primary industry extracts cobalt, copper, iron |
| CN102560130A (en) * | 2010-12-15 | 2012-07-11 | 北京有色金属研究总院 | Selective leaching technology of copper and zinc in scrap copper smelting slag |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439357A (en) * | 2015-12-28 | 2016-03-30 | 中南大学 | Mine acid wastewater utilization and deep purification method |
| CN110819816A (en) * | 2019-12-26 | 2020-02-21 | 中国葛洲坝集团绿园科技有限公司 | Method for recovering zinc from scrap copper smelting slag |
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Effective date of registration: 20190625 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: YOUYAN ENGINEERING TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. Address before: No. 2, Xinjie street, Xicheng District, Beijing, Beijing Patentee before: General Research Institute for Nonferrous Metals |
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Effective date of registration: 20210402 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Youyan resources and Environment Technology Research Institute (Beijing) Co.,Ltd. Address before: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee before: YOUYAN ENGINEERING TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. |
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Granted publication date: 20150819 Termination date: 20211228 |
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