CN105177284B - A kind of method that recovery valuable metal is leached in the ambrose alloy manganeisen from cobalt - Google Patents

A kind of method that recovery valuable metal is leached in the ambrose alloy manganeisen from cobalt Download PDF

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CN105177284B
CN105177284B CN201510504237.8A CN201510504237A CN105177284B CN 105177284 B CN105177284 B CN 105177284B CN 201510504237 A CN201510504237 A CN 201510504237A CN 105177284 B CN105177284 B CN 105177284B
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alloy
cobalt
manganeisen
valuable metal
melt
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CN105177284A (en
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肖松文
任国兴
毛拥军
沈裕军
谢美求
潘炳
郑铁铮
陈坚
樊友奇
赵早文
王奉刚
钟山
夏星
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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Abstract

The invention discloses a kind of method that recovery valuable metal is leached in ambrose alloy manganeisen from cobalt, comprise the following steps:(1) the cobalt ambrose alloy manganeisen is melted to form alloy melt, wherein, the mass fraction of manganese is not less than 5% in cobalt ambrose alloy manganeisen;(2) into the alloy melt, containing silicon materials, simultaneously being passed through gas carries out blowing slag making simultaneously for addition;(3) slag making of gained is separated from melt;(4) melt atomization after slag making will be isolated into alloy powder, the mass fraction of Mn elements is 0.5%~20% in the alloy powder;(5) by the alloy powder acidleach, valuable metal is reclaimed.The present invention is by adding containing the manganese generation low melting point in silicon materials and cobalt ambrose alloy manganeisen, the MnO SiO of good fluidity2Clinker type, so as to reach the effect of removing manganese, there is the advantages of demanganize effect is good, valuable metal loss is few.

Description

A kind of method that recovery valuable metal is leached in the ambrose alloy manganeisen from cobalt
Technical field
The invention belongs to field of metallurgy, is related to a kind of method that recovery valuable metal is leached in ambrose alloy manganeisen from cobalt, More particularly to a kind of cobalt ambrose alloy manganeisen leaches Call Provision, nickel, the process of copper.
Background technology
Cobalt ambrose alloy manganeisen, is the intermediate products that waste and old ion battery adds the slag former melting such as pyrolusite to obtain, cobalt, Copper, nickel, iron, manganese mass content are all higher:Co 5-35%, Ni 1-10%, Cu 5-35%, Fe 10-50%, Mn 5-40%, With very high economic use value.But at present, it can preferably utilize the cobalt ambrose alloy ferromanganese without the technology of maturation Alloy.
At present, contain while document resource can be found cobalt, copper, nickel, iron, manganese element alloy material recycling Technique, the manganese content handled in alloy material is relatively low (less than 5%), before the molten leaching of alloy, is handled without demanganize.Such as marine manganese nodule Alloy obtained by reduction melting directly carries out corrosion Oxidation Leaching, its alloying component Fe 89.49%, Cu 2.5%, Co 2.08%, Ni 4.78%, Mn 0.43%, because its Mn content is not high, the alloy can directly carry out corrosion Oxidation Leaching.Certain useless high temperature Nickel cobalt technical study is reclaimed in nickel cobalt (alloy) material, and (Hou Xiaochuan, Xiao Liansheng, height is from Congjie etc., the leaching nickel from useless high temperature nickel cobalt (alloy) With the experimental study of cobalt, hydrometallurgy, 2009:28(3):164-169), Ni 46.36%, Co in its alloying component 14.08%th, Fe 6.22%, Cr 12.46%, Mn contents only account for 0.13%, and the alloyed scrap is calcined using oxidizing atmosphere, then Alkali soluble, the alkali insoluble matter containing cobalt, nickel, iron, copper are enriched in slag, acidleach insoluble slag under the conditions of chlorine, reclaim nickel therein, cobalt. But for the higher cobalt ambrose alloy manganeisen of manganese content, if directly molten leaching processing, subsequent separation process need demanganize ring Section, intractability are big.Therefore, develop a kind of cobalt ambrose alloy manganeisen higher from manganese content and leach Call Provision, nickel, the technique of copper Method has been highly desirable.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided a kind of technique is simple, safety and environmental protection From cobalt ambrose alloy manganeisen efficiently leach recovery valuable metal method, valuable metal cobalt, nickel, the extraction time of copper are short, It is high to leach the rate of recovery.
