CN1187223A - Method for recovering copper - Google Patents
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- CN1187223A CN1187223A CN96194537A CN96194537A CN1187223A CN 1187223 A CN1187223 A CN 1187223A CN 96194537 A CN96194537 A CN 96194537A CN 96194537 A CN96194537 A CN 96194537A CN 1187223 A CN1187223 A CN 1187223A
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Abstract
An improved process is described for the recovery of copper from an aqueous feed solution using solvent extraction and electrowinning in which the electrowinning is conducted in a first step wherein the electrolyte is flowing perpendicular to the cathode surface without auxiliary mixing of the electrolyte between electrodes, and a second step wherein the electrolyte is flowing parallel to the cathode surface. In a second embodiment, solvent extraction of copper and solvent extraction of acid are conducted in alternate steps to allow more complete recovery of copper.
Description
The present invention relates to from acidic aqueous solution, reclaim improving one's methods of copper effectively by solvent extraction.
The starting raw material that is used for extensive solvent extraction is the leaching aqueous solution that obtains by from ore leaching cupric ion.In groove, make the described aqueous solution and be dissolved in for example extraction reagent mix in the kerosene of organic thinner.Reagent comprises the chemical extraction agent, and they are forming METAL EXTRACTION agent title complex with optionally cooperating with cupric ion before other metal ion cooperates.Simultaneously, because extraction agent is to play a role,, in the process of carrying out the copper extraction continuously, strengthened the acidity of solution gradually on hydrogen exchange basis so hydrogen ion is transferred in the aqueous solution.The step that people will form title complex is called the extraction or the load step of solvent-extraction process.
Solution through cooperating is transported to the big clarifying tank continuously from the outlet of mixing tank, and the organic solvent (organic phase) that will contain copper extraction agent title complex in groove now in solution is separated from barren water solution (water).Some situation is called this process in the following text for being separated.In order to extract copper more completely, repeat leaching process by two or more mixer-settler steps usually.
When adopting two or more mixer-settler steps to extract, make feed water solution and organic phase or extraction agent solution counter-current flow.In typical 3 step extraction systems, for example feed water solution at first flows through the mixer-settler (" E of first step
1"), follow mixer-settler (" E by second step
2"), the mixer-settler (" E by final step then
3").Organic phase is in turn elder generation and E then
3In feed water solution contact, then with E
2In feed water solution contact, last and E
1In feed water solution contact.As a result, arrive the mixer-settler step e in feed water solution
3The time, from solution, isolated a large amount of copper, and what be touched will be the lower organic phase of copper amount.Correspondingly, as organic phase arrival mixer-settler E
1The time, a large amount of extraction agents will exist with the form of copper extraction agent title complex, and organic phase will contact with feed water solution (feed water solution of this moment only contains on a small quantity, if any, the lysed copper that has been extracted).
After extraction, discharge barren water solution (raffinate) or carry out recirculation and be used for further from ore leaching copper.Contain from extracting solution that the load organic phases of dissolved copper extraction agent title complex is admitted in the another set of mixer-settler, sulfuric acid counter the extract aqueous solution higher in this groove with concentration.The acid high anti-extraction aqueous solution separates copper extraction agent title complex, and makes copper pure, that concentration is big transfer to anti-extraction aqueous phase.As described in the extraction method above, mixture is transported to the another set of clarifying tank that is used for being separated.The process of separating copper extraction agent title complex is called as anti-extraction step, randomly, presses reflux type, repeats anti-the extraction by two or more mixer-settler steps and operates, thereby instead extract copper more completely from organic phase.
The anti-organic phase of extracting of regenerated is recycled to the extraction mixing tank from anti-extraction clarifying tank, begin once more to extract, and will instead extract water (being referred to as rich electrolytic etching of metal liquid) usually and be transported in the electrolytic deposition pond, in this pond, make useful copper metal deposition on pole plate by electro-deposition method.At the sedimentary hydrogen ion that produces simultaneously of copper, and make the anti-acidity of extracting water strengthen gradually.Behind the useful copper of electrolytic deposition from the anti-extraction aqueous solution, the solution that will be called waste electrolyte turns back in the anti-extraction mixing tank counter once more the extraction.
In order from organic phase, to extract copper efficiently, require a large amount of copper of extraction agent load as much as possible during milking, and during anti-the extraction, contain a small amount of as far as possible copper in the anti-extracting solution.Difference between these two content is referred to as " clean copper shifts ".But, because the reaction of extracting and instead extracting is balanced reaction, can be restricted so carry out the degree of this reaction, shift thereby reduce clean copper.To the influential important factor of this balance is the acidity of water, the coordination intensity of the concentration of copper and extraction agent in water and the organic phase.
Process in anti-the extraction for example improves the degree of reaction by high acidity and low copper concentration.But, the concentration limit of acid should be less than about 200 grams per liter sulfuric acid, because excessive acid can be corroded the anode in the electrolytic deposition battery excessively.Equally with the copper concentration limit more than about 25-30 grams per liter, because when being lower than this content, can reduce the current efficiency of electrolytic deposition.Therefore, the organic phase of any given composition all has the anti-minimum concentration that reaches that extracts of waste electrolyte of available electrolytic deposition.For the more weak extraction agent of coordination strength ratio, described minimum is almost all extracted by counter.But for strong extraction agent hydroxyaryl ethylidenehydroxylamine for example, minimum anti-extraction quantitative change is big, and the result is that clean copper shifts and diminishes, and only can extract the operation of organic phase with lower efficient.Even so-called poor efficiency extraction agent in other words has high coordination intensity, from the anti-process recycling that extracts extraction, it also can only extract a spot of copper at every turn.On the other hand, if can instead more completely extract strong extraction agent, even so than also extracting copper effectively in the presence of the high acid concentration.
A kind of method that is used for improving the strong extraction agent ability of anti-extraction is to add the balance improving agent in organic phase, nonyl phenol for example, and different tridecyl alcohol and 2,2,4-trimethylammonium-1, the 3-pentanediol diisobutyrate is as properties-correcting agent.People be sure of that leaching process is to carry out with strong combining of extraction agent by hydrogen, the effect of equilibrium modifier is the anti-extraction of copper is more become fully or more to extract under the demulcent condition, but, the shortcoming of these properties-correcting agent is to have reduced the extraction intensity of extraction agent, thereby has also reduced the efficient of extracting.What particularly need is instead more completely to extract extraction agent, does not weaken extraction intensity again.
