CN105274331A - Method for recycling copper through heating and leaching low-grade copper tailings by means of air energy - Google Patents
Method for recycling copper through heating and leaching low-grade copper tailings by means of air energy Download PDFInfo
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- CN105274331A CN105274331A CN201410343427.1A CN201410343427A CN105274331A CN 105274331 A CN105274331 A CN 105274331A CN 201410343427 A CN201410343427 A CN 201410343427A CN 105274331 A CN105274331 A CN 105274331A
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Abstract
The invention discloses a method for recycling copper through heating and leaching copper flotation tailings by means of air energy. The method is characterized in that (1) the flotation copper tailings are heated and leached out through air energy, that is, tailing ore pulp after being selected through flotation is circularly heated and leached out through an air energy heating device; (2) iron depositing is performed, that is, the potential of hydrogen (PH) value of a leaching solution is adjusted through NaOH, the end point of the PH value is controlled to be 3.5, and therefore iron ions in the solution are deposited in a mode of Fe(OH)3; and (3) copper depositing is performed, that is, the PH value of the solution after iron depositing continues to be adjusted through NaOH, the end point of the PH value is controlled to be 7.0, and therefore the copper in the solution is deposited in a mode of Cu(OH)2. The flotation tailings of the low-grade copper oxide ore are subjected to sulfuric acid enhancing leaching under the normal pressure, the leaching temperature is controlled by an air energy heating system, and the obtained copper-contained leaching solution is subjected to iron depositing and then copper depositing so as to recycle the copper therein. Compared with traditional electric heating or oil bath heating leaching processes, the process can save energy by over 35%.
Description
Technical field
The present invention relates to a kind of hydrometallurgical processes processing Treating Low-grade Copper Ores, particularly relate to a kind of air that utilizes and can heat the method leaching low-grade copper mining tailing copper, namely novel air energy heating unit is adopted to carry out normal pressure sulfuric acid leaching to low grade copper oxide ore, most copper is made to enter into leach liquor with the form of copper sulfate, immersion liquid is heavy copper again after heavy iron first, belongs to wet type copper smelting technical field.
Background technology
Copper is one of important raw and processed materials of the development of the national economy.Along with the development of national economy, the demand of copper constantly increases, and then constantly exploits with copper mine, and its ore grade also constantly declines, thus creates a large amount of flotation ore deposits, lean ore, mine tailing, tailings and refractory copper oxide ore.Hydrometallurgy, just because of processing the not treatable low grade copper oxide ore of these pyrometallurgy and flotation tailings grows up, develops into again process copper-sulphide ores subsequently.Because copper hydrometallurgical technology process low-grade complex ore deposit has, production cost is low, resources utilization degree is high, investment of production is few, industrial scale is changeable, cathode copper quality product is high, the construction period is short, equipment is simple, easy to operate, less energy consumption, the superiority such as environmental pollution is little, why the research and apply of wet type copper smelting is subject to people's attention day by day.
At present, copper hydrometallurgical technology has become the first-selected technique of process low grade copper oxide ore stone and secondary copper sulfide ore, and is widely applied in the industrial production, and the copper of annual produced worldwide about has 1/4 to produce with wet method copper-extracting process.Leaching-solvent extraction-electrodeposition process is unanimously thought ripe, low cost, low-risk technology by industry, the copper that the whole world utilizes this technology to produce, annual production is more than 2,000,000 t, exceed 20% of ore deposit copper turnout, and scale is also increasing, mechanize and level of automation more and more higher, wherein U.S. Philips-Phelps Dodge Corp's Morenci copper mine cathode copper yearly capacity has reached 26.5 ten thousand t.The wet type copper smelting technology of Chile, Zambia, Peru, Australia etc. have also been obtained fast development in recent years.
This technology have also been obtained significant progress at home, since from the sixties in last century, this technique obtains production application, some research units of China have carried out the research of the aspects such as leaching (acidleach, ammonia leaching, Bioleaching and biological metallurgy) technique, extraction process, extraction agent respectively.After the eighties, define than more complete Leaching-solvent Extraction-electrowinning Technology and obtain Preliminary Applications aborning.
