CN1037620C - Compound alloy anode for electrolytic production of metal manganes and its preparation method - Google Patents
Compound alloy anode for electrolytic production of metal manganes and its preparation method Download PDFInfo
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Abstract
The present invention relates to a composite alloy anode for the electrolytic production of metal manganese and a preparation method thereof. The anode contains a plumbum-coating conductive cross beam (1), a pure lead conductive strip (2) and a corrosion-resistance porous plumbum alloy plate (4). The composite alloy anode is characterized in that the alloy plate (4) is made by rolling and punching, and a corrosion-resistant alloy transition strip (3) or an organic high polymer packaging belt (3) horizontally extending is arranged on the surface of the alloy plate at the connecting position of the conductive strip (2) and the alloy plate (4); the alloy plate (4) comprises the basic components of 0.1 to 1.0% of Ag and balance of Pb, and a certain amount of Ca, Sr, Al and/or RE is added on the basis so that the performance of the composite alloy anode can be further improved.
Description
The present invention relates to electrolysis production metal anode, or rather, relate to compound alloy anode for electrolytic production of metal manganes and preparation method thereof.
The processing requirement of electrolysis production manganese metal is carried out in diaphragm electrolytic cell.Usually used diaphragm material is acidproof woven dacron, and cathode material is a stainless steel, and anode material is insoluble argentiferous lead alloy.Electrolytic solution is manganese sulfate solution.Electrolytic result deposits manganese metal on negative electrode, might produce oxygen and/or manganese dioxide precipitate on anode.But produce the factory of manganese for majority, hope only generates oxygen and does not generate Manganse Dioxide on anode, because generation Manganse Dioxide will consume the mn ion in the manganous sulfate electrolytic solution, reduce the direct yield of manganese metal, thereby reduce the technico-economical comparison of electrolysis production.For this reason, must create the condition help generating oxygen and to be unfavorable for generating manganese dioxide precipitate in the positive column, these conditions are: a) electrolyte temperature is below 40 ℃, this point during with cathodic area metal refining manganese to temperature require consistent; B) anodic current density reaches 600-750A/M
2Or bigger, and cathode current density only is 400-500A/M
2Or littler, promptly anodic current density is preferably big 30-70% than the big 20-87% of cathode current density.Be to realize b) requirement of some condition, can not only realize to reduce anodic physical dimension, otherwise can cause the cathode surface electric force lines distribution inhomogeneous, thereby reduce current efficiency.For this reason, general factory all adopts porous anode, promptly has many holes to reduce its useful area on positive plate.According to calculating, as require current density to increase 30%, 50%, 70%, then the percentage of open area of battery lead plate must correspondingly reach 23%, 33% and 41%.And the aperture in each hole (being the minor face size when rectangular opening) is unsuitable excessive, otherwise electric force lines distribution is inhomogeneous.If the aperture is too small, then can cause the rib between hole meticulous, the disconnected muscle that is corroded easily, and also aperture easily stopped up by sedimentary Manganse Dioxide, influences the circulation of electrolytic solution.And owing to Manganse Dioxide can conduct electricity, thereby just the anode useful area increases again.In general, the suitable size of the aperture in each hole (or minor face size of rectangular opening) is 10-70mm, is preferably 15-50mm.The arrangement in hole and distribution are evenly to be advisable as far as possible.For reaching this purpose, generally all adopt casting technique to make the positive plate that electrolysis production manganese is used at present.And hole generally all adopts the narrow and long rectangular hole.And casting hole less porous anode plate requires the fusing point of this alloy lower and require the flowability (castibility) of this liquid metal very good.If the fusing point of alloy is too high, then still just solidify during the terminal of no show mold at liquid metal, can not get complete positive plate.If the flowability of liquid metal is good inadequately, then liquid metal can not fill up complex-shaped mold, causes in the positive plate metal strip between two holes meticulous or damaged, and the result reduces anodic work-ing life greatly.So in order to make this anode, involutory lsp request is very high, promptly should fusing point lower, require mobile very good after the fusing again, also requiring has enough erosion resistances in acidic medium, and require to have certain intensity, in order to avoid warpage takes place in installation process or in electrolytic process.Usually all adopt a kind ofly to have cerrobase necessarily corrosion-resistant, certain intensity and make this kind anode, it consists of 20-40%Sn, 1.0%Sb, 1.0%Ag, and all the other are Pb.The fusing point of this kind alloy is lower, is about 270-275 ℃, and castability is fine.For the ease of casting, also hole is made long strip shape.This positive plate has satisfied the processing requirement of electrolysis production manganese metal to a certain extent, yet still there is the following bigger shortcoming in it;
1, the content height of alloying element costs an arm and a leg;
2, the erosion resistance of positive plate is good inadequately, the life-span short (being generally 4-6 month).