When extracting (be basically anti-extract reversible reaction), high acidity in the leaching aqueous solution and low copper concentration limit the degree of reaction.Have extra high initial copper concentration for example 15-30 grams per liter copper or higher acid leaching solution be difficult to handle with solvent extraction itself be restricted because the gathering of acid makes abstraction reaction tend to become.Because extraction agent is to play a role on hydrogen exchange basis, so each copper atom that is extracted in the organic phase makes hydrionic two atom transfer to aqueous phase, makes that the acidity of solution is higher.If this exchange is to be undertaken by extracting enough a large amount of copper, so quite a large amount of acid gathers extraction agent no longer can make more acid transfer to the degree of aqueous phase, so the extraction of copper is ended.Owing to recently the technology that is used for the leaching cupric sulfide is improved, concentrate the leaching solution that produces and have high copper concentration, although so be attended by the gathering of acid when extracting, people press for by solvent extraction and come copper in these solution of purifying.
A kind ofly overcome that excess acid accumulative method is to use neutralizing agent when extracting, for example sodium hydroxide is controlled the pH of water.But this method can cause the gathering of aqueous phase salt when further circulating leaching, finally will discharge the content of a large amount of leaching vats with control salt.Another kind method is to use in the lime behind each extraction step and leaching vat, is settled out calcium sulfate (gypsum).But gypsum can make precipitation process slack-off fully, when solution being turned back in the next extraction step, any lasting precipitation all can be brought problem of phase separation owing to producing " throw out " (a kind of emulsive organic phase, water and solid stabilized mixture).In addition, requiring the acid with producing in extracting to be recycled to the system that is used for dissolving more copper in the leaching vat, neutralization needs double cost--with in the alkali and the acid that produces in extracting with must add again to carry out the used acid of leaching.
For many years, people have adopted direct strike to come deposited copper, i.e. direct plating coating copper from leaching vat, and need not to purify by solvent extraction.Yet foreign matter content is too high usually in use for the copper that reclaims by direct electrolytic deposition, must purify.The verified method by solvent extraction purifying copper from leaching solution is a kind of successful method, and this method can provide the spissated copper solutions that is suitable for electrolytic deposition high pure metal copper.
Conventional electrolytic deposition battery is made of the rectangular slot of elongation usually, is inserted with flat copper negative electrode parallel with the vertically disposed upper hanging type that alternately occurs of the major axis of groove and flat alloy lead anode in the groove.Copper bearing leaching solution enters in the groove at an end of groove, with the plane of anode that be arranged in parallel and negative electrode surrounding electric poles and below them, flowing in vertical state, and flow out at the other end of groove.Because flowing through most of liquid of the leaching solution of battery flows vertical with the plane of electrode, and the electrolytic solution between counter electrode does not apply auxiliary mixing, the interelectrode solution of result is immobilized comparatively speaking, only in convection current with emit at anode under the internal action of oxygen bubbles and just cause stirring.
Apply volts DS between negative electrode and anode, copper is deposited on the negative electrode, water is electrolyzed to produce oxygen and proton on anode.Adopt conventional electrolytic deposition battery, be subjected to arriving the restriction of the cupric ion speed of cathode surface by the galvanic flow velocity of battery effectively by solution.Be called as this speed that limits current density and be for example copper concentration, the function of battery configuration and aqueous solution stirring extent factors.The result who attempts to operate under the situation that surpasses the restriction current density is the efficient that has reduced electric current, causes porous or NA copper deposition, and has increased the foreign matter content in the deposited copper.Although can adjust actual operational parameters for example current density and copper concentration, conventional direct electrolytic deposition battery is normally at 20-35 ampere/foot
2Operate under the current density of cathode surface, the concentration of copper is greater than about 30 grams per liters in the waste electrolyte of generation.
People have proposed many improving one's methods as increasing current density or reducing the mode of concentration of the copper of electrolytic deposition to the electrolytic deposition battery.In general, these improvement comprise that householder method or redesign battery are to cause interelectrode stirring or electrolyte flow.People such as T.Balberyski (chemical abstracts 78:118,395,1973) disclose a kind of electrolytic solution distribution system, adopted an inlet tube that is provided with along the medullary ray of battery, inlet tube has and 1/4 inch aperture of interelectrode spatial alignment and the outlet pipe that be arranged in parallel with inlet tube.Electrolytic solution carries out recirculation by the pump of outside between pipe, it is reported that in current density be 35-40 ampere/foot
2, recirculation rate is 0.1-0.2 gallon per minute/foot
2Deposition is good during cathode surface.U.S. Pat 3876516 discloses a kind of copper electrodeposition system, wherein makes circulation of elecrolyte by external pump, overflows evenly up by interelectrode divider, and at the sidewall of battery; By keeping the SO in the electrolytic solution
2Concentration reduce voltage in the battery.It is reported that this battery is is 30 amperes/foot in current density
2, copper concentration is reduced to be moved under the situation of 1 grams per liter.
Other improvement comprises the configuration that changes conventional electrolytic deposition battery.CHEMELEC
TM(Inst.Chem.Eng.Symp.Ser. (1975), 42 (hydrometallurgies) 29.1-29.7) are a kind of battery that can for example operate under 0.1 grams per liter at extremely low metal concentration to battery.It includes the net form grid, in interelectrode space granulated glass sphere is arranged, and makes circulation of elecrolyte in the bottom of battery and makes granulated glass sphere fluidizing divider.It is believed that the fluidizing granulated glass sphere impacts cathode surface, and reduce the thickness of the border surface layer that has drained metal, improve metal ion thus from the speed of electrolytic solution to the cathode surface migration.Though this battery be under the extremely low condition of metal concentration, operate and be used to dispose waste liquid, it is not suitable for large-scale metal deposition.Current density only is 5-10 ampere/foot usually
2
U.S. Pat 4776941 discloses a kind of electrolytic deposition battery, adopts the hollow flat negative electrode that has aperture from the teeth outwards, and electrolytic solution is passed through wherein under stressed situation.Electrolytic solution flows to the space between anode and the negative electrode, and the generation mixed flow is also operated under the situation that improves current efficiency, and the density of electric current is up to 1500 amperes per meter
2(140 amperes/foot
2).But how the document is not open removes copper from this class negative electrode on a large scale.
WO92/14865 discloses a kind of battery, and this battery is furnished with the housing of elongation, and being determined on a case-by-case basis is drum, has an inner conductive surface of playing cathodic process, is inserted into the intravital anode of shell and the shell end of liquid-inlet and outlet is housed.Described import and the axis normal that exports best and housing and tangent with surface of shell are so that apply a spiral motion effect to the electrolytic solution by battery.Spiral helicine liquid form and high flow rate bonded result produce good stirring at cathode surface, thereby allow current density to reach 2000 amperes per meter
2(186 amperes/foot
2).When copper concentration was the 1-4 grams per liter, current efficiency was more than 95%, and when copper concentration was the 0.2-0.3 grams per liter, current efficiency was 80%.Housing can be made by copper pipe, wherein when sedimentary copper gathers the thickness of requirement, whole housing is removed as copper products.Housing can also be made by the thin slice of other conducting metal, wherein after copper is assembled, takes off thin slice from copper, removes the copper as product, thin slice is made the housing of battery again.
