CN1030944A - gold refining method and device thereof - Google Patents
gold refining method and device thereof Download PDFInfo
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- CN1030944A CN1030944A CN88104347A CN88104347A CN1030944A CN 1030944 A CN1030944 A CN 1030944A CN 88104347 A CN88104347 A CN 88104347A CN 88104347 A CN88104347 A CN 88104347A CN 1030944 A CN1030944 A CN 1030944A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/085—Removing impurities
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
Comprise in the gold refining method with iodine and/or iodide and dissolve not refining gold and form and contain au iodide solution, tell the insoluble substance in the solution, contain gold ion with the alkali reduction and go out the high purity gold with selective precipitation, wherein iodine is electrolysis iodide and getting.Other method and device comprise that also the solution circulated of will separate with precipitation of gold uses, and the alkali that wherein can both economical land productivity generates simultaneously with above-mentioned electrolysis.
Description
The present invention relates to the gold refining method, comprising with low-purity refining gold pass into solution and make the gold precipitation to make the high purity gold not with alkali.The invention still further relates to the device that carries out gold refining effectively, wherein do not add any reagent can with low-purity not behind the refining gold pass into solution with alkali precipitation and the high purity gold, and can be, and the gold refining method of using this device with used refining solution circulated.
Up to the present, known have following and other gold refining method: dissolve low-grade gold and make golden reduction method with reductive agent such as hydrazine selectivity with chloroazotic acid or hydrochloric acid-chlorine solution; The low-grade golden reduction method of electrolysis in the hydrochloric acid sour environment.
But last method needs discharging waste gas equipment and manpower; Then a method has the shortcoming that generates chlorine at anode again, owing to wherein make ionogen with hydrochloric acid, so its electrolytic efficiency is low.
In addition, back one method should keep very high gold concentration always, and in order not generate chlorine, electrolysis should not be higher than 3A/dm
2Low current density under carry out, this causes throughput low and need large number quipments.
Also known gold reclaims and to improve one's methods, and comprising with iodine and iodide gold compound being dissolved into the potassiumiodide gold, and making it precipitation and reclaims golden (US3957505) with reductive agent reduction gold compound.Because this method is not gold refining method but golden recovery method, so do not consider the impurity problem of removing with in the iodine equal solvent dissolving gained potassiumiodide gold especially, yes has had realized that the existence of impurity itself.
In the gold refining process, require in rectification systems, to use effectively reagent to improve operation efficiency.In comprising the prior art of above-mentioned United States Patent (USP), not consider at all or not consider basically to improve the operation efficiency problem, gained gold grade and purity thereof have caused the public's attention.
Inventor's further investigation has also been developed the apparatus and method of not having above-mentioned shortcoming, thereby has finished the present invention.
The objective of the invention is to propose from low-grade gold, to obtain the method for high purity gold, wherein only carry out simple operation and do not produce gas basically.
Another object of the present invention provides the apparatus and method that obtain the high purity gold from the low-purity gold continuously, wherein makes minimum quantity reagent effectively and also uses effectively, and this can not produce waste gas and not need reagent basically certainly.
First aspect present invention is the gold refining method, comprising: dissolve not refining gold and form and contain au iodide solution with iodine and/or iodide; Remove the insoluble substance in the solution; PH value of solution is reached be not less than 12 strong basicity and make the gold solution reduction optionally to be settled out gold; And after the reduction proof gold that is settled out is told from solution.
Second aspect present invention is the gold refining device, comprising: electrolyzer, in order to form the solution that contains au iodide with iodine and/or iodide reaction by refining is golden, wherein be divided into anolyte compartment and cathode compartment and will contain the electrolysis of iodide electrolytic solution and form alkali metal hydroxide, and form iodine in the anolyte compartment at cathode compartment with barrier film; Trash eliminator, in order to tell impurities in the solution that contains au iodide, this trash eliminator is connected with electrolyzer anode chamber; Reducer, in order to from au iodide, optionally to reduce and to be settled out gold, wherein will mix making solution become pH to be not less than 12 strong basicity by the solution that trash eliminator is removed impurity with above-mentioned electrolysis gained alkali metal hydroxide, this reducer links to each other with electrolysis catholyte chamber with trash eliminator; Refining gold separator in order to obtain the refining gold, is wherein told precipitation of gold from the solution after the reduction; And cycle facilities, recycle in order to sending into electrolyzer with the solution that the refining gold separates.
Third aspect present invention is the gold refining method, comprising: the electrolytic solution that electrolysis contains iodide in membranous electrolyzer forming alkali metal hydroxide and iodine respectively at cathode compartment and anolyte compartment, thereby in cathode compartment, obtain containing the solution of the au iodide that not refining gold and iodine and/or iodide reaction form; Tell the impurity in the solution; Make golden iodine compound reduction to be settled out gold, wherein the alkali metal hydroxide that electrolysis is produced adds solution so that solution reaches the strong basicity that is not less than pH12; From the solution after the reduction, tell precipitation of gold and obtain the refining gold; And will send into electrolyzer with the solution that the refining gold separates and recycle.
