CN103540954A - Metal electrolytic method in alkaline solutions - Google Patents
Metal electrolytic method in alkaline solutions Download PDFInfo
- Publication number
- CN103540954A CN103540954A CN201310292375.5A CN201310292375A CN103540954A CN 103540954 A CN103540954 A CN 103540954A CN 201310292375 A CN201310292375 A CN 201310292375A CN 103540954 A CN103540954 A CN 103540954A
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- Prior art keywords
- lead
- zinc
- electrolytic
- electrolysis
- compound
- Prior art date
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 15
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 229910000754 Wrought iron Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009858 zinc metallurgy Methods 0.000 description 1
- ISWJOCMVDARDLS-UHFFFAOYSA-L zinc;hydrogen sulfate Chemical compound [Zn+2].OS([O-])(=O)=O.OS([O-])(=O)=O ISWJOCMVDARDLS-UHFFFAOYSA-L 0.000 description 1
Images
Abstract
The invention discloses a metal electrolytic method in alkaline solutions, which comprises the following steps: casting deposited lead or deposited zinc or commercially available crude lead or crude zinc to a 0.2-6 cm thick anode plate, and preparing a lamelliform cathode through pure lead, pure zinc or an inert electrode; electrolytic refining in alkaline electrolyte, and finally obtaining high-purity electrolytic lead or electrolytic zinc on the cathode, wherein the metal electrolytic method further comprises: 1) dissolving a lead compound or a zinc compound into the alkaline electrolyte, and adding a reducing agent to reduce lead dioxide existing in the lead compound or the zinc compound to a soluble lead complex; and 2) selecting the lamelliform cathode prepared by the pure lead, pure zinc or inert electrode in the electrolysis process, selecting the anode as iron with purity larger than 94%, and finally obtaining the deposited lead or deposited zinc on the cathode. According to the metal electrolytic method disclosed by the invention, the lead compound or the zinc compound is dissolved under an alkaline condition through a complexing agent, the electrolytic lead or electrolytic zinc is obtained by electrolyzing the cathode, and a byproduct ferric oxide or ferric hydroxide is obtained by separation.
Description
Technical field
The metal Wet-smelting method that the object of this invention is to provide a kind of economy, efficient and environmental protection.
Background technology
Plumbous, zinc is important Industrial Metal, and along with scientific and technological development, the demand of highly purified lead, zinc is more and more higher.The method of the smelting of lead, zinc is mainly pyrometallurgical smelting at present.The thermal process of plumbous zinc is comparatively ripe, but in smelting process, pollutes comparatively serious.In the reduction process of plumbous pyrometallurgical smelting, can produce lead steam and lead powder dirt, environment is caused to severe contamination.In zinc pyrometallurgical smelting, because zinc is normal and cadmium symbiosis, in the process of smelting, can produce containing cadmium dust and waste water, environment is caused to serious cadmium pollution.
Comparatively serious in view of pyrometallurgical smelting environmental pollution plumbous, zinc, the wet process smelting technique of relative environmental protection obtains developing comparatively rapidly.Wherein the plumbous raw material of smelting is mainly the lead plaster of waste lead acid battery, lead plaster contains a large amount of lead sulfates, plumbous oxide, plumbic oxide, lead, composition is comparatively complicated, first the plumbous technology of current hydrometallurgic recovery is converted into lead sulfate by lead plaster, lead sulfate obtains plumbous oxide or lead carbonate after using sodium hydroxide or carbonate desulfurization, and plumbous oxide or lead carbonate carry out electrolysis and obtain oxygen and deposit lead afterwards.Wherein in the lead plaster transformation stage, need to consume a large amount of reductive agents, sulfuric acid, lead sulfate desulfurization stage need to consume a large amount of sweetening agents, in electrolysis stage, can produce alkali mist or acid mist impacts environment, more than in comparatively ripe acid lead salt electrolysis system, electrolysis voltage reaches 2.7V at present, plumbous electrolysis energy consumption reaches 700kWh/t.
Zinc wet process smelting technique is mainly sulfuric acid-zinc sulfate electrolysis system at present, and zinc oxide or zinc sulfate are dissolved in the sulphuric acid soln that contains zinc sulfate, by electrolysis, at anode, obtain oxygen, and negative electrode obtains deposition zinc.This method has been avoided the pollution of pyrometallurgical smelting, but in electrolytic process, theoretical bath voltage reaches 1.99V, the groove reaching in actual electrolytic process more than 3.0V is pressed, more than the electrolysis energy consumption of zinc reaches 2400kWh/t, meanwhile, zinc is easier autolyze solution phenomenon in acidic solution, reduce current efficiency, further increased the cost of electrolytic zinc.
At present, highly purified lead, zinc need carry out electrorefining and improve purity plumbous, zinc on the basis of pyrometallurgical smelting.
The method of the refining of plumbous, zinc comprises two kinds of pyrorefining and electrorefinings.Fire refining process is comparatively ripe, but in refining process, easily causes the loss of valuable metal, and meanwhile, plumbous, zinc more easily forms steam polluting environment in refining process.For overcoming the above problems, electrorefining is used widely gradually.