WO94/02663 discloses a kind of method that reclaims metal from ore, comprises leaching, and the battery of solvent extraction and employing WO92/14865 carries out electrolytic deposition.
Usually, wherein the electrolyte flow direction electrolytic deposition system parallel with electrode surface can work under the situation of the copper concentration that is lower than standard electrolytic sedimentary system (oxygen that this system produces when depending on the positive effect of convection current and the electrolytic solution between stirring electrode) significantly.Usually need higher cost but produce direct mobile system between electrode, this comprises investment cost and process cost.This just requires to utilize the lower waste electrolyte of copper concentration in solvent-extraction process, and the cost of the large-scale electrolytic deposition system that produces this class waste electrolyte is increased.
U.S. Pat 3857919 discloses the method for separating useful rare earth metal, comprise feed water solution is alternately contacted with the first kind of organic solvent that is used for first kind of metal of selective extraction, contact with the second kind of organic solvent that is used for second kind of metal of selective extraction then.The initial application of this method comprises uses alkyl amine as extracting Pr, and first kind of organic solvent of Nd and Sm, two-2-ethylhexyl phosphoric acid be as the second kind of organic solvent that extracts Dy and Y, Gd is arranged through the aqueous phase that extracts is residual.
U.S. Pat 4275234 discloses a kind of method that adopts immiscible secondary amine extraction agent of water or the solvent extraction acid from the aqueous solution of tertiary amine extraction agent.With with the counter organic phase of extracting load acid of alkaline solution different be that this method is by in that only water is counter under the high at least 20 ℃ service temperature of temperature extracts than extracting.The example of this method is to extract phosphoric acid and many water-soluble organic acids.
U.S. Pat 4291007 discloses a kind of method that adopts mixture solvent extraction mineral acid from the aqueous solution of amine compound and organic acid.The result who uses mixture to extract is the regeneration that has promoted organic phase.
Fig. 1-the 4th, the present invention adopt the synoptic diagram of the embodiment of the two-step approach that copper electrodeposition combines with solvent extraction systems.
In solvent extraction systems, the hocket synoptic diagram of the embodiment that acid extraction and copper extracts of Fig. 5-the 6th, the present invention.
In the following description, except other clear and definite explanation, on behalf of the numeral of amounts of components or reaction conditions, all be interpreted as can making amendment with term " approximately " when describing wide region of the present invention.But the present invention's practice of carrying out in the precise figure scope is normally preferred.
The invention provides by solvent extraction and electrolytic deposition, especially under the situation that the strong extraction agent of employing is realized extracting, improve the method that reclaims copper effectiveness and efficient.More particularly, method of the present invention has improved the clean copper in the solvent extraction and has shifted, thereby extracts copper more completely from feed water solution.
In first embodiment of the present invention, electrolytic deposition carries out in two steps, the first step is vertical with cathode surface in the electrolyte flow direction, and need not to carry out under the situation of electrolytic solution between auxiliary stirring electrode, second step was to carry out under the electrolyte flow direction situation parallel with cathode surface.The first step of electrolytic deposition makes the copper concentration in the electrolytic solution be reduced to about 30 grams per liters, and second step of electrolytic deposition is reduced to below about 30 grams per liters the copper concentration in the waste electrolyte.Be determined on a case-by-case basis, second step of electrolytic deposition is reduced to below about 25 grams per liters the copper concentration in the waste electrolyte, and more being determined on a case-by-case basis is reduced to below about 20,15,10,5 or 1 grams per liter.
Low copper concentration in the waste electrolyte has improved from organic phase the anti-efficient of extracting copper, obtains the anti-extraction organic phase that copper concentration has wherein reduced.Anti-extraction organic phase more completely can be extracted copper again conversely more completely from feedstock solution, the result has improved clean copper by organic phase to shift.
The layout of electrolytic deposition and organic opposite extraction can be by the variety of way setting, as shown in Fig. 1-4.The simplest layout is shown in Fig. 1, in the figure, rich electrolytic etching of metal liquid 1 is transported to first step e W1 of electrolytic deposition from anti-extraction step, electrolytic solution is to flow with the vertical direction of cathode surface in this step, copper concentration is lowered to about 30 grams per liters, the electrolytic solution 2 that will partly reduce is transported in second step e 2 of electrolytic deposition then, and electrolytic solution flows with the direction parallel with cathode surface in this step, and copper concentration is lowered to below about 30 grams per liters.The waste electrolyte 3 that is produced is transported among the anti-extraction step S1, and here they contact with the organic phase 4 of load, produce the rich electrolytic etching of metal liquid 1 of anti-organic phase of extracting 5 and regenerated.
Layout and Fig. 1 of Fig. 2 are similar, and just anti-the extraction is to carry out in two or more steps in the mode of adverse current.In the figure, load organic phases 4 at first contacts with the anti-solution 7 that extracts in step S1, contacts with waste electrolyte 3 in anti-extraction step S2 then, produces the anti-organic phase 5 of extracting.Waste electrolyte 3 has replenished the anti-extraction solution 7 of copper earlier by the S2 generating portion, and then produces the rich electrolytic etching of metal liquid 1 of regenerated by S1.Subsequently, identical with Fig. 1, rich electrolytic etching of metal liquid is by electrolytic deposition EW1 and two steps of EW2.The layout of this counter-current flow need spend the expense that constitutes the second anti-extraction step, but it can make the anti-extraction of organic phase more complete, and meanwhile, the copper concentration that the rich electrolytic etching of metal liquid that it produced contains is higher.
In addition, described system also can be by the transverse flow configuration layout of Fig. 3.The organic phase 15 of load is extracted by counter in step S1, produces the anti-organic phase 16 and the first rich electrolytic etching of metal liquid 11 that extracts of part.In electrolyte flow direction and the vertical electrolytic deposition step e of cathode surface W1, from liquid stream 11, reclaim copper, and produce the first kind of waste electrolyte 12 that is used for turning back to anti-extraction step S1.Further anti-extraction organic phase 16 in anti-extraction step S2, thus the anti-organic phase 17 and the second rich electrolytic etching of metal liquid 13 of extracting produced.In the electrolyte flow direction electrolytic deposition step e W2 parallel, from liquid stream 13, reclaim copper, and produce the second kind of waste electrolyte 14 that is used for turning back to anti-extraction step S2 with cathode surface.The advantage of this system is that first kind of copper concentration in the electrolytic solution is high more, the just easy more copper that instead extracts from load organic phases.Correspondingly, behind the first anti-extraction step, be retained in copper in the organic phase and be difficult to more that counter to extract the copper concentration of then carrying out the electrolytic deposition step in the second anti-extraction step just low more.The result that copper concentration is lower can more effectively instead extract copper from this class organic phase.
