CN1066301A - Make the fused salt electrolysis process of plumbous calcium strontium ternary master alloy - Google Patents
Make the fused salt electrolysis process of plumbous calcium strontium ternary master alloy Download PDFInfo
- Publication number
- CN1066301A CN1066301A CN 91106094 CN91106094A CN1066301A CN 1066301 A CN1066301 A CN 1066301A CN 91106094 CN91106094 CN 91106094 CN 91106094 A CN91106094 A CN 91106094A CN 1066301 A CN1066301 A CN 1066301A
- Authority
- CN
- China
- Prior art keywords
- alloy
- calcium
- strontium
- plumbous
- electrolytic solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention is the fused salt electrolysis process of producing plumbous calcium strontium ternary master alloy.The anode of this kind method is anti-oxidant graphite, and negative electrode is a molten lead liquid, and the composition of its electrolytic solution is the mixture of the anhydrous chloride of fused calcium-strontium-potassium.As long as the muriatic ratio of the calcium-strontium-potassium that control is certain, the just ternary master alloy of the synthetic plumbous calcium strontium of energy once electrolytic.The utilization ratio height of calcium strontium, metal loss is little.In addition, processing unit is simple, be easy to grasp, and the production less investment, industrialization is easy, and industrial scale is changeable.The ternary master alloy of being produced is again the starting material of production quaternary or multicomponent alloy, thereby has widened the scope of application of alloy.
Description
The present invention relates to make the manufacture method of ternary master alloy (mother alloy).Be the lead-based anode of making metals such as electrowinning zinc, copper, nickel, and hermetically sealed nothing is safeguarded the mother alloy of lead-acid battery electrode material (grid).
Now, adopt two kinds of metal eutectic methods usually, production binary mother alloy is as lead-calcium alloy.This method of mixing, melt, casting with elemental metals, during for the production lead-calcium alloy, complicated operation, cost is higher.Because the calcium of alkaline-earth metal, chemically reactive is big, under the high temperature of about 851 ℃ of its molten points, in case be exposed among the air, easily makes the calcium oxidational losses.Plumbous calcium proportion differs greatly simultaneously, and both are difficult for mixing, and cause deviation.For mixing, need in the inert atmosphere protection, to stir, therefore operation is complicated.Expect that a certain proportion of lead-calcium alloy is difficult to, and the casting yield of calcium is low.
Because the calcium metal that eutectic method uses, adopt compound such as electrolysis or fire reduction calcium chloride, calcium oxide and get, so the cost of the lead-calcium alloy of output is higher.
Along with science and technology development, day patent of the disclosure (clear 54-136501) proposes a kind of fused salt electrolysis process of making plumbous calcium binary alloy.Make anode with graphite, molten metal lead is made negative electrode, and the fusion calcium salt is made electrolytic solution.The vertical formation binary alloy that connects of calcium that electrolysis is separated out and negative electrode.
The fused calcium salt uses the lower anhydrous calcium salt of fusing point, as calcium chloride, Calcium Fluoride (Fluorspan) etc.
The composition of its lead-calcium alloy, along with the electric current that feeds electrode what, the speed speed that metallic lead is supplied with is regulated, and the calcium amount is changed in certain scope.
The main drawback of this kind method is: when commercial scale production, the calcium amount in the alloy is difficult to reach give calibrates standard.Because in electrolytic process, because the proportion (1.54) of calcium is more than little many of the proportion (11.34) of lead.Even it is also littler than the proportion of fused salt mixt.Therefore, the calcium that electrolysis is separated out, be very easy to swim in plumbous liquid or fused salt surface, the nascent chlorine oxidation that is produced by anode falls, and causes current efficiency to reduce, and electrolysing period prolongs.
Secondly, equipment is complicated.Because electrolytic temperature will be controlled at more than the fusing point of alloy.Under the pyritous condition, for obtaining high-quality lead-calcium alloy.Must protect lead-calcium alloy with a tapping equipment that is set with the inert gas protection.
Purpose of the present invention, be to want to overcome above-mentioned shortcoming to produce plumbous calcium strontium ternary master alloy, reduce the loss of alloy component metal, mother alloy as production quaternary or multicomponent alloy, further improve alloy property, satisfy the anode material of metal electrodeposition, and do not have the demand of safeguarding the acid accumulator grid material, thereby widened the scope of application of alloy.
Content of the present invention is:
1, this produces the fused salt electrolysis process of plumbous calcium strontium ternary alloy, is to do negative electrode with molten lead liquid, and graphite is done anode, and fused calcium salt and strontium salt are done electrolytic solution, carry out electrolysis, and the calcium strontium is separated out on the fused lead electrode, and forms alloy.
