CN105063349A - Method of leaching copper, cobalt and nickel from smelting alloy - Google Patents
Method of leaching copper, cobalt and nickel from smelting alloy Download PDFInfo
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- CN105063349A CN105063349A CN201510506019.8A CN201510506019A CN105063349A CN 105063349 A CN105063349 A CN 105063349A CN 201510506019 A CN201510506019 A CN 201510506019A CN 105063349 A CN105063349 A CN 105063349A
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Abstract
A method of leaching copper, cobalt and nickel from smelting alloy comprises the following steps: the smelting alloy containing at least two of copper, cobalt and nickel and iron impurities is molten, and then the molten smelting alloy is atomized into alloy powder by high-pressure gas or high-pressure water; the atomized alloy powder is added into a stir aeration reaction device, a sulfuric acid solution is used as a leaching medium in the stir aeration reaction device, air or oxygen is uniformly brought from a stirring shaft system of the stir aeration reaction device, the brought gas is uniformly dispersed under the shear action of stirring blades in high-speed rotation at the bottom of the stirring shaft system, and under the effects of an oxidizing agent and a catalyst, the alloy powder is subjected to corrosion oxidizing leaching reaction in the stir aeration reaction device; after reaction is completed, most iron impurities enter a leaching residue, and solid-liquid separation is finally carried out to collect and obtain a leaching liquid containing at least two of copper, cobalt and nickel. The method of leaching copper, cobalt and nickel from the smelting alloy has the advantages that the process cost is low; the technology is convenient to control; the production is stable and reliable; the environment pollution is low and the like.
Description
Technical field
The present invention relates to hydrometallurgy and chemical production technical field, be specifically related to the separation method of copper cobalt nickel and iron in a kind of molten alloy.
Background technology
Waste and old lithium ion battery molten alloy system waste and old lithium ion battery is through high temperature reduction melting process gained, and this alloy raw material is a kind of iron alloy of cupric cobalt nickel, is 10% ~ 40% containing cobalt, cupric is 10 ~ 50%, nickeliferous is 0.1% ~ 5%, and iron content is 10% ~ 80%, containing manganese 0.1% ~ 5%.
At present, from copper cobalt-nickel alloy, the method for leaching valuable metal mainly contains:
1, High Temperature High Pressure lixiviation process: leached by high pressure with sulfuric acid or hydrochloric acid or in conjunction with normal pressure leaching, the cobalt in cobalt-copper alloy, copper, nickel leached and enters solution.The method equipment is complicated, must solve the Anticorrosion of equipment under high temperature, condition of high voltage.
2, chlorine leaching process: adopt chlorine as leaching agent, because chlorine is toxic substance, transport, storage and use all have certain danger; Chlorine, villaumite leach, be chloride system, system corrodibility increase, equipment anticorrosion and environmental requirement high.
3, add sodium chlorate lixiviation process with sulfuric acid, be a kind of leaching velocity method that is fast and that easily realize, but the price of sodium chlorate is higher, production cost is high.
4, direct pickling process: leach with sulfuric acid, hydrochloric acid or nitric acid or two kinds of composition mixing acid wherein.The method at ambient pressure speed of response is slow, and copper cobalt nickel leaching efficiency is not high, and leaching yield is low, and technical process is long, and production cost is high.
5, electro-dissolving: in a cell with cobalt-copper alloy raw material for anode, in sulfuric acid or hydrochloric acid system by electrolysis make cobalt, copper from anode dissolve enter solution, manganese, iron also together dissolve enter solution.The method current efficiency is lower, power consumption is higher, and the rate of recovery of cobalt is lower.
Above-mentioned various method, comparatively large for this complicated component, constitutionally stable high melt alloy treatment difficulty, ubiquity copper cobalt nickel leaches the shortcomings such as low, technical process is long, production cost is high.In addition, while in alloy, copper cobalt nickel leaches, a large amount of iron leaches and enters leach liquor, brings difficulty, increase follow-up deironing homework burden, and cause the loss of cobalt, copper, affect the rate of recovery of cobalt, copper, nickel to follow-up deironing.