Can be in the last method or do not obtain iodine by electrolysis by electrolysis, and solution is capable of circulation, also can not circulate.But the feature of a method and apparatus is that electrolysis obtains iodine and with solution circulated behind the present invention.
The step of a method comprises that (I) formation contains the not solution of refining au iodide behind the present invention; (II) removes insoluble substance from solution; Gold kind in (III) reducing solution and be settled out gold wherein makes the pH value of solution of removing insoluble substance reach strong basicity; (IV) tells precipitation of gold from the solution after the reduction; And (V) will be delivered to above-mentioned steps (I) with the solution that gold separates and recycle.In last method, not necessarily must adopt step (V).Each step below is described in detail in detail.
(I) obtains iodide solution
Wherein, dissolve the relatively low not refining gold of purity to form au iodide solution with iodine and/or iodide.
The relatively low not refining gold of purity comprises the gold of 8 karat golds (purity 33%) to purity 99.99%, is lower than by the purity after the refining of the present invention and relatively low purity means said purity.
In the purity that further improves the solid-state gold of above-mentioned purity range that contained gold extract from waste liquid and further improving available not refining gold under the purity situation of common this metal of auri etc.The form of used gold can be any solid-state as plate, particle, flakes, powder, thin slice, piece etc. in the method for refining of the present invention.Although the also available above-mentioned gold that is dissolved in liquid, gold at least once should convert to any solid-state.
In one method of back, contain iodide such as alkaline metal iodide solution obtains iodine and/or iodide with diaphragm electrolysis.But, in last method, also can obtain by other method beyond the electrolysis.
In the gold refining method of the present invention, preferably use iodine and potassiumiodide simultaneously.
Details are as follows for the used membrane electrolysis of the present invention:
Diaphragm electrolysis combines following each factor and carries out.The advantage of using membrane electrolysis of the present invention is, because au iodide produces in the anolyte compartment and the while alkali metal hydroxide produces in the anolyte compartment, so alkali metal hydroxide can be used as alkali source in following golden precipitation process.
(ⅰ) electrolytic solution is formed:
Anolyte can be selected from following 3 kinds of compositions easily, that is:
(a) Me I(Me is potassium or sodium, and promptly Me I is sodium iodide or potassiumiodide);
(b) Me I+Me IO
3(potassiumiodide+Potassium Iodate or sodium iodide+sodium iodate, or potassiumiodide+sodium iodate, or sodium iodide+Potassium Iodate), and:
(c) Me I+Me IO
3+ conducting salt (as vitriol); Wherein the Me total concn is 1～5M/l.
Remove above-mentioned (a), (b) with (c) and outward, catholyte can be selected from:
(d) Me OH(potassium hydroxide or sodium hydroxide);
(e) conducting salt+Me OH;
(f) conducting salt;
(g) water only;
When during as catholyte, just need not carrying out off gas treatment again,, so do not produce hydrogen because reaction undertaken by following general formula (3) with the basic metal iodate.
Preferably when the reaction beginning, two kinds of electrolytic solution are all remained pH8～14 by adding 0～2N potassium hydroxide.
Conducting salt mainly is to increase the electric conductivity of electrolytic solution to reduce used expensive iodide amount in the reaction.
When promptly making anolyte with liquor kalii iodide with above-mentioned composition and carrying out electrolysis with potassium iodate solution as catholyte, react by following general formula and produce iodine cathode compartment and anolyte compartment.
(anolyte compartment)
(cathode compartment)
(ⅱ) electrolysis process:
(a) directly electrolysis:
Comprise in the direct electrolysis method and adopt not the refining gold to make electrode and electrode is dissolved in electrolytic solution by diaphragm electrolysis.Gold is by above-mentioned formula (2 ') dissolving in this method.
In this direct electrolysis method, adopt proper method (as with sheet anode arranged transversely and will the refining gold be placed on above) with sheet or porous shape not the refining gold anode support or electric current flows after the refining gold is not placed on the noble metal electrode of dimensional stabilizing, wherein with following barrier film with the anolyte compartment be with the cathode compartment of negative electrode such as stainless steel to separate.
(b) indirect electrolytic:
Electric current flows and carries out electrolysis in the indirect electrolytic method, wherein in the anolyte compartment, carry out electrolysis, also under such condition, carry out in case of necessity, promptly replace not the refining gold to make anode, and the refining gold does not add the anolyte compartment of electrolyzer with particle form with the stable noble metal electrode of Commonly Used Size.Gold is by above-mentioned formula (2) dissolving in this method.
In apparatus of the present invention and method, be used for electrolytic solution and do not circulate, thereby operation is intermittently carried out with the gold precipitation.Because direct method requires to change electrode, because carry out along with electrolytic, gold is dissolving constantly, so the preferred indirect method that does not require the exchange electrode that adopts.