2, calcium salt and strontium salt are anhydrous chloride.Melt formation electrolytic solution together with Repone K according to a certain percentage.
3, utilize the insulation electrolytic furnace to carry out electrolysis, alloy is cast into ingot metal, need not with inert gas protection, industrial scale, changeable as required.
Electrolyzer of the present invention as figure-shown in:
(1) anode-treated anti-oxidant Graphite Electrodes; (2) be the insulation insulation electrolyzer of the iron plate inner lining refractory block of 8～15mm; (3) electrolytic solution (being the fused salt mixt that the calcium-strontium-potassium muriate is formed); (4) negative electrode-fused solution lead; (5) cathode leg; (6) alloy escape orifice; (7) chlorine relief outlet.
Electrolysis technology condition:
1, electrolytic solution composition ratio: CaCl
2: SrCl
2: KCl=1.3～1.5: 1: 2;
2, the volume ratio of electrolytic solution and plumbous liquid: 2～3: 1;
3, positive cathode current density ratio: 2～3: 1;
4, bath voltage: 6～7 volts;
5, fused salt (electrolytic solution) temperature: between 600～780 ℃;
6, electrolysing period: 24～48 hours;
Operation steps:
1, blow-on: earlier electrolyzer is given heat, baking, adds the calcium-strontium-potassium salt of getting ready in proportion and carry out congruent melting, wait to melt the back and add liquid lead, adjust pole span (about 100mm), the starting rectifier send electric electrolysis.
2, process control: in the electrolytic process, regularly add and give dry earlier good calcium chloride, the mixing salt of strontium chloride, and suitable stirring, to promote the diffusion of calcium strontium in the plumbous liquid.Add a little calcium oxide or strontium oxide in case of necessity, eliminate contingent anode effect.After the suitable cycle of electrolysis, the viscosity of electrolytic solution rises, and at this moment, in putting the lead alloy process, emits a part of electrolytic solution simultaneously, adjusts viscosity, in order to normal electrolysis.
3, come out of the stove: behind the electrolysis one-period, during the content conformance with standard of sampling analysis calcium strontium, be that alloy contains Ca+Sr 〉=3%(wherein Ca 〉=1.5%, Sr 〉=1.5%) time, open valve, allow qualified plumbous calcium strontium ternary alloy, inject vertical die, ingot bar is unsuitable blocked up, avoids the calcium strontium to produce deviation in alloy.Constantly adjust graphite anode when coming out of the stove, make it to be unlikely to expose the fused salt liquid level, cause outage, cool off the situation of dead stove.After alloy is come out of the stove, in electrolyzer, add the liquid lead of equal amts, continue electrolysis.
Advantage of the present invention: (1) this fused salt electrolysis process, its electrolytic solution are made up of the muriatic mixture of calcium-strontium-potassium.As long as the ratio of the calcium-strontium-potassium muriate that control is certain, just the energy once electrolytic synthesizes the ternary alloy of plumbous calcium strontium, therefore, the utilization ratio height of calcium strontium, metal loss is few.
(2) can produce calcic is 1.5～2.5%; Strontium is 1.5～3.0%, and surplus is plumbous ternary master alloy.
(3) adopt the muriatic mixture of calcium-strontium-potassium to do electrolytic solution, fusing point is lower, and is promptly fusible about 600～700 ℃.Add Repone K, play dilution, go the effect of the utmost point and reduction fusing point,,, use repeatedly so once add by proportioning because Repone K itself is not separated out and do not consumed.The good flowing properties of molten electrolyte, viscosity is little, and the chlorine that electrolysis produces is easy to therefrom discharge.Simultaneously, because temperature of fusion is not high, plumbous vapour pressure is not high yet.Harm to the operator significantly reduces, and reaches not only safety but also economic purpose.
(4) graphite anode is the impregnated anti-oxidation electrode of phosphoric acid and phosphoric acid salt, in electrolytic process, is difficult for oxidation loss.
(5) production unit of this method is simple, is easy to grasp.The production less investment, industrialization is easy.Industrial scale is changeable.
(6) plumbous calcium strontium ternary alloy is a kind of type material that is applied to field of metallurgy.Plumbous calcium strontium silver quad alloy is the regeneration product of the lead-silver anode of electrowinning zinc.It can reduce by 70～80% silver consumption than lead-silver anode.And prolonged anodic work-ing life, improved the situation of adhering to of the anode sludge, thereby improved the quality of electrowinning zinc.In addition, plumbous calcium strontium ternary alloy is applied to make the grid material that hermetically sealed nothing is safeguarded acid accumulator, and is on probation through store battery producer, than single lead-calcium alloy, can strengthen rotproofness, reduces self-discharge, the long-term storing, and it is very little to leak electricity.