In another embodiment shown in Figure 4, this system is the configuration layout by blended transverse flow and counter-current flow.Similar with Fig. 3, the anti-load organic phases 25 of extracting in step S1 produces anti-organic phase 26 and the first kind of rich electrolytic etching of metal liquid 20 of extracting of part.In electrolyte flow direction and the vertical electrolytic deposition step e of cathode surface W1, from liquid stream 20, reclaim copper, and produce the first kind of waste electrolyte 21 that is used for turning back to anti-extraction step S1.The part liquid stream 22 of liquid stream 21 is transferred among the electrolyte flow direction second electrolytic deposition step e W2 parallel with cathode surface.Copper concentration in second kind of waste electrolyte 23 is lower than about 30 grams per liters, thereby makes when this liquid stream conduct is instead extracted solution more effective.In anti-extraction step S2, second kind of waste electrolyte 23 partly contacted with anti-extraction organic phase 26, produce anti-organic phase 27 and the rich copper bearing electrolyte stream 24 extracted.Liquid stream 24 and first kind of waste electrolyte 21 are merged, and be passed among the anti-extraction step S1, contact with the organic phase 25 of load again.Be transferred to the ratio of the waste electrolyte 21 in the liquid stream 22 by change, thereby have an opportunity to determine the ability of the second more expensive electrolytic deposition step, so that whole system reaches optimum.
The optimal way of finishing the first step electrolytic deposition is to use the battery that is well-known design form, this battery is to have hung the planar cathode and the anode that alternately occur in long rectangle electrolytic bath, apply galvanic current between negative electrode and anode, electrolytic solution is to flow with the vertical direction in the plane of electrode.The speed of the electrolytic solution by this type cell is lower, is in the oxygen that the most of electrolytic solution in the space is emitted by convection current and anode between two electrodes and stirs passively.Can be recycled to the input terminus of battery at the effusive electrolytic solution of battery one end, thereby increase whole electrolyte flow speed in the battery.But flow pattern is constant substantially.The pumping cost of such electrolytic deposition battery when operation is lower, and labor cost has benefited from large-scale cathode treatment.
Can assist the advantage of the electrolytic deposition battery that the stirs electrolytic solution battery parallel with cathode plane with making the electrolyte flow direction between electrode is that the easier cupric ion that makes is transferred to from electrolytic solution on the cathode surface, is reduced on cathode surface and should the surface as the metallic copper plating.Thereby can under higher current density, operate, perhaps produce the copper of low concentration, perhaps it be arranged between the two by electrolytic deposition.Although require to increase current density, because this method can obtain bigger throughput under adopting than the situation of skinny device,, lower copper concentration can be provided when operating according to the present invention basically.Lower copper concentration makes that the anti-extraction of load organic phases is more complete, and the result makes that the extraction of copper is more complete, and obtains bigger clean copper transfer by solvent extraction systems.Can stir electrolytic solution or make the pumping cost of the electrolyte flow direction electrolytic deposition battery parallel with negative electrode higher, labor force's expense of handling and reclaiming cathode is higher.Another feature of the present invention adopts lower-cost electrolyte flow direction and the vertical conventional electrolysis sedimentation of electrode exactly, to remove the copper that is easy to reclaim most, then adopt cost higher between electrode, can stir or make the electrolyte flow direction strike parallel with electrode more be difficult to the copper that reclaims so that only remove.These two steps are combined and can make the copper concentration in the waste electrolyte reach lower level under the minimum situation of cost.
A kind of preferred wherein electrolyte flow direction electrolytic deposition device parallel with negative electrode is the battery shown in Figure 3 of patent application WO92-14865, and Fig. 3 that the document and specification sheets thereof are described is incorporated herein by reference.In this battery, negative electrode has thin wall cylindrical tubes, anode has the pole that places on the tubular axis, with pipe cap at arbitrary end of pipe vertical setting with tubular axis and the input and output device tangent with tube-surface is housed, so that the electrolytic solution of this pipe of flowing through is applied spiral motion.Apply galvanic current between anode and negative electrode, the situation of helicoidal flow makes to operate in to increase under current density and the low copper concentration carries out.Flow rate will depend on the size of accurate geometrical shape and battery, but preferably make electrolytic solution longitudinally along battery the axle with about 10 meters/minute velocity flow mistake of about 0.5-.More be determined on a case-by-case basis, vertical flow velocity of electrolytic solution be about 6-8.5 rice/minute.For diameter is 10 centimetres battery, the flow velocity corresponding with volumetric flow rate be determined on a case-by-case basis into about 4-80 liter/minute, the flow velocity that more is determined on a case-by-case basis be about 50-70 liter/minute.Because electrolytic solution is by spiral motion form mobile in battery, so with respect to cathode surface, the actual flow velocity of electrolytic solution is bigger than the vertical flow velocity along battery shaft in fact.For reaching desired flow velocity, can make electrolytic solution carry out recirculation by battery.
The benefit that produces the low waste electrolyte of copper concentration obtains the most effective performance when carrying out solvent extraction with the organic phase that contains strong extraction agent.Strong extraction agent is a kind of and the tight coordinate extraction agent of copper, and therefore, they can extract copper under low pH value, but anti-extraction is also more difficult.Normally use the pH of extraction agent
1/2The intensity of extraction agent is described, pH
1/2Be commonly defined as the pH value when 50% bronze medal is extracted.With regard to purpose of the present invention, because definite pH
1/2Value is by employed conditional decision, so with pH
1/2Value defined is the pH value the when copper solutions of 0.2mol extraction agent solution and 0.1mol cupric perchlorate form reaches balance in the aliphatic hydrocarbon solution, and this extraction agent solution load the copper of 50% theoretical value.Adopt this define method, the pH of strong copper extraction agent
1/2Value is less than 1.0.