As previously mentioned, in the presence of potassiumiodide, the iodine dissolving that gold is generated by the potassiumiodide electrolysis: in indirect method, the electrolyzer that forms the electrolyzer of iodine and dissolve gold can divide and is arranged, and so containing the anolyte that above-mentioned iodine forms the iodine that generates in the electrolyzer can send into golden dissolution cell so that gold wherein dissolves by suitable pipeline.
In direct and indirect electrolytic process, the dissolution process of gold not only carries out in the anolyte compartment, also carry out in the reactor electrolyzer outside simultaneously, thereby gold grain is housed and the raising dissolved efficiency that links to each other with electrolyzer anode chamber in the reactor between anolyte compartment and reactor so that anolyte can circulate.The dissolving of gold only limits in the reactor in the indirect electrolytic process in addition.
(ⅲ) electrolyzer:
The used electrolyzer of the present invention is not done special restriction.New electrobath be can adopt, wherein anolyte compartment and cathode compartment are divided into following barrier film.New electrobath can be divided into a plurality of anolyte compartments and a plurality of cathode compartment constituting bipolar cell, thereby electrolytic solution is circulated in a plurality of electrode vessels.Except aforementioned electrolyzer and, also can adopt the electrolyzer of Any shape and structure.
In this diaphragm electrolysis process, the formation of iodine and the dissolving of not refining gold can be carried out with iodine in single electrolyzer also can be carried out in the electrolyzer that separates separately.From economy and operation efficiency angle, these operations can preferentially be carried out in single electrolyzer.
(ⅳ) electrolytic condition:
Although it is little that gold dissolves the influence of the electrolytic condition of originally experiencing, electrolysis is preferably carried out under the following conditions.
Electrolysis temperature ... 20～80 ℃;
Current density ... 2～50A/dm
2;
The one side pH of anolyte compartment ... 8～13;
Cathode compartment one side pH ... be not less than 12.
(ⅴ) barrier film:
Can use any barrier film such as the asbestos film that have adopted so far, hydrocarbon film, ion-exchange membrane etc.But,, particularly have the exchange membrane containing fluorine of sulfonate radical and/or carbonate so preferred the employing has superior alkali-resisting ion-exchange membrane owing to will generate alkali metal hydroxide as described above in the cathode compartment.
Used au iodide generation method in the last method below is described.
(A) chelated iodine method:
Comprise in this method alkaline metal iodide (as potassiumiodide) and Iod R are formed iodide ion, and iodide ion and refining gold reaction not are dissolved in solution with refining gold not with the au iodide ion.Adopt potassiumiodide to represent as the available following general formula of the reaction in the alkaline metal iodide method.
According to art methods, this reaction adopts common unit to carry out in solution.Only need with potassiumiodide iodine and not mixing of refining gold and heating in the reaction process.
(B) south, road (Donnan) dialysis:
The solution that will contain iodine and iodate in this method is put into one of the container chamber that is divided into two Room with cationic exchange membrane, and another chamber is linked to each other so that its electrolytic solution circulates with saltcake electric tank cathode chamber.When containing the solution of iodine and iodate in inciting somebody to action not refining gold adding container, the refining gold does not dissolve with the au iodide ionic state.
(C) dry type reaction method:
Allow not refining gold and iodine in solid phase, react in this method and form au iodide, and au iodide is dissolved in solution.
The solid state reaction between refining gold and the iodine is not undertaken by following general formula.
(D) hydrochloro-auric acid method:
Will be not in this method the refining gold be dissolved in the chloroazotic acid forming hydrochloro-auric acid (or chloraurin acid) or gold trichloride, and it is changed into hydroiodo-auric acid (or iodine Asia auric acid) or golden potassiumiodide with alkaline metal iodide such as potassiumiodide reaction.These reactions are represented with following general formula.
(E) gold trichloride method:
Will be not in this method refining gold and chlorine in solid phase, react and gold trichloride and alkaline metal iodide such as potassiumiodide is reacted the golden potassiumiodide of formation after forming gold trichloride.Reacting available following general formula represents.
(II) removes insoluble substance from au iodide solution
Contain insoluble substance and ion thereof in the au iodide solution that forms in step (I), this mainly is because do not contain impurity such as iron in the refining gold, cobalt, nickel, tin, lead, silver, copper, calcium, the ion of magnesium etc. or compound.Wherein also may comprise not refining gold of non-dissolubility.
Insoluble substance can pass through to filter (common filter operation and centrifuge dehydration operation) and sedimentation, or removes simultaneously and with ultrafiltration process.Among the present invention, only this lock out operation by insoluble substance can obtain the high purity gold.But,, just must tell above-mentioned various ion for the purity of gained gold further is provided.
For this reason, can adopt following operation.
(a) adopt liquid composite with iodate states of matter precipitating ion:
This method has been utilized solubility change, for example is settled out insoluble basically iodide by changing ionic solubleness, wherein dilute with water solution so that solution metal ion and iodide ion react and form insoluble basically iodide.The ion that this method is easily told is silver, and lead etc. are told with Silver iodide and lead iodide respectively.
