CN101328542A - Method for directly preparing copper sulfate and cathode copper from copper ore concentrate - Google Patents
Method for directly preparing copper sulfate and cathode copper from copper ore concentrate Download PDFInfo
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- CN101328542A CN101328542A CNA2008100714909A CN200810071490A CN101328542A CN 101328542 A CN101328542 A CN 101328542A CN A2008100714909 A CNA2008100714909 A CN A2008100714909A CN 200810071490 A CN200810071490 A CN 200810071490A CN 101328542 A CN101328542 A CN 101328542A
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Abstract
The invention relates to a method for directly preparing bluestone and cathode copper from copper concentrate. The method orderly comprises the following technological steps: sulphating roasting, water immersion, filtration, acid dipping, filtration washing, extraction, back extraction, electrodeposition and the circular utilization of local working procedures; and when products of bluestone and electrolytic copper with high purity are obtained, side products such as sulphuric acid, iron oxide red and waste residues are simultaneously generated. The method of the invention has the characteristics of low production cost, strong material adaptability, high working efficiency, low investment, simple operation, high utilization rate of copper, diversified products and easy industrialized production, etc., so that the method is suitable to exploit and apply low-grade copper ores.
Description
One. technical field
The present invention relates to a kind ofly directly produce the method for copper sulfate and cathode copper, be suitable for low-grade copper mine exploitation and use with copper ore concentrates.
Two. background technology
With the copper ore concentrates is the raw material production copper products, mainly contains three kinds of methods:
First method is that pyrometallurgical smelting is produced product cathode copper and byproduct copper sulfate, generally comprise operations such as roasting, melting, blowing, refining, the copper ore concentrates that is suitable for grade 20～30% is used, this method exists that one-time investment is big, technical process is long, technical requirements is high, pyrogenic process dilution process energy consumption height and exhaust emission etc. are obviously not enough, and a large amount of exploitations along with copper mine, rich ore is fewer and feweri, and the concentrate source that can satisfy the requirement of higher-grade copper smelting by pyrometallurgy is fewer and feweri, has hindered the development of copper smelting by pyrometallurgy.
Second method is that hydrometallurgy is produced cathode copper, mainly contain copper ore concentrates sulfurization roasting-normal pressure acidleach-clean liquid-electrodeposition flow process, roasting-ammonia leaching-extraction-electrodeposition flow process, catalysis preoxidation leaching-extraction-electrodeposition flow process etc., the more low-grade copper ore concentrates of general adaptation, and these technologies all exist the rate of recovery of copper lower, be generally about 90%, be up to 94%, productivity and metal recovery rate are low, cause production cost higher.
The third method is a copper by iron replacement, and the production process of courage copper comprises two aspects: the one, and acidleach copper, the 2nd, concentrate, cupric sulfate crystals and deposited copper.Wherein researcher has been done great deal of experimental work, carried out continuous perfect soaking process for copper and purification process, but still there is certain problem: 1. no matter be preroasting extraction or direct extraction, the basic dilute sulphuric acid that adopts leaches, leach liquor acidity and foreign matter content are higher, direct crystallization is difficult to obtain qualified product, if in adopting and impurity such as technology iron purification, then cost copper higher, loss is difficult to washing and recycling, complex process.2. because leach liquor copper concentration is higher, cause the leached mud washing flow longer, and the copper in this part washing water returns and leaches flow process and cause leach liquor copper concentration greatly to reduce, and makes the facility investment of copper sulfate evaporative crystallization big, energy consumption is high, labour intensity is big, running expense is many.3. owing to preparing the copper sulfate mother liquor, condensing crystal circulates for a long time, cause impurities accumulation serious, for addressing this problem, the electrodeposition decopper(ing)s that adopt are produced black copper or iron replacement method production copper sponge more, because these products are work in-process, cause added value of product low, turnover of funds waits problem slowly, has also restricted the development of enterprise.
