CN1113520A - Hydrometallurgical process for the recovery of copper and zinc from copper and zinc materials - Google Patents

Hydrometallurgical process for the recovery of copper and zinc from copper and zinc materials Download PDF

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Publication number
CN1113520A
CN1113520A CN94106347A CN94106347A CN1113520A CN 1113520 A CN1113520 A CN 1113520A CN 94106347 A CN94106347 A CN 94106347A CN 94106347 A CN94106347 A CN 94106347A CN 1113520 A CN1113520 A CN 1113520A
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zinc
copper
ammonia
extraction
liquid
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CN94106347A
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杨佼庸
胡福成
詹惠芳
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Beijing General Research Institute of Mining and Metallurgy
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Beijing General Research Institute of Mining and Metallurgy
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The invention relates to a method for recovering copper and zinc from copper-zinc materials, which is characterized in that the copper-zinc materials are leached by ammonia, then the copper and the zinc in the leaching solution are separated by an extraction method, copper-rich liquid is sent to electrodeposition for producing electrolytic copper, basic zinc carbonate is obtained by ammonia evaporation of raffinate, and active zinc oxide is obtained by calcination. The method has mature process, good copper-zinc separation and high metal recovery rate, and is suitable for treating copper-zinc materials such as brass scraps, copper-zinc dross and various oxidation residues.

Description

Wet metallizing process for recovering copper and zinc from materials containing the both
Present method includes the non-ferrous metal metallurgical method, be a kind of adopt ammonia soak-solvent extration reclaims the Wet-process metallurgy method of copper and zinc, is specially adapted to the processing of various copper zinc materials from copper zinc material.
Copper zinc material is handled and is reclaimed the wherein copper and the zinc of valuable metal, research at present and the method for using are more, leach copper-zinc chip as U.S.'s report with sal volatile, infusion solution is heated in control then, depositing zinc ammonium oxide compound-carbonate complex compound optionally, and cuprammonium carbonate remains in the method in the solution; And for example Britain report adopts the high pressure ammoniumsulphate soln to leach to contain the low copper sulfurized ore of high zinc, boils solution then and disperses ammonia and be precipitated out from solution with the sulfide state up to copper, with the remaining sulfate liquor of carbon dioxide treatment zinc is precipitated out; U.S.'s report adopts the volatile salt high pressure to learn out processing copper zinc material well and is settled out metallic copper with carbon monoxide as reducing gas then, and zinc remains in the solution.It is not thorough that above several method exists the separation of copper zinc, is mingled with cost height, shortcomings such as complicated operation mutually.The low-grade complex ore deposit that India's report adopts acid lixiviation process Treatment of Copper zinc, being about to copper zinc material is ground to certain fineness and a certain amount of acidic solution and sizes mixing and put into leaching vat and carry out agitation leach, through solid-liquid separation, leach liquor is with solvent-extracted method separating copper zinc, this method is owing to adopt acidleach, iron, manganese, calcium, foreign metals such as magnesium leach simultaneously and enter solution, after the solid-liquid separation, solution is through extracting copper, iron, manganese and zinc residue in the raffinate, through purification and impurity removal, obtain zinc product, it is big that this method exists acid consumption, the impurity and purification complex procedures, copper zinc separates bad, shortcomings such as cost height.
The objective of the invention is to seek a kind of copper zinc separator well, operation simple, be convenient to operate, the method for processing copper zinc material that cost is low.
The invention is characterized in: a, employing normal pressure ammonia leaching process leach copper zinc material, and the condition of leaching is: solvent adopts NH 3, bicarbonate of ammonia or CO 2, total NH 3Concentration 4～6M, NH 3/ CO 2=1.0,50～60 ℃ of temperature, liquid-solid ratio is decided on raw material, guarantees that leach liquor contains Zn 15～30g/l; B, ammonia leach liquor extracting and separating copper zinc, extraction agent adopt collection agent of ketoxime class such as LIX84, and thinner is 260# kerosene or common kerosene, extractant concentration 10～30%(volume), compares A/O=1/1～1/3, mixing time 2～5 minutes, copper enters organic phase, and zinc resides in raffinate; C, extraction liquid employing zinc powder purify, and liquid ammonia still process heavy zinc in purification back gets zinc subcarbonate, gets active zinc flower in 2 hours through 350～400 ℃ of calcinings; D, the organic back extraction of load are adopted to contain Cu～40g/l, H 2SO 4The waste electrolyte of～160g/l mixed with load organic phases 2～5 minutes, the clarification phase-splitting, and getting water is rich copper liquid (Cu～45g/l, H 2SO 4～150g/l), directly send the electrolysis production electrolytic copper.Waste electrolyte returns back extraction.
Method of the present invention is owing to adopt normal pressure ammonia to soak, and production safety is reliable, processing ease, copper, zinc are dissolved in the solution, and impurity such as calcium, magnesium, manganese, iron residue in the slag, reduce solvent consumption, cost is low, reduces cleaning section, is convenient to carry out copper zinc with extraction process and separates.Method of the present invention can be widely used in handles the industrial and mining enterprises that copper zinc material reclaims copper zinc, also applicable to the nonferrous metallurgy factories and miness.Can be widely used in the transformation of Non-ferrous Metallurgy industrial enterprise processing copper zinc material smelting technology, also applicable to handling other industrial and mining enterprises that copper zinc material comprehensively reclaims copper zinc.
Fig. 1 is that copper zinc material is handled the hydrometallurgical processes schema.
As shown in Figure 1, copper zinc material is added in the immersion trough, in groove, add liquefied ammonia and ammonium hydrogencarbonate again. The intensification leaching, liquid-solid separation, solution send extraction, and extract gets rich copper liquid through back extraction, send electrodeposition to get electrolytic copper; Raffinate is through purification, filtration, filtrate ammonia still process basic zinc carbonate, again through calcining to get activated zinc oxide.
The present invention be directed to various copper zinc materials, comprise brass bits, copper zinc dross and various oxidation residua, copper zinc grandidierite etc. Leach these materials with normal pressure ammonia, leaching condition is: 50～60 ℃ of temperature; Total NH3; Concentration 4～6M; NH3/CO 2=1.0; Liquid-solid ratio is decided on raw material, guarantees that leachate contains Zn 15～30g/l; But blowing air oxidation when needing. Copper zinc all enters leachate with complex form, and leaching rate reaches more than 90%. Selective extraction copper from leachate then, extractant is 10～30%(V/V) LIX84, diluent is 260# kerosene or common kerosene, 2～3 grades of extractant progression, 1～2 grade of back extraction, otherwise extraction and 1～2 grade of washing section of need also are so that the organic NH that carries secretly of flush away load3, washing agent is subacidity water, and extraction and back-extraction is compared on feed concentration and organic phase concentration and is decided, and is generally A/O=1/1～1/3, and washing is compared and is generally A/O=1/3～1/10. Copper is extracted that to enter load organic, and extraction yield is 99.90%, and zinc then is not extracted substantially, and 99.95% zinc retains in raffinate, and copper zinc is able to thorough separation, and separation is up to 1.08 * 106 The NH that load organic phases is carried secretly through washing3After, with containing Cu～40g/l, H2SO 4The solution of～160g/l (waste electrolyte that returns) back extraction gets cupric Cu～45g/l, H2SO 4The rich copper liquid of 150g/l, rich copper liquid gets final product to get one-level electrolytic copper (Cu〉99.95%) through the insoluble anode electrolytic deposition, and organic phase is regenerated after the back extraction, returns extraction cycle and uses, and the waste electrolyte after the electrolysis then returns back extraction.
After copper is selectively extracted, raffinate is and contains the zinc ammonia solution, also contain in addition a small amount of beavy metal impurity ion, such as nickel, cobalt, lead, manganese, iron etc., because of when extraction these heavy metal ion all not enter organic phase mainly be to be present in the raffinate, so use earlier a small amount of zinc powder with these foreign ion displacement precipitation before the heavy zinc of ammonia still process, sediment filters, filter cake can return use repeatedly, therefrom can further reclaim valuable metal wherein then or discards. The heavy zinc of raffinate ammonia still process gets basic zinc carbonate after purifying, and basic zinc carbonate can obtain the active oxidation zinc product in 2 hours 350～400 ℃ of calcinings. Ammonia still process gas during ammonia still process is absorbed, and reclaims NH wherein3And CO2, the rate of recovery is more than 98%.
Embodiment 1:
The copper cadmia that raw material gets through the lime neutralization for certain ore deposit mine water, its composition following (%): Cu5.90, Zn20.50, Fe2.70, Ni0.023, Co0.072, CaO5.18, MgO9.60, Al 2O 36.89, SiO 27.18, H 2O55.70.This raw material is because of containing Ca, Mg height, and is not only uneconomical with acidleach, and owing to impurity such as Ca, Mg are difficult to separate after Zn enters solution, thereby can not get qualified zinc product.The present invention's ammonia leaching process takes by weighing the copper cadmia that the is equivalent to dry weight 500g glass there-necked flask of packing into, and liquid-solid ratio L/S=6 is by total NH 3Concentration 6M and NH 3/ CO 2=1.0 add ammoniacal liquor and bicarbonate of ammonia, then at 55 ℃ of following agitation leach 6h of temperature.Slag is soaked in finish suction filtration and washing of leaching, leach liquor 450ml, its composition is Cu6.02g/l, Zn21.21g/l, Fe＜0.005g/l, Mg＜0.01g/l, Cu leaching yield 92.0%, Zn leaching yield 93.10%, leached mud can discard.
Ammonia leaching solution 18%(V/V) LIX84 extracting copper.Measure 100ml leach liquor and 100ml18%(V/V) LIX84 organic solution, the same separating funnel of packing into mixes 3min on health formula vibrator, leave standstill phase-splitting then, and copper is extracted into organic phase, and percentage extraction reaches 99.90%.And zinc is not extracted basically, and 99.42% zinc retains in that copper zinc separation factor can reach 1.08 * 10 in the raffinate 6Emit raffinate from the separating funnel bottom, and then adding 100ml contains Cu40g/l, H 2SO 4The waste electrolyte back extraction of 160g/l still mixes 3min on health formula vibrator, the copper in the load organic phases is got off by back extraction, obtains containing Cu45g/l, H 2SO 4The rich copper liquid of 150g/l, but this solution electrodeposition output one-level electrolytic copper (Cu〉99.95%) product.
Zinc can add recovery from raffinate.Raffinate is earlier used a little zinc powder substitution, and beavy metal impurities such as coprecipitated nickel hydroxide, cobalt are measured the 200ml raffinate beaker of packing into, add zinc powder then while stirring, and the zinc powder add-on is 2kg/m 3Solution is replaced and after 2 hours slag is leached.Purification back liquid heats ammonia still process 1 hour on resistance furnace, zinc precipitates with zinc subcarbonate, filters the back oven dry and calcines 2 hours in the retort furnace of 350～400 ℃ of temperature, promptly gets qualified active oxidation zinc product, contains ZnO〉97%, specific surface〉60m 2/ g.
Whole process copper, zinc recovery are respectively 91.91% and 92.56%.
Embodiment 2:
Raw material is the smelting slag of copper source mill, its composition following (%): Cu9.20, Zn8.70, Fe2.35, Ni0.032, Co0.002, Pb0.84, Mn0.08, H 2O 40 leaching conditions are: total NH 34.5M, NH 3/ CO 2=1.0,55 ℃ of temperature, blowing air leach 4h, and by the same operation of example 1, the result obtains that leach liquor contains Cu16.25g/l, Zn27.50g/l, Cu, the Zn leaching yield is respectively 99.67% and 98.36%.
By method operation same in the example 1, use the 20%LIX84 extracting Cu then, compare O/A=2/1, percentage extraction 99.90%.The organic back extraction of load gets rich copper liquid, and the electrolysis of rich copper liquid gets one-level electrolytic copper (Cu〉99.95%).99.6% zinc enters raffinate, purify back ammonia still process and get zinc subcarbonate, zinc subcarbonate calcine the active oxidation zinc product, contain ZnO＞97%, specific surface〉60m 2/ g.
Whole process copper, zinc recovery are respectively 99.57% and 97.97%.