(b) by pH regulator and with oxyhydroxide or oxide precipitation ion.
The changes in solubility of metal hydroxides or metal oxide when this method has utilized pH to change, for example alkali metal hydroxide is added in the solution to keep its pH8～12, gold can not precipitate in this scope, and iron, cobalt, nickel, tin, plumbous plasma can oxyhydroxide or oxide precipitation come out, and then tell with filtration or settling process.
(c) with air in carbonic anhydride reaction form insoluble basically carbonate:
It is soluble that II A family element in the above-mentioned ion is that the carbonate of calcium and magnesium is gone up substantially, so be easy to separate, it can be told because stir air-blowing in solution.
(d) doping forms basically not dissolved salt
Additive can be vitriol, carbonate (or carbonic anhydride), and ammonium salt (or ammonia or ammoniacal liquor), EDTA etc., and can select suitable additive according to metal species to be separated.
(e) solution is cooled off and crystallization:
The solution cooling can be settled out a large amount of silver iodates, thereby silver ions is told from solution.
(III) the reduction gold that makes the solution of telling insoluble substance be strong basicity so that alkali in the solution decomposes also is settled out metallic gold
Telling insoluble substance and adding filtration adjuvant where necessary in above-mentioned steps (II) and after telling this metal ion species, the strong basicity that solution is be not less than pH12 goes out metallic gold with selective precipitation the ion that comprises au iodide ion etc. in solution.
Precipitin reaction can be represented with following general formula.
Solution temperature when step (II) finishes, pH and be respectively about 20～80 ℃, about 8～12 and about 5～100g/l in the gold concentration of metallic gold.
In order to make solution be alkalescence, available suitable pipeline is sent to the place that this step is carried out with the potassium hydroxide or the sodium hydroxide solution that generate in the electric tank cathode chamber by diaphragm electrolysis in the step (I) from electrolyzer, and no longer further handle, because this sees it is very favourable from the angle that improves operation efficiency and economy.
Be absolutely necessary although behind the present invention, use the alkali metal hydroxide of electrolysis generation in the method and apparatus, in last method, also can adopt other reagent such as commercially available alkali metal hydroxide, ammonia, ammoniacal liquor etc.
Add basic solution concentration be 0.1～6N on request, and previous solution and alkali lye volume ratio are preferably about 1: 0.15～1: 5.
Although this method gained precipitation of gold particle diameter is generally about 1～50 μ, can makes particle growth by the following method and obtain macrobead.
The first, will from contain the solution that adds the gold that alkali lye is settled out, take out supernatant liquid, add the solution (solution when the step II finishes) that contains the prereduction gold in the precipitation of gold particulate slurry to remaining containing, and add alkali lye again so that gold reduces again and particle is grown up.After handling like this, the particle of about 5～10 μ can be grown the particle that is not less than 25 μ.
The second, after reduction gained gold once filters, the gold grain that therefrom obtains is added in the above-mentioned solution that contains the prereduction gold, and add alkali lye again with reduction on gold grain and deposit gold, thereby particle diameter is increased.
The 3rd, in the solution that contains reduction and the gold that is settled out, add the solution that contains the prereduction gold and alkali lye so that deposited gold increases particle diameter on by the gold grain that is being settled out.In case of necessity, such processing can be carried out repeatedly so that gold grain reaches satisfactory size.
Precipitation of gold is told in (IV) reduction back from solution
Because when step (III) finishes, except precipitation of gold and, iodate ion, alkalimetal ion and iodine all dissolve in solution, thus precipitation of gold should be able to be told from solution, thereby obtain proof gold.Used filtration and sedimentation in step (II) and, also available organic solvent operation such as washes and tells precipitation of gold.Flushing means water and organic solvent carries out common extracting operation.When leaving standstill after organic solvents such as chloroform being added above-mentioned solution and shaking, gold enters organic phase, and other iodate ions, alkalimetal ion, iodine are still stayed aqueous phase, therefore just can reclaim gold from organic phase.
The gold grain appropriate amount of telling is preferably no more than its washing water of 3 times and washs, and satisfactory be 40～100 ℃ pure water, remove remaining composition and after drying, obtain the high purity gold with this.
The purity of refining gold of the present invention is also with the purity of refining gold is not relevant before the refining.8 karat golds (purity is not less than 33%) but refining to the purity that is not less than 95%, but purity is not less than 80% not refining gold refining to the purity that is not less than 95%, but purity is not less than 98% not refining gold refining to the purity that is not less than 99.99%, but and purity is not less than 99.99% not refining gold refining to the purity that is not less than 99.999%.
(V) will be told the solution of gold and deliver to step (I) and recycle:
Although behind the present invention in the method and apparatus this step be absolutely necessary, in last method, also can.
Contain excessive Potassium Iodate and potassiumiodide in the solution when step (IV) finishes, its circulation can be sent into the anolyte compartment and the cathode compartment of electrolyzer, need not further processing because can be used as the electrolytic solution of step (I).