Embodiment 1
One, equipment: fused-salt bath is shown in accompanying drawing one.
Two, electrolysis technology condition:
(1) composition of electrolytic solution ratio: CaCl
2: SrCl
2: KCl=1: 1: 1
(2) positive cathode current density ratio is: 2.5～1
Anodic current density: 13000A/m
2
(3) electrolyte temperature: 600～670 ℃
(4) bath voltage: 6 volts
(5) volume ratio of liquid fused salt and plumbous liquid is 2: 1
(6) electrolysing period: 24 hours
Three, concrete operations rules:
1, blow-on: earlier electrolyzer is given heat, baking.The composition part that adds the electrolytic solution for preparing is carried out congruent melting.After waiting to melt, at this moment, the temperature of fused salt reaches more than 600 ℃, adds to have given the good liquid lead of fusing in market pot earlier.The volume ratio of regulating electrolytic solution and liquid lead is two-to-one.Insert graphite anode then through antioxidation treatment.About the about 100mm of levelling pole span.The starting rectifier send electrolysis.
2, the control of process: per hour add 4.5～6 kilograms calcium chloride for preparing in proportion and strontium chloride in the electrolytic process.Constantly adjust liquid level, and regularly stir, to promote the diffusion of calcium strontium in the plumbous liquid.
3, come out of the stove: electrolysis is after 24 hours, and sampling analysis, alloy contain the amount of Ca+Sr greater than more than 3%, and wherein Ca is 1.58%, and Sr is 1.63%, the rest is lead.At this moment, open outlet valve, cast,, cast thin piece for avoiding the composition deviation.
Electrolyzer is with embodiment 1
Electrolysis technology condition:
1, the composition of electrolytic solution ratio: CaCl
2: SrCl
2: KCl=1.3: 1: 1
2, positive cathode current density ratio: 2.5: 1
Anodic current density: 15000A/m
2
3, electrolyte temperature: 670～740 ℃
4, bath voltage: 6～7 volts
5, the volume ratio of electrolytic solution and plumbous liquid: 2: 1
6, electrolysing period: 24 hours.
Working specification is with embodiment 1, and electrolytic solution only adds the proportional quantity of calcium chloride and strontium chloride.Because Repone K has been dilution and has gone utmost point cooling effect in electrolytic process.Itself does not consume, and gets final product so keep primary proportional quantity.
The composition of output alloy: calcic is 1.7%, and containing strontium is 1.67%, and all the other are plumbous.
One, electrolyzer is with embodiment 1.
Two, electrolysis technology condition:
1, electrolytic solution composition ratio: CaCl
2: SrCl
2: KCl=1.3: 1: 1
2, positive cathode current density ratio: 2.5～1
Anodic current density: 15000A/m
2
3, the temperature of electrolytic solution: 730～780 ℃
4, the volume ratio of electrolytic solution and plumbous liquid is 2: 1
5, bath voltage: 6～7 volts
6, the production cycle: 24 hours
Three, the electrolysis procedure rules are as embodiment 1 or 2.But because continuous production is after 10 cycles, the viscosity of electrolytic solution rises to some extent, as the case may be, in putting the process of alloy, emits a part of electrolytic solution simultaneously, about 1/4, adjust viscosity, in order to normal electrolysis.When discovery had anode effect to produce, so in electrolytic solution, add 2% calcium oxide of total fused salt amount, strontium oxide was eliminated.
The composition of alloy: containing Ca is 1.68%, and containing Sr is 1.70%, the rest is lead.
Claims (3)
1, produces the fused salt electrolysis process of plumbous calcium strontium ternary master alloy.It is characterized in that, the anti-oxidant Graphite Electrodes of anode, the negative electrode molten lead liquid, the composition of electrolytic solution is with the mixture of fused anhydrous chloride.Carry out electrolysis then, the calcium strontium is separated out in the fused lead electrode, and form alloy.Its electrolysis technology condition is as follows:
(1) electrolytic solution is formed: CaCl
2: SrCl
2: KCl=1.3～1.5: 1: 2
(2) electrolytic solution (volume): plumbous liquid (volume)=2～3:1
(3) anodic current density: cathode current density=2～3:1
(4) bath voltage: 6～7 volts
(5) electrolyte temperature remains between 600～780 ℃.