The method that current industrial electrolytic lead refining generally adopts is Bai Zifa, and Bai Zifa was proposed by A.G.Betts in more than 100 years, and is applied and continues into the present in next year.Bai Zifa be take lead bullion as anode, and electrolytic lead is negative electrode, adopts the aqueous solution of silicofluoric acid and plumbous silicofluoride to make electrolytic solution, and control electrolyte temperature is 30-50 ℃, then with current density 180-200A/m
2in electrolyzer, carry out electrolysis.Because the dissolution potential of the metals such as the Cu in anode, Sb, Bi and Ag is higher than plumbous stripping current potential, the form with the anode sludge in electrorefining process is residual at anode, thereby finally at anode, obtains surface with the anode scrap of the anode sludge.Although Bai Zifa is the classical way of refined lead, under working temperature, silicofluoric acid easily decomposes, volatilization HF gas, contaminate environment, harm workers ' health; Yin Xi (0.14V) approaches with the sedimentation potential of plumbous (0.126V), easily causes tin and plumbous codeposition, makes the tin content of deposit lead higher, need to before refining or after refining, carry out detin processing; Meanwhile, silicofluoric acid is weak acid, and electrolysis temperature is lower, so the voltage of refined lead is higher, approaches 0.5V, makes the process energy consumption of refined lead higher.In recent years, some scholar proposes to carry out plumbous refining in high density NaOH solution, in NaOH solution, electrolytic lead can obtain lower bath voltage (not higher than 0.2V), and this NaOH that has benefited from high density improves the electroconductibility of solution, has eliminated the pollution of HF gas to environment simultaneously.But, in alkaline environment, the sedimentation potential of tin (0.91V), antimony (0.66V) is far below plumbous (0.54V), tin in anode, antimony is constantly enrichment in electrolytic solution, need regularly electrolytic solution to be removed to antimony, detin, electrorefining process is continued, reduced efficiency, cost increases; Meanwhile, the NaOH solution of high density inevitably produces alkali mist in electrolytic process, and etching apparatus, causes certain harm to operator.
At present industrial comparatively ripe zinc refining method is pyrogenic process rectifying zinc metallurgy, rectification method utilizes multi-stage evaporation and condensation to remove impurity output essence zinc in crude zinc, zinc per ton consumes 0.4-0.5 ton standard coal and 70kWh electric energy, can obtain purity is the rectifying zinc of 99.99-99.999%, but this method energy consumption is higher, in rectifying, the leakage of steam will work the mischief to environment.Wet-process refining zinc is representational is H
2sO
4-ZnSO
4with NaOH-Na
2znO
2system, in these two kinds of methods, can obtain the electrolytic zinc of higher degree, but in electrolytic process, crude zinc anode and electrolytic zinc negative electrode all can autolyze in strongly-acid and strong basicity environment with return molten phenomenon, zinc concentration in electrolytic solution is constantly raise, finally make electrolytic process not continue, this has also limited the industrial applications of electrorefining zinc.
Summary of the invention
The present invention is directed to the shortcoming of prior art, the electrolytic smelting method of a kind of electrolysis for lead, zn cpds and lead, zinc is provided, the method can obtain electrolytic lead or electrolytic zinc preferably.
It is as follows that the present invention solves the problems of the technologies described above taked technical scheme:
In an electrolytic etching of metal method, comprise the following steps:
It is 0.2-6cm positive plate that deposit lead or deposition zinc or commercially available lead bullion or crude zinc are cast to thickness, with pure lead, pure zinc or the noble electrode shape negative electrode of laminating;
In alkaline electrolyte, carry out refining electrolysis, and finally on negative electrode, obtain highly purified electrolytic lead or electrolytic zinc.
Wherein, preferred method is that described deposit lead or deposition zinc are prepared from by following method:
1) lead compound or zn cpds are dissolved in alkaline electrolyte, and add plumbic oxide that reductive agent makes to exist in lead compound or zn cpds to be reduced to the lead complex of solubility;
2), in electrolytic process, negative electrode is chosen the plate-like cathode that pure lead, pure zinc or noble electrode are made, anode be purity at more than 94% iron, and finally on negative electrode, obtain deposit lead or deposition zinc.
Wherein, include complexing agent, conducting salt, metallic compound, galvanic deposit additive in described alkaline electrolyte, pH value is between 7.0-14.0.
After the present invention has taked such scheme, utilize complexing agent that lead or zn cpds are dissolved under alkaline condition, add reductive agent that the plumbic oxide that may exist is dissolved in the lump, adopt iron as anode, adopt pure lead, pure zinc or inertia electrolysis as negative electrode, by electrolysis, at negative electrode, obtain electrolytic lead or electrolytic zinc, iron anode dissolves gradually with the form of ferrous complex, ferrous complex in solution is ferric oxide or ferric hydroxide precipitate by air, oxygen-rich air, oxygen or hydrogen peroxide oxidation, and separation obtains by product ferric oxide or ironic hydroxide.
And, above-mentioned deposit lead or deposition zinc are carried out to refining electrolysis, can obtain smooth, fine and close highly purified electrolytic lead and electrolytic zinc at negative electrode, can effectively reduce deposit lead, the deposition zinc oxidative phenomena in fusion-casting process, there is good effect.
Further, preferably, in step 1), further comprise:
In described alkaline electrolyte, add lead, by the method for displacement, remove the plumbous active soluble metal impurity of the ratio existing in solution;
Or, in alkaline electrolyte, add zinc, by the method for displacement, remove the active soluble metal impurity of ratio zinc existing in solution.
Further, preferably method is, step 2) in, also comprise:
In electrolytic process, the ferrous compound that described Dissolution of Iron exists for the form with complex compound;
Electrolytic solution is carried out to air, oxygen-rich air, oxygen or hydrogen peroxide oxidation, make the described ferrous compound existing with the form of complex compound in solution become ferric oxide or ferric hydroxide precipitate.
In the method for the invention, in the process of electrolytic lead, zinc, not only its electrolysis energy consumption, far below existing electrolysis process, can obtain by product ferric oxide or ironic hydroxide simultaneously, and ferric oxide and ironic hydroxide are all important Chemicals.
Wherein, in step 1), one or more in the complexone that described complexing agent is characterized as the vitriol of complexing agent and lead or zinc or a-amino acid, organic amine compound that oxide compound forms soluble complexes between pH value 9.0-10.5, contain amino oxalic acid group or Padil group, concentration be 0.4-4.0mol/L one or more;
Described metallic compound is one or more in oxide compound, vitriol, nitrate or the muriate of lead or zinc, and concentration is 0.05-1.0mol/L;
The positively charged ion of described conducting salt is Na
+, K
+, NH
4 +in one or more, the negatively charged ion of described conducting salt is Cl
-, SO
4 2-, NO
3 -, P
2o
7 4-in one or more, conducting salt concentration is 0.5-4mol/L;
Described galvanic deposit additive is one or more in gelatine, gelatin, rosin, 2-Naphthol, ethylene glycol, trolamine, and described additive concentration is controlled at 0.1-9.0g/L;
Described reductive agent is one or more in lead, iron, hydrogen peroxide, sulfurous gas, sulphite.
Wherein, preferably, the alkaline environment of described alkaline electrolyte and alkaline electrolyte be pH value between 7.0-14.0, wherein, in electrolytic process, constantly supplement lead compound or zn cpds and maintain lead or zinc ion concentration;
Constantly supplement pH buffer solvent to maintain alkaline environment, wherein, described pH buffer solvent is one or more that contain in methylamine, ethamine, quadrol, propylene diamine, ammonia, sodium hydroxide, potassium hydroxide, sodium bicarbonate-sodium hydroxide, Sodium phosphate dibasic-sodium hydroxide, quadrol-hydrochloric acid, hydrochloric acid-thanomin, and mass concentration is at the solution of 1-50%.
Wherein, preferably, described iron anode comprises a kind of in iron plate, steel plate, iron filings or steel cuttings;
Wherein, in described electrolytic process, electrolyte temperature is controlled between 35-100 ℃, adopts constant-current electrolysis or constant-potential electrolysis mode.
Wherein, preferably, in step 1), described complexing agent comprises:
One or more in methylamine, ethamine, quadrol, propylene diamine, thanomin, trolamine, imidazoles, Diethylenetriamine, three second tetramines, ethylenediamine-N,N'-diacetic acid(EDDA), propylene diamine oxalic acid, nitrilotriacetic acid(NTA), iminodiethanoic acid, aspartic acid, L-Ala, α-amino-isovaleric acid, L-glutamic acid, proline(Pro), sarkosine, phenylalanine, leucine, Histidine, l-asparagine, glycine, Threonine, Serine, glutamine, citrulline, Methionin, arginine, halfcystine, methionine(Met), ornithine, concentration is 0.4-4.0mol/L.
Wherein, preferably, in constant-potential electrolysis mode, lead compound adopts constant voltage-0.2 to 0.35V electrolysis, and zn cpds adopts constant voltage 0.4-1.0V electrolysis; Or refining electrolysis adopts constant voltage 0.05-0.35V electrolysis;
Under constant-current electrolysis mode, constant-current electrolysis adopts 50-1200A/m
2current density, in the time of within the scope of the electrolyte temperature of 35-55 ℃, anodic current density is at 50-200A/m
2, cathode current density is at 100-350A/m
2;
Electrolysis temperature is within the scope of 55-80 ℃ time, and anodic current density is at 200-400A/m
2, cathode current density is at 350-650A/m
2;
Electrolysis temperature is within the scope of 80-100 ℃ time, and anodic current density is at 400-700A/m
2, cathode current density is at 650-1200A/m
2.
Wherein, preferably, in step 1), described lead compound is at least one containing in plumbous oxide, lead nitrate, lead chloride, plumbic oxide, lead sulfate, sublimed lead;
In described zn cpds, contain at least one in zinc oxide, zinc sulfate, zinc nitrate, zinc chloride.
Other features and advantages of the present invention will be set forth in the following description, and, partly from specification sheets, become apparent, or understand by implementing the present invention.Object of the present invention and other advantages can be realized and be obtained by specifically noted structure in the specification sheets write, claims and accompanying drawing.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is described in detail, so that above-mentioned advantage of the present invention is clearer and more definite.
Fig. 1 is the schematic diagram of the electrolytic etching of metal method in basic solution of the embodiment of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be described in detail.
In a preferred embodiment, the method of a kind of basic solution electrolytic lead zinc of the present invention is as follows: step 1): lead compound or zn cpds metallic compound are dissolved in alkaline electrolyte, and add plumbic oxide that reductive agent makes to exist in lead compound or zn cpds to be reduced to the lead complex of solubility;
Step 2): in electrolytic process, negative electrode is chosen the plate-like cathode that pure lead, pure zinc or noble electrode are made, anode be purity at more than 94% iron, and on negative electrode, obtain deposit lead or deposition zinc.
Specifically comprise: preparation contains complexing agent, conducting salt, metallic compound, galvanic deposit additive, the pH value alkaline electrolysis solution between 7.0-14.0, and negative electrode is the plate-like cathode that pure lead, pure zinc or noble electrode are made, anode is that purity is at more than 94% iron.
Wherein, lead compound or zn cpds are dissolved in electrolytic solution, add plumbic oxide that reductive agent makes to exist to be reduced to the lead complex of solubility.
In electrolytic process, iron anode is dissolved as ferrous complex gradually, electrolytic solution is carried out to air, oxygen-rich air, oxygen or hydrogen peroxide oxidation, make the ferrous complex in solution obtain ferric oxide or ferric hydroxide precipitate through air, oxygen-rich air, oxygen or hydrogen peroxide oxidation, negative electrode obtains deposit lead or the deposition zinc of smooth densification.
Wherein, one or more in the complexone that complexing agent described above is characterized as the vitriol of complexing agent and lead or zinc or a-amino acid, organic amine compound that oxide compound forms soluble complexes between pH value 9.0-10.5, contain amino oxalic acid group or Padil group, concentration is 0.4-4.0mol/L one or more one or more.
In a preferred embodiment, one or more in described complexing agent armored amine, ethamine, quadrol, propylene diamine, thanomin, trolamine, imidazoles, Diethylenetriamine, three second tetramines, ethylenediamine-N,N'-diacetic acid(EDDA), propylene diamine oxalic acid, nitrilotriacetic acid(NTA), iminodiethanoic acid, aspartic acid, L-Ala, α-amino-isovaleric acid, L-glutamic acid, proline(Pro), sarkosine, phenylalanine, leucine, Histidine, l-asparagine, glycine, Threonine, Serine, glutamine, citrulline, Methionin, arginine, halfcystine, methionine(Met), ornithine.Concentration is 0.4-4.0mol/L;
Described metallic compound is the oxide compound of lead or zinc or one or more in vitriol, and concentration is 0.05-1.0mol/L; Described reductive agent is a kind of in lead, iron, hydrogen peroxide, sulfurous gas, sulphite;
The positively charged ion of described conducting salt is Na
+, K
+, NH
4 +in one or more, the negatively charged ion of described conducting salt is Cl
-, SO
4 2-, NO
3 -, P
2o
7 4-in one or more, conducting salt concentration is 0.5-4mol/L; The alkaline environment of described solution is for being used pH buffered soln regulator solution pH value between 8.0-14.0, pH buffer solvent is to contain a kind of in methylamine, ethamine, quadrol, propylene diamine, ammonia, sodium hydroxide, potassium hydroxide, sodium bicarbonate-sodium hydroxide, Sodium phosphate dibasic-sodium hydroxide, quadrol-hydrochloric acid, hydrochloric acid-thanomin, and mass concentration is at the solution of 1-50%.Described galvanic deposit additive is one or more in gelatine, gelatin, rosin, 2-Naphthol, ethylene glycol, trolamine, and described additive concentration is controlled at 0.1-9.0g/L.
Wherein, in electrolytic process, constantly supplementing metallic compound maintains GOLD FROM PLATING SOLUTION and belongs to ionic concn.The iron level of described iron anode is more than 94%, comprises a kind of in iron plate, steel plate, iron filings or steel cuttings.
Wherein, in electrolytic process, electrolyte temperature is controlled between 35-100 ℃, adopts constant-current electrolysis or constant-potential electrolysis mode.
Specifically, in constant-potential electrolysis mode, lead compound adopt constant voltage-0.2 to 0.1V electrolysis (because of the electropotential of iron in solution lower than plumbous, therefore in electrolytic process, theoretical electrolysis voltage is-0.31V, in actual electrolytic process because the lead of the spontaneous replacement(metathesis)reaction of the polarization of iron anode and iron anode surface exists that to make electrolysis voltage be between-0.2 to 0.35V), zn cpds adopts constant voltage 0.4-1.0V electrolysis.
Under constant-current electrolysis mode, constant-current electrolysis adopts 50-1200A/m
2current density.Within the scope of the electrolyte temperature of 35-100 ℃, along with the increase of electrolyte temperature, the rate of migration of effects of ion increases, resistivity decreased, the polarized potential of negative electrode and positive electrode reduces, therefore in constant-current electrolysis, electrolysis temperature is within the scope of 35-55 ℃, and anodic current density is at 50-200A/m
2, cathode current density is at 100-350A/m
2; Electrolysis temperature is within the scope of 55-80 ℃, and anodic current density is at 200-400A/m
2, cathode current density is at 350-650A/m
2; Electrolysis temperature is within the scope of 80-100 ℃, and anodic current density is at 400-700A/m
2, cathode current density is at 650-1200A/m
2.
In addition, in electrolytic process, further comprise: in basic solution (lead compound solution), add excessive lead, by the method for displacement, remove the plumbous active soluble metal of the ratio that may exist in solution, for example copper, silver;
In basic solution (zn cpds electrolytic solution), add excessive zinc, by the method for displacement, remove the active soluble metal of ratio zinc that may exist in solution, for example copper, lead, cadmium, silver.In addition,, although constantly electrolytic solution is carried out to removal of impurities in electrolytic process, still have a small amount of foreign metal in cathodic deposition, therefore can select deposit lead or deposition zinc to carry out refining raising purity.
Therefore, in an embodiment, further comprise:
Step 3): it is 0.2-6cm positive plate that above-mentioned deposit lead or deposition zinc are cast to thickness with pure lead, pure zinc or the noble electrode shape negative electrode of laminating, and is carried out refining electrolysis in alkaline electrolyte, obtains highly purified electrolytic lead or electrolytic zinc on negative electrode.
Wherein, alkaline electrolyte is consistent with the composition of alkaline electrolyte, and thus, the present embodiment can be realized refining electrolysis.
Specifically, the alkaline environment of described solution is for being used pH buffered soln regulator solution pH value between 7.0-14.0, buffered soln be contain in methylamine, ethamine, quadrol, propylene diamine, ammonia, sodium hydroxide, potassium hydroxide, sodium bicarbonate-sodium hydroxide, Sodium phosphate dibasic-sodium hydroxide, quadrol-hydrochloric acid, water glass, sodium hydroxide a kind of, mass concentration is at the solution of 1-50%.Lead compound or zn cpds are one or more in the oxide compound, muriate, nitrate, vitriol of lead or zinc, and concentration is 0.05-1.0mol/L.Electrolysis to electrolysis voltage stops higher than 0.25-0.45V, and now the metal of anode almost all dissolves, and only the surplus anode sludge is residual, and negative electrode obtains electrolytic lead or the electrolytic zinc of smooth densification.
Wherein, in electrolytic process, electrolyte temperature is controlled between 35-100 ℃, adopts constant-current electrolysis or constant-potential electrolysis mode.Wherein, in constant-potential electrolysis mode, plumbous and zinc refining all adopts constant voltage 0.05-0.35V electrolysis.Constant-current electrolysis adopts 70-1200A/m
2current density.
Within the scope of the electrolyte temperature of 35-100 ℃, increase along with electrolyte temperature, the rate of migration of effects of ion increases, resistivity decreased, the polarized potential of negative electrode and positive electrode reduces, therefore in the constant-current electrolysis refining of plumbous and zinc, electrolysis temperature is within the scope of 35-55 ℃, and anodic current density is at 50-200A/m
2, cathode current density is at 100-350A/m
2; Electrolysis temperature is within the scope of 55-80 ℃, and anodic current density is at 200-40A/m
2, cathode current density is at 350-650A/m
2; Electrolysis temperature is within the scope of 80-100 ℃, and anodic current density is at 400-700A/m
2, cathode current density is at 650-1200A/m
2.
Wherein, in step 1) of the present invention, lead compound is at least one containing in plumbous oxide, lead nitrate, lead chloride, plumbic oxide, lead sulfate, sublimed lead, for example the lead plaster in waste lead acid battery, waste lead acid battery thermal decomposition product, plumbous oxide ore, lead glance oxidation products; In zn cpds, contain at least one in zinc oxide, zinc sulfate, zinc nitrate, zinc chloride, for example zinc oxide ore.
Step 2 of the present invention) lead bullion in, crude zinc can be the products of step 1), can be also to obtain lead bullion or crude zinc by other existing methods.
It is that 0.2-6cm lead bullion or crude zinc anode dissolve completely that the present invention can make thickness, and refining time is 1-10 days, and negative electrode obtains highly purified electrolytic lead or electrolytic zinc.
The present invention utilizes complexing agent that lead or zn cpds under alkaline condition (pH is between 7.0-14.0) are dissolved, add reductive agent that the plumbic oxide that may exist is dissolved in the lump, adopt iron as anode, adopt pure lead, pure zinc or inertia electrolysis as negative electrode, by electrolysis, at negative electrode, obtain electrolytic lead or electrolytic zinc, iron anode dissolves gradually, and the ferrous complex oxidation by air in solution is ferric oxide or ferric hydroxide precipitate, and separation obtains by product ferric oxide or ironic hydroxide.
Wherein, in electrolytic process, because tin, antimony, bismuth, silver, ferric iron, arsenic impurities is precipitation forms in solution, in the dissolution process of metallic compound, can obtain separation, for lead compound electrolysis process, soluble impurity is mainly zinc, copper, copper can add excessive lead or iron rear substitution copper removal in lead compound dissolution phase, ferrous compound obtains ferric oxide or ferric hydroxide precipitate separation through oxidation, zinc can enrichment in solution in electrolytic process, because plumbous, differ more (more than 0.5V) with the sedimentation potential of zinc, when zinc is enriched to after higher concentration, the solution that contains higher concentration zinc is carried out to plumbous deep electrolytic to be obtained not deposit lead containing zinc (concentration after plumbous electrolysis is less than 10
-5mol/L), solution deep electrolytic separation, can obtain respectively deposit lead and deposition zinc, the about 0.1V of its actual bath voltage, the about 26kWh/t of energy consumption.
For zn cpds electrolysis process, soluble impurity is mainly copper, plumbous, cadmium, can in zn cpds dissolution process, add excess zinc or iron displacement to remove copper, plumbous, cadmium, in the present invention, complexing agent is stronger to the complexing action of ferrous ion, ferrous complex has higher galvanic deposit overvoltage, its sedimentation potential is lower than zinc sedimentation potential, the preferential deposition of iron of zinc in this solution system, ferrous complex becomes ferric oxide or ferric hydroxide precipitate and then separation by oxidation, in electrolytic process, can obtain the deposition zinc that purity is higher, its actual bath voltage is 0.4-1.0V, energy consumption is 320-812kWh/t.In the method for the invention, in the process of electrolytic lead, zinc, not only its electrolysis energy consumption, far below existing electrolysis process, can obtain by product ferric oxide or ironic hydroxide simultaneously, and ferric oxide and ironic hydroxide are all important Chemicals.
In addition, in electrolytic process, although adopting adds the method for excess metal to remove the most of soluble impurity in solution, still have a small amount of foreign metal in cathodic deposition, in order further to obtain electrolytic lead or the electrolytic zinc that purity is higher, electrolytic process product deposit lead or deposition zinc are carried out to electrorefining.
Under alkaline condition, in being dissolved with the electrolytic solution of complexing agent, conductive agent, metal-salt, lead bullion or crude zinc are as anode, adopt pure lead, pure zinc or inertia electrolysis as negative electrode, by electrolysis, at negative electrode, obtain highly purified electrolytic lead or electrolytic zinc, the foreign metal that anode may contain is stayed anode with the form of the anode sludge, realizes the recovery of valuable metal.For lead bullion electrorefining process, major impurity tin in lead bullion, antimony, bismuth, silver, iron, arsenic are insolubles in this solution system, copper stripping current potential is far above plumbous stripping current potential, zinc and plumbous sedimentation potential differ comparatively many, can realize separated comparatively thoroughly, the Pb that is difficult to realization can effectively realize traditional technology in electrorefining process in is separated with Sn, and eliminated inevitably alkali mist and the pollution of HF gas to environment in strong basicity and silicofluoric acid refining system, simultaneously at current density 400A/m
2condition under, electrolytic lead refining groove is pressed only has 0.1V.For crude zinc electrorefining process, because the stripping current potential of zinc is far below other foreign metals, in refining process, impurity is with the isolated in form of the anode sludge, in this solution, can avoid the self-dissolving of zinc in strong acid and strong alkali environment and return molten phenomenon simultaneously, and suppress negative electrode comparatively significantly cathode hydrogen evolution reaction under higher electrolysis temperature in strong acid and strong alkali environment, be beneficial to raising electrolysis temperature, reduce refining voltage, at current density 400A/m
2condition under, zinc refining cell is pressed only has 0.09V., zinc plumbous for electrorefining, after having added effectively additive, negative electrode can obtain smooth, fine and close electrolytic lead and electrolytic zinc, can effectively reduce deposit lead, the deposition zinc oxidative phenomena in fusion-casting process.
Fig. 1 is the schematic diagram of the electrolytic etching of metal method in basic solution of the embodiment of the present invention, and according to above-mentioned schematic flow sheet, the present invention can take following specific embodiment.
embodiment 1:
Get 12V100Ah waste lead acid battery, broken rear separation obtains lead plaster (lead-containing compounds).
The electrolytic solution that configuration 10L contains 0.7mol/L nitrilotriacetic acid(NTA), 1mol/L SODIUMNITRATE, 0.1g/L rosin, adopting hydrochloric acid-thanomin buffered soln to regulate pH value is 8.0 ± 0.5.In electrolytic solution, add 1kg lead plaster and excessive lead powder, the lead compound in lead plaster is all dissolved.Electrolytic solution is heated to 55 ℃.Negative electrode is that the wide * of the long * of 40*50*0.1(is thick) cm
3the stainless steel plate of potassium permanganate passivation, anode is that the wide * of the long * of 40*50*1(is thick) cm
3the purity wrought iron plate that is 99%, adopt current density 400A/m
2constant-current electrolysis 15 hours, average electrolysis voltage is 0.03V, during constantly to passing into air in solution, make ferrous complex be oxidized to iron oxide precipitation, add lead plaster simultaneously and maintain lead content in solution and be not less than 0.1mol/L.
Getting above-mentioned electrolysis obtains part lead bullion to cast the wide * of the long * of 30*30*0.5(thick) cm
3positive plate, negative electrode adopts the wide * of the long * of 30*30*0.1(thick) cm
3pure stereotype, the pole span of anode and negative electrode is 1.5-2.0cm, is placed in electrolytic solution.In electrolytic solution, contain 0.7mol/L nitrilotriacetic acid(NTA), 0.1mol plumbous oxide, 1mol/L SODIUMNITRATE, 0.1g/L rosin, adopting hydrochloric acid-thanomin buffered soln to regulate pH value is 8.0 ± 0.5.Electrolytic solution is heated to 55 ℃.Adopt 500A/m
2current density constant-current electrolysis to electrolysis voltage reaches 0.3V and stops electrolysis, takes out cathodic deposition lead, and after cleaning, founding becomes pure lead pig, and electrorefining process average voltage is 0.08V.
Through ICP quantitative analysis, the metals content impurity in this lead pig is as the Chemical Analysis of Wire Rod of table 1(lead pig) as shown in.
Table 1
Contrast lead pig GB/T469-2005 national standard, this lead pig has reached the standard of national Pb99.994.As calculated, the power consumption of lead plaster electrolytic process ton lead is 7.3 degree electricity, and the power consumption of electrorefining process ton lead is 20.6 degree electricity.
embodiment 2:
The electrolytic solution that configuration 100L contains 0.8mol/L phenylalanine, 1mol/L vitriolate of tartar, 5g/L gelatin, adopting Sodium phosphate dibasic-sodium hydroxide solution to regulate pH value is 13.8 ± 0.2, in electrolytic solution, adds 4kg to contain the ore of plumbous oxide 95%.Electrolytic solution is heated to 70 ℃.Negative electrode is that the wide * of the long * of 100*100*0.1(is thick) cm
3stereotype, anode is that the wide * of the long * of 100*100*0.5(is thick) cm
3the purity pig iron plate that is 95%, adopt current density 600A/m
2constant-current electrolysis 5 hours, during constantly to passing into air in solution, make ferrous compound be oxidized to iron oxide precipitation, add plumbous oxide ore simultaneously and maintain lead content in solution and be not less than 0.2mol/L, the average electrolysis voltage of electrolytic process is-0.05V.