The metal that also contains minute quantity when step (IV) finishes in the solution.Do not send into electrolyzer if further do not handle just circulation, metal will be deposited on the electrolytic tank electrode, therefore requires regularly to remove.And electrolyzer quits work and means stopping of whole refining operation, and this can lower efficiency.Therefore, the electrolyzer or the complex construction electrolyzer of simple structure electrolyzer such as accommodating plate-shaped electrode preferably are set to cathode compartment separately in the appropriate location of above-mentioned solution circulated line, promptly comprising the electrolyzers in a plurality of mutually bipolar electrolytic deposition ponds that couple together so that electrolytic solution by this electrolyzer and with the impurity electrolytic deposition to its negative electrode.
Electrodeposit is preferably at 0.5～10A/dm
2Carry out under current density and 20～80 ℃ removing the gold of purifying, other precious metal and base metal to divide.
In the electrodeposit process, the electrodeposit of metal and the decomposition of iodate ion are all carried out at cathode side, and form iodate ion in anode side.The mass balance of whole system will never multilated, because can not produce gas.
Except the electrolytic solution deposit and, also can adopt electrodialysis, reverse osmosis, methods such as resins exchange are as above-mentioned separate impurities method.
The solution that is circulated to step (I) can carry out refining to refining gold not by abovementioned steps again.
Although the yield under the circulate soln situation not ratio of gained refining gold (the used not refining gold with) is about 95%, when recycling solution, yield can rise to 98～99%.
From device, reclaim and obtain all residue gold of 1～2%, after suitably handling this device is gone in its loopback.
The available following general formula of the reaction in above-mentioned each step of the present invention is represented.
Step (I)
(anode)
(negative electrode)
Step (II)
Reactionless
Step (III)
Step (IV) and (V)
Reactionless
Reaction formula left side addition gets following formula.
On the other hand, the addition of reaction formula right side gets following formula.
Both sides fit like a glove.
In other words, the chemical reaction of circulation method of purification is complete closed reaction, and the electric power that does not therefore have to add reagent and only provide step (I) to require can make purification semipermanent ground carry out continuously.
Because in fact therefore reagent consumption seldom only needs minimum reagent,, institute only is potassiumiodide, i.e. one of basic raw material but adding reagent.
A method forms the solution that contains au iodide with iodine and/or iodide refining gold not being carried out comprising in the purified process behind the present invention, wherein iodine or the similar substance that generates with electrolysis dissolves not refining gold, remove the insoluble substance in the solution, selective reduction and be settled out and contain gold ion in the solution, wherein solution is be not less than the strong basicity of pH12 with the alkali metal hydroxide that generates with iodine in the electrolytic process, the solution circulated after telling precipitation of gold and will tell gold from solution is used.
Therefore, the first, do not need to adopt extensive chemical reagent such as chloroazotic acid, need not handle generation gas, and obviously improve efficient.
The second, owing to adopt electrolytic process formation iodine and carry out the dissolving of gold, electrolysis also generates alkali metal hydroxide with iodine simultaneously.Again because alkali metal hydroxide can be used as alkali source and two kinds of all available same power supplies electrolysis of compound make in golden precipitation process, thus economical effectiveness obviously improve because need not to be provided with off-set facility and need not buy reagent.
The 3rd, because electrolysis does not produce gas in the circulation means of the present invention, so can not destroy mass balance during circular electrolyte.Therefore, supply with electrolyzer with the solution composition that forms iodine and dissolve gold constant always, and but operation semipermanent ground carries out continuously, wherein supply with not refining gold and a small amount of propiodal and need not to add other reagent, thereby can obtain the high purity gold, relatively obtain tangible Technological Economy superiority with existing gold refining method.
Promptly use last method to carry out gold refining, also can obtain the high purity gold and improve electrolytic efficiency simultaneously.And do not need strong reagent in this method and need not to handle the gas of generation.
Now the present invention is described in detail in detail, but this does not limit the present invention with following preferred embodiment.
Accompanying drawing produces iodine for septation electrolysis of the present invention and dissolve the schema of one of the embodiment of refining gold not in same electrolyzer.
Liquor kalii iodide is sent in the anolyte compartment 2 of the electrolyzer 4 that produces iodine, electrolyzer is divided into anolyte compartment 2 and cathode compartment 3 with exchange membrane containing fluorine 1, and potassium iodate solution is sent into cathode compartment 3 simultaneously.The plate electrode that is made of gold or make and coat the dimensionally stable electrode of precious metals such as platinum as anode 5 with titanium plate etc.Make negative electrode 6 with the electrode that typical electrode materials such as stainless steel are made.
When electric current flow through electrolyzer 4, all or part of potassiumiodide was electrolyzed to produce iodine and potassium ion by above-mentioned reaction formula (1), and potassium ion enters cathode compartment 3 and electrolysis generation potassium hydroxide through ion-exchange membrane 1.
