CN101736152A - Acid washed ore leaching process for low-grade copper oxide ores with high mud content - Google Patents
Acid washed ore leaching process for low-grade copper oxide ores with high mud content Download PDFInfo
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Abstract
The invention provides an acid washed ore leaching process for low-grade copper oxide ores with high mud content, which comprises the following steps: after the raw ores are crushed and sieved, conveying the ores of +50mm size fraction to a storage yard for stacking, and carrying out acid washed ore treatment on the ores of -50mm size fraction; by adding sulfuric acid into the washing liquid, rewashing the ores to remove partial basic gangue; after the washing liquid is separated and deposited, recycling the acid liquid; after the ores are treated by an acid washed ore system, conveying the sand ores of +0.074mm size fraction to the storage yard for stacking, and stirring and leaching the mud ores of -0.074mm size fraction; after the leaching liquid generated by stirring and the leaching liquid generated by heap leaching are mixed, carrying out extracting and electrodepositing processes; and finally, obtaining cathode copper products. The process of the invention has the advantages of short procedures, simple equipment, small investment, low cost and little pollution to the environment, further solves the problems of poor heap leaching penetrability, low copper leaching rate and the like caused by existence of mud ores and dissolution and deposition of basic gangue, improves the recovery rate of copper, and comprehensively utilizes the mineral resources of the low-grade copper oxide with high mud content.
Description
Technical field
The present invention relates to the copper technical field of wet metallurgy, particularly a kind of acid washup extract technology is used this technology and can be made the cupric ion in the low-grade copper oxide ores with high mud obtain efficient recovery.
Background technology
Exist the low grade copper oxide ore of larger proportion in China's copper ore resource, characteristics such as the type mineral generally all have the oxidation ratio height, disseminated grain size is thin, silt content is big, multi-metal complex symbiosis adopt acid leaching-extraction-electrodeposition process to handle such ore than using conventional selecting and smelting technology can obtain better technico-economical comparison.But often be mixed with Ni Heshui to a certain degree in the copper oxide ore ore, when containing the mud water content in the ore when too much, can cause disadvantageous effect to leaching process, sludge can stop up feeding warehouse, funnel and disintegrating apparatus, simultaneously basic cpd is molten enters leach liquor after soaking for the calcium magnesium oxide in the gangue etc., also can produce a large amount of throw outs and complex compound, work with sludge one and to cause leaching process chats heap poor permeability, ventilation property is poor, soak the surperficial hydrops channel of heap, the copper leaching velocity is slow, a series of problems such as leaching yield is low, thereby worsen leaching effect and leach index, increase production cost.Therefore adopt the method that leaches after the first washup to handle these type of mineral and just seem necessary.Ore washing method can effectively separate mud ore deposit and lump ore (ore in sand form), strengthens the perviousness and the ventilation property of ore deposit heap, strengthens leaching effect, improves and leaches index.
In general, when the ore silt content greater than 6%, water content greater than 5% the time, should consider to carry out washup.Washup is generally all carried out in the crushing and screening process.
Kind, ratio and the plasticity-thereof of contained gangue material composition and clay, swelling property, perviousness etc. are relevant in the selection of ore washing method and the ore.According to apparent state, plasticity index and the coefficient of cohesion value of institute's argillaceous in the copper oxide ore ore, the mud ore that contains to be washed roughly can be divided into three types.
1, easy washup stone: have sandy clay, the plasticity index of clay is less than 5, the coefficient of cohesion (t/m
2)≤0.5, these type of mineral can be washed by water and be sieved and washed.
But 2, medium washup stone: clay can pulverize in hand.The plasticity index 5～10 of clay, the coefficient of cohesion (t/m
2) be 0.5～2, these type of mineral can be washed 1～2 time with washing machinery.
3, difficult washup stone: clay is difficult to pulverize in hand.The plasticity index of clay is greater than 10, the coefficient of cohesion (t/m
2) 〉=2, these type of mineral need to wash more than 2 times with washing machinery.
The common washup equipment that is adopted in the washup process comprises screw classifier, hydrocyclone or launder washer etc.