Summary of the invention
Technical problem to be solved by this invention is, overcomes the deficiency and defect mentioned in above background technology, provides a kind of a kind of method leaching copper cobalt nickel from molten alloy that process costs is low, technique is convenient to control, administration measure is reliable, environmental pollution is few.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of method leaching copper cobalt nickel from molten alloy, comprises the following steps:
Carry out melting by containing the molten alloy of at least two kinds and iron contamination in copper cobalt nickel, then utilize high pressure gas or high-pressure water mist to change into powdered alloy;
Powdered alloy after atomization is added in a stirring inflation reaction unit, using sulphuric acid soln as leaching medium in this stirring inflation reaction unit, air or oxygen is evenly blasted from described stirring the stir shaft system of inflation reaction unit, bottom stir shaft system, the shearing action of the agitating vane of high speed rotating makes the gas uniform dispersion blasted, under the effect of oxygenant, catalyzer, powdered alloy carries out the reaction of corrosion Oxidation Leaching in stirring inflation reaction unit;
After having reacted, major part impurity iron enters in leached mud, finally carry out solid-liquid separation, the filter plant of described solid-liquid separation is preferably the one in whizzer, chamber-type press filter, plate-and-frame filter press, pipe filter, collects the leach liquor obtaining in cupric cobalt nickel at least two kinds.
In above-mentioned method, preferred: described molten alloy is waste and old lithium ion battery molten alloy, and simultaneously containing at least two kinds of valuable metals in copper cobalt nickel three kinds of valuable metals and iron contamination in this molten alloy.
In above-mentioned method, preferred: melt temperature during described melting is greater than 1300 DEG C.
In above-mentioned method, preferred: described in the particle diameter of powdered alloy that is atomized into be greater than 80% for-0.15mm (-100 order), more preferably-0.15mm (-100 order) is greater than 90%.
In above-mentioned method, preferred: in described corrosion Oxidation Leaching reaction process, the consumption of described sulfuric acid presses 1.05 times ~ 2.0 times interpolations of theoretical amount of cobalt in molten alloy, copper, nickel metallic element summation, and during reaction, liquid-solid ratio controls is 2: 1 ~ 20: 1, and temperature of reaction is greater than 50 DEG C.
In above-mentioned method, preferred: described catalyzer is one or more in ammonium sulfate, ammonium persulphate, copper sulfate, ferrous sulfate, and the concentration of catalyzer controls within 150g/L; Described oxygenant is oxygen or air.
Further improve as to aforesaid method: described stirring inflation reaction unit comprises stirring cell body, mounting base, drive unit and stir shaft system, described drive unit is installed in by mounting base and stirs on cell body, described stirring cell body offers opening for feed and discharge port, described drive unit drives stir shaft system to rotate, stir shaft system to stretch in the inner chamber stirring cell body and is positioned at the center of inner chamber, described stir shaft system comprises outer shaft sheathed with one heart and interior axle, described outer shaft and interior axle are hollow structure, and interior axle is arranged in the hollow cavity of outer shaft, the hollow cavity of described interior axle is set to induction trunk, and the bottom of interior axle is set to the air outlet of described induction trunk, described outer shaft is provided with the upper agitator being mainly used in mixing material, described interior axle is provided with the lower agitator being mainly used in gas dispersion near the position of its air outlet.
In the stirring inflation reaction unit of above-mentioned improvement, preferred: described upper agitator is arm stirrer, according to the specific design height of reaction unit, this arm stirrer also preferably can arrange multiple (such as 1,2 or 3) along different heights on outer shaft; Described lower agitator is then preferably the turbine turbine type agitator of a rotating speed higher than upper agitator speed.
In the stirring inflation reaction unit of above-mentioned improvement, preferred: the bottom of described interior axle is near the bottom surface of described stirring cell body, the bottom of described outer shaft exceeds the bottom certain altitude of described interior axle, and described upper agitator is installed on the bottom end vicinity of outer shaft, described lower agitator is then installed on the bottom of interior axle.