2, said according to claim 1, as to produce plumbous calcium strontium ternary master alloy fused salt electrolysis process is characterized in that, graphite anode is the mixture with phosphoric acid and sodium phosphate or sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC etc., through the dipping antioxidation treatment in a week.
3, said according to claim 1 or 2, produce the dissolved salt electrolysis method of plumbous calcium strontium ternary alloy, the composition that it is characterized in that electrolytic solution is by the molecule proportioning.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106094 CN1025227C (en) | 1991-04-30 | 1991-04-30 | Melting salt electrolysis for prodn. of lead, calcium and strontium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106094 CN1025227C (en) | 1991-04-30 | 1991-04-30 | Melting salt electrolysis for prodn. of lead, calcium and strontium alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1066301A true CN1066301A (en) | 1992-11-18 |
| CN1025227C CN1025227C (en) | 1994-06-29 |
Family
ID=4907531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91106094 Expired - Fee Related CN1025227C (en) | 1991-04-30 | 1991-04-30 | Melting salt electrolysis for prodn. of lead, calcium and strontium alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1025227C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103695960A (en) * | 2014-01-09 | 2014-04-02 | 申中军 | Manufacturing method of electrolytic manganese metal alloy lead-plastic composite anode |
| CN107557818A (en) * | 2017-08-22 | 2018-01-09 | 中南大学 | It is a kind of can continuous electrolysis production copper calcium alloy large scale industry electrolytic cell |
-
1991
- 1991-04-30 CN CN 91106094 patent/CN1025227C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103695960A (en) * | 2014-01-09 | 2014-04-02 | 申中军 | Manufacturing method of electrolytic manganese metal alloy lead-plastic composite anode |
| CN107557818A (en) * | 2017-08-22 | 2018-01-09 | 中南大学 | It is a kind of can continuous electrolysis production copper calcium alloy large scale industry electrolytic cell |
| CN107557818B (en) * | 2017-08-22 | 2019-04-09 | 中南大学 | It is a kind of can continuous electrolysis production copper calcium alloy large scale industry electrolytic cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1025227C (en) | 1994-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5024737A (en) | Process for producing a reactive metal-magnesium alloy | |
| SU1416060A3 (en) | Method of producing metals | |
| CN103484891B (en) | A kind of electrolgtic aluminium electrolyzer and use the electrolysis process of this electrolyzer | |
| CN101654796B (en) | Method for preparing Al-Li alloy through molten salt electrolytic method | |
| EP3859052A1 (en) | Method for preparing titanium-aluminum alloy | |
| CN106967998A (en) | The method that Al Li foundry alloys are prepared as the nearly room temperature electro-deposition of raw material using lithia | |
| CN110106526A (en) | The method for preparing lithium metal based on solid electrolyte | |
| CN101914699B (en) | Fused salt electrosynthesis method of hydrogen storage alloy containing magnesium, lithium, sodium and potassium | |
| CN111705337B (en) | Method for preparing lead-calcium master alloy by molten salt galvanic cell method | |
| CN1025227C (en) | Melting salt electrolysis for prodn. of lead, calcium and strontium alloy | |
| CA1251162A (en) | Method of producing a high purity aluminum-lithium mother alloy | |
| CN110306052B (en) | Metallic lithium elementary substance and preparation method and application thereof | |
| CN115305505A (en) | Molten salt electrolysis method for preparing metal lithium | |
| CN101376992A (en) | Method for preparing magnesium lithium alloy by fused salt electrolysis process | |
| CN115161714B (en) | Method for preparing metallic titanium by molten salt solid-state deoxidization method | |
| CN1010486B (en) | Process for producing grid alloy of battery | |
| CN115305507B (en) | Method for producing metal aluminum by molten salt electrolysis of aluminum oxide | |
| CN113185857B (en) | Graphite anode plate antioxidant coating composition and application thereof | |
| CN104357880A (en) | Method for preparing copper-lithium mother alloy by self-consuming cathode fused salt electrolysis | |
| CN108118366A (en) | A kind of method of alumina dissolution speed in quickening aluminium cell | |
| US3034972A (en) | Electrolytic production of aluminum | |
| KR101801453B1 (en) | Electrolyte used for aluminum electrolysis and electrolysis process using the electrolyte | |
| JPS6312150B2 (en) | ||
| CN1063582A (en) | The multicomponent alloy of battery grid and process for making | |
| CN1208860C (en) | Plumbum-rare earth mulaticomponent alloy being used as positive plate grid of lead accumulator and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |