CN1896327A - Bi-polar composite electrode for electrolyzing aluminum - Google Patents
Bi-polar composite electrode for electrolyzing aluminum Download PDFInfo
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- CN1896327A CN1896327A CN 200610046982 CN200610046982A CN1896327A CN 1896327 A CN1896327 A CN 1896327A CN 200610046982 CN200610046982 CN 200610046982 CN 200610046982 A CN200610046982 A CN 200610046982A CN 1896327 A CN1896327 A CN 1896327A
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Abstract
The present invention provides a bipolar composite electrode for aluminum electrolysis that is composed of cathode material with aluminum wetness and inert anode material. The anode layer and the cathode layer both of 2-200mm thick are joined together by compaction or cementing. The cathode layer is also a porous structure with aperture of 1mm-10mm and the interstitial surface area takes 20-80% of the electrode area. This bipolar composite electrode features that small amount of Aluminium that deposits at cathode is moved to the working face of the anode to form a compact protecting oxide film with equal dissolving rate and forming rate to depress the corrosion of the anode. The electrodes are arranged in series without connecting wires solving the connection problem of inert eletrodes. The electrolysis tank has a simple structure and convenient operation, which will reduce the cost of aluminum production.
Description
Technical field
The present invention relates to technical field of aluminum electrolysis, be specifically related to a kind of used for aluminium electrolysis bipolarity combined electrode.
Background technology
Aluminium electrolytic industry is the basic industry of national economy, and is celebrated to consume energy.Producing 1 ton of aluminium needs consumed power 14000-15000 degree, needs about 2 tons of raw alumina, about 500 kilograms of high-quality carbon material.To environmental emission 1.6-2.0 ton CO2 gas, reach some other obnoxious flavoures simultaneously.China 2005 produces about 7,800,000 tons of aluminium amounts per year, account for world aluminum 3,187 ten thousand tons of ultimate productions 1/4.Aluminium electrolytic industry also consumes a large amount of resources every year except that consuming big energy, wherein only carbon anode consumption just needs more than 300 ten thousand tons of high-quality petroleum cokes every year, more than 200 ten thousand tons of fat coal pitches.
Energy-conservation and environmental protection is two root problems that aluminium electrolytic industry faces.Saving the energy and resource, reduce the discharging to environment, is the direction that aluminum electrolyzation technology further develops.The development that integrates the noble electrode electrolyzer of inert anode technology, inert cathode technology and low-temperature aluminum electrolysis technology is the basic outlet that addresses the above problem.
The development of noble electrode electrolyzer, its key issue is the exploitation of inert anode technology, and the development of inert anode, is to solve the contradiction of the erosion resistance of the electroconductibility of electrode and electrode again.Research about inert anode both at home and abroad has many articles and patent report, and its electrode composition mainly divides following several: (1) SnO
2The based ceramic metal electrode; (2) with NiFe
2O
4, ZnFe
2O
4Spinel based cermet electrodes for representative.(3) be the metal and the alloy-based inert anode of representative with metals such as Ni, Cu, Fe, Al, Ag.There are the U.S., Norway, Switzerland, France, Canada, Russia, Japan, China etc. in the country that participates in research.What research was more at present is the U.S., Norway, Switzerland and China.Alcoa 1986 and carried out the industrial test of inert anode in 2002 respectively, from the data of open report, the problem of existence mainly is the connection of electrode