Summary of the invention
The purpose of this invention is to provide a kind of acid washup extract technology that is used for low-grade copper oxide ores with high mud, this technical process is short, equipment simple, reduced investment, cost is low, environmental pollution is little, neutralization is removed part and is easy to the dissolved basic gangue in the washup process, problems such as the heap leaching permeability that causes because of the stripping precipitation of the existence in mud ore deposit and basic gangue is poor, copper leaching rate is low have further been solved, improved the rate of recovery of copper, fully utilize high mud low grade copper oxide ore and produced resource, can obtain bigger economic benefit.
For achieving the above object, novel process adopts following design:
The present invention carries out mineral identification, fractional analysis and impurity component analysis to the raw ore mineral.If the mineral identification result shows that the copper mine mineral are that malachite, copper lazur, tenorite, ruby copper, brochantite or chrysocolla and disseminated grain size are thin, the fractional analysis result shows when having a large amount of calcium magnesium oxides in this mineral silt content ratio 〉=10%, the impurity component in these mineral, adopt this technology to carry out subsequent operations.Processing step of the present invention has:
(1) raw ore is behind crushing and screening, and the coarse fraction ore is sent to the stockyard and builds heap, and the fine fraction ore is sent to the washup system and carries out the washup classification;
(2) add dilute sulphuric acid in the washup process, remove the part basic gangue;
(3) placer that obtains after the washup is sent to the stockyard and builds heap, and the mud ore deposit is sent to steel basin and is carried out agitation leach; The leach liquor that dump leaching and agitation leach operation are come out is delivered to the extraction electrodeposition operation, obtains qualified cathode copper product.
Raw ore carries out fragmentation through jaw crusher, sieves through vibratory screening apparatus, coarse fraction (+50mm) ore is sent to the stockyard and builds heap, and (50mm) contain the mud ore and enter acid washup system, carry out the washup classification than fine fraction.
Adopt dilute sulphuric acid to carry out the washup operation to the copper oxide ores with high mud ore, granularity is wherein thought sludge less than the mineral of 0.074mm.Adopting concentration during washup is the dilute sulphuric acid of 0.05～0.1mol/l, can adjust at the coefficient of cohesion value of mineral gangue medium clay soil and the content size of calcium magnesium oxide, adopt equipment such as screw classifier, hydrocyclone or launder washer, get rid of in the gangue mineral about 10～15% calcium magnesium oxide (basic gangue) through the dilute sulphuric acid washup, finally make sludge eluting rate＞85%, wash-out-50mm～+ the 0.074mm mineral enter the stockyard, carry out the dump leaching operation.
The mud that obtains after the acid washup is carried out precipitate and separate, in precipitation process, can add cationic flocculant, quicken the precipitation process of sludge in the mud.Obtain sludge through separation and be sent to steel basin and carry out agitation leach, liquid is got back to acid washup system, adds an amount of sulfuric acid, carries out recycle.
To with behind the crushing and screening+ore and washup of 50mm grade after+placer of 0.074mm grade builds heap, builds will keep ore to form nature as far as possible in the heap process stacking, form porous and pile naturally, it is 2m～4m that height is piled in the ore deposit.After building heap and finishing, adopt to drip drench or the mode of spray according to 30～50L/m
2The speed of h leaches carries copper, drips (spray) pouring liquid acidity and remains on 50～70g/L H
2S0
4Dripping the spacing of drenching pipe is 0.5m～1m.
With after the washup-the mud ore deposit of 0.074mm grade enters mechanical agitating tank and carries out agitation leach, solids content 35%～50% (weight percent), add acid and transfer to pH value 1.0～1.5, mixing speed is 120～150 commentaries on classics/min, in steel basin, stop about 2～3h, leach liquor cupric 2～3g/L is sent to extraction workshop section.After the leached mud neutralizing treatment, when soaking slag pH value 〉=5, be sent to tailings reservoir for piling.The leach liquor that dump leaching and agitation leach operation obtain is delivered to follow-up extraction and electrodeposition operation, obtain qualified cathode copper product.
Advantage of the present invention is: technical process is short, equipment simple, reduced investment, cost is low, environmental pollution is little, neutralization is removed part and is easy to the dissolved basic gangue in the washup process, problems such as the heap leaching permeability that causes because of the stripping precipitation of the existence in mud ore deposit and basic gangue is poor, copper leaching rate is low have further been solved, improved the rate of recovery of copper, fully utilize high mud low grade copper oxide ore and produced resource, can obtain bigger economic benefit.
Description of drawings
Fig. 1: principle process flow sheet of the present invention
Among Fig. 1, operation 1 is for using preparatory process (the raw ore mineral are carried out mineral identification, fractional analysis and impurity component analysis) and the crushing and screening that carries out before this technology;
Operation 2 is an acid washup system, carries out the washup classification by it;
Embodiment
As shown in Figure 1, raw ore is through crushing and screening, and the ore of+50mm grade is sent to the stockyard and builds heap ,-50mm grade ore by the washup system handles after, the placer of+0.074mm grade is sent to the stockyard and builds heap, the mud ore deposit of-0.074mm grade enters the agitation leach operation.The leach liquor of agitation leach and the leach liquor of dump leaching enter the extraction electrodeposition operation after converging, finally obtain the cathode copper product.
The invention will be further described below in conjunction with embodiment:
This process application is contained the high low grade copper oxide ore of mud in western China, identify that through raw ore this copper oxide mineral is mainly malachite, chessylite, a small amount of blue stone, tenorite; Gangue mineral mainly is clay mineral, feldspar alteration thing and a spot of sericite and carbonate minerals.Cu content is 1.65% in the ore, and Fe 9.45%, and Ca 18.66%, Mg9.25%, SiO
238.13%, Al
2O
34.56%.The impurity principal constituent is calcium magnesium oxide, carbonate and phosphorus alum compound.Fractional analysis shows+and the 0.074mm mineral content is 80%, and-0.074mm content is 20%.Acid washup-leaching-extraction electrodeposition technology involved in the present invention is suitable for these mineral.
1, ore pre-treatment: raw ore carries out crushing and screening through jaw crusher, and the ore of+50m grade directly is sent to the stockyard and builds heap, and the ore of-50mm grade enters acid washup system,
2, adopt dilute sulphuric acid to carry out the washup operation to the copper oxide ores with high mud ore, granularity is wherein thought sludge less than the mineral of 0.074mm.Adopting concentration during washup is the dilute sulphuric acid of 0.1mol/l, and washup equipment is hydrocyclone, and washup speed is 10m
3/ min, the floating matter of-layer white visible on the washing lotion surface is the throw out of calcium sulfate magnesium by analysis.Get rid of in the gangue mineral about 12.5% calcium magnesium oxide through the dilute sulphuric acid washup, final sludge eluting rate is 88.5%, and simultaneously, through operation back observation in 3 months, washup equipment was not seen obvious corrosion.Wash-out obtains-50mm～+ the 0.074mm mineral enter the stockyard, carry out the dump leaching operation, mud is separated.
3, the mud that obtains after the acid washup is carried out precipitate and separate, in the washing lotion pond, carry out sedimentary natural subsidence, in precipitation process, add cationic flocculant, quicken the precipitation process of sludge in the mud, after about 20 hours, mud can be accomplished the basic separation of solid-liquid.The sludge that obtains through separation is sent to steel basin and carries out agitation leach, and liquid is added an amount of sulfuric acid, carries out recycle.
4, general+50mm and+0.074mm～-ore of 50mm grade is sent to the stockyard and builds heap, build in the heap process in order to keep ore to form multiple hole, draughty heap naturally as far as possible, adopted retrusive to build the heap method and carried out, building stack height is 3.0m, heap be shaped as bucking ladder.After building heap and finishing, install to drip drench pipe, dripping the spacing of drenching pipe is 0.8m.Dripping the acidity of drenching liquid is 50～70g/L H
2SO
4, dripping pouring speed is 15～20L/m
2H; Unless heavy rain or heavy snow weather occur, drip to drench and carry out always, do not lie fallow.Utilize winter insulating cotton to ore deposit heap insulation.After the copper ion concentration in the leach liquor reaches 2.0g/L, deliver to the extraction and the back extraction operation of leach liquor and handle.
Through after 3 months drip to drench leach, the leaching yield of copper has reached 85% in the ore, stops this moment dripping drenching, and leaches and finishes, and drench a pipe and dismantle and give over to the next round dump leaching and use dripping.Simultaneously, can pile the dump leaching of building that carry out a new round in old ore deposit goes out.
5, with obtain after the washup-sludge of 0.074mm grade is sent to mechanical agitating tank and carries out agitation leach, solids content 40% adds acid and transfers to pH value about 1.5, mixing speed is 150 commentaries on classics/min, in steel basin, stop about 3h, after the leach liquor cupric reaches 2.5g/L, be sent to extraction workshop section and handle.Leached mud utilizes lime to carry out neutralizing treatment, when the pH value of soaking slag 〉=5, is sent to tailings reservoir for piling.
6, the extraction of cupric leach liquor and back extraction: composition of leaching is: Cu 2.45g/L; Acidity is 17.25g/L H
2SO
4Adopt M5640 as extraction agent, extractant concentration 10%, extraction phase are than O: A=1: 1, and by the two-stage countercurrent extraction, the copper percentage extraction reaches 96.78%, through the secondary countercurrent reextraction, compares O: A=1: 2, the back extraction ratio of copper is 97.22%.Electrodeposition produces copper: solution composition is after the back extraction: Cu 29.8g/L.Enter that iron level need be lower than 5g/L in the solution of electrodeposition, current density is 100～180A/m
2, bath voltage is 1.6～2.2V, the Winning cell temperature is 30 ℃.Resulting cathode copper quality reaches country's mark vertebra, and the electrodeposition rate of recovery of copper reaches 99.5%.Lean electrolyte returns ore and leaches.
Effect of the present invention is: solved and contain the problems such as the ore deposit heap poor permeability, the copper leaching rate that cause when the high cupric oxide ore of mud leaches are low, be suitable for the exploitation of the copper oxide ore resource of low-grade high mud, enlarge the scope of utilizing of Copper Resources, improve the comprehensive utilization ratio of copper.
Claims (11)
1. acid washup extract technology that is used for low-grade copper oxide ores with high mud, it is characterized in that: it comprises following step:
(1) raw ore is behind crushing and screening, and the coarse fraction ore is sent to the stockyard and builds heap, and the fine fraction ore is sent to the washup system and carries out the washup classification;
(2) add dilute sulphuric acid in the washup process, remove the part basic gangue;
(3) ore in sand form that obtains after the washup is sent to the stockyard and builds heap, and the mud ore deposit is sent to steel basin and is carried out agitation leach; The leach liquor that dump leaching and agitation leach operation are come out is delivered to the extraction electrodeposition operation, obtains qualified cathode copper product.
2. the acid washup extract technology of low-grade copper oxide ores with high mud according to claim 1 is characterized in that: described coarse fraction ore is the ore of+50mm grade; Described fine fraction ore is-ore of 50mm grade.
3. the acid washup extract technology of low-grade copper oxide ores with high mud according to claim 1 is characterized in that: adopting concentration during washup is that the dilute sulphuric acid of 0.05～0.1mol/l is as washing lotion.
4. the acid washup extract technology of low-grade copper oxide ores with high mud according to claim 1 is characterized in that: after the washup+ore in sand form of 0.074mm grade is sent to the stockyard and builds heap, and the mud ore deposit of-0.074mm grade is sent to mechanical agitating tank and is carried out agitation leach.
5. according to claim 1 or the acid washup extract technology of 2 or 3 described low-grade copper oxide ores with high mud, it is characterized in that: in the ore in sand form that obtains after the washup-0.074mm grain size content≤5%.
6. the acid washup extract technology of low-grade copper oxide ores with high mud according to claim 1, it is characterized in that: described stockyard is permanent stockyard, ore deposit heap floor height is 2m～4m.
7. according to claim 1 or the acid washup extract technology of 2 or 3 described low-grade copper oxide ores with high mud, it is characterized in that: in the described dump leaching operation, dripping (spray) pouring speed is 30～50L/m
2H, dripping (spray) pouring liquid acidity is 50～70g/LH
2SO
4
8. according to claim 1 or the acid washup extract technology of 2 or 3 described low-grade copper oxide ores with high mud, it is characterized in that: in the described agitation leach operation, solids content 35%～50%, add acid and transfer to pH value 1.0～1.5, mixing speed is 120～150 commentaries on classics/min, when leach liquor cupric 2～3g/L, be sent to extraction electrodeposition workshop section; Leached mud is after neutralizing treatment, and tailings reservoir for piling is sent in its pH value 〉=5 o'clock.
9. the acid washup extract technology of low-grade copper oxide ores with high mud according to claim 1 is characterized in that: newly-built ore deposit heap can be accumulated on initial pile and increase; The leached mud of agitation leach is sent to tailings reservoir for piling after neutralizing treatment.
10. the acid washup extract technology of low-grade copper oxide ores with high mud according to claim 1, it is characterized in that: described copper-bearing mineral is one or more in malachite, copper lazur, tenorite, ruby copper, brochantite, the chrysocolla.
11. the acid washup extract technology of low-grade copper oxide ores with high mud according to claim 1, it is characterized in that: the main body composition of gangue is the calcium magnesium oxide in the described mineral.
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Cited By (7)
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| CN102363890A (en) * | 2011-10-26 | 2012-02-29 | 广州有色金属研究院 | Method for recovering metal copper in waste circuit board |
| CN102747224A (en) * | 2012-07-30 | 2012-10-24 | 昆明理工大学 | Process for recovering organic matters from copper extraction floccules |
| 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 |
| CN106062221A (en) * | 2013-10-23 | 2016-10-26 | Bhp智利股份有限公司 | Heap leaching of copper |
| CN107779596A (en) * | 2017-11-08 | 2018-03-09 | 紫金矿业集团股份有限公司 | A kind of process integration for handling copper-sulphide ores |
| CN108118160A (en) * | 2017-12-04 | 2018-06-05 | 云南驰宏资源综合利用有限公司 | A kind of method of chrysocolla type cupric oxide ore wet underwater welding copper |
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| CN1049693C (en) * | 1996-03-22 | 2000-02-23 | 核工业北京化工冶金研究院 | Method for extracting copper from ore |
| CN1049012C (en) * | 1996-10-14 | 2000-02-02 | 北京矿冶研究总院 | Leaching extraction electrodeposition method for treating copper oxide ore |
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| CN102363890A (en) * | 2011-10-26 | 2012-02-29 | 广州有色金属研究院 | Method for recovering metal copper in waste circuit board |
| 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 |
| CN102747224A (en) * | 2012-07-30 | 2012-10-24 | 昆明理工大学 | Process for recovering organic matters from copper extraction floccules |
| CN102747224B (en) * | 2012-07-30 | 2014-01-08 | 昆明理工大学 | Process for recovering organic matters from copper extraction floccules |
| CN106062221A (en) * | 2013-10-23 | 2016-10-26 | Bhp智利股份有限公司 | Heap leaching of copper |
| CN106062221B (en) * | 2013-10-23 | 2019-08-06 | Bhp智利股份有限公司 | The dump leaching of copper |
| CN107779596A (en) * | 2017-11-08 | 2018-03-09 | 紫金矿业集团股份有限公司 | A kind of process integration for handling copper-sulphide ores |
| CN108118160A (en) * | 2017-12-04 | 2018-06-05 | 云南驰宏资源综合利用有限公司 | A kind of method of chrysocolla type cupric oxide ore wet underwater welding copper |
| CN112143878A (en) * | 2020-08-24 | 2020-12-29 | 核工业北京化工冶金研究院 | Treatment method for separating mud and sand of uranium ore of sandy mudstone |
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