Above-mentioned electrolysis is obtained to lead bullion, and to cast the wide * of the long * of 50*50*2(thick) cm
3positive plate, negative electrode is that the wide * of the long * of 50*50*0.1(is thick) cm
3pure stereotype, the pole span of negative electrode and positive electrode is 2.0-3.0cm.The electrolytic solution that contains 0.8mol/L phenylalanine, 1mol/L vitriolate of tartar, 5g/L gelatin in electrolytic solution, adopting Sodium phosphate dibasic-sodium hydroxide solution to regulate pH value is 13.8 ± 0.2, and electrolytic solution is heated to 70 ℃.Adopt 700A/m
2current density constant-current electrolysis to electrolysis voltage reaches 0.35V and stops electrolysis, takes out cathodic deposition lead, and after cleaning, founding becomes pure lead pig, and electrorefining process average voltage is 0.12V.Wherein, through ICP quantitative analysis, the metallic impurity in this lead pig (Chemical Analysis of Wire Rod of lead pig) content is as shown in table 2.
Table 2
Contrast lead pig GB/T469-2005 national standard, this lead pig has reached the standard of national Pb99.994.As calculated, the generating 13 degree electricity of plumbous oxide ore electrolytic process ton lead, the power consumption of electrorefining process ton lead is 31 degree electricity.
embodiment 3:
The electrolytic solution that configuration 500L contains 1.1mol/L ethylenediamine-N,N'-diacetic acid(EDDA), 0.5mol/L trisodium phosphate, 0.5g/L 2-Naphthol, 1g/L gelatine, adopting quadrol-hydrochloric acid buffer solution to regulate pH value is 10.0 ± 0.3, in electrolytic solution, adds 10kg to contain the ore of zinc oxide 98%.Electrolytic solution is heated to 45 ℃.Negative electrode is that the wide * of the long * of 200*200*0.1(is thick) cm
3zine plate, anode is that the wide * of the long * of 200*200*1.5(is thick) cm
3304 stainless steel plates, adopt current density 200A/m
2constant-current electrolysis 48 hours, during constantly to passing into air in solution, make ferrous compound be oxidized to iron oxide precipitation, add zinc oxide ore simultaneously and maintain zinc content in solution and be not less than 0.15mol/L, the average electrolysis voltage of electrolytic process is 0.51V.
Above-mentioned electrolysis is obtained to crude zinc, and to cast the wide * of the long * of 100*100*0.5(thick) cm
3positive plate, negative electrode is that the wide * of the long * of 100*100*0.1(is thick) cm
3pure zine plate, the pole span of negative electrode and positive electrode is 2.0-3.0cm.The electrolytic solution that contains 1.1mol/L ethylenediamine-N,N'-diacetic acid(EDDA), 0.5mol/L trisodium phosphate, 0.5g/L 2-Naphthol, 1g/L gelatine in electrolytic solution, adopting quadrol-hydrochloric acid buffer solution to regulate pH value is 10.0 ± 0.3, and electrolytic solution is heated to 45 ℃.Adopt 250A/m
2current density constant-current electrolysis to electrolysis voltage reaches 0.25V and stops electrolysis, takes out cathodic deposition zinc, and after cleaning, founding becomes pure plumbous zinc, and electrorefining process average voltage is 0.09V.Through ICP quantitative analysis, the metals content impurity in this zinc ingot metal is as the Chemical Analysis of Wire Rod of table 3(zinc ingot metal) as shown in.
Table 3:
Contrast zinc ingot metal GB/T470-1997 national standard, this lead pig has reached the standard of national Zn99.995.As calculated, the power consumption of zinc oxide ore electrolytic process ton zinc is 418 degree electricity, and the power consumption of electrorefining process ton zinc is 74.0 degree electricity.
After the present invention has taked such scheme, because above-mentioned complexing agent is to the anode of lead or zinc and cathodic polarization potential is lower and in use environment friendly and pollution-free, can realize the electrolysis and the refining that under lower voltage, realize plumbous zinc.
And, the present invention utilizes in electrolytic process, use the electrolysis voltage of iron anode lower, first iron anode becomes the ferrous complex of solubility in process in leaching simultaneously, the air that ferrous complex is passed in solution be oxidized to insoluble ironic hydroxide or ferric oxide, and then realize separated, in electrolytic process, the stripping of iron anode is comparatively easy, and iron can make electrolysis voltage significantly reduce as the lower metal of a kind of stripping current potential.
Again, the current density that present method allows is higher, and the present invention can use galvanic deposit additive can make deposit lead or deposit lead obtain the deposition surface of smooth densification, for example, for deposition zinc, can reach the smooth effect of coating surface light.
Finally it should be noted that: the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (11)
1. the electrolytic etching of metal method in basic solution, is characterized in that, comprising:
It is 0.2-6cm positive plate that deposit lead or deposition zinc or commercially available lead bullion or crude zinc are cast to thickness, with pure lead, pure zinc or the noble electrode shape negative electrode of laminating;
In alkaline electrolyte, carry out refining electrolysis, and finally on negative electrode, obtain highly purified electrolytic lead or electrolytic zinc.
2. the electrolytic etching of metal method in basic solution according to claim 1, is characterized in that, described deposit lead or deposition zinc are prepared from by following method:
1) lead compound or zn cpds are dissolved in alkaline electrolyte, and add plumbic oxide that reductive agent makes to exist in lead compound or zn cpds to be reduced to the lead complex of solubility;
2) the above-mentioned electrolytic solution of electrolysis, negative electrode is chosen the plate-like cathode that pure lead, pure zinc or noble electrode are made, anode be purity at more than 94% iron, and finally on negative electrode, obtain deposit lead or deposition zinc.