3, the resistance of this alloy is higher, so power consumption is bigger.
Therefore, people wish to develop the positive plate that a kind of electrolysis production manganese metal that can overcome above-mentioned various shortcomings is used very much.
The objective of the invention is to provide a kind of shortcoming that can overcome above-mentioned prior art, alloying element content is lower, good corrosion resistance, and long service life, resistance is less, and the better simply compound alloy anode for electrolytic production of metal manganes of production technique and preparation method thereof.
The inventor has passed through the research of long period, found that,, just can not require that alloy has the enough good flowability of enough low fusing point and fusing back if adopt rolling method to make positive plate, thereby can reduce alloying element greatly, the content of (particularly tin).But adopting rolling method to be shaped then requires alloy to have ductility preferably.And, in order to make this anode have erosion resistance preferably and lower resistivity and enough intensity, the inventor studies the composition of alloy again, find that a class does not contain Sn and Sb, only contain a small amount of Ag, the lead alloy that randomly also contains a small amount of other alloying elements can reach above-mentioned requirements basically.But the contriver found again afterwards; though the erosion resistance of alloy sheets main body has improved greatly; but the corrosion phenomenon at the liquid-gas interface place is still more serious; so adopt a kind of alloy transition bar of good corrosion resistance or protect the liquid-gas interface of positive plate with acidproof plastics transition strips; thereby prolonged anodic work-ing life on the whole greatly; promptly can use at least 1 year or the longer time, that is to say, its work-ing life is than prior art long 1-3 anode life times even more.Because these results of study, thereby finished the present invention.
Thereby, the invention provides a kind of compound alloy anode for electrolytic production of metal manganes, contain lead-sheathing conducting beam, pure plumbous busbar and solidity to corrosion porous lead alloy sheets, it is characterized in that,
The porous alloy plate of said alloy sheets for forming by rolling and punching,
Non-corrosive metal transition strips that has on the alloy sheets surface of pure plumbous busbar and alloy sheets junction that a width extends for the 15-80mm along continuous straight runs and weld mutually with alloy sheets or the organic polymer Wrapping belt of pasting mutually with alloy sheets,
Said porous alloy plate contains following composition;
Ag 0.1-1.0 weight %
The Pb surplus.
In the composite alloy anode of the invention described above, define battery lead plate for form by rolling and punching rather than directly form by casting, because the porous alloy plate that forms by rolling and punching all is being much better than the casting product aspect the compactness two of profile integrity and inner quality, its resistivity is also lower, and aspect intensity, also be much better than the casting product, therefore can obtain long work-ing life.
In the feature of the invention described above, alloying constituent also is important feature, contained silver and plumbous in the composite alloy anodic alloy sheets of the invention described above, it is the basic essential feature of composite alloy anode of the present invention, if on the basis of this essential characteristic, add a certain amount of Ca, Sr, Al and/or RE (RE is the mixture that is selected from a certain in the rare earth element or is made up of multiple rare earth element) again, perhaps replace part silver, then can further improve composite alloy anodic performance of the present invention with several elements of wherein certain or certain.
That is to say that according to the compound alloy anode for electrolytic production of metal manganes of the invention described above, its additional technical characterictic is that wherein said porous alloy plate contains the composition of following any composition:
Composition 1:
Ag 0.1-1.0 weight %
RE 0.01-0.10 weight %
The Pb surplus
Composition 2:
Ag 0.1-1.0 weight %
Ca 0.05-0.15 weight %
Al 0.01-0.10 weight %
RE 0.01-0.10 weight %
The Pb surplus
Composition 3:
Ag 0.15-0.30 weight %
Ca 0.05-0.15 weight %
Al 0.01-0.10 weight %
RE 0.01-0.10 weight %
The Pb surplus
Combination 4:
Ag 0.1-1.0 weight %
Ca 0.01-0.10 weight %
Sr 0.01-0.10 weight %
The Pb surplus
Composition 5:
Ag 0.15-0.30 % by weight Ca 0.01-0.10 % by weight Sr 0.01-0.10 % by weight Pb surplus composition 6:Ag 0.1-1.0 % by weight Ca 0.01-0.10 % by weight Sr 0.01-0.10 % by weight Al 0.01-0.10 % by weight Pb surplus composition 7:Ag 0.15-0.30 % by weight Ca 0.01-0.10 % by weight Sr 0.01-0.10 % by weight Al 0.01-0.10 % by weight Pb surplus composition 8:Ag 0.1-1.0 % by weight Ca 0.01-0.10 % by weight Sr 0.01-0.10 % by weight Al 0.01-0.10 % by weight RE 0.01-0.10 % by weight Pb surplus composition 9:Ag 0.15-0.30 % by weight Ca 0.01-0.10 % by weight
Sr 0.01-0.10 weight %
Al 0.01-0.10 weight %
RE 0.01-0.10 weight %
The Pb surplus
In above-mentioned various compositions, with the best results of composition 3.
In addition, lip-deep alloy transition bar of above-mentioned alloy sheets in pure plumbous busbar and alloy sheets junction or organic polymer Wrapping belt must have certain width.In the present invention, its width is defined as 15-80mm.When carrying out electrolysis, this transition strips or Wrapping belt just in time are in the liquid-gas interface place, thereby have prevented that battery lead plate is in the too fast corrosion of liquid-gas interface or stoped corrosion herein fully.The thickness of this alloy transition bar or organic polymer Wrapping belt does not have strict restriction, and this will decide on the corrosion resistance nature of this kind material.For example, when using the various materials identical with above-mentioned alloy sheets to make transition strips, its thickness is suitably 8-20mm.In addition, also can use to contain Sn 20-40 weight %, Ag 0.1-2.0 weight %, Sb 0.1-2.0 weight %, all the other are the quad alloy transition strips of Pb, and its thickness also is suitably 8-20mm.Though the solidity to corrosion of this alloy in manganous sulfate electrolytic solution is not as good as the used alloy of above-mentioned battery lead plate, its solidity to corrosion under gas, liquid, solid (referring to separate the matter precipitate) three-phase coexistence condition all is better than above-mentioned alloy, so preferablyly use as transition strips.In addition, also can use the transition strips of other corrosion resisting alloys, but it must have good weldability with the lead alloy as battery lead plate, and the polarized potential of best and battery lead plate alloy is approaching, otherwise increases corrosion speed on the contrary.If use the organic polymer Wrapping belt, then can select tetrafluoroethylene, polyvinyl chloride, polypropylene, Resins, epoxy, glass reinforced plastic etc. for use, wherein be preferably tetrafluoroethylene, polyethylene and Resins, epoxy.Can be pressure sintering, spraying method, spread coating or mull technique etc. with the organic polymer sealing label to the method on the electroplax plate, and this will decide on adopting any superpolymer.For example, when adopting polyethylene, preferably adopt pressure sintering, when adopting tetrafluoroethylene, can adopt spraying method, when adopting Resins, epoxy, then should adopt spread coating.When adopting the organic polymer Wrapping belt, its suitable depth can be 0.5-5mm.
The physical dimension of battery lead plate does not have any restriction, and this can decide according to the shape and the size of electrolyzer.And the thickness of battery lead plate does not have strict restriction yet, and the technician can suitably select according to its intensity and corrosion resistance nature, and for alloy of the present invention, suitable thickness is 2-12mm, is preferably 4-8mm.
The shape of hole does not have any restriction yet on the battery lead plate, but wherein this is several comparatively suitable with rectangle, square and circle.Under rectangular situation, its suitable width is 15-40mm, and suitable length is 30-100mm, and its suitable percentage of open area is 25-50%.Under foursquare situation, its suitable length of side is 15-50mm, and its suitable percentage of open area is 25-50%, and its arrangement mode is preferably square.Under the situation of circle, its suitable diameter is 15-50mm, and its suitable percentage of open area is 25-50%, as for its suitable arrangement mode, is preferable with square pitch arrangement and this dual mode of triangular arranged, wherein most preferably is the arrangement mode of equilateral triangle.
Features such as above-mentioned shape all about battery lead plate, structure and size all belong to supplementary features of the present invention.
In addition, the present invention also provides a kind of preparation method of compound alloy anode for electrolytic production of metal manganes, this anode contains lead-sheathing conducting beam, pure plumbous busbar and solidity to corrosion porous lead alloy sheets, on the alloy sheets surface of pure plumbous busbar and alloy sheets junction, have non-corrosive metal transition strips or organic polymer Wrapping belt that a width extends for the 15-80mm along continuous straight runs, it is characterized in that this method comprises following steps:
(1) according to following alloying constituent melting solidity to corrosion lead alloy
Ag 0.1-1.0 weight %
The Pb surplus
(2) above-mentioned lead alloy is made the porous alloy plate of desired shape with rolling, shearing and perforated method,
(3) above-mentioned lead-sheathing conducting beam, pure plumbous busbar and porous alloy plate are linked together with the lead welding method,
(4) on the alloy sheets surface of pure plumbous busbar and alloy sheets junction along continuous straight runs with burn-on non-corrosive metal transition strips that a width is 15-80mm or paste the organic polymer Wrapping belt that width is 15-80mm of lead welding method with any method in spraying method, pressure sintering, spread coating, the mull technique.
In addition, if on the basis of the used alloying constituent of above-mentioned steps (1), add a certain amount of Ca, Sr, Al and/or RE (RE is the mixture that is selected from a certain in the rare earth element or is made up of multiple rare earth element) again, perhaps replace part silver, then can make method of the present invention obtain better effect with several elements of wherein certain or certain.
That is to say that according to the preparation method of the compound alloy anode for electrolytic production of metal manganes of the invention described above, its additional technical characterictic is that wherein said step (1) is come melting solidity to corrosion lead alloy according to the alloying constituent of following any composition;
1：Ag 0.1-1.0％RE 0.01-0.10％Pb 2：Ag 0.1-1.0％Ca 0.05-0.15％Al 0.01-0.10％RE 0.01-0.10％Pb 3：Ag 0.15-0.30％Ca 0.05-0.15％Al 0.01-0.10％RE 0.01-0.10％Pb 4：Ag 0.1-1.0％Ca 0.01-0.10％Sr 0.01-0.10％Pb 5：Ag 0.15-0.30％Ca 0.01-0.10％Sr 0.01-0.10％Pb 6：Ag 0.1-1.0％Ca 0.01-0.10％Sr 0.01-0.10％Al 0.01-0.10％Pb 7：Ag 0.15-0.30％Ca 0.01-0.10％Sr 0.01-0.10％Al 0.01-0.10％Pb 8：Ag 0.1-1.0％Ca 0.01-0.10％Sr 0.01-0.10％Al 0.01-0.10％RE 0.01-0.10％Pb 9：Ag 0.15-0.30％Ca 0.01-0.10％Sr 0.01-0.10％Al 0.01-0.10％RE 0.01-0.10％
The Pb surplus
In above-mentioned various compositions, with the best results of composition 3.
In addition, another supplementary features of the inventive method are that the composition of wherein said non-corrosive metal transition strips is identical with the composition of said porous alloy plate.
Another supplementary features are that the composition of wherein said non-corrosive metal transition strips is:
Sn 20-40 weight %
Ag 0.1-2.0 weight %
Sb 0.1-2.0 weight %
The Pb surplus
Another supplementary features are, the material of wherein said organic polymer Wrapping belt is a polyethylene, and used method of attaching is a pressure sintering.
Another supplementary features are, the material of wherein said organic polymer Wrapping belt is a tetrafluoroethylene, and used method of attaching is a spraying method.
Another supplementary features are, the material of wherein said organic polymer Wrapping belt is a Resins, epoxy, and used method of attaching is a spread coating.
Essential features of the present invention and additional technical characterictic have been made detailed description above, those of ordinary skill can be realized the present invention according to these technical characterictics.
Compared with prior art, the advantage of compound alloy anode for electrolytic production of metal manganes of the present invention and preparation method thereof is as follows: 1, the content of alloying element is much lower, so cheap; 2, corrosion resistance is much better than, long 1-3 of its life-span times even longer; 3, resistance is less, so power consumption is low by 4, production technique is simple, the yield rate height.
Explain the present invention below in conjunction with accompanying drawing, wherein:
Fig. 1 is the structural representation of the 1st kind of scheme of composite alloy anode of the present invention, wherein shows rectangular hole;
Fig. 2 is the structural representation of the 2nd kind of scheme of composite alloy anode of the present invention, wherein shows foursquare hole;
Fig. 3 is the structural representation of the 3rd kind of scheme of composite alloy anode of the present invention, wherein shows the circular opening by square pitch arrangement;
Fig. 4 is the structural representation of the 4th kind of scheme of composite alloy anode of the present invention, wherein shows the circular opening by triangular arranged.
In Fig. 1-4, parts or position that identical witness marker numeral is identical.Wherein: 1, lead-sheathing conduction crossbeam; 2, pure plumbous busbar; 3, protectiveness alloy transition bar or organic polymer Wrapping belt; 4, rolling punching alloy sheets; 5, hole; 6, the electrical contact on the conduction crossbeam.
Fig. 5 is the synoptic diagram of the used electrolyzer of embodiments of the invention.Wherein: 7, cell body; 8, barrier film; 9, fresh electrolyte; 10, electrolysis tail washings; (+) is anode; (-) is negative electrode.
Enumerate embodiment below and further explain the present invention, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
Use diaphragm sell as shown in Figure 5, diaphragm material is acidproof woven dacron, and barrier film only slows down mass transfer (diffusion) and do not influence conduction.Negative electrode is in batten to be done in the chamber of septum (anolyte compartment) of framework.Use 21 anodes and 20 negative electrodes altogether.
The composition of anode material (add-on during melting) is that 0.20%Ag, 0.14%Ca, 0.10%Al, 0.10%RE (mishmetal), surplus are Pb.Transition strips is partly made the alloy bar of thick 12.0mm, wide 40mm through---rolling---shearing of casting with the alloy of 30.0%Sn, 1.0%Ag, 1.0%Sb, 68.0%Pb.Top conductive head is partly sealed with pure plumbous casting and is formed, and the three welds and constitutes whole anode through lead welding.
It is tabular that negative electrode is made the rectangle atresia with the 1Cr18Ni9Ti stainless steel, and its physical dimension is: high 570mm (referring to height under the liquid level), wide 375mm, thick 4mm.
Anodic physical dimension is high (referring to height under the liquid level) 565mm, wide 355mm, thick 6mm.As shown in Figure 1, have rectangular hole on the anode, the long limit of hole is of a size of 80mm, and minor face is of a size of 15mm, and the branch width between hole is 18mm.Percentage of open area on the anode is about 30%.Cathode area is 1.52 with the ratio of anode useful area.
As shown in Figure 5, fresh MnSO
4Electrolytic solution 9 is from electrolyzer one endfeed, and electrolysis tail washings 10 is then discharged from the other end.The processing condition of electrolytic process are: anodic current density 670A/m
2, cathode current density 400A/m
2The manganese ion concentration that enters in the fresh electrolyte of cathode compartment is 40 ± 1g/l, with ammoniacal liquor with the acidity control of cathode compartment in pH7.8 ± 0.2.With this understanding, the manganese ion concentration of anolyte compartment maintains 15 ± 3.0g/l automatically, the free sulfuric acid (H of anolyte compartment
2SO
4) concentration maintains 37.5 ± 2.5g/l automatically.Making the electrolyzer non-stop run write down single groove day output, power consumption, anode life three data of manganese metal after 2 years under such condition, obtaining data are listed in the table 1 to estimate.