In the stirring inflation reaction unit of above-mentioned improvement, preferred: described outer shaft and interior axle are respectively by independently drive unit driving, and the rotating speed of outer shaft is lower than the rotating speed of interior axle.Preferred: described drive unit comprises the first drive-motor and the second drive-motor, described first drive-motor is connected with the upper end of outer shaft by outer shaft belt and belt pulley, described second drive-motor is connected with the upper end of interior axle by interior axle belt and belt pulley, and the upper end of interior axle exceeds the upper end certain distance of outer shaft.Interior axle and outer shaft is driven respectively by drive unit independently, make agitator and lower agitator can reach different optimized rotating speeds according to its different type of stirrer and action function, the rotating speed of lower agitator (turbine type agitator) is higher, its mainly with the generation and the dispersion that control microbubble together with stator, and the rotating speed of upper agitator (arm stirrer) is relatively low, then the liquid or solid mainly born in whole container forms circulation in vertical direction.
In the stirring inflation reaction unit of above-mentioned improvement, preferred: the position that the bottom surface of described stirring cell body corresponds to interior axle bottom is equiped with stator, and stator is formed with a groove, this groove is the outside that half-packaging is enclosed in described lower agitator, so-called half-packaging refers to that stator arrangement is in the downside of lower agitator and outside, and the top of lower agitator does not then have stator surrounding.Preferred, leave gap between described stator and described lower agitator and form slit cavity.Described stator is laid with lower agitator is concentric, and described stator comprises chassis and is fixed in the multiple drainage plates on chassis; Multiple drainage plate is distributed on the periphery above chassis, and the middle axial plane of multiple drainage plate is all crossing with the periphery tangent line on chassis and in an equal angular.In this preferred scheme, stator and lower agitator form one group of whipping appts jointly, this group whipping appts is mainly used to the gas disperseing to enter from interior axle, produce micro bubble, instantly when agitator rotates, drive liquid throws away, produce local decompression, outside gas enters gap between lower agitator and stator (can self-priming or gas blower blast) along interior axle, in the shearing of lower agitator and stator, under the acting in conjunction of the reactive forces such as friction, continuous generation microfine bubble and with liquid or solid high-speed mixing, finally spray radially under the drainage of stator, constitute a small-sized and efficient gas dispersing system.
In above-mentioned stirring inflation reaction unit, preferred: described mounting base is fixed in the end face stirring cell body, described stir shaft system stretches in the inner chamber stirring cell body through mounting base, the inlet mouth of described induction trunk is arranged on the top of interior axle, this inlet mouth is fixed by support, and this inlet mouth place is provided with the air intake valve of adjusting air inflow quantity.Air intake valve is fixed on mounting base by support.
In above-mentioned stirring inflation reaction unit, preferred: described stir shaft system comprises clutch shaft bearing and the second bearing, the outside of described outer shaft is installed on described mounting base by clutch shaft bearing, and described interior axle passes through the second bearing nested, concentric in the hollow cavity of outer shaft.
Adopt the method for the invention described above can realize effective leaching of copper cobalt nickel in molten alloy under normal pressure leaching condition, and while effectively leaching copper cobalt nickel, can realize and being separated of iron contamination, and then reach effective leaching valuable metal and the object of imurity-removal iron, reduce next step wet separation and reclaim valuable metal deironing homework burden.As further improvement, in order to improve gas-solid-liquid phase reaction speed, ensure that alloy fully reacts, the leaching of molten alloy is placed in a reaction unit of stirring inflation efficiently and carries out by us, leaching agent is made with the sulfuric acid of cheapness, use air or oxygen as oxygenant, gas evenly blasts from described stirring the stir shaft system of inflation reaction unit, blade shear gas through high speed rotating realizes that it is dispersed, under oxygenant, catalyst action, realize the efficient leaching of valuable metal in alloy.Whipping device due to routine does not generally have the effect of gas dispersion, and in the stirring inflation reaction unit of the above-mentioned improvement of the present invention, by the agitator of layered arrangement different structure form, and lay induction trunk dexterously, make whipping device of the present invention can have inflation response function concurrently simultaneously; Agitator and Accessory Members thereof is descended to have the effect of ventilation and gas dispersion in the present invention, be conducive to promoting gas-liquid two-phase mixing or gas-liquid-solid three-phase mixing, but stir iff the lower agitator of dependence, then easily cause the deficiency of convection current up and down, the undercompounding of reaction mass, therefore on this basis, the present invention is provided with again agitator in the middle part of reaction unit, to strengthen the material convection current in vertical direction, accomplishes the whole abundant mixing and the sufficient reacting that stir material in inflation reaction unit.
Compared with prior art, the invention has the advantages that:
(1) the present invention adopt corrodibility less than hydrochloric acid sulfuric acid as leaching agent, and using air or oxygen as oxygenant, using ammonium salt as catalyzer, cheaper starting materials, be easy to get, simple to operate, production cost is low, the erosion of leaching plant material antiseptic is less demanding, easy and simple to handle.
(2) have employed high-efficiency stirring inflation reaction unit in the present invention, in atmospheric conditions, using sulfuric acid as leaching medium, under the effect of oxygenant and catalyzer, achieve cobalt in molten alloy, copper, nickel effectively leaches, and the object be separated with iron, copper cobalt nickel leaching yield reaches 90%-99%, iron rule in alloy is present in leached mud with the form of ferric oxide or pyrrhosiderite, can be processed into magneticsubstance, other industrial chemicals or Returning smelting further and use.
(3) the present invention improve after stirring inflation reaction unit ore pulp in device can be made to circulate up and down quickenings, the mixing of material evenly, reaction more fully, reaction efficiency is higher, better effects if; Adopt turbine type agitator and stator and Accessory Members fit system thereof, this can complete spreading the work of gas better, and add the touch opportunity of gas and solid liquid phase, gas effciency is higher; By to the further improvement of stator structure and shape and optimization, make the gas that passes in stirring inflation reaction unit dispersedly evenly, bubble is less, and microfine bubble is more, and chemical reaction is faster; By improving driving arrangement and arranging mode of connection, the turbine type agitator selected in the present invention and arm stirrer can be operated within the scope of required different optimum revolutions, this fully combines two kinds of dissimilar agitators advantage separately, make gas in the reactor dispersedly evenly, react faster.
Generally speaking, method of the present invention has the advantages such as process costs is low, technique is convenient to control, administration measure is reliable, environmental pollution is few; And the present invention improve after stirring inflation reaction unit structure simple, be easy to assembling, be conducive to increasing substantially speed of reaction and gas-liquid-solid heterogeneous reaction effect.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the structural representation stirring inflation reaction unit in the embodiment of the present invention.
Fig. 2 is the front view of the arm stirrer in the embodiment of the present invention.
Fig. 3 is the vertical view of the arm stirrer in the embodiment of the present invention.
Fig. 4 is the side-view of the arm stirrer in the embodiment of the present invention.
Fig. 5 is the vertical view of the first turbine turbine type agitator in the embodiment of the present invention.
Fig. 6 is the sectional view at A-A place in Fig. 5.
Fig. 7 is the vertical view of the second turbine turbine type agitator in the embodiment of the present invention.
Fig. 8 is the sectional view at B-B place in Fig. 7.
Fig. 9 is the vertical view of the first stator in the embodiment of the present invention.
Figure 10 is the sectional view at C-C place in Fig. 9.
Figure 11 is the vertical view of the second stator in the embodiment of the present invention.
Figure 12 is the sectional view at D-D place in Figure 11.
Marginal data
1, cell body is stirred; 2, mounting base; 3, drive unit; 31, the first drive-motor; 32, the second drive-motor; 4, stir shaft system; 41, clutch shaft bearing; 42, the second bearing; 5, outer shaft; 6, outer shaft belt and belt pulley; 7, interior axle belt and belt pulley; 8, interior axle; 9, air intake valve; 10, support; 11, upper agitator; 12, lower agitator; 13, stator; 14, opening for feed; 15, discharge port; 16, chassis; 17, drainage plate; 18, middle axial plane.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
It should be noted that, when a certain element is described on " be fixed on, be fixed in, be connected to or be communicated in " another element, it can be directly fixing, affixed, connect or be communicated with on another element, also can be by other intermediate connectors indirectly fixing, affixed, connection or connection on another element.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various starting material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.