In a word, compare the different process of copper ore concentrates production of copper product, preceding two kinds of technology subject ranges have limitation: pyrometallurgical smelting incompatibility small-scale production and low-grade copper ore concentrates; Hydrometallurgy is produced cathode copper, and the rate of recovery of copper is low, incompatible copper ore concentrates than higher-grade.Though last a kind of copper by iron replacement adapts to the copper ore concentrates than higher-grade, but exist facility investment and labour intensity big, problems such as working cost is many, and added value of product is low.
Three. summary of the invention
The object of the present invention is to provide that a kind of production cost is lower, adaptability to raw material is strong, efficiency is high, less investment, simple to operate, copper utilization ratio height, product diversification, easy a kind of method of directly producing copper sulfate and cathode copper with copper ore concentrates of industrializing implementation.
For realizing above purpose, to invent and a kind ofly directly produce the method for copper sulfate and cathode copper with copper ore concentrates, this method comprises following processing steps in sequence:
(a) sulfurization roasting is the copper ore concentrates water pulp of 78%-0.074mm, grade about 13% with sulfur-bearing 28%, granularity and stir, and delivers in 400～900 ℃ of temperature ranges in fluidizing furnace inherence and carries out sulfurization roasting 1～5h, again with the dust-laden SO of roasting output
2Flue gas carries out relieving haperacidity after dust removal installation gathers dust, make byproduct sulfuric acid;
(b) water logging is delivered to the water logging groove together with the calcining of roasting output and the collected flue dust that gathers dust and carry out water logging 0.2～4h in 40～95 ℃ of temperature range;
(c) filter, the water logging ore pulp is filtered, again the high-copper leach liquor that filters out is carried out deironing, condensing crystal, centrifuging successively, make product copper sulfate;
(d) acidleach through the pulp of copper raffinate, is carried out acidleach 0.2～4h with the water logging slag in 45～95 ℃ of temperature ranges;
(e) filtration washing adds water acid leaching ore pulp is carried out filtration washing, and the acid leaching residue based on ferric oxide that again filtration washing is gone out carries out the iron oxide red preparation, makes byproduct iron oxide red and waste residue;
(f) extraction, the partial mother liquid that low-concentration sulfuric acid copper solutions that filtration washing is gone out and centrifuging go out extracts with copper extractant;
(g) back extraction is carried out back extraction with the load organic phases of extraction with sulfuric acid, makes copper sulfate obtain enrichment, purification, again the load organic phases after the back extraction is returned extraction process;
(h) electrodeposition carries out electrodeposition with the rich copper liquid after the back extraction, makes the product cathode copper.
Method of the present invention further comprises following circulation technology step:
(a) the mother liquor part after the centrifuging is returned the condensing crystal operation, another part returns extraction process, carries out recycle again;
(b) the raffinate part after will extracting is returned the acidleach operation, carries out recycle again, and another part can carry out discharging after the water treatment;
(c) the useless electric effusion behind the electrodeposition is returned the back extraction operation, carry out recycle again.
Advantage of the present invention:
1. adopt water logging technology by copper ore concentrates calcining that sulfurization roasting is produced and flue dust, can obtain the copper concentration copper-bath, and copper leach liquor acidity and impurity are lower, are that solution purification is created very strong condition.
2. the water logging slag has been guaranteed the leaching effect of copper, and has been simplified the copper washing flow through the copper-bath of acidleach output low concentration.
3. copper concentration copper-bath condensing crystal copper sulfate process and high acidity, polymictic low-concentration sulfuric acid copper extraction electrodeposition technology reclaims process for copper, it is big to have overcome the investment that exists in the known copper ore concentrates production copper sulfate process, operation cost height and copper ore concentrates are produced problems such as the electro deposited copper copper recovery is low, obtaining high-purity sulphuric acid copper, go back output sulfuric acid in the time of the electrolytic copper product, iron oxide red and waste residue byproduct, realized product diversification, improved the rate of recovery of copper greatly, resource utilization, this method has less investment, risk is little, profitable, characteristics such as have a extensive future.
Four. description of drawings
The concrete grammar of invention is provided by the following drawings.
Fig. 1 is a kind of process flow sheet of directly producing the method for copper sulfate and cathode copper with copper ore concentrates that proposes according to the present invention.
The present invention is described in further detail below in conjunction with accompanying drawing.