In order to solve the above technical problems, technical scheme proposed by the present invention is:
A kind of method that recovery valuable metal is leached in ambrose alloy manganeisen from cobalt, comprises the following steps:
(1) the cobalt ambrose alloy manganeisen is melted to form alloy melt, wherein, the quality of manganese in cobalt ambrose alloy manganeisen Fraction is not less than 5%;
(2) into the alloy melt, containing silicon materials, simultaneously being passed through gas carries out blowing slag making simultaneously for addition;
(3) slag making of gained is separated from melt;
(4) melt atomization after slag making will be isolated into alloy powder, the mass fraction of Mn elements in the alloy powder For 0.5%~20%;
(5) by the alloy powder acidleach, valuable metal is reclaimed.
The above-mentioned method that recovery valuable metal is leached from cobalt ambrose alloy manganeisen, it is preferred that using high in step (4) Water injection is pressed, makes melt atomization into alloy powder, the mass fraction of Mn elements is 0.5%~15% in the alloy powder;Close Mn element portions in bronze end exist in the form of MnO, form the alloy powder of loose and porous structure, play reduction alloy structure The effect of intensity.
The above-mentioned method that recovery valuable metal is leached from cobalt ambrose alloy manganeisen, it is preferred that by the step (3) Isolate in the melt return to step (2) after slag making and repeat the above steps (2), step (3) circulate operation for several times, until alloy The content of Mn in powder meets to require.Based on our achievement in research, it has been found that retain in copper, cobalt, nickel alloy melt A certain amount of manganese, obtain containing appropriate MnO in alloy powder, because Cu, Co, Ni, Fe of MnO and metallic state are immiscible, The structural strength of alloyed powder can be significantly reduced, acid solution can be quickly penetrated into alloy powder particles during ensureing subsequent operation Portion, accelerate Leach reaction and carry out, improve its leaching performance, what this required to add in present invention process need not incite somebody to action containing silicon materials Mn is all removed in alloy.
The above-mentioned method that recovery valuable metal is leached from cobalt ambrose alloy manganeisen, it is preferred that the step (3) obtains Slag making be containing MnO and SiO2Blowing slag type, MnO/SiO in slag making2>=0.3, the slag making under the conditions of this will have more significant Low melting point, high fluidity property, ensure that the blowing slagging process of step (2) is more smoothly carried out towards target.
The above-mentioned method that recovery valuable metal is leached from cobalt ambrose alloy manganeisen, it is preferred that described to be containing silicon materials One or more in oxide containing silicon and silicon-containing alloy;The siliceous oxide selects silica, and the silicon-containing alloy is selected One or more combination in manganese-silicon, ferro-silicium.Because the present invention is used as in the cobalt ambrose alloy manganeisen of raw material typically It is not siliceous, in order to preferably obtain slag making, addition it is a certain amount of containing silicon materials to be aoxidized with the manganese in cobalt ambrose alloy manganeisen The MnO of formation is coordinated, and collectively acts as slag former.
The above-mentioned method that recovery valuable metal is leached from cobalt ambrose alloy manganeisen, it is preferred that in the step (2), The gas being passed through is oxygen, the one or more in air, nitrogen, inert gas, and not limited to this.Gas is to alloy melt What internal and/or surface was passed through, the intake of gas and flow velocity is passed through depending on the partial pressure of oxygen in stove, by controlling suitable oxygen Partial pressure makes valuable metal copper, cobalt, nickel, iron in stove hardly aoxidize, and most manganese is oxidized.Based on our research into Fruit, the above-mentioned gas being passed through to melt inside and/or surface not only control suitable partial pressure of oxygen in stove, promote the Mn of metallic state MnO (divalence) and SiO are separately converted to Si2;Another important effect is to ensure that the conjunction for being atomized and obtaining in step (4) Golden powder particle have loose and porous inner surface and it is in irregular shape the characteristics of, such alloy powder structural strength is low, surface live Property point is more, specific surface area is big, so as to significantly improve the leaching performance of alloy powder particles.Alloy melt without adding gas is straight Connect inside the alloy powder particles that powder by atomization obtains without gas hole, rule of surface is spherical in shape, structural strength is big, leaching performance Difference.It is worthy of note that the Mn and Si of metallic state conversion process can release substantial amounts of heat, or even it can reach and maintain furnace temperature Effect, this significantly reduces the energy consumption of technique, in addition, above-mentioned process is simple to operate, it is good in economic efficiency.
The above-mentioned method that recovery valuable metal is leached from cobalt ambrose alloy manganeisen, it is preferred that in the step (1), The process of cobalt ambrose alloy manganeisen fusing is carried out using electric furnace, and preferable electric furnace is electric induction furnace;Cobalt ambrose alloy manganeisen melts Smelting temperature needed for changing is at least higher than the fusing point of cobalt ambrose alloy manganeisen 50 DEG C.