Copper oxide ore is the important component part of China's copper ore resource, and reserves are abundanter, along with the easily copper-sulphide ores of choosing and the consumption in high grade copper oxide ore deposit, in, the Utilizing question of low grade copper oxide ore causes concern and the attention of people increasingly.Therefore, seeking the copper oxide ore treatment process of technically feasible, reasonable in economy, is one of important topic of modern Copper making technology.Copper oxide ore generally has the features such as grade is low, oxidation ratio is high, combination rate is high, easy argillization, be difficult to obtain good technico-economical comparison with conventional selecting and smelting technology, both at home and abroad relevant scientific worker is to this has been large quantifier elimination, make copper oxide ore treatment technology particularly low grade copper oxide ore treatment technology achieve significant progress.
Because of the difference of its component, there is various multi-form scheme, with regard to processing method, had flotation process and lixiviation process in the process of copper oxide ore and mixed copper ore.At present, the process of copper oxide ore and mixed copper ores still more adopts flotation process, but some copper oxide ore is difficult to use flotation process process, in recent years, adopt hydrometallurgical technology process copper oxide ore to occupy critical role and achieved very large development, can excellent measure be obtained.
Chambishi Copper Mine of Zambia is first nonferrous metal mine of Chinese government's approval in development & construction overseas.Copper metal reserves 5,010,000 tons have been verified in this mine, and ore is containing copper grade 2.19%, and the copper metal content in mineral deposit is equivalent to 2.5 times that the average geologic grade of copper deposit is verified by China, has good Development volue.Chambishi copper mine copper-bearing mineral based on purple copper, chalcopyrite, and contains a small amount of copper glance, native copper; The oxide mineral of copper is mainly malachite, and a small amount of ruby copper, chrysocolla, and this brings certain difficulty to raising Cu Concentrate Grade.Containing more oxidized ore in ore body, high and mineral species is many in conjunction with cupric oxide, character is complicated, and occurrence condition is poor, and determine mineral processing circuit complexity, medicament kind is many, and ore beneficiation feasibility is poor compared with single copper.
By the restriction of technical qualification, only develop the ore body of oxidation ratio lower (20% ~ 40%) at present, the relatively high a part of ore body of oxidation ratio is then owing to temporarily stacking without economically viable art breading.According to the data presentation that Chambishi hydrometallurgy company provides, when oxidation ratio about 60%, the Floatation of Copper rate of recovery is only 20% ~ 25%, and flotation tailings copper leaching rate also only has 35% ~ 40%.Obviously, adopt single flotation process or lixiviation process process to be difficult to efficient recovery copper, obtain gratifying technico-economical comparison.
Flotation and hydrometallurgy are organically combined optimum combination by selecting smelting combination facture exactly in same flow process, maximize favourable factors and minimize unfavourable ones, a kind of method of mutual supplement with each other's advantages.At present, in the research with dressing and smelting united process copper oxide ore, develop acid leaching process, ammonia lixiviation process and segregation process three major types type more than ten and planted technique, comprising: leach cementation one electrodeposition method; Leach an extraction one electrodeposition (LEX method); Extraction one electrodeposition is leached in roasting one; Leach cementation one flotation (LPE method); To emanate a flotation process; Chloridizing roasting one flotation process etc.In the research of selecting smelting combination facture, various technical process perfect, the development of new extractant and the release of novel process etc., for the exploitation of refractory copper oxide ores and mixed copper ore open new way.
In the leaching-Extraction electrodeposition technology of copper extraction and electrodeposition process very mature and stable, not quite, extract technology then looks the difference of ore type and different in change.Be applied to industrial production or reached the leaching method in pilot-plant test stage at present and mainly contain pickling process, ammonia leaching process, chloride leaching method and Bioleaching method etc.Pickling process is the Main Means of wet processing copper oxide ore, is generally to make leaching agent with dilute sulphuric acid.It is main cupric oxide ore that acid leaching process is applicable to processing containing acid gangue, is usually used in extracting copper from low-grade, unbalanced-ore, residual ore deposit.According to the occurrence of ore body and the proterties of ore, pickling process can be divided into diafiltration leaching and agitation leach.This technological advantage is: leaching efficiency is high, leaching agent low price, technique, simple to operate.Its shortcoming is: process containing acid consumption during basic gangue high, leach selectivity poor, in leach liquor, foreign matter content is high, not good with the leaching effect in conjunction with copper to chalcopyrite ore.