Claims (1)

1, a kind of method that adopts the ammonia leaching technology from copper zinc material, to reclaim copper and zinc, its invention is characterised in that:
A, the leaching condition that adopts normal pressure ammonia to soak are solvent NH 3, bicarbonate of ammonia or CO 2, total NH 3Concentration 4～6M, NH 3/ CO 2=1.0,50～60 ℃ of temperature, liquid-solid ratio is decided on raw material, guarantees that leach liquor contains Zn15～30g/l;
B, ammonia leach liquor extracting and separating copper zinc, extraction agent adopt collection agent of ketoxime class such as LIX84, and thinner is 260# kerosene or common kerosene, and extractant concentration 10～30% (volume) is compared A/O=1/1～1/3, mixing time 2～5 minutes;
C, extraction liquid employing zinc powder purify, and liquid ammonia still process heavy zinc in purification back gets zinc subcarbonate, through 350～400 ℃ of calcinings 2 hours, gets active zinc flower;
D, the organic back extraction of load contain Cu 40g/l, H 2SO 4The waste electrolyte of about 160g/l mixed with load organic phases 2～5 minutes, the clarification phase-splitting, and getting water is rich copper liquid (Cu～45g/l, H 2SO 4150g/l), directly send the electrolysis production electrolytic copper, waste electrolyte returns back extraction.
CN94106347A 1994-06-13 1994-06-13 Hydrometallurgical process for the recovery of copper and zinc from copper and zinc materials Pending CN1113520A (en)

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CN94106347A CN1113520A (en) 1994-06-13 1994-06-13 Hydrometallurgical process for the recovery of copper and zinc from copper and zinc materials

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Application Number Priority Date Filing Date Title
CN94106347A CN1113520A (en) 1994-06-13 1994-06-13 Hydrometallurgical process for the recovery of copper and zinc from copper and zinc materials

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CN1113520A true CN1113520A (en) 1995-12-20

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1102175C (en) * 1998-12-30 2003-02-26 王犇 Method for recovering copper and zinc oxide from copper-zinc waste catalyst
CN1332047C (en) * 2003-01-30 2007-08-15 Bhp比利通Ssm技术有限公司 Process for nickel and cobalt extraction from laterite ores
CN100366771C (en) * 2005-07-25 2008-02-06 方建军 Normal temperature normal pressure ammonia infusion-extraction-electrodeposition-slag infusion flotation of copper oxide green ore
CN101451196B (en) * 2007-12-03 2010-08-11 灵宝市金源矿业有限责任公司 Wet-smelting method of copper and zinc bulk concentrate
CN101538648B (en) * 2009-03-13 2012-07-04 昆明理工大学 Method for activating ammonia leaching for high calcium-magnesium zinc oxide ore
CN103122416A (en) * 2013-02-26 2013-05-29 史汉祥 Equipment for extracting pure copper and pure zinc from brass and using method thereof
CN103131871A (en) * 2013-02-26 2013-06-05 史汉祥 Method for extracting pure copper and pure zinc from brass
CN106282572A (en) * 2016-08-11 2017-01-04 李果 A kind of method of comprehensive utilization of the complex multi-metal materials such as cupric zinc
CN106399698A (en) * 2016-10-27 2017-02-15 北京科技大学 Method for recovering copper and aluminum from copper clad aluminum bar processing waste

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1102175C (en) * 1998-12-30 2003-02-26 王犇 Method for recovering copper and zinc oxide from copper-zinc waste catalyst
CN1332047C (en) * 2003-01-30 2007-08-15 Bhp比利通Ssm技术有限公司 Process for nickel and cobalt extraction from laterite ores
CN100366771C (en) * 2005-07-25 2008-02-06 方建军 Normal temperature normal pressure ammonia infusion-extraction-electrodeposition-slag infusion flotation of copper oxide green ore
CN101451196B (en) * 2007-12-03 2010-08-11 灵宝市金源矿业有限责任公司 Wet-smelting method of copper and zinc bulk concentrate
CN101538648B (en) * 2009-03-13 2012-07-04 昆明理工大学 Method for activating ammonia leaching for high calcium-magnesium zinc oxide ore
CN103122416A (en) * 2013-02-26 2013-05-29 史汉祥 Equipment for extracting pure copper and pure zinc from brass and using method thereof
CN103131871A (en) * 2013-02-26 2013-06-05 史汉祥 Method for extracting pure copper and pure zinc from brass
CN103122416B (en) * 2013-02-26 2014-03-26 慈溪市玖发铜业有限公司 Equipment for extracting pure copper and pure zinc from brass and using method thereof
CN106282572A (en) * 2016-08-11 2017-01-04 李果 A kind of method of comprehensive utilization of the complex multi-metal materials such as cupric zinc
CN106399698A (en) * 2016-10-27 2017-02-15 北京科技大学 Method for recovering copper and aluminum from copper clad aluminum bar processing waste

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