Comparative Examples 1
One with embodiment 1 identical electrolyzer in, adopts identical processing condition, the use by casting the conventional anode of directly making, it consists of 30%Sn, 1.0%Sb, 1.0%Ag, all the other are Pb.The physical dimension of this conventional anode and perforate situation and embodiment 1 are identical, but do not have protectiveness alloy transition bar.Three same data are write down in non-stop run after 2 years, obtaining data are listed in the table 1 to estimate.
Two kinds of anodic performance comparison of table 1
Can find out obviously that by table 1 composite alloy anode of the present invention is at the anode that is better than prior art aspect the groove output of electrolytic manganese, power consumption, work-ing life three all significantly.Particularly be equivalent to 3.5 times of prior art anodic aspect work-ing life.And because the used alloying element of anode of the present invention is far below the anode of prior art, therefore, its comprehensive economic index is higher than the anode of prior art far away.
Embodiment 2
Use and embodiment 1 identical electrolyzer and processing condition, different just anodes change the anode of structure as shown in Figure 2 into, have 40 on the anode and be the evenly distributed square hole of square, the length of side of square hole is 40mm
2The anodic percentage of open area is about 32%.The result shows, the groove output that is obtained, power consumption and anode life three data and the data of embodiment 1 very near (differ be at most about 5%, can think in the experimental error scope).
Embodiment 3
Use identical electrolyzer of embodiment 1-2 and processing condition, different just anodes change the anode of structure as shown in Figure 3 into, have 54 on the positive plate and be the evenly distributed circular hole of square, the diameter of circular hole is 38mm.The anodic percentage of open area is about 30.5%.The result shows, the groove output that is obtained, power consumption and anode life three data and the data of embodiment 1 very approaching.
Embodiment 4
Use and identical electrolyzer of embodiment 1-3 and processing condition, different just anodes change the anode of structure as shown in Figure 4 into, have 55 on the positive plate and be the evenly distributed circular hole of equilateral triangle, the diameter of circular hole is 38mm.The anodic percentage of open area is about 31.1%.The result shows, the groove output that is obtained, power consumption and anode lives three number and the data of embodiment 1 very approaching.
Embodiment 5
Use and identical electrolyzer of embodiment 1-5 and processing condition; the shape of hole, big or small all identical on its anode with embodiment 4 with arrangement mode; institute's difference is not have protectiveness non-corrosive metal transition strips on this anode, and what replace it is the thick polyethylene of pasting by hot pressing of 2mm.The result who is obtained shows that its performance is almost completely consistent with embodiment 4 used anodic performances.
Some preferred embodiments of the present invention have been enumerated above, yet those of ordinary skill in the art is at the embodiment that also can make many variation schemes under the condition of spirit of the present invention, but all these variation schemes, as long as fall in claims institute restricted portion of the application, all should be considered to belong to the present invention.
Claims (25)
1, a kind of compound alloy anode for electrolytic production of metal manganes contains lead-sheathing conduction crossbeam (1), pure plumbous busbar (2), solidity to corrosion porous lead alloy sheets (4), it is characterized in that,
The porous alloy plate of said alloy sheets (4) for forming by rolling and punching,
Non-corrosive metal transition strips (3) that has on the alloy sheets surface of pure plumbous busbar (2) and alloy sheets (4) junction that a width extends for the 15-80mm along continuous straight runs and weld mutually with alloy sheets (4) or the organic polymer Wrapping belt of pasting mutually with alloy sheets (3)
Said porous alloy plate contains following composition:
Ag 0.1-1.0 weight %
The Pb surplus.