Five. embodiment
Embodiment one: as shown in Figure 1, a kind ofly directly produce the method for copper sulfate and cathode copper with copper ore concentrates, this method comprises following processing steps in sequence:
(a) sulfurization roasting, be the copper ore concentrates water pulp of 78%-0.074mm, grade about 13% with sulfur-bearing 28%, granularity and stir, deliver to 400～900 ℃ of temperature in fluidizing furnace inherence ,-carry out sulfurization roasting 1～5h in 30～0Pa scope, again with the dust-laden SO of roasting output
2Flue gas carries out relieving haperacidity after dust removal installation gathers dust, make byproduct sulfuric acid;
(b) water logging is delivered to the water logging groove together with the calcining of roasting output and the collected flue dust that gathers dust and carry out water logging 0.2～4h in 40～95 ℃ of temperature range;
(c) filter, the water logging ore pulp is filtered, again the high-copper leach liquor that filters out is carried out deironing, condensing crystal, centrifuging successively, make product copper sulfate;
(d) acidleach through the pulp of copper raffinate, is carried out acidleach 0.2～4h with the water logging slag in 45～95 ℃ of temperature ranges;
(e) filtration washing adds water acid leaching ore pulp is carried out filtration washing, and the acid leaching residue based on ferric oxide that again filtration washing is gone out carries out the iron oxide red preparation, makes byproduct iron oxide red and waste residue;
(f) extraction, the partial mother liquid that low-concentration sulfuric acid copper solutions that filtration washing is gone out and centrifuging go out extracts with copper extractant;
(g) back extraction is carried out back extraction with the load organic phases of extraction with sulfuric acid, makes copper sulfate obtain enrichment, purification, again the load organic phases after the back extraction is returned extraction process;
(h) electrodeposition carries out electrodeposition with the rich copper liquid after the back extraction, makes the product cathode copper.
Embodiment two: with reference to Fig. 1, this method further comprises following processing steps in sequence:
(a) sulfurization roasting, be the copper ore concentrates water pulp of 78%-0.074mm, grade about 13% with sulfur-bearing 28%, granularity and stir, deliver to 500～700 ℃ of temperature in fluidizing furnace inherence ,-carry out sulfurization roasting 1～3h in 20～0Pa scope, again with the dust-laden SO of roasting output
2Flue gas carries out relieving haperacidity after dust removal installation gathers dust, make byproduct sulfuric acid;
(b) water logging is delivered to the water logging groove together with the calcining of roasting output and the collected flue dust that gathers dust and carry out water logging 0.5～2.5h in 60～90 ℃ of temperature range;
(c) filter, the water logging ore pulp is filtered, again the high-copper leach liquor that filters out is carried out deironing, condensing crystal, centrifuging successively, make product copper sulfate;
(d) acidleach through the pulp of copper raffinate, is carried out acidleach 0.5～2.5h with the water logging slag in 65～95 ℃ of temperature ranges;
(e) filtration washing adds water acid leaching ore pulp is carried out filtration washing, and the acid leaching residue based on ferric oxide that again filtration washing is gone out carries out the iron oxide red preparation, makes byproduct iron oxide red and waste residue;
(f) extraction, the partial mother liquid that low-concentration sulfuric acid copper solutions that filtration washing is gone out and centrifuging go out extracts with copper extractant;
(g) back extraction is carried out back extraction with the load organic phases of extraction with sulfuric acid, makes copper sulfate obtain enrichment, purification, again the load organic phases after the back extraction is returned extraction process;
(h) electrodeposition carries out electrodeposition with the rich copper liquid after the back extraction, makes the product cathode copper.
This method further comprises the following circulation technology step of dotted line indication:
(a) the mother liquor part after the centrifuging is returned the condensing crystal operation, another part returns extraction process, carries out recycle again;
(b) the raffinate part after will extracting is returned the acidleach operation, carries out recycle again, and another part can carry out discharging after the water treatment;
(c) the useless electric effusion behind the electrodeposition is returned the back extraction operation, carry out recycle again.
Directly produce copper sulfate and cathode copper with method of the present invention from low-grade smart copper mine, detect every technical indicator such as following table through relevant department:
| The leaching yield of copper | The percent crystallization in massecuite of copper | The percentage extraction of copper | The electrodeposition rate of copper | The rate of recovery of copper | The copper sulfate quality | The cathode copper quality | |
| 97.58 | 70.00 | 99.20 | 99.50 | 96.32 | 1 grade of | GB | 1 # |
From last table as seen, the copper comprehensive recovery reaches more than 96%.
Claims (3)
1. directly produce the method for copper sulfate and cathode copper with copper ore concentrates for one kind, this method comprises following processing steps in sequence:
(a) sulfurization roasting, be the copper ore concentrates water pulp of 78%-0.074mm, grade about 13% with sulfur-bearing 28%, granularity and stir, deliver to 400～900 ℃ of temperature in fluidizing furnace inherence ,-carry out sulfurization roasting 1～5h in 30～0Pa furnace top pressure scope, again with the dust-laden SO of roasting output
2Flue gas carries out relieving haperacidity after dust removal installation gathers dust, make byproduct sulfuric acid;
(b) water logging is delivered to the water logging groove together with the calcining of roasting output and the collected flue dust that gathers dust and carry out water logging 0.2～4h in 40～95 ℃ of temperature range;
(c) filter, the water logging ore pulp is filtered, again the high-copper leach liquor that filters out is carried out deironing, condensing crystal, centrifuging successively, make product copper sulfate;
(d) acidleach through the pulp of copper raffinate, is carried out acidleach 0.2～4h with the water logging slag in 45～95 ℃ of temperature ranges;
(e) filtration washing adds water acid leaching ore pulp is carried out filtration washing, and the acid leaching residue based on ferric oxide that again filtration washing is gone out carries out the iron oxide red preparation, makes byproduct iron oxide red and waste residue;
(f) extraction, the partial mother liquid that low-concentration sulfuric acid copper solutions that filtration washing is gone out and centrifuging go out extracts with copper extractant;
(g) back extraction is carried out back extraction with the load organic phases of extraction with sulfuric acid, makes copper sulfate obtain enrichment, purification, again the load organic phases after the back extraction is returned extraction process;
(h) electrodeposition carries out electrodeposition with the rich copper liquid after the back extraction, makes the product cathode copper.
2. according to claim 1ly a kind ofly directly produce the method for copper sulfate and cathode copper with copper ore concentrates, this method further comprises following processing steps in sequence:
(a) sulfurization roasting, be the copper ore concentrates water pulp of 78%-0.074mm, grade about 13% with sulfur-bearing 28%, granularity and stir, deliver to 500～700 ℃ of temperature in fluidizing furnace inherence ,-carry out sulfurization roasting 1～3h in 20～0Pa furnace top pressure scope, again with the dust-laden SO of roasting output
2Flue gas carries out relieving haperacidity after dust removal installation gathers dust, make byproduct sulfuric acid;
(b) water logging is delivered to the water logging groove together with the calcining of roasting output and the collected flue dust that gathers dust and carry out water logging 0.5～2.5h in 60～90 ℃ of temperature range;
(c) filter, the water logging ore pulp is filtered, again the high-copper leach liquor that filters out is carried out deironing, condensing crystal, centrifuging successively, make product copper sulfate;
(d) acidleach through the pulp of copper raffinate, is carried out acidleach 0.5～2.5h with the water logging slag in 65～95 ℃ of temperature ranges;
(e) filtration washing adds water acid leaching ore pulp is carried out filtration washing, and the acid leaching residue based on ferric oxide that again filtration washing is gone out carries out the iron oxide red preparation, makes byproduct iron oxide red and waste residue;
(f) extraction, the partial mother liquid that low-concentration sulfuric acid copper solutions that filtration washing is gone out and centrifuging go out extracts with copper extractant;
(g) back extraction is carried out back extraction with the load organic phases of extraction with sulfuric acid, makes copper sulfate obtain enrichment, purification, again the load organic phases after the back extraction is returned extraction process;
(h) electrodeposition carries out electrodeposition with the rich copper liquid after the back extraction, makes the product cathode copper;
3. according to claim 1 and 2ly a kind ofly directly produce the method for copper sulfate and cathode copper with copper ore concentrates, this method further comprises following circulation technology step:
(a) the mother liquor part after the centrifuging is returned the condensing crystal operation, another part returns extraction process, carries out recycle again;
(b) the raffinate part after will extracting is returned the acidleach operation, carries out recycle again, and another part can carry out discharging after the water treatment;
(c) the useless electric effusion behind the electrodeposition is returned the back extraction operation, carry out recycle again.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643993A (en) * | 2012-04-27 | 2012-08-22 | 福建金山黄金冶炼有限公司 | Balance control technique for efficient extraction of electro-deposited copper and impurities from complex solution |
| CN103184333A (en) * | 2011-12-30 | 2013-07-03 | 北京有色金属研究总院 | High grade copper oxide-containing material sulfuric acid leaching and stage extraction technology |
| CN103422119A (en) * | 2013-07-19 | 2013-12-04 | 紫金矿业集团股份有限公司 | Method for producing tough cathode with cupric sludge |
| CN103643037A (en) * | 2013-12-25 | 2014-03-19 | 昆明理工大学 | Separating method of copper and iron-lead in complex copper-iron-lead mixed sulphide ores |
| CN107723460A (en) * | 2017-10-23 | 2018-02-23 | 湖南华信稀贵科技股份有限公司 | A kind of smelting process of complex lead-zinc copper mine |
| CN114560491A (en) * | 2022-03-10 | 2022-05-31 | 浙江大学 | Preparation method of copper oxide heat storage base material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5431788A (en) * | 1993-06-28 | 1995-07-11 | Cominco Engineering Services Ltd. | Chloride assisted hydrometallurgical copper extraction |
| CN1094014A (en) * | 1994-03-22 | 1994-10-26 | 南开大学 | The method that directly prepares copper sulfate by chalcopyrite |
| CN1255561C (en) * | 2003-11-13 | 2006-05-10 | 河北科技大学 | Method for preparing copper sulfate using copper concentrate |
| CN100395354C (en) * | 2006-11-27 | 2008-06-18 | 紫金矿业集团股份有限公司 | Comprehensive recovering process of multimetal sulfide mineral |
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- 2008-07-25 CN CN2008100714909A patent/CN101328542B/en active Active
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| CN103184333A (en) * | 2011-12-30 | 2013-07-03 | 北京有色金属研究总院 | High grade copper oxide-containing material sulfuric acid leaching and stage extraction technology |
| CN103184333B (en) * | 2011-12-30 | 2014-08-06 | 北京有色金属研究总院 | High grade copper oxide-containing material sulfuric acid leaching and stage extraction technology |
| CN102643993A (en) * | 2012-04-27 | 2012-08-22 | 福建金山黄金冶炼有限公司 | Balance control technique for efficient extraction of electro-deposited copper and impurities from complex solution |
| CN103422119A (en) * | 2013-07-19 | 2013-12-04 | 紫金矿业集团股份有限公司 | Method for producing tough cathode with cupric sludge |
| CN103422119B (en) * | 2013-07-19 | 2016-05-04 | 紫金矿业集团股份有限公司 | A kind of method of utilizing copper-contained sludge to produce tough cathode |
| CN103643037A (en) * | 2013-12-25 | 2014-03-19 | 昆明理工大学 | Separating method of copper and iron-lead in complex copper-iron-lead mixed sulphide ores |
| CN103643037B (en) * | 2013-12-25 | 2015-09-09 | 昆明理工大学 | The separation method of copper and galvanized iron in a kind of Complicated Copper galvanized iron mixing sulphide ores |
| CN107723460A (en) * | 2017-10-23 | 2018-02-23 | 湖南华信稀贵科技股份有限公司 | A kind of smelting process of complex lead-zinc copper mine |
| CN107723460B (en) * | 2017-10-23 | 2019-03-19 | 湖南华信稀贵科技股份有限公司 | A kind of smelting process of complex lead-zinc copper mine |
| CN114560491A (en) * | 2022-03-10 | 2022-05-31 | 浙江大学 | Preparation method of copper oxide heat storage base material |
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