The above-mentioned method that recovery valuable metal is leached from cobalt ambrose alloy manganeisen, it is preferred that in the step (5), Oxidant is additionally added during acidleach, oxidant is one or more of in oxygen, air and hydrogen peroxide;Acidleach process is in normal pressure Lower progress, extraction temperature are more than 50 DEG C;Sulfuric acid solution is selected in acidleach, and the dosage of sulfuric acid is to make cobalt in alloy powder, copper, nickel whole 1.05 times of theoretical amount needed for leaching~2.5 times.Cobalt, nickel, copper in leaching process in alloy are extracted into solution, copper, cobalt Leaching rate be higher than 98%, the iron rule in alloy is present in leached mud in the form of iron oxide or goethite, in the leached mud Fe contents (dry meter) are more than 40%, the step both effective leaching cobalt, nickel, copper, and be stripped of impurity iron simultaneously, reduce wet method point From the homework burden of recovery valuable metal iron removaling.It is worthy of note that just because of the aforementioned treatment Step of copper CoNiFe alloy, Most of Mn is not only effectively stripped of, and substantially improves the leaching performance of alloyed powder, and then avoids corrosion Oxidation Leaching Process earlier technique need to add the operation of the catalyst such as ammonium sulfate, while it also avoid the introducing of other impurity element/ions, show Writing reduces the difficulty of subsequent purification cobalt, nickel, copper.
The above-mentioned method that recovery valuable metal is leached from cobalt ambrose alloy manganeisen, it is preferred that in the step (1), Co mass fraction is the quality point that 5-35%, Ni mass fraction are 1-15%, Cu in pending cobalt ambrose alloy manganeisen Number is that 5-35%, Fe mass fraction are that 10-50%, Mn mass fraction is 5-45%, and hardly siliceous.
The present invention takes full advantage of MnO stability between SiO2With valuable metal oxide (CoO, CuO, NiO, FeO) Between property, control stove in partial pressure of oxygen (oxygen gesture) can realize added into stove containing the Mn in silicon materials and melt with oxygen Compound form is present, and can guarantee that valuable metal Co, Cu, Ni and Fe in alloy melt are not oxidized.Recycle siliceous Itself a small amount of SiO in material2And the SiO that siliceous material conversion comes2Low melting point, good fluidity can be formed with MnO “MnO-SiO2" binary system clinker, so as to realize the separation of manganese and copper, cobalt, nickel, be advantageous to the progress of follow-up acidleach.
Compared with prior art, the advantage of the invention is that:
(1) present invention generates low melting point, good fluidity by adding containing the manganese in silicon materials and cobalt ambrose alloy manganeisen MnO-SiO2Clinker type, so as to reach the effect of removing manganese, there is the advantages of demanganize effect is good, valuable metal loss is few.
(2) present invention obtains having irregularly by being passed through gas to cobalt ambrose alloy manganeisen melt inside and/or surface The good alloyed powder of loose porous pattern, leaching performance, not only solve the unfavorable of high Mn content pairing Gold leaching and subsequent process Influence, and ensured that the fast selective of alloyed powder leaches, realize the high efficiente callback of the valuable metals such as cobalt, nickel.
(3) the follow-up corrosion Oxidation Leaching process of the present invention need not add associated catalysts, and it is miscellaneous to avoid other in system The introducing of matter and poisonous and harmful element, reduce follow-up cobalt, nickel, the difficulty of copper separating-purifying, equipment is easily realized, technique it is comprehensive It is very notable to close economy, environment-friendly advantage.
Brief description of the drawings
Fig. 1 is the process chart that recovery valuable metal is leached from cobalt ambrose alloy manganeisen of the present invention.
Embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or Person can pass through product made from known method.
Embodiment 1:
A kind of method that recovery valuable metal is leached in ambrose alloy manganeisen of the invention from cobalt, its process chart is as schemed Shown in 1, comprise the following steps:
1) by 30kg cobalt ambrose alloys manganeisen (mass content of main component be respectively Co 15.62%, Ni 4.80%, Cu12.79%, Fe 24.44%, Mn 36.26%) it is put into 50kg middle frequency furnaces, 1550 DEG C of smelting temperature is set, by cobalt nickel Copper manganeisen melts to form alloy melt.