2, composite alloy anode as claimed in claim 1 is characterized in that, it is characterized in that, wherein said porous alloy plate (4) contains following composition:
Ag 0.1-1.0 weight %
RE (is selected from the rare earth element
One or more mixture)
0.01-0.10 weight %
The Pb surplus.
3, composite alloy anode as claimed in claim 1 is characterized in that, wherein said porous alloy plate (4) contains following composition:
Ag 0.1-1.0 weight %
Ca 0.05-0.15 weight %
Al 0.01-0.10 weight %
RE 0.01-0.10 weight %
The Pb surplus.
4, composite alloy anode as claimed in claim 3 is characterized in that, wherein said porous alloy plate (4) contains following composition:
Ag 0.15-0.30 weight %
Ca 0.05-0.15 weight %
Al 0.01-0.10 weight %
RE 0.01-0.10 weight %
The Pb surplus.
5, composite alloy anode as claimed in claim 1 is characterized in that, wherein said porous alloy plate (4) contains following composition:
Ag 0.1-1.0 weight %
Ca 0.01-0.10 weight %
Sr 0.01-0.10 weight %
The Pb surplus.
6, composite alloy anode as claimed in claim 5 is characterized in that, wherein said porous alloy plate (4) contains following composition:
Ag 0.15-0.30 weight %
Ca 0.01-0.10 weight %
Sr 0.01-0.10 weight %
The Pb surplus.
7, composite alloy anode as claimed in claim 1 is characterized in that, wherein said porous alloy plate (4) contains following composition:
Ag 0.1-1.0 weight %
Ca 0.01-0.10 weight %
Sr 0.01-0.10 weight %
Al 0.01-0.10 weight %
The Pb surplus.
8, composite alloy anode as claimed in claim 7 is characterized in that, wherein said porous alloy plate (4) contains following composition:
Ag 0.15-0.30 weight %
Ca 0.01-0.10 weight %
Sr 0.01-0.10 weight %
Al 0.01-0.10 weight %
The Pb surplus.
9, composite alloy anode as claimed in claim 1 is characterized in that, wherein said porous alloy plate (4) contains following composition:
Ag 0.1-1.0 weight %
Ca 0.01-0.10 weight %
Sr 0.01-0.10 weight %
Al 0.01-0.10 weight %
RE 0.01-0.10 weight %
The Pb surplus.
10, composite alloy anode as claimed in claim 9 is characterized in that, wherein said porous alloy plate (4) contains following composition:
Ag 0.15-0.30 weight %
Ca 0.01-0.10 weight %
Sr 0.01-0.10 weight %
Al 0.01-0.10 weight %
RE 0.01-0.10 weight %
The Pb surplus.
11, composite alloy anode as claimed in claim 1 is characterized in that, the contained composition of wherein said alloy transition bar (3) is identical with the composition of said porous alloy plate (4), and its thickness is 8-20mm.
12, composite alloy anode as claimed in claim 1 is characterized in that, the contained composition of wherein said alloy transition bar (3) is
Sn 20-40 weight %
Ag 0.1-2.0 weight %
Sb 0.1-2.0 weight %
Its thickness of Pb surplus is 8-20mm.
13, composite alloy anode as claimed in claim 1 is characterized in that, the material of wherein said organic polymer Wrapping belt (3) is a polyethylene, and its thickness is 0.5-5mm.
14, composite alloy anode as claimed in claim 1 is characterized in that, the material of wherein said organic polymer Wrapping belt (3) is a tetrafluoroethylene, and its thickness is 0.5-5mm.
15, composite alloy anode as claimed in claim 1 is characterized in that, the material of wherein said organic polymer Wrapping belt (3) is a Resins, epoxy, and its thickness is 0.5-5mm.
16, composite alloy anode as claimed in claim 1 is characterized in that, wherein said hole is a rectangle, and its width is 15-40mm, and length is 30-100mm, and its percentage of open area is 25-50%.
17, composite alloy anode as claimed in claim 1 is characterized in that, wherein said hole is a square, and its length of side is 15-50mm, and its percentage of open area is 25-50%.
18, composite alloy anode as claimed in claim 1 is characterized in that, wherein said hole is circular, and its diameter is 15-50mm, and its percentage of open area is 25-50%, and its arrangement mode is a square.