The pH of preferred extraction agent
1/2Value is more preferably less than about 0.5 less than about 1.0.The preferred extraction agent of Shi Yonging comprises that those contain the compound of the hydroxyaryl oxime of one or more hydroxyaryl ketoximes or ethylidenehydroxylamine type in the present invention.Preferred hydroxyaryl ketoxime extraction agent is the compound shown in following formula I and the II:
R and R ' can be identical or different respectively in the formula, and expression has the radical of saturated aliphatic group of 1-25 carbon atom, have 3-25 carbon atom the ethylenically unsaturated aliphatic group or-OR ", wherein R " is defined saturated or ethylenically unsaturated aliphatic group; N represents 0 and 1; And a and b represent 0,1,2,3 or 4 separately, and just they can not be 0 and R simultaneously
aAnd R
b' on the total number of carbon atoms be 3-25,
R and a define suc as formula I in the formula, and R represents the alkylene unsaturated aliphatic group that has the radical of saturated aliphatic group of 1-25 carbon atom or have 3-25 carbon atom, just at R
aWith the total number of carbon atoms on the R be 3-25.
Preferred formula I compound is that wherein a is 1, and b is 0, and R represents to have the straight or branched alkyl of 7-12 carbon atom and R and is connected locational those compounds with the hydroxyl contraposition.In these compounds, more being determined on a case-by-case basis is that wherein R is those materials of isomer mixture.Preferred formula II compound be wherein R represent methyl and R and a by formula I as specified those compounds of preferred compound.
Preferred formula I compound (wherein n represents 0 (being the dihydroxy benaophenonel oxime compound)) comprises having those compounds of going up the single alkyl substituent (having 7-12 carbon atom) of hydroxyl contraposition with ring, and wherein alkyl substituent is the mixture of isomers.The example of this compounds is 2-hydroxyl-5-nonyl diphenylketoxime and 2-hydroxyl-5-dodecyl diphenylketoxime, and they are that mixture as alkyl isomers form obtains when using commercially available nonyl phenol and 4-dodecylphenol respectively in synthetic.
Phenylalkyl ketoxime shown in the preferred formula II be with ring on hydroxyl have those compounds on to bit position as a single substituent 7-12 carbon atom alkyl isomer mixt.Preferred compound comprises that wherein R alkyl is the compound of methyl.Preferred phenyl alkyl ketone oxime compound is by using the 2-hydroxyl-5-nonyl benzene ylmethyl ketoxime of commercially available nonyl phenol preparation.
Operable in the present invention hydroxyaryl ethylidenehydroxylamine extraction agent is those compounds that formula III is represented
C represents numerical value 1,2 in the formula, 3 or 4, and the ethylenically unsaturated aliphatic group that R represents to have the radical of saturated aliphatic group of about 25 carbon atoms of about 1-or has about 25 carbon atoms of 3-, and at R
cLast carbon atom add up to 3-about 25.Preferred compound is that wherein a represents 1, and it is locational those compounds that are connected with the hydroxyl contraposition that R represents to have the straight or branched alkyl of about 7-12 carbon atom and R wherein.In these compounds, more being determined on a case-by-case basis is that wherein R represents those compounds of isomer mixt.Useful especially compound is 2-hydroxyl-5-heptyl benzene formoxime, 2-hydroxyl-5-octyl group benzaldoxime, 2-hydroxyl-5-nonyl benzene formoxime and 2-hydroxyl-5-dodecyl benzaldoxime.
According to the present invention, extraction agent can contain formula I, the mixture of the oxime of II or III.Preferred mixture is 2-hydroxyl-5-nonyl phenyl methyl ketone oxime and 2-hydroxyl-5-nonyl benzene formoxime or and the mixture of 2-hydroxyl-5-dodecyl benzaldoxime.
Usually extraction agent is dissolved in water-insoluble, in water unmixability aliphatic solvent or the aromatic solvent.Suitable solvent comprises kerosene, benzene, toluene and dimethylbenzene etc.Preferred solvent is aliphatics and aromatic hydrocarbons, and they have flash-point is more than 130 °F and 130 °F, be determined on a case-by-case basis to be at least 150 °F, and the solvability in water is lower than 0.1% (weight).Typical commercially available solvent is that (the Standard 0il by California sells Chevron ion-exchange solvent, flash-point is 195 °F), Escaid 100 and 110 (is sold by European Exxon, flash-point is 180 °F), Conoco 170 Exempt solvents (are sold by Conoco, flash-point is 170 °F), Exxon Aromatic 150 (a kind of aromatic series kerosene of selling by U.S. Exxon, flash-point is 150 °F), Phillips SX 1 and 7 (is sold by the Philips oil company, flash-point is 160 °F) and various other kerosene and the petroleum fractions of selling by other oil company.
Except extraction agent, organic phase can comprise one or more equilibrium modifier, and this improving agent can improve effective pH of extraction agent
1/2Value.The effect of equilibrium modifier is the extraction intensity that weakens extraction agent, makes it be easier to anti-the extraction.Be sure of equilibrium modifier normally by bringing into play their effect with extraction agent bonded hydrogen according to people, the balance that makes abstraction reaction moves towards the direction of the extraction agent that does not cooperate.The example of equilibrium modifier comprises alcohols for example tridecyl alcohol or 2-Ethylhexyl Alcohol, and phenols is nonyl phenol for example, and the ester class is tributyl phosphate or 2 for example, 2,4-trimethylammonium-1,3-pentanediol two-isobutyrate, ethers be benzyl 2-butoxy ether for example, ketone is isobutyl-heptyl ketone for example, nitrile is undecyl cyanogen for example, and amino formate is N-octyl group isotridecyl carbamate for example, and amides is N for example, N '-two-2-ethylhexyl urea and sulfoxide class be two-2-ethylhexyl sulfoxide for example.
Be determined on a case-by-case basis, organic phase does not contain equilibrium modifier, and perhaps organic phase contains the least possible equilibrium modifier.Under this feelings, the objective of the invention is to improve anti-extractability rather than make anti-extraction more complete by the ability that weakens extraction agent extraction copper by the copper concentration that reduces in the anti-extraction aqueous solution.But,,, shift as long as adopt the present invention just can improve clean copper no matter whether they contain the balance improving agent for specified organic phase.
Another advantage of the present invention is instead to extract the acid that can use lower concentration in the solution, and can not weaken the completeness of organic opposite extraction.Therefore, can make the copper recovery system reach best, the anti-extraction of the organic phase that is enhanced with balance and reduce the anti-advantage of extracting acid concentration.