2) 6.0kg silicas (SiO is disposably added into alloy melt2Mass content is 98%), and to be melted simultaneously to alloy Mixed gas (the wherein air mass flow 3m of air and oxygen is passed through in body3/ h, oxygen flow 2.5m3/ h) carry out blowing slag making (MnO-SiO2), by controlling suitable partial pressure of oxygen the valuable metal copper in stove, cobalt, nickel, iron is hardly aoxidized, and it is most of Manganese be oxidized.
3) slag making of generation in step 2) is separated from alloy melt.
4) the melt return to step 2 after slag making will be isolated) in and repeat the above steps 2), step 3) circulate operation three It is secondary, until Mn content meets to require in alloy powder.The alloy melt for being finally recovered out slag making is used into high-pressure water jet mist Alloy powder is melted into, alloy powder is 22.5kg (dry meter), and the mass fraction of its main component is:Co 18.52%, Cu 16.68%th, Ni 5.69%, Fe 38.12%, MnO 15.09%;MnO/SiO in the slag making of acquisition2=0.39.
5) alloy powder is leached using sulfuric acid corrosion oxidation technology, oxidant use oxygen, sulfuric acid dosage be make cobalt, 1.4 times of theoretical amount, 90 DEG C of extraction temperature, extraction time 3.0h needed for copper, nickel whole leaching.Cobalt, nickel, the leaching rate point of copper Not Wei 99.10%, 99.89%, 98.06%, (mass fraction) containing Fe 48.35% in oxidation scum (dry meter).
Embodiment 2:
A kind of method that recovery valuable metal is leached in ambrose alloy manganeisen of the invention from cobalt, its process chart is as schemed Shown in 1, comprise the following steps:
1) by 800kg cobalt ambrose alloys manganeisen (mass fraction of main component be respectively Co 28.52%, Ni 6.71%, Cu19.33%, Fe 11.47%, Mn 25.51%, P 4.29%) it is put into 1000kg middle frequency furnaces, setting smelting temperature is 1450 DEG C, cobalt ambrose alloy manganeisen is melted to form alloy melt.
2) 50kg silicas (SiO is disposably added into alloy melt298%) and manganese-silicon (Si mass mass content is Content is mixture (wherein silica quality accounts for 90%, manganese-silicon quality and accounts for 10%) 18%), and simultaneously into alloy melt It is passed through mixed gas (the wherein air mass flow 15.0m of air and oxygen3/ h, oxygen flow 10.0m3/ h) carry out blowing slag making (MnO-SiO2), by controlling suitable partial pressure of oxygen the valuable metal copper in stove, cobalt, nickel, iron is hardly aoxidized, and it is most of Manganese be oxidized.
3) slag making of generation in step 2) is separated from alloy melt.
4) the melt return to step 2 after slag making will be isolated) in and repeat the above steps 2), step 3) circulate operation four It is secondary, until Mn content meets to require in alloy powder.The alloy melt for being finally recovered out slag making is used into high-pressure water jet mist Alloy powder is melted into, alloy powder is 638kg (dry meter), and the mass fraction of its main component is Co 37.01%, Cu 24.16%, Ni 8.59%, Fe 14.92%, MnO 1.01%;MnO/SiO in the blowing slag making of acquisition2=1.45.
5) alloy powder is leached using sulfuric acid corrosion oxidation technology, oxidant is using air and the gaseous mixture of purity oxygen Body, sulfuric acid dosage be make cobalt, copper, nickel all leach needed for 1.7 times of theoretical amount, 90 DEG C of extraction temperature, extraction time 1.5h. Cobalt, nickel, the leaching rate of copper are respectively 99.20%, 99.41%, 98.32%, (the matter containing Fe 53.53% in oxidation scum (dry meter) Measure fraction).
Embodiment 3:
A kind of method that recovery valuable metal is leached in ambrose alloy manganeisen of the invention from cobalt, its process chart is as schemed Shown in 1, comprise the following steps:
1) by 40kg cobalt ambrose alloys manganeisen (mass fraction of main component be respectively Co 10.63%, Ni 7.71%, Cu29.57%, Fe 35.16%, Mn 11.90%) it is put into 50kg middle frequency furnaces, it is 1500 DEG C to set smelting temperature, by cobalt Ambrose alloy manganeisen melts to form alloy melt.
2) 1.25kg silicas (SiO is disposably added into alloy melt2Mass content is 98%), and to be melted simultaneously to alloy Mixed gas (the wherein air mass flow 3.5m of air and oxygen is passed through in body3/ h, oxygen flow 5.0m3/ h), carry out blowing slag making (MnO-SiO2), by controlling suitable partial pressure of oxygen the valuable metal copper in stove, cobalt, nickel, iron is hardly aoxidized, and it is most of Manganese be oxidized.