Embodiment 1:
The method leaching copper cobalt nickel from molten alloy of the present invention, comprises the following steps:
Waste and old lithium ion battery retailoring alloy containing copper cobalt nickel three kinds of metals and iron contamination is carried out melting, and melt temperature during melting is 1400 DEG C, then utilizes high-pressure water mist to change into powdered alloy; Powdered alloy is crossed 100 mesh sieves, screen underflow size-grade distribution is as shown in table 1 below, and the composition of powdered alloy is as shown in table 2 below:
Table 1: the size-grade distribution of embodiment 1 interalloy powder
| Particle diameter/mm | Distributive law/% | Cumulative distribution rate/% |
| -0.043 (-325 order) | 73.22 | 73.22 |
| -0.074 ~+0.043 (200 ~ 325 order) | 16.46 | 89.68 |
| -0.098 ~+0.074 (150 ~ 200 order) | 6.28 | 95.96 |
| -0.150 ~+0.098 (100 ~ 150 order) | 4.04 | 100 |
Table 2: the size-grade distribution of embodiment 1 interalloy powder
| Main metal | Add up to | Fe | Cu | Co | Ni | |||||
| Content/% | 96.05 | 66.00 | 11.31 | 15.10 | 3.64 | |||||
| Other element | Add up to | Mn | Zn | Al | Ca | As | Cd | Cl | F | Other |
| Content/% | 3.95 | 0.12 | 0.02 | 0.13 | 0.12 | 0.13 | 0.19 | 0.10 | 0.04 | 3.10 |
Above-mentioned powdered alloy 300g after atomization is added in a stirring inflation reaction unit, using the vitriol oil of 98% as leaching medium in this stirring inflation reaction unit, acid consumption is cobalt in molten alloy, copper, 1.4 times of the theoretical amount of the summation of nickel metallic element, air or oxygen is evenly blasted from described stirring the stir shaft system of inflation reaction unit, the shearing action of stir shaft system makes the gas uniform dispersion blasted, liquid-solid ratio during leaching is 10: 1, extraction temperature is 95 DEG C, mixing speed is 1500 revs/min, under the effect of catalyst sulfuric acid ammonium (concentration 50g/L), powdered alloy carries out the reaction of corrosion Oxidation Leaching in stirring inflation reaction unit, the Leaching reaction time is 8h,
After having reacted, most of impurity iron enters in leached mud, finally carries out solid-liquid separation, collects the leach liquor 2360mL obtaining cupric cobalt nickel, and washing and drying precipitates, and obtains leached mud 368g.
After testing, containing cobalt 15.72g/L, copper 12.41g/L, nickel 4.78g/L in the leach liquor that above-mentioned the present embodiment method obtains, leached mud composition is containing cobalt 0.38%, copper 0.6%, nickel 0.14%, and slag meter leaching yield is cobalt 95.88%, copper 95.13%, nickel 95.28%.
Embodiment 2:
The method leaching copper cobalt nickel from molten alloy of the present invention, comprises the following steps:
Waste and old lithium ion battery retailoring alloy containing copper cobalt nickel three kinds of metals and iron contamination is carried out melting, and melt temperature during melting is 1400 DEG C, then utilizes high-pressure water mist to change into powdered alloy; Powdered alloy is crossed 100 mesh sieves, screen underflow size-grade distribution is for as above shown in table 1, table 2;
Getting the 150-200 object powdered alloy 250g after above-mentioned atomization adds in a stirring inflation reaction unit, using the vitriol oil of 98% as leaching medium in this stirring inflation reaction unit, acid consumption is cobalt in molten alloy, copper, 1.7 times of the theoretical amount of the summation of nickel metallic element, air or oxygen is evenly blasted from described stirring the stir shaft system of inflation reaction unit, the shearing action of stir shaft system makes the gas uniform dispersion blasted, liquid-solid ratio during leaching is 8: 1, extraction temperature is 85 DEG C, mixing speed is 1800 revs/min, under the effect of catalyst sulfuric acid ammonium (concentration 20g/L), powdered alloy carries out the reaction of corrosion Oxidation Leaching in stirring inflation reaction unit, the Leaching reaction time is 6h,
After having reacted, most of impurity iron enters in leached mud, finally carries out solid-liquid separation, collects the leach liquor 2620mL obtaining cupric cobalt nickel, and washing and drying precipitates, and obtains leached mud 343g.
After testing, containing cobalt 16.11g/L, copper 12.95g/L, nickel 4.79g/L in the leach liquor that above-mentioned the present embodiment method obtains, leached mud composition is containing cobalt 0.55%, and copper 0.44%, nickel 0.099%, slag meter leaching yield is cobalt 93.33%, copper 96.01%, nickel 96.37%.
Embodiment 3:
The method leaching copper cobalt nickel from molten alloy of the present invention, comprises the following steps:
Waste and old lithium ion battery retailoring alloy containing copper cobalt nickel three kinds of metals and iron contamination is carried out melting, and melt temperature during melting is 1400 DEG C, then utilizes high-pressure water mist to change into powdered alloy; Powdered alloy is crossed 100 mesh sieves, screen underflow size-grade distribution is for as above shown in table 1, table 2;
Getting the 200-325 object powdered alloy 250g after above-mentioned atomization adds in a stirring inflation reaction unit, using the vitriol oil of 98% as leaching medium in this stirring inflation reaction unit, acid consumption is cobalt in molten alloy, copper, 2.0 times of the theoretical amount of the summation of nickel metallic element, air or oxygen is evenly blasted from described stirring the stir shaft system of inflation reaction unit, the shearing action of stir shaft system makes the gas uniform dispersion blasted, liquid-solid ratio during leaching is 15: 1, extraction temperature is 90 DEG C, mixing speed is 1500 revs/min, under the effect of catalyst sulfuric acid ammonium (concentration 100g/L), powdered alloy carries out the reaction of corrosion Oxidation Leaching in stirring inflation reaction unit, the Leaching reaction time is 10h,
After having reacted, most of impurity iron enters in leached mud, finally carries out solid-liquid separation, collects the leach liquor 2320mL obtaining cupric cobalt nickel, and washing and drying precipitates, and obtains leached mud 355g.
After testing, containing cobalt 13.32g/L, copper 10.41g/L, nickel 4.32g/L in the leach liquor that above-mentioned the present embodiment method obtains, leached mud composition is containing cobalt 0.33%, and copper 0.52%, nickel 0.088%, slag meter leaching yield is cobalt 93.47%, copper 96.90%, nickel 96.57%.
The stirring inflation reaction unit used in the various embodiments described above is as shown in Fig. 1-Figure 12, comprise and stir cell body 1, mounting base 2, drive unit 3 and stir shaft system 4, drive unit 3 is installed in by mounting base 2 and stirs on cell body 1, stir on cell body 1 and offer opening for feed 14 and discharge port 15, drive unit 3 drives stir shaft system 4 rotation, and stir shaft system 4 to stretch in the inner chamber stirring cell body 1 and is positioned at the center of inner chamber.The stir shaft system 4 of the present embodiment comprises outer shaft 5 sheathed with one heart and interior axle 8, outer shaft 5 and interior axle 8 are hollow structure, and interior axle 8 is arranged in the hollow cavity of outer shaft 5, the hollow cavity of interior axle 8 is set to induction trunk, and the bottom of interior axle 8 is set to the air outlet of induction trunk.Stir shaft system 4 also comprises clutch shaft bearing 41 and the second bearing 42, the outside of outer shaft 5 is installed on mounting base 2 by clutch shaft bearing 41, interior axle 8 is by the second bearing 42 nested, concentric in the hollow cavity of outer shaft 5, and what can realize outer shaft 5 and interior axle 8 in the present embodiment by the Accessory Members such as aforementioned bearings and bottom bracket is rotatably connected mode.In practice, the rotating speed of interior axle 8 and outer shaft 5 can need adjust according to the technique of reality, to reach best result of use with turning to.
In the stirring inflation reaction unit of the present embodiment, outer shaft 5 is provided with the upper agitator 11 being mainly used in mixing material, interior axle 8 is provided with the lower agitator 12 being mainly used in gas dispersion near the position of its air outlet.Upper agitator 11 is arm stirrer, and lower agitator 12 is the turbine turbine type agitator of a rotating speed higher than upper agitator 11 rotating speed.The bottom of interior axle 8 is near the bottom surface of stirring cell body 1, and the bottom of outer shaft 5 exceeds the bottom certain altitude of interior axle 8, and upper agitator 11 is installed on the bottom end vicinity of outer shaft 5, and lower agitator 12 is installed on the bottom of interior axle 8.In the present embodiment, the agitating vane of upper agitator 11 is 2 chips, and its three-view diagram as shown in Figure 2 to 4.Lower agitator 12 in the present embodiment can be the structure formation shown in Fig. 5, Fig. 6, also can adopt the structure formation shown in Fig. 7, Fig. 8.
In the stirring inflation reaction unit of the present embodiment, the bottom surface of stirring cell body 1 corresponds to the position of interior axle 8 bottom and is equiped with stator 13, stator 13 is formed with a groove, this groove is the periphery that half-packaging is coated on described lower agitator 12, lower agitator 12 half built-in be placed in this groove, but lower agitator 12 does not contact with stator 13, in the bottom of lower agitator 12 and leave gap between outside and stator 13 and form slit cavity (see Fig. 1).Stator 13 is laid with lower agitator 12 is concentric.The stator 13 of the present embodiment can adopt the structure formation shown in Fig. 9, Figure 10, multiple drainage plate 17 that this stator 13 comprises chassis 16 and is fixed on chassis 16; Multiple drainage plate 17 is distributed on the periphery above chassis 16, and the middle axial plane 18 of multiple drainage plate 17 is all vertical with the periphery tangent line on chassis 16.But the preferred stator 13 of the present embodiment is as shown in Figure 11, Figure 12, multiple drainage plate 17 that this stator 13 comprises chassis 16 equally and is fixed on chassis 16; Multiple drainage plate 17 is distributed on the periphery above chassis 16, and all crossing with the periphery tangent line on chassis 16 acute angle in an equal angular of the middle axial plane 18 of multiple drainage plate 17.The structure formation of the stator 13 preferably adopted in the present embodiment can match with the lower agitator 12 of interior axle 8 better, while gas is dispersed, can also disperses come and form eddy flow effect more uniformly to reaction unit inner chamber.
In the stirring inflation reaction unit of the present embodiment, mounting base 2 is fixed in the end face stirring cell body 1, stir shaft system 4 stretches into through mounting base 2 in the inner chamber stirring cell body 1, and the inlet mouth of induction trunk is arranged on the top of interior axle 8, and this inlet mouth place is provided with the air intake valve 9 of adjusting air inflow quantity.Air intake valve 9 is fixed on mounting base 2 by support 10.
In the stirring inflation reaction unit of the present embodiment, outer shaft 5 and interior axle 8 are driven by independently drive unit 3 respectively, and the rotating speed of outer shaft 5 is lower than the rotating speed of interior axle 8.Drive unit 3 comprises the first drive-motor 31 and the second drive-motor 32, first drive-motor 31 is connected with the upper end of outer shaft 5 by outer shaft belt and belt pulley 6, second drive-motor 32 is connected with the upper end of interior axle 8 by interior axle belt and belt pulley 7, and the upper end of interior axle 8 exceeds the upper end certain distance of outer shaft 5.
From above embodiment, the coaxial inside and outside axle combination alr mode arranged is adopted in the present invention, interior axle stirs and adopts the design of turbine turbine type agitator can gas dispersion effectively, the microvesicle that generation particle diameter is enough little, quantity is abundant also makes it to permeate in reaction solution phase system, improve the content of gas in reaction solution phase system, increase the touch opportunity of gas and liquid or solid, accelerate chemical reaction rate; Simultaneously, the present invention also utilizes the arm stirrer of outer shaft to implement to be uniformly mixed to the material of periphery, make, in reaction unit, vertical direction forms convection circulation, achieve the mixing of gas-liquid-solid three-phase omnibearing uniform stirring under Double stirring effect, make that gas disperses in the reactor evenly, utilization ratio is higher, reaction is faster.
Claims (10)
1. from molten alloy, leach a method for copper cobalt nickel, comprise the following steps:
Carry out melting by containing the molten alloy of at least two kinds and iron contamination in copper cobalt nickel, then utilize high pressure gas or high-pressure water mist to change into powdered alloy;
Powdered alloy after atomization is added in a stirring inflation reaction unit, using sulphuric acid soln as leaching medium in this stirring inflation reaction unit, air or oxygen is evenly blasted from described stirring the stir shaft system of inflation reaction unit, bottom stir shaft system, the shearing action of the agitating vane of high speed rotating makes the gas uniform dispersion blasted, under the effect of oxygenant, catalyzer, powdered alloy carries out the reaction of corrosion Oxidation Leaching in stirring inflation reaction unit; After having reacted, most of impurity iron enters in leached mud, finally carries out solid-liquid separation, collects the leach liquor obtaining in cupric cobalt nickel at least two kinds.