In second embodiment of the present invention, an individual system is provided, this system can improve from the higher feed water solution of copper concentration and reclaims copper.This class solution can form by the whole bag of tricks, for example by the extra-fine grinding copper sulfide mineral, then presses oxidation to form the copper solutions of 25-30 grams per liter a little.In the ion exchange process that copper solvent extracts, each copper atom that is extracted in the organic phase will correspondingly make two hydrogen ions transfer to aqueous phase.So if the copper concentration height in the feedstock solution, the acidity of water will become big gradually when carrying out the copper extraction so.When if acidity reaches sufficiently high degree, abstraction reaction will reach balance or reaction is ended.The present invention is by increasing the recovery system that some steps have been improved whole copper in the method again.In the method for solvent extraction copper from feed water solution, described feed water solution is contacted with first kind of organic extraction agent solution, produce rich copper bearing first kind of load organic solution and discharge copper and be rich in aqueous acid, the anti-solution that extracts of first kind of load organic solution and strong acid is contacted, produce first kind of anti-organic solution and anti-solution that extracts of rich copper bearing rich metal strong acid of extracting of discharging copper, improvements comprise has increased step: (1) makes described discharge copper and is rich in aqueous acid and contact with second kind of organic solution of the extraction agent that can extract mineral acid, (2) be separated, generation is rich in second kind of load organic solution of acid and is discharged aqueous acid, (3) the described aqueous solution of discharging acid is contacted with the second section of first kind of organic extraction agent solution, (4) be separated, produce rich copper bearing first kind of load organic solution and further discharge copper and be rich in aqueous acid once more.
In separating step, remove the accumulative acidic aqueous solution that hinders the copper extraction by this method, make and in follow-up contact procedure, further extract copper.Illustrated among Fig. 5 feed water solution 30 to be contacted method of the present invention with first kind of organic extraction agent solution 34, produced a kind of part and discharged copper and be rich in aqueous acid 31 and rich copper bearing first kind of load organic solution 35.The anti-load organic solution 35 of extracting produces the anti-extraction organic solution 34 that is used for turning back to extraction step E1 in anti-extraction step S1.Aqueous stream 31 is contacted with the second kind of organic solution 36 that contains the extraction agent that can extract acid, produce rich acidiferous second kind of load organic solution 37 and discharge aqueous acid 32.Anti-acid of extracting in the load organic solution 37 produces the anti-extraction organic solution 36 that is used for turning back to extraction step E2 in anti-extraction step S2.The aqueous solution 32 is contacted with the second section 38 of first kind of organic extraction agent solution, produce the moisture raffinate 33 of rich copper bearing load organic solution 39 and discharge copper.In the anti-load organic solution 39 of extracting of anti-extraction step S3 kind, produce the anti-extraction organic solution 38 that is used for turning back to extraction step E3.Should know that extraction or anti-extraction step can carry out one or many in the physics osculating element.Be determined on a case-by-case basis, when adopting repeatedly osculating element, solution passes through counter current contact each other.Randomly, anti-extraction step S1 and S3 are merged, this is because they play identical chemical action.
Can not extract cmpletely under the situation of copper by method shown in Figure 5, carry out for the third time before copper extracts contact, can increase contacting between water and the acid extraction organic solution.As shown in Figure 6, contact with the second section 42 of second kind of organic solution, produce rich acidiferous load organic solution 43 has been expanded Fig. 5 with discharging aqueous acid 40 method by in extraction step E4, making moisture raffinate 33.Anti-acid of extracting in the load organic solution 43 produces the anti-extraction organic solution 42 that is used for turning back to extraction step E4 in anti-extraction step S4.The aqueous solution 40 is contacted with the second section 44 of first kind of organic extraction agent solution, produce the moisture raffinate 41 of rich copper bearing load organic solution 45 and discharge copper.The anti-load organic solution 45 of extracting produces the anti-extraction organic solution 44 that is used for turning back to extraction step E5 in anti-extraction step S5.As shown in Figure 5, can make extraction or anti-extraction step carry out one or many in the physics osculating element, being determined on a case-by-case basis is when adopting repeatedly osculating element, makes organic solution and aqueous solution counter-current flow.Be determined on a case-by-case basis, contact is to carry out in the continuous mixer-settler under the condition of organic solution and aqueous solution counter-current flow.Randomly, can make anti-extraction step S1 in the large-scale anti-extraction step of copper, S3 and S5 merge, and anti-extraction step S2 and S4 are merged.
As described in first embodiment of the present invention, the first kind of organic extraction agent solution that is used to extract copper is one or more formulas I preferably, the hydroxyaryl oxime solution of II or III
R in the formula, R ', R ", R , a, b, c and n as above define.Preferred compound is that wherein a and c represent 1, and b and n represent 0, and R represents methyl, and R represents to have the straight or branched alkyl of about 7-12 carbon atom and R and is connected locational those compounds with the hydroxyl contraposition.In these compounds, more being determined on a case-by-case basis is that wherein R represents those compounds of isomer mixt.Particularly preferred oxime is those compounds of formula III representative, comprises 2-hydroxyl-5-heptyl benzene formoxime, 2-hydroxyl-5-octyl group benzaldoxime, one or more in 2-hydroxyl-5-nonyl benzene formoxime and 2-hydroxyl-5-dodecyl benzaldoxime.
The second kind of organic extraction agent solution that is used for extracting acid is a kind ofly to be at least 1 with pH value, preferably be at least about 2 water when contacting its alkalescence be enough to make its in organic phase by the organic solution of protonated compound.Preferred acid extractant is oil-soluble, and water-insoluble amine both can be primary amine, and secondary amine also can be tertiary amine.Particularly preferred acid extractant is three-alkyl tertiary amine, and wherein the total number of carbon atoms on the alkyl is at least 22, preferably is at least 24, and each alkyl has at least 4 carbon atoms.The example of preferred tertiary amine is three-iso-octyl amine, three-lauryl amine and three-(C
8-C
10Alkyl) amine, a kind of amine in back is a kind of like this compound, its moieties is produced by fatty alkyl source (wherein 8 carbon atoms and 10 carbon atom alkyls are preponderated).
Another kind of preferred acid extractant is the mixture of amine and strong organic acid, and these two kinds of materials all are oil-soluble and water-insoluble.Disclose this class mixture in the U.S. Pat 4291007, the content of the document is incorporated herein by reference.Preferred amine is previously described trialkyl tertiary amine.Preferred strong organic acid is a sulfonic acid, phosphoric acid ester, phosphonate ester and dialkyl phosphinic acid.
Can from second kind of load organic solution, instead extract sour process with a kind of the finishing in two kinds of methods.Reclaim useful acid if desired and be used for being recycled to the leaching step, load organic solution can be contacted with water so, make acid be distributed to aqueous phase.The anti-extraction contacts and can carry out at elevated temperatures, so that produce the acid of bigger concentration at aqueous phase; Preferred temperature range is 30-60 ℃.If need not recovered acid, load organic solution can be contacted with alkaline aqueous solution so.Basic solution can have sufficiently high basicity, so that they can consume acid whole in the organic solution when contacting with organic solution, perhaps when contact, in the mixing solutions of organic phase and water, add alkaline matter, so that pH remains in the preferred range.When the main component of leaching system was sulfuric acid, preferred alkaline matter was sodium hydroxide and ammonium hydroxide.When using other acid for example when hydrochloric acid or nitric acid, the same preferred calcium hydroxide that uses.
Usually adopt the waste electrolyte of electrolytic deposition system to realize the anti-copper that extracts from first kind of load organic solution, described electrolytic deposition system includes sulfuric acid and copper sulfate.For anti-extraction the farthest, improve the copper amount that can be extracted thus, preferably carry out electrolytic deposition, promptly adopt the first step (the electrolyte flow direction is vertical with cathode surface) of electrolytic deposition and second step (the electrolyte flow direction is parallel with cathode surface) of electrolytic deposition according to first embodiment of the present invention.Being determined on a case-by-case basis especially is second step that disclosed battery carries out the electrolyte flow direction electrolytic deposition parallel with cathode surface among the employing patent application WO92-14865.
Embodiment
By 100 milliliters of LIX 860 of dissolving in SK-1 kerosene (a kind of kerosin of the 5-nonyl salicyl aldooxime of buying from Henkel limited-liability company) and be diluted to LIX 860 solution of 500 milliliters of preparation 20 volume/volume %.By making this organic solution and 500 milliliters contain 39.5 gram CuSO
45H
2The aqueous solution contact of O makes described organic solution load copper; The organic solution of filtration load is also analyzed, and finds to contain 11.09 grams per liter copper.Preparation contains 225 grams per liter H
2SO
4Anti-extraction solution.By shaking by various organic phase/waters (O/A) than in separating funnel, making load organic solution contact 10 minutes, the organic phase of filtering separation and water with the anti-solution that extracts.Measure copper concentration with atomic absorption spectrometry.Multiply by 98/63.5 and deduct sulfuric acid concentrations in the 225 anti-extraction solution that calculate to produce with the copper concentration in the aqueous solution.The results are shown in the table 1.Copper concentration and acid concentration are to the influence of anti-extraction in table 1. aqueous solution
| Organic phase/water ratio | Copper content in the organic phase, grams per liter | The anti-per-cent that extracts | Aqueous phase copper concentration, grams per liter | The H of aqueous phase 2SO 4, grams per liter |
| ????10/1 | ????7.13 | ????36 | ????40.0 | ????163 |
| ????5/1 | ????5.69 | ????49 | ????28.0 | ????181 |
| ????2/1 | ????3.48 | ????69 | ????14.8 | ????202 |
| ????1/1 | ????2.20 | ????80 | ????8.66 | ????212 |
| ????0.5/1 | ????1.26 | ????89 | ????4.85 | ????218 |
Data clearly illustrate that the increase along with the acid concentration correspondence, and the concentration of aqueous phase copper is low more, from strong extraction agent for example the 5-nonyl salicyl aldooxime the anti-efficient of extracting copper just high more.Efficient and the clean copper of the anti-extraction organic solution that only contains 1.26 grams per liter copper when extracting copper shifts to be higher than far away and contains 7.13 or even contain the anti-extraction organic solution of 5.69 grams per liter copper.
Claims (36)
1. by solvent extraction, anti-extraction and electrolytic deposition reclaim improving one's methods of copper from feed water solution, improvements comprise and carry out the first electrolytic deposition step, the electrolyte flow direction is vertical with cathode surface and need not auxiliary mixed electrolytic solution between electrode in this step, with carry out the second electrolytic deposition step, the electrolyte flow direction is parallel with cathode surface in this step, thereby the copper concentration of the electrolytic solution after the second electrolytic deposition step is reduced to below about 30 grams per liters.
2. according to the process of claim 1 wherein that described anti-extraction is to carry out at least two anti-extraction steps of contact device.
3. according to the method for claim 2, wherein said contact device comprises mixer-settler.
4. according to the method for claim 2, the electrolytic solution of the wherein said first electrolytic deposition step with the airtight loop of the first anti-extraction step in carry out recirculation, the electrolytic solution of the described second electrolytic deposition step with the airtight loop of remaining anti-extraction step in carry out recirculation.
5. according to the method for claim 2, the electrolytic solution of the wherein said first electrolytic deposition step with first loop of the first anti-extraction step in carry out recirculation, and behind electrolytic deposition, from described first loop, shift part first electrolytic solution in second loop, second loop comprises that (1) carry out electrolytic deposition in the described second electrolytic deposition step, (2) in remaining anti-extraction step counter extract and (3) and described first loop in electrolytic solution reconsolidate.
6. use the organic solution that comprises one or more hydroxyaryl oxime extraction agents to carry out the solvent extraction of described copper according to the process of claim 1 wherein.
7. according to the method for claim 6, wherein carry out the solvent extraction of described copper with the organic solution of strong extraction agent.
8. according to the method for claim 7, wherein said strong extraction agent comprises the hydroxyaryl ethylidenehydroxylamine of formula III
C represents numerical value 1,2 in the formula, 3 or 4, and the olefinic unsaturated aliphatic group that R represents to have the saturated aliphatic groups of about 1-25 carbon atom or has 3-25 carbon atom, and at R
cOn the total number of carbon atoms be 3-about 25.
9. method according to Claim 8, wherein said hydroxyaryl ethylidenehydroxylamine is selected from 2-hydroxyl-5-heptyl benzene formoxime, 2-hydroxyl-5-octyl group benzaldoxime, 2-hydroxyl-5-nonyl benzene formoxime and 2-hydroxyl-5-dodecyl benzaldoxime.
10. according to the method for claim 7, wherein said organic solution also comprises the balance improving agent.
11. according to the method for claim 6, wherein said organic solution comprises the mixture of hydroxyaryl ketoxime and hydroxyaryl aldoxime.
12. according to the method for claim 11, wherein said hydroxyaryl ketoxime is 2-hydroxyl-5-alkyl phenyl methyl ketone ketoxime, described hydroxyaryl aldoxime is 2-hydroxyl-5-alkylbenzene formoxime.
13. method according to claim 1, wherein provide the electrolyte flow direction condition parallel in the described second electrolytic deposition step with cathode surface by one or more batteries, each battery comprises the cylindrical housings of elongation, this housing has the inner conductive surface that is used as negative electrode, extend to the anode that is positioned in the housing on the cylindrical housings axle, be used for electric clearing end that circuit and described conductive surface and described anode are coupled together, shell end and be positioned at the other end and the axis normal of housing and the input and output device tangent of housing with surface of shell.
14., wherein make the electrolytic solution that flows through battery for the helical movement according to the method for claim 13.
15. be used for improving one's methods from feed water solution solvent extraction copper, comprise described feed water solution is contacted with first kind of organic extraction agent solution, produce rich copper bearing first kind of load organic solution and discharge copper and be rich in aqueous acid, the anti-solution that extracts of first kind of load organic solution and strong acid is contacted, produce first kind of anti-organic solution and anti-solution that extracts of rich copper bearing rich metal strong acid of extracting of discharging copper, improvements comprise the increase step: (1) makes described discharge copper and is rich in aqueous acid and contact with second kind that can extract mineral acid organic extraction agent solution, (2) be separated, produce rich acidiferous second kind of load organic solution and discharge aqueous acid, (3) the described aqueous solution of discharging acid is contacted with the second section of first kind of organic extraction agent solution, (4) be separated, produce rich copper bearing first kind of load organic solution and further discharge copper and be rich in aqueous acid once more.
16. method according to claim 15, comprise the increase step: (5) make the further discharge copper and the rich once more acidiferous described aqueous solution contact with the second section of described second kind of organic solution of the extraction agent that can extract mineral acid, (6) be separated, produce another part of the rich acidiferous second load organic solution and discharge aqueous acid for the second time, (7) make and discharge aqueous acid the described second time and contact with the third part of first kind of organic extraction agent solution, (8) be separated, produce the third part of first kind of load organic solution and further discharge copper and be rich in aqueous acid once more.
17. according to the method for claim 15, wherein said first kind of organic extraction agent solution comprises the organic solution of the strong extraction agent that is used for copper.
18. according to the method for claim 17, the wherein said strong extraction agent that is used for copper comprises the hydroxyaryl ethylidenehydroxylamine of formula III
C represents numerical value 1,2 in the formula, 3 or 4, and the olefinic unsaturated aliphatic group that R represents to have the saturated aliphatic groups of about 1-25 carbon atom or has about 25 carbon atoms of 3-, and at R
cOn the total number of carbon atoms be 3-about 25.
19. according to the method for claim 18, wherein said hydroxyaryl ethylidenehydroxylamine is selected from 2-hydroxyl-5-heptyl benzene formoxime, 2-hydroxyl-5-octyl group benzaldoxime, 2-hydroxyl-5-nonyl benzene formoxime and 2-hydroxyl-5-dodecyl benzaldoxime.
20. according to the method for claim 17, wherein said organic solution also comprises equilibrium modifier.
21. according to the method for claim 17, wherein said organic solution comprises the mixture of hydroxyaryl ketoxime and hydroxyaryl aldoxime.
22. according to the method for claim 21, wherein said hydroxyaryl ketoxime is 2-hydroxyl-5-alkyl phenyl methyl ketone oxime, and described hydroxyaryl aldoxime is 2-hydroxyl-5-alkylbenzene formoxime.
23. according to the method for claim 15, wherein said second kind of organic extraction agent solution is included in can be by the organic solution of protonated alkaline extraction agent in organic phase when the pH value is at least about 1 water and contacts.
24. according to the method for claim 23, wherein said alkaline extraction agent comprises amine.
25. according to the method for claim 24, wherein said amine is trialkylamine, wherein the total number of carbon atoms on the alkyl is at least 22, and each alkyl has at least 4 carbon atoms.
26. according to the method for claim 25, wherein said trialkylamine is selected from three-iso-octyl amine, three-lauryl amine and three-(C
8-C
10Alkyl) amine.
27. according to the method for claim 23, wherein said alkaline extraction agent comprises the mixture of amine and strong organic acid.
28. according to the method for claim 27, wherein said amine is trialkylamine, wherein the total number of carbon atoms on the alkyl be at least 22 and each alkyl have at least 4 carbon atoms.
29. according to the method for claim 27, wherein said strong organic acid is selected from sulfonic acid, phosphoric acid ester, phosphonate ester and dialkyl phosphinic acid ester.
30. according to the method for claim 15, comprise that increase is anti-from described second kind of load organic solution to extract acid, produce the step of the anti-extraction organic solution that is used for being recycled to step (1).
31., wherein realize the described anti-step of extracting acid by described second kind of load organic solution is contacted with water according to the method for claim 30.
32. according to the method for claim 31, wherein said contact is to carry out under at least 30 ℃ temperature.
33., wherein realize the described anti-step of extracting acid by described second kind of load organic solution is contacted with alkaline aqueous solution according to the method for claim 30.
34. according to the method for claim 15, comprising increasing by electrolytic deposition from the anti-step of removing copper the solution of extracting of the copper bearing rich metal strong acid of described richness.
35. method according to claim 34, wherein said electrolytic deposition is included in and makes the electrolyte flow direction vertical with cathode surface and carry out the first step under the situation that need not auxiliary mixed electrolytic solution between electrode, carried out under the electrolyte flow direction situation parallel for second step making, make the copper concentration of the electrolytic solution behind the electrolytic deposition be reduced to below about 30 grams per liters thus with cathode surface.
36. method according to claim 35, wherein provide the electrolyte flow direction condition parallel in the described second electrolytic deposition step with cathode surface by one or more batteries, each battery comprises the cylindrical housings of elongation, this housing has the inner conductive surface that is used as negative electrode, extend to the anode that is positioned in the housing on the cylindrical housings axle, be used for electric clearing end that circuit and described conductive surface and described anode are coupled together, shell end, with the axis normal of the other end that is positioned at housing and housing and tangent, so that make the electrolytic solution input and output device for the helical movement that flows through battery with surface of shell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96194537A CN1187223A (en) | 1995-06-06 | 1996-05-30 | Method for recovering copper |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/466,166 | 1995-06-06 | ||
| CN96194537A CN1187223A (en) | 1995-06-06 | 1996-05-30 | Method for recovering copper |
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| Publication Number | Publication Date |
|---|---|
| CN1187223A true CN1187223A (en) | 1998-07-08 |
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|---|---|---|---|
| CN96194537A Pending CN1187223A (en) | 1995-06-06 | 1996-05-30 | Method for recovering copper |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234816A (en) * | 2011-07-27 | 2011-11-09 | 金川集团有限公司 | Method for extracting copper from copper electrolyte |
| CN106068336A (en) * | 2014-03-07 | 2016-11-02 | 巴斯夫欧洲公司 | For controlling the method and system of the foreign metal concentration during metallurgical process |
-
1996
- 1996-05-30 CN CN96194537A patent/CN1187223A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234816A (en) * | 2011-07-27 | 2011-11-09 | 金川集团有限公司 | Method for extracting copper from copper electrolyte |
| CN106068336A (en) * | 2014-03-07 | 2016-11-02 | 巴斯夫欧洲公司 | For controlling the method and system of the foreign metal concentration during metallurgical process |
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