3) slag making of generation in step 2) is separated from alloy melt, MnO/SiO in slag making2=2.80.
4) alloy melt for isolating slag making is atomized into alloy powder using high-pressure water jet, alloy powder is 34.54kg (dry meter), the mass fraction of its main component is Co 12.42%, Ni 8.92%, Cu 32.05%, Fe 37.77%th, MnO 5.77%.
5) alloy powder is leached using sulfuric acid corrosion oxidation technology, oxidant use hydrogen peroxide, sulfuric acid dosage be make cobalt, 1.1 times of theoretical amount, 55 DEG C of extraction temperature, extraction time 6.0h needed for copper, nickel whole leaching.Cobalt, nickel, the leaching rate point of copper Not Wei 99.34%, 99.26%, 98.32%, (mass fraction) containing Fe 56.10% in oxidation scum (dry meter).

Claims (5)

1. the method for recovery valuable metal is leached in a kind of ambrose alloy manganeisen from cobalt, it is characterised in that comprise the following steps:
(1) the cobalt ambrose alloy manganeisen is melted to form alloy melt, wherein, the mass fraction of manganese in cobalt ambrose alloy manganeisen Not less than 5%;In pending cobalt ambrose alloy manganeisen Co mass fraction be 5-35%, Ni mass fraction be 1-15%, Cu mass fraction is that 5-35%, Fe mass fraction are that 10-50%, Mn mass fraction is 5-45%, and hardly siliceous;
(2) into the alloy melt, containing silicon materials, simultaneously being passed through gas carries out blowing slag making simultaneously for addition;Gas is melted to alloy What internal portion and/or surface were passed through, the intake of gas and flow velocity is passed through depending on the partial pressure of oxygen in stove, it is suitable by controlling Partial pressure of oxygen makes valuable metal cobalt in stove, nickel, copper, iron hardly aoxidize, and most manganese is oxidized;
(3) slag making of gained is separated from melt;Wherein, the slag making of acquisition is containing MnO and SiO2Blowing slag type, MnO/ SiO2≥0.3;
(4) melt atomization after slag making will be isolated into alloy powder, the mass fraction of Mn elements is in the alloy powder 0.5%~20%;Mn element portions in alloy powder exist in the form of MnO, form the alloy powder of loose and porous structure;
(5) by the alloy powder acidleach, valuable metal is reclaimed;Be additionally added oxidant during acidleach, oxidant be oxygen, It is one or more of in air and hydrogen peroxide;Acidleach process is carried out at ambient pressure, and extraction temperature is more than 50 DEG C;Acidleach is molten from sulfuric acid Liquid, the dosage of sulfuric acid are make theoretical amount needed for the whole leachings of cobalt in alloy powder, copper, nickel 1.05 times~2.5 times;
It will isolate in the melt return to step (2) after slag making and repeat the above steps (2) in the step (3), step (3) is followed Ring operates for several times, until the content of the Mn in alloy powder meets to require.
2. the method for recovery valuable metal is leached from cobalt ambrose alloy manganeisen as claimed in claim 1, it is characterised in that institute The mass fraction for stating Mn elements in alloy powder is 0.5%~15%.
3. the method for recovery valuable metal is leached from cobalt ambrose alloy manganeisen as claimed in claim 1, it is characterised in that institute It is the one or more in oxide containing silicon and silicon-containing alloy to state containing silicon materials;The oxide containing silicon selects silica, described to contain Silicon alloy is from the one or more combination in manganese-silicon, ferro-silicium.
4. the method for recovery valuable metal is leached from cobalt ambrose alloy manganeisen as claimed in claim 1, it is characterised in that institute State in step (2), the gas being passed through is the one or more in oxygen, air, nitrogen, inert gas.
5. the method as leached recovery valuable metal in the ambrose alloy manganeisen according to any one of claims 1 to 4 from cobalt, its It is characterised by, in the step (1), the process of cobalt ambrose alloy manganeisen fusing is carried out using electric furnace;Cobalt ambrose alloy manganeisen Smelting temperature needed for fusing is at least higher than the fusing point of cobalt ambrose alloy manganeisen 50 DEG C.
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CN104087758B (en) * 2014-07-15 2016-05-11 长沙矿冶研究院有限责任公司 Full hydrometallurgy extracts the method for valuable metal in cobalt-copper alloy
CN104674013B (en) * 2015-03-11 2017-11-17 长沙矿冶研究院有限责任公司 A kind of recovery and treatment method of the old and useless battery containing Co and/or Ni

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