2. method according to claim 1, is characterized in that: described molten alloy is waste and old lithium ion battery molten alloy, and simultaneously containing at least two kinds of valuable metals and iron contamination in copper cobalt nickel in this molten alloy.
3. method according to claim 1, is characterized in that: melt temperature during described melting is greater than 1300 DEG C.
4. method according to claim 1, is characterized in that: described in the particle diameter of powdered alloy that is atomized into be greater than 80% for-0.15mm.
5. method according to claim 1, it is characterized in that: in described corrosion Oxidation Leaching reaction process, described sulfuric acid dosage presses 1.05 times ~ 2.0 times interpolations of theoretical amount of cobalt in molten alloy, copper, nickel metallic element summation, and liquid-solid ratio control is 2: 1 ~ 20: 1 during reaction, temperature of reaction is greater than 50 DEG C.
6. method according to claim 1, is characterized in that: described catalyzer is one or more in ammonium sulfate, ammonium persulphate, copper sulfate, ferrous sulfate, and the concentration of catalyzer controls within 150g/L; Described oxygenant is oxygen or air.
7. the method according to any one of claim 1 ~ 6, it is characterized in that, described stirring inflation reaction unit comprises stirring cell body (1), mounting base (2), drive unit (3) and stir shaft system (4), described drive unit (3) is installed in by mounting base (2) and stirs on cell body (1), described stirring cell body (1) offers opening for feed (14) and discharge port (15), described drive unit (3) drives stir shaft system (4) to rotate, stir shaft system (4) to stretch in the inner chamber stirring cell body (1) and is positioned at the center of inner chamber, described stir shaft system (4) comprises outer shaft (5) sheathed with one heart and interior axle (8), described outer shaft (5) and interior axle (8) are hollow structure, and interior axle (8) is arranged in the hollow cavity of outer shaft (5), the hollow cavity of described interior axle (8) is set to induction trunk, and the bottom of interior axle (8) is set to the air outlet of described induction trunk, described outer shaft (5) is provided with the upper agitator (11) being mainly used in mixing material, described interior axle (8) is provided with near the position of its air outlet the lower agitator (12) being mainly used in gas dispersion.
8. method according to claim 7, is characterized in that, described upper agitator (11) is arm stirrer, and described lower agitator (12) is the turbine turbine type agitator of a rotating speed higher than upper agitator (11) rotating speed.
9. method according to claim 7, it is characterized in that, the bottom of described interior axle (8) is near the bottom surface of described stirring cell body (1), the bottom of described outer shaft (5) exceeds the bottom certain altitude of described interior axle (8), and described upper agitator (11) is installed on the bottom end vicinity of outer shaft (5), described lower agitator (12) is installed on the bottom of interior axle (8); Described outer shaft (5) and interior axle (8) are respectively by independently drive unit (3) driving, and the rotating speed of outer shaft (5) is lower than the rotating speed of interior axle (8).
10. method according to claim 9, it is characterized in that, the position that the bottom surface of described stirring cell body (1) corresponds to interior axle (8) bottom is equiped with stator (13), and stator (13) is formed with a groove, this groove is the periphery that half-packaging is coated on described lower agitator (12); Leave gap between described stator (13) and described lower agitator (12) and form slit cavity; Described stator (13) is laid with lower agitator (12) is concentric, and described stator (13) comprises chassis (16) and is fixed in the multiple drainage plates (17) on chassis (16); Multiple drainage plate (17) be distributed on chassis (16) top periphery, and the middle axial plane (18) of multiple drainage plate (17) all crossing with the periphery tangent line of chassis (16) and be an equal angular.
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| CN109666804A (en) * | 2019-02-28 | 2019-04-23 | 宁波锦越新材料有限公司 | A kind of purifying partial crystallization device of ultra-pure aluminum |
| CN109811142A (en) * | 2019-02-28 | 2019-05-28 | 宁波锦越新材料有限公司 | A kind of control method of ultra-pure aluminum purifying partial crystallization device |
| CN113728118A (en) * | 2019-04-19 | 2021-11-30 | 尤米科尔公司 | Method for preparing precursor compound of lithium battery cathode |
| CN110564978A (en) * | 2019-10-15 | 2019-12-13 | 俞杰 | operation process for recovering nickel and cobalt in ternary battery material by wet method |
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