19, composite alloy anode as claimed in claim 1 is characterized in that, wherein said hole is circular, and its diameter is 15-50mm, and its percentage of open area is 25-50%, and its arrangement mode is an equilateral triangle.
20, a kind of preparation method of compound alloy anode for electrolytic production of metal manganes, this anode contains lead-sheathing conducting beam (1), pure plumbous busbar (2) and solidity to corrosion porous lead alloy sheets (4), on the alloy sheets surface of pure plumbous busbar (2) and alloy sheets (4) junction, have non-corrosive metal transition strips (3) or organic polymer Wrapping belt (3) that a width extends for the 15-80mm along continuous straight runs, it is characterized in that this method comprises following steps:
(1) according to each described alloying constituent melting solidity to corrosion lead alloy among the claim 1-10,
(2) above-mentioned lead alloy is made the porous alloy plate (4) of desired shape with rolling, shearing and perforated method,
(3) above-mentioned lead-sheathing conducting beam (1), pure plumbous busbar (2) and porous alloy plate (4) are linked together with the lead welding method,
(4) on the alloy sheets surface of pure plumbous busbar (2) and porous alloy plate (4) junction along continuous straight runs with burn-on non-corrosive metal transition strips (3) that a width is 15-80mm or with the organic polymer Wrapping belt (3) that to paste a last width be 15-80mm of any method in spraying method, pressure sintering, spread coating, the mull technique of lead welding method.
As the method for claim 20, it is characterized in that 21, the composition of wherein said non-corrosive metal transition strips (3) is identical with the composition of said porous alloy plate (4).
As the method for claim 20, it is characterized in that 22, the composition of wherein said non-corrosive metal transition strips (3) is:
Sn 20-40 weight %
Ag 0.1-2.0 weight %
Sb 0.1-2.0 weight %
The Pb surplus.
23, as the method for claim 20, the material of wherein said superpolymer Wrapping belt (3) is a polyethylene, and used method of attaching is a pressure sintering.
24, as the method for claim 20, the material of wherein said superpolymer Wrapping belt (3) is a tetrafluoroethylene, and used method of attaching is a spraying method.
25, as the method for claim 20, the material of wherein said superpolymer Wrapping belt (3) is a Resins, epoxy, and used method of attaching is a spread coating.
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| CN95102425A CN1037620C (en) | 1995-03-17 | 1995-03-17 | Compound alloy anode for electrolytic production of metal manganes and its preparation method |
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| CN95102425A CN1037620C (en) | 1995-03-17 | 1995-03-17 | Compound alloy anode for electrolytic production of metal manganes and its preparation method |
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| CN1037620C true CN1037620C (en) | 1998-03-04 |
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| CN112605522A (en) * | 2020-12-16 | 2021-04-06 | 厦门理工学院 | Welding method of Pb-Ag-RE alloy anode plate |
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| CN85104334A (en) * | 1985-06-06 | 1986-09-03 | 福建师范大学 | Produce the method for electrolytic metal Mn and fibrous electrolytical manganese dioxide simultaneously |
| CN1048732A (en) * | 1989-07-14 | 1991-01-23 | 帕马斯坎德公司 | Electrode |
| CN1071975A (en) * | 1991-10-31 | 1993-05-12 | 福建师范大学 | Produce the technology and the electrode special of electrolytic metal Mn with rich manganese slag and Manganous chloride tetrahydrate-ammonium chloride system |
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| CN85104334A (en) * | 1985-06-06 | 1986-09-03 | 福建师范大学 | Produce the method for electrolytic metal Mn and fibrous electrolytical manganese dioxide simultaneously |
| CN1048732A (en) * | 1989-07-14 | 1991-01-23 | 帕马斯坎德公司 | Electrode |
| CN1071975A (en) * | 1991-10-31 | 1993-05-12 | 福建师范大学 | Produce the technology and the electrode special of electrolytic metal Mn with rich manganese slag and Manganous chloride tetrahydrate-ammonium chloride system |
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