The anolyte that contains potassiumiodide in the anolyte compartment 2 is sent into the chamber, the left side of anolyte storage tank 9 with pipeline 7, has been divided into two chambers with next door 8 in the storage tank, and makes the overflow of segment anode electrolytic solution cross the next door and enter right-hand chamber to send into anolyte compartment 2 by pipeline 10 circulations.The solution of chamber, the left side is also sent in the garden barrel reactor 12 with pipeline 11 in the anolyte storage tank 9, and this reactor upper end is opened wide, and the lower end is tapered, and the summit is the heart therein.Not refining gold grain 13 is housed in a large number in this reactor 12, wherein itself and solution is fully contacted to react with iodine and iodide ion by above-mentioned formula (2) or (2 ') and to be dissolved in the solution with the au iodide ion with agitator 14.Be connected with pipeline 16 on the sidewall of reactor 12 so that solution circulated that will be is wherein sent in the anolyte compartment 2 of electrolyzer 4 and also this solution imported in reducer 15 simultaneously, wherein dissolve gold is reduced and is precipitated out.
Catholyte in the cathode compartment 3 of electrolyzer 4 is sent into the right-hand chamber of catholyte storage tank 20 with pipeline 18, storage tank has been divided into two chambers with next door 19, and allows the overflow of part catholyte cross next door 19 and flow into chamber, the left side and send into cathode compartment 3 so that circulate with pipeline 21.The solution of catholyte storage tank 20 right-hand chamber infeeds reducer 15 by pipeline 23, wherein is provided with the strainer of telling dust etc.
Reducer 15 is a jar, wherein the anolyte that infeeds and alkaline catholyte is mixed and is settled out gold.Can adopt any type of jar, as long as its structure is suitable for two kinds of solution being mixed and the au iodide ion fully being contacted with potassium hydroxide.Preferably give this canned suitable agitator.
The au iodide ion is precipitated out with metallic gold by above-mentioned reaction formula (4) reduction back in the reducer 15.
The solution that will contain precipitation of gold is sent into centrifuge separator 25 and the surplus solution in the reducer 15 is sent into garden tube storage tank 27 with pipeline 26 by pipeline 24.The gold of telling from solution with centrifuge separator 25 is reclaimed after the drying in moisture eliminator such as rotary kiln 28.Reclaim in the surplus solution behind the gold and be dissolved with potassiumiodide and Potassium Iodate, it can be sent in the electrolyzer 4 and recycle rather than emit.
Solution in the centrifuge separator 25 is imported washing liquor tanks 30 with pipeline 29, send centrifuge separator 25 again back to after can steaming water without further processing or in contiguous distiller 31 then.Strong solution in the distiller 31 is sent in the storage tank 27 with pipeline 32.Circulation is used as anolyte in the anolyte storage tank 9 and the solution in the storage tank 27 can be sent into by pipeline 33 without further processing, or solution metal is deposited in electrode 36 send into the tabular electrolyzer 35 of no barrier film with pipeline 34, after on 37, send into again in the catholyte storage tank 20 and circulate as catholyte.
In anolyte compartment 2 and cathode compartment 3, be dissolved with excessive potassiumiodide and Potassium Iodate in the electrolytic once more circulation fluid, therefore can be in anolyte compartment 2 electrolysis potassiumiodide and the reaction that produces iodine, and electrolytic sulfonic acid potassium and the reaction that produces potassium hydroxide in cathode compartment, from and can repeat above-mentioned circulation.
Although solution has carried out circulation and has adopted utility appliance such as electrolytic solution storage tank 9 and 20 in this embodiment, washing liquor tank 30, distiller 31, storage tank 27 and tabular electrolyzer 35, solution also can not circulate and save these equipment.
The embodiment of following the inventive method.
Fluorine-containing cationic exchange membrane with the band iodate will long 20cm, and the new electrobath of wide 40cm and high 30cm is divided into anolyte compartment and cathode compartment.Will long 180mm, purity 99.99% gold medal plate (6950g) and the long 180mm of wide 250mm and thick 8mm, the stainless steel plate of wide 250mm and thick 2mm is supported on respectively in the electrolyzer as anode and negative electrode.
Anolyte compartment and cathode compartment inject the potassium iodate solution (53.5g/l) that 101 liquor kalii iodides (456.6g/l) and 101 usefulness potassium hydroxide are adjusted to pH12.8 respectively.The about 50cm of anolyte compartment and internal diameter, high about 50cm and that the garden barrel reactor of purity 99.99% gold grain (about 5000g) is housed is continuous so that circulating anode electrolytic solution.
Electrolyte temperature and current density are respectively about 50 ℃ and 20A/dm when carrying out electrolysis
2After 60 minutes, record in the anolyte au iodide ionic concn and be about 0.23mol/l.
Begin continuously electrolytic solution to be sent into settling vessel from electrolyzer during from about 60 minutes with pipeline.Tell except that gold and metal after, anolyte is imported in the reducer of internal diameter 20cm and dark 30cm.The catholyte that has generated potassium hydroxide is being sent into reducer through after the settling vessel.Reach about pH12.8 after two kinds of electrolytic solution fully mix, and begin to be settled out gold.Centrifugation goes out precipitation of gold, and after washing and the drying, recording purity is 99.999%, and particle diameter is 15 μ.