Summary of the invention
Object of the present invention is just to solve prior art above shortcomings, for the problem that high oxidation rate difficult Treating Low-grade Copper Ores copper recovery is low, through lot of experiments with repeatedly study, give a kind of air that utilizes and can heat the method leaching low-grade copper mining tailing copper.The present invention adopts selecting smelting combination wet type copper smelting technique to process such low grade copper oxide ore, and first Copper Ores carries out flotation separation after fragmentation, grind grading, and the raw ore that grade is lower is able to enrichment and becomes copper ore concentrates to send pyrometallurgical smelting; Flotation tailings carries out vitriol intensified leaching at ambient pressure, and extraction temperature is controlled by air energy heating system, the cupric immersion liquid that obtains adopt first after heavy iron heavy copper to reclaim copper wherein.Compared with heating leaching with traditional electrically heated or oil bath, this energy saving technology can reach more than 35%.
The technical solution that the present invention provides is, this employing air can heat the method leaching copper flotation tailings recovery copper, forms primarily of following steps.
(1) air can heat leaching Floatation of Copper mine tailing, namely the mine tailing ore pulp after flotation is leached by air energy heating unit circulating-heating mechanical stirring, leaching agent is mainly sulfuric acid, extract technology major technique condition is as follows: extraction temperature 60 ~ 75 DEG C, sulfuric acid starting point concentration 10 ~ 12g/L, extraction time 3 ~ 6h, liquid-solid volume mass is than 3:1 ~ 4:1.In leaching process, depending on the height of copper tailing character and copper leaching rate, can blowing air or add MnO
2strengthen education is carried out in oxygenant.
(2) heavy iron, regulates leach liquor pH value with NaOH, controls pH value terminal 3.5, heavy iron time more than 1h, and heavy iron temperature 50 ~ 60 DEG C, the iron ion in solution is with Fe (OH)
3form precipitates.
(3) heavy copper, continue with liquid pH value after the heavy iron of NaOH adjustment, control pH value terminal 7.0, heavy copper time more than 1h, heavy iron temperature 50 ~ 60 DEG C, the copper in solution is with Cu (OH)
2form precipitates.
The air energy heating unit that the present invention adopts forms primarily of compressor, vaporizer, condenser, strainer, expansion valve and Controlling System.Adopt electrical energy drive heat pump, compressor consumes a part of electric energy, the refrigerant gas of low-temp low-pressure is compressed into the gas of High Temperature High Pressure, the gas of High Temperature High Pressure is released heat within the condenser and is heated by solution, and oneself temperature is lowered, after expansion valve reducing pressure by regulating flow, become the gas-liquid mixture of low-temp low-pressure, absorb the heat in other media (as air) at evaporator refrigerant, become the gas of low-temp low-pressure, and then absorbed by compressor, be compressed into the gas heating solution of High Temperature High Pressure.By the thermodynamic cycle process of this continuous evaporation-compression-condensation-throttling-evaporation, thus by the transfer of heat of dispersion a large amount of in air in the aqueous solution, reach the effect of heating and thermal insulation.Its structural representation as depicted in figs. 1 and 2.
This selecting smelting combination technique that the present invention adopts processes the difficult copper mine of this type of high oxidation rate, the core content place that vitriol intensified leaching is its inventive point is carried out to the mode that the mine tailing after flotation adopts air to heat, the present invention has widened the scope of available copper ore resource, make to fail effective exploitation utilization in the past or be considered as useless low grade copper ores to be developed, can good economic benefit and social benefit be produced, there is good development prospect.
Compared with prior art, beneficial effect of the present invention is.
(1) the present invention be directed to high oxidation rate refractory copper ore exploitation, but be applicable to too process other low grade copper oxide ore.Think that the unbalanced-ore, mine tailing etc. that cannot process all can be used as copper resource and be re-used in the past, substantially increase the comprehensive utilization ratio of resource.
(2) the present invention heats leaching-out technique with traditional electrically heated or oil bath and compares, and can save energy 30% ~ 40%, power savings advantages is obvious.
(3) in the present invention, intensified leaching process (lower than 80 DEG C) can carry out at normal pressure, lower temperature, and general Strengthen education temperature is higher than 90 DEG C usually.
(4) compared with leaching-extraction-electrolysis maturation process of the prior art, the present invention is not high to the control overflow of equipment and process condition, invests little, and simple, operability is higher, and copper can the form of copper hydroxide intermediates sell.
Accompanying drawing explanation
Fig. 1 is air energy heating unit schematic diagram.
Fig. 2 is air energy heating unit structural representation.
Fig. 3 adopts air to heat to leach the process flow sheet that copper flotation tailings reclaims copper.
Embodiment
Below in conjunction with accompanying drawing and embodiment, concrete technical scheme of the present invention is described further.
Embodiment 1.
The copper flotation tailings main component used in the present embodiment and material phase analysis result are respectively as shown in table 1, table 2.
Table 1. copper flotation tailings chemistry multielement analysis result.
| Raw ore | Cu | Fe | Co | SiO 2 | Al 2O 3 | CaO | MgO | S | P | Ag(g/t) |
| Composition/% | 0.825 | 4.53 | 0.026 | 64.53 | 12.58 | 0.475 | 4.01 | 0.06 | 0.093 | 1.29 |
Table 2. copper flotation tailings material phase analysis result.
| Occurrence status | Copper in chalcopyrite | Copper in secondary copper sulfide | Copper in copper sulfate and free copper oxide | In conjunction with copper in cupric oxide | Full copper |
| Content/% | 0.013 | 0.020 | 0.382 | 0.41 | 0.825 |
| Distributive law/% | 1.58 | 2.42 | 46.30 | 49.70 | 100.00 |
First copper flotation tailings is carried out air and can heat leaching, leaching condition is as follows :-200 order particles account for more than 85%, extraction temperature 70 DEG C, extraction time 4h, sulfuric acid concentration 10g/L, and liquid-solid volume mass is than 4:1, and copper leaching rate can reach 85.13%, iron leaching yield 2.86%.Carry out solid-liquid separation after leaching terminates, leach liquor is containing Cu
2+1.61g/L, Fe
3+0.245g/L, regulates leach liquor pH value with the NaOH aqueous solution of mass concentration 5%, controls terminal pH value 3.5, heavy iron time 1h, and heavy iron temperature 50 C carries out solid-liquid separation after heavy iron, and after heavy iron, liquid is containing Cu
2+1.83g/L, Fe
3+0.0015g/L, heavy iron rate is 99.86%.After heavy iron, liquid continues, with NaOH aqueous solution regulator solution pH value, to control terminal pH value 7.0, heavy copper time 1h, heavy copper temperature 50 C, treats solid-liquid separation after heavy copper, copper ashes cupric 62.43%, heavy copper rate 99.92%.
Embodiment 2.
The raw copper mine tailing used in this example is in the same manner as in Example 1, first copper flotation tailings is carried out air and can heat leaching, leaching condition is as follows :-200 order particles account for more than 85%, extraction temperature 70 DEG C, extraction time 6h, sulfuric acid concentration 12g/L, liquid-solid volume mass is than 4:1, and blowing air also adds 1%MnO
2, leach after terminating and carry out solid-liquid separation, copper leaching rate 90.46%, iron leaching yield 3.77%, leach liquor is containing Cu
2+1.88g/L, Fe
3+0.311g/L.Then regulate leach liquor pH value with the NaOH aqueous solution of mass concentration 5%, control terminal pH value 3.5, heavy iron time 1h, heavy iron temperature 50 C, carry out solid-liquid separation after heavy iron, after heavy iron, liquid is containing Cu
2+2.03g/L, Fe
3+0.0017g/L, heavy iron rate is 99.84%.After heavy iron, liquid continues, with NaOH aqueous solution regulator solution pH value, to control terminal pH value 7.0, heavy copper time 1h, heavy copper temperature 50 C, treats solid-liquid separation after heavy copper, copper ashes cupric 62.54%, heavy copper rate 99.93%.
Embodiment 3.
The raw copper mine tailing used in this example is in the same manner as in Example 1, first copper flotation tailings is carried out air and can heat leaching, leaching condition is as follows :-200 order particles account for more than 85%, extraction temperature 60 DEG C, extraction time 4h, sulfuric acid concentration 10g/L, liquid-solid volume mass is than 3:1, and copper leaching rate can reach 80.56%, iron leaching yield 1.89%, carry out solid-liquid separation after leaching terminates, leach liquor is containing Cu
2+1.956g/L, Fe
3+0.204g/L.Then regulate leach liquor pH value with the NaOH aqueous solution of mass concentration 5%, control terminal pH value 3.5, heavy iron time 1h, heavy iron temperature 50 C, carry out solid-liquid separation after heavy iron, after heavy iron, liquid is containing Cu
2+2.18g/L, Fe
3+0.0009g/L, heavy iron rate is 99.91%.After heavy iron, liquid continues, with NaOH aqueous solution regulator solution pH value, to control terminal pH value 7.0, heavy copper time 1h, heavy copper temperature 50 C, treats solid-liquid separation after heavy copper, copper ashes cupric 62.48%, heavy copper rate 99.95%.
Claims (2)
1. adopt air to heat and leach the method that copper flotation tailings reclaims copper, it is characterized in that forming primarily of following steps:
(1) air can heat leaching Floatation of Copper mine tailing, namely the mine tailing ore pulp after flotation is leached by air energy heating unit circulating-heating mechanical stirring, leaching agent is mainly sulfuric acid, extract technology major technique condition is as follows: extraction temperature 60 ~ 75 DEG C, sulfuric acid starting point concentration 10 ~ 12g/L, extraction time 3 ~ 6h, liquid-solid volume mass is than 3:1 ~ 4:1, in leaching process, depending on the height of copper tailing character and copper leaching rate, can blowing air or add MnO
2strengthen education is carried out in oxygenant;
(2) heavy iron, regulates leach liquor pH value with NaOH, controls pH value terminal 3.5, heavy iron time more than 1h, and heavy iron temperature 50 ~ 60 DEG C, the iron ion in solution is with Fe (OH)
3form precipitates;
(3) heavy copper, continue with liquid pH value after the heavy iron of NaOH adjustment, control pH value terminal 7.0, heavy copper time more than 1h, heavy iron temperature 50 ~ 60 DEG C, the copper in solution is with Cu (OH)
2form precipitates.
2. employing air according to claim 1 can heat the method leaching copper flotation tailings recovery copper, it is characterized in that described air energy heating unit is primarily of compressor, vaporizer, condenser, strainer, expansion valve and Controlling System composition, adopt electrical energy drive heat pump, compressor consumes a part of electric energy, the refrigerant gas of low-temp low-pressure is compressed into the gas of High Temperature High Pressure, the gas of High Temperature High Pressure is released heat within the condenser and is heated by solution, oneself temperature is lowered, after expansion valve reducing pressure by regulating flow, become the gas-liquid mixture of low-temp low-pressure, the heat in other media (as air) is absorbed at evaporator refrigerant, become the gas of low-temp low-pressure, and then absorbed by compressor, be compressed into the gas heating solution of High Temperature High Pressure, by the thermodynamic cycle process of this continuous evaporation-compression-condensation-throttling-evaporation, thus by the transfer of heat of dispersion a large amount of in air in the aqueous solution, reach the effect of heating and thermal insulation.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680602A (en) * | 2020-12-18 | 2021-04-20 | 衢州华友钴新材料有限公司 | Treatment method for improving leaching efficiency of copper-containing sulfide ore |
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| CN1139704A (en) * | 1996-03-22 | 1997-01-08 | 核工业北京化工冶金研究院 | Method for extracting copper from ore |
| CN102703693A (en) * | 2012-05-22 | 2012-10-03 | 北京大学 | Method for enriching and recovering metal nickel, copper and cobalt from tailings of copper and nickel mines |
| CN102787237A (en) * | 2011-05-20 | 2012-11-21 | 中国科学院广州地球化学研究所 | Process for recovering iron, copper, zinc, and lead in copper tailing by leaching |
| CN103657555A (en) * | 2013-11-25 | 2014-03-26 | 扬州百思德新材料有限公司 | Air energy heating reaction kettle |
-
2014
- 2014-07-18 CN CN201410343427.1A patent/CN105274331B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139704A (en) * | 1996-03-22 | 1997-01-08 | 核工业北京化工冶金研究院 | Method for extracting copper from ore |
| CN102787237A (en) * | 2011-05-20 | 2012-11-21 | 中国科学院广州地球化学研究所 | Process for recovering iron, copper, zinc, and lead in copper tailing by leaching |
| CN102703693A (en) * | 2012-05-22 | 2012-10-03 | 北京大学 | Method for enriching and recovering metal nickel, copper and cobalt from tailings of copper and nickel mines |
| CN103657555A (en) * | 2013-11-25 | 2014-03-26 | 扬州百思德新材料有限公司 | Air energy heating reaction kettle |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680602A (en) * | 2020-12-18 | 2021-04-20 | 衢州华友钴新材料有限公司 | Treatment method for improving leaching efficiency of copper-containing sulfide ore |
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