3. the electrolytic etching of metal method in basic solution according to claim 2, is characterized in that, includes complexing agent, conducting salt, metallic compound, galvanic deposit additive in described alkaline electrolyte, and pH value is between 7.0-14.0.
4. the electrolytic etching of metal method in basic solution according to claim 2, is characterized in that, in described step 1), further comprises:
In described alkaline electrolyte, add lead, by the method for displacement, remove the plumbous active soluble metal impurity of the ratio existing in solution;
Or, in alkaline electrolyte, add zinc, by the method for displacement, remove the active soluble metal impurity of ratio zinc existing in solution.
5. the electrolytic etching of metal method in basic solution according to claim 2, is characterized in that step 2) in, also comprise:
In electrolytic process, the ferrous compound that described Dissolution of Iron exists for the form with complex compound;
Electrolytic solution is carried out to air, oxygen-rich air, oxygen or hydrogen peroxide oxidation, make the described ferrous compound existing with the form of complex compound in solution become ferric oxide or ferric hydroxide precipitate.
6. according to the electrolytic etching of metal method in the basic solution described in claim 2 or 3, it is characterized in that, in step 1), one or more in the complexone that described complexing agent is characterized as the vitriol of complexing agent and lead or zinc or a-amino acid, organic amine compound that oxide compound forms soluble complexes between pH value 9.0-10.5, contain amino oxalic acid group or Padil group, concentration is 0.4-4.0mol/L;
Described metallic compound is one or more in oxide compound, vitriol, nitrate or the muriate of lead or zinc, and concentration is 0.05-1.0mol/L;
The positively charged ion of described conducting salt is Na
+, K
+, NH
4 +in one or more, the negatively charged ion of described conducting salt is Cl
-, SO
4 2-, NO
3 -, P
2o
7 4-in one or more, conducting salt concentration is 0.5-4mol/L;
Described galvanic deposit additive is one or more in gelatine, gelatin, rosin, 2-Naphthol, ethylene glycol, trolamine, and described additive concentration is controlled at 0.1-9.0g/L;
Described reductive agent is one or more in lead, iron, hydrogen peroxide, sulfurous gas, sulphite.
7. according to the electrolytic etching of metal method in the basic solution described in claim 2 or 6, it is characterized in that, the alkaline environment of described alkaline electrolyte is that pH value is between 7.0-14.0;
Wherein, constantly supplement pH buffer solvent to maintain alkaline environment, wherein, described pH buffer solvent is one or more that contain in methylamine, ethamine, quadrol, propylene diamine, ammonia, sodium hydroxide, potassium hydroxide, sodium bicarbonate-sodium hydroxide, Sodium phosphate dibasic-sodium hydroxide, quadrol-hydrochloric acid, hydrochloric acid-thanomin, and mass concentration is at the solution of 1-50%;
And, in basic solution electrolytic process, constantly supplement lead compound or zn cpds and maintain lead or zinc ion concentration.
8. the electrolytic etching of metal method in basic solution according to claim 1, is characterized in that, described iron anode comprises a kind of in iron plate, steel plate, iron filings or steel cuttings;
Wherein, in described electrolytic process, electrolyte temperature is controlled between 35-100 ℃, adopts constant-current electrolysis or constant-potential electrolysis mode.
9. the electrolytic etching of metal method in basic solution according to claim 5, is characterized in that, in step 1), described complexing agent comprises:
One or more in methylamine, ethamine, quadrol, propylene diamine, thanomin, trolamine, imidazoles, Diethylenetriamine, three second tetramines, ethylenediamine-N,N'-diacetic acid(EDDA), propylene diamine oxalic acid, nitrilotriacetic acid(NTA), iminodiethanoic acid, aspartic acid, L-Ala, α-amino-isovaleric acid, L-glutamic acid, proline(Pro), sarkosine, phenylalanine, leucine, Histidine, l-asparagine, glycine, Threonine, Serine, glutamine, citrulline, Methionin, arginine, halfcystine, methionine(Met), ornithine, concentration is 0.4-4.0mol/L.
10. the electrolytic etching of metal method in basic solution according to claim 8, is characterized in that, in constant-potential electrolysis mode, lead compound adopts constant voltage-0.2 to 0.35V electrolysis, and zn cpds adopts constant voltage 0.4-1.0V electrolysis; Or refining electrolysis adopts constant voltage 0.05-0.35V electrolysis;
Under constant-current electrolysis mode, constant-current electrolysis adopts 50-1200A/m
2current density, in the time of within the scope of the electrolyte temperature of 35-55 ℃, anodic current density is at 50-200A/m
2, cathode current density is at 100-350A/m
2;
Electrolysis temperature is within the scope of 55-80 ℃ time, and anodic current density is at 200-400A/m
2, cathode current density is at 350-650A/m
2;
Electrolysis temperature is within the scope of 80-100 ℃ time, and anodic current density is at 400-700A/m
2, cathode current density is at 650-1200A/m
2.
Electrolytic etching of metal method in 11. basic solutions according to claim 2, is characterized in that, in step 1), described lead compound is at least one containing in plumbous oxide, lead nitrate, lead chloride, plumbic oxide, lead sulfate, sublimed lead;
In described zn cpds, contain at least one in zinc oxide, zinc sulfate, zinc nitrate, zinc chloride.
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| CN108640390A (en) * | 2018-05-31 | 2018-10-12 | 阳谷祥光铜业有限公司 | A kind of processing method of stibium-containing wastewater |
| CN112281188A (en) * | 2020-09-17 | 2021-01-29 | 安徽省淮河制胶有限公司 | Processing technology of bone glue additive for lead and zinc smelting |
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