To tell the solution separated into two parts of gold, a part is entering with 2A/dm through storage tank
215cm * 25cm the stainless steel plate of work is made negative electrode and 15cm * 25cm and is coated with platinum titanium plate and does to send into the electric tank cathode chamber after the board-like electrolyzer of anodic 201 volumes and recycle, and another part is then sent into the anolyte compartment similarly and recycled.
After beginning from electrolysis 6 hours stop electrolysis.Record do anodic not in refining gold and the reaction chamber reduction of gold grain be respectively 945g and 1832g.
On the other hand, purification gained gold gross weight is 2638g, and yield is 95%, and its purity is 99.999%.From board-like electrolyzer, be recovered to all the other gold of 139g purity 98.4%.
Embodiment 2
Carry out the refining of gold with the device that is similar to embodiment 1.With being coated with platinum titanium electrode rather than making anode, and only in reactor, adorn gold grain (purity 99.5%) among this embodiment with gold.Gold grain constantly reduces along with electrolytic carrying out in the reactor, therefore will replenish, and also replenish the 5g potassiumiodide every day, makes electrolysis with 2A/dm like this
2Current density carried out 3 months continuously.
At 95.0kg not in the refining gold grain gross weight, 89.6kg dissolving and in addition refining are arranged.And purity is 99.996% refining gold gross weight 87.8kg(yield 98%).From board-like electrolyzer, be recovered to all the other gold of 1.8kg.Except that the gold and, from board-like electrolyzer and settling vessel, also obtain silver (0.38kg).
The refining process of gold is similar to embodiment 1, and just solution does not circulate.
Gained gold purity and yield be respectively 99.91% and 98% and particle diameter be 15 μ.Residue Jinliu is not reduction in solution.
Claims (18)
1, gold refining method, comprising:
A) dissolve not refining gold with iodine and/or iodide and form and contain au iodide solution;
B) remove insoluble substance in the solution;
C) pH value of solution is reached be not less than 12 strong basicity and make and contain the gold ion reduction optionally to be settled out gold; And
D) precipitation of gold is told in the reduction back from solution.
2, the process of claim 1 wherein that the ion precipitation operation that contains in the au iodide solution except that gold also tells this impurity to increase impurity level.
3, the method for claim 2, wherein precipitation operation is to add water so that insoluble basically iodide are precipitated out in containing au iodide solution.
4, the method for claim 2, wherein precipitation operation be with contain the au iodide pH value of solution be adjusted to 8～12 so that except that the gold metal hydroxides and/or oxide precipitation come out.
5, gold refining device, comprising:
A) electrolyzer, in order to form the solution that contains au iodide with iodine and/or iodide reaction by refining is golden, wherein be divided into anolyte compartment and cathode compartment and will contain the electrolysis of iodide electrolytic solution and form alkali metal hydroxide, and form iodine in the anolyte compartment at cathode compartment with barrier film;
B) trash eliminator, in order to tell impurities in the solution that contains au iodide, this trash eliminator is connected with electrolyzer anode chamber;
C) reducer, in order to from au iodide, optionally to reduce and to be settled out gold, wherein will mix making solution become pH to be not less than 12 strong basicity by the solution that trash eliminator is removed impurity with above-mentioned electrolysis gained alkali metal hydroxide, this reducer links to each other with the electric tank cathode chamber with separator;
D) refining gold separator in order to obtain the refining gold, is wherein told precipitation of gold from the solution after the reduction; And
E) cycle facilities recycles in order to sending into electrolyzer with the solution that the refining gold separates.
6, the device of claim 5, wherein diaphragm electrolysis produce iodine and not the refining gold be reflected in the same electrolyzer with iodine and/or iodide and carry out.
7, the device of claim 5 wherein carries out electrolysis with refining gold not as anode.
8, the device of claim 5, wherein will be not the refining gold grain anolyte compartment of packing into be dissolved in the anolyte with electrolysis.
9, the device of claim 5, wherein anolyte compartment 5 and reactor addition that refining gold grain not is housed are so that anolyte circulates between anolyte compartment and reactor, the refining gold grain is dissolved in anolyte compartment and/or reactor thereby make not.
10, the device of claim 5 wherein contains in the au iodide solution impurity and separates and undertaken by filtration or sedimentation in separator.
11, the device of claim 10 wherein is provided with ultra-fine filter behind the separator so that carry out ultrafiltration in ultra-fine filter.
12, the device of claim 10, the ion precipitation operation that wherein contains in the au iodide solution except that gold is also told this impurity to increase impurity level.
13, the device of claim 12, wherein precipitation operation is to add water so that insoluble basically iodide are precipitated out in containing au iodide solution.
14, the device of claim 12, wherein precipitation operation be with contain the au iodide pH value of solution be adjusted to 8～12 so that except that the gold metal hydroxides and/or oxide precipitation come out.
15, golden method of purification, comprising:
A) electrolytic solution that electrolysis contains iodide in membranous electrolyzer to be forming alkali metal hydroxide and iodine respectively at cathode compartment and anolyte compartment, thereby obtains containing the solution of the au iodide that not refining gold and iodine and/or iodide reaction form in cathode compartment;
B) tell impurity in the solution;
C) make the au iodide reduction to be settled out gold, wherein the alkali metal hydroxide that electrolysis is produced adds solution so that solution reaches the strong basicity that is not less than pH12;
D) from the solution after the reduction, tell precipitation of gold and obtain the refining gold; And
E) will send into electrolyzer with the solution that the refining gold separates recycles.
16, the method for claim 15 is wherein filtered or the impurity that contains in the au iodide solution is told in sedimentation.
17, the method for claim 15 wherein further contains precipitation of gold solution to strong basicity and adds and contain au iodide solution and pH value of solution is adjusted to strong basicity and the precipitation of gold particle diameter is increased.
18, the method for claim 15 is sent solution into electrolyzer after wherein impurity is told in the solution and is recycled.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62175518A JPS6417826A (en) | 1987-07-14 | 1987-07-14 | Refining method for gold |
| JP17551987A JP2685755B2 (en) | 1987-07-14 | 1987-07-14 | Gold refining equipment |
| JP175519/87 | 1987-07-14 | ||
| JP175518/87 | 1987-07-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1030944A true CN1030944A (en) | 1989-02-08 |
Family
ID=26496773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88104347A Pending CN1030944A (en) | 1987-07-14 | 1988-07-13 | gold refining method and device thereof |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR890002443A (en) |
| CN (1) | CN1030944A (en) |
| RU (1) | RU2020192C1 (en) |
Cited By (7)
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| CN103937964A (en) * | 2014-04-28 | 2014-07-23 | 南华大学 | Novel microwave roasting and gold-extracting method for gold-bearing concentrated dimorphite |
| CN105648232A (en) * | 2016-04-11 | 2016-06-08 | 许良秋 | Method for refining gold by using I2 and KI |
| CN105838900A (en) * | 2016-04-11 | 2016-08-10 | 许良秋 | Method for refining gold through I2 and NaI |
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| US11319613B2 (en) | 2020-08-18 | 2022-05-03 | Enviro Metals, LLC | Metal refinement |
| CN114453589A (en) * | 2022-02-18 | 2022-05-10 | 贵研铂业股份有限公司 | Preparation method of high-purity gold |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100968727B1 (en) * | 2008-05-27 | 2010-07-08 | 한국지질자원연구원 | Refining method of High purity gold from gold bonding wire scrap |
| KR101038105B1 (en) * | 2009-05-29 | 2011-06-01 | 한국수력원자력 주식회사 | Pre-hardening Apparatus and Method of Spherical Uranium Compound Solution Droplets Surface |
-
1988
- 1988-06-09 KR KR1019880006980A patent/KR890002443A/en not_active Application Discontinuation
- 1988-06-28 RU SU4356017 patent/RU2020192C1/en active
- 1988-07-13 CN CN88104347A patent/CN1030944A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103937964A (en) * | 2014-04-28 | 2014-07-23 | 南华大学 | Novel microwave roasting and gold-extracting method for gold-bearing concentrated dimorphite |
| CN103937964B (en) * | 2014-04-28 | 2016-06-15 | 南华大学 | A kind of containing gold sulfur arsenic concentrate microwave calcining gold extracting method |
| CN105648232A (en) * | 2016-04-11 | 2016-06-08 | 许良秋 | Method for refining gold by using I2 and KI |
| CN105838900A (en) * | 2016-04-11 | 2016-08-10 | 许良秋 | Method for refining gold through I2 and NaI |
| CN105648232B (en) * | 2016-04-11 | 2017-09-26 | 许良秋 | One kind uses I2The method that gold refining is carried out with KI |
| CN106256914A (en) * | 2016-08-29 | 2016-12-28 | 许良秋 | A kind of bromine sodium bromide gold method of refining |
| CN106256914B (en) * | 2016-08-29 | 2021-03-23 | 许良秋 | Bromine-sodium bromide gold refining method |
| CN110863215A (en) * | 2019-12-27 | 2020-03-06 | 有研亿金新材料有限公司 | Method for preparing gold electrolyte by using gold electrolysis anode mud |
| US11319613B2 (en) | 2020-08-18 | 2022-05-03 | Enviro Metals, LLC | Metal refinement |
| US11578386B2 (en) | 2020-08-18 | 2023-02-14 | Enviro Metals, LLC | Metal refinement |
| CN114453589A (en) * | 2022-02-18 | 2022-05-10 | 贵研铂业股份有限公司 | Preparation method of high-purity gold |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2020192C1 (en) | 1994-09-30 |
| KR890002443A (en) | 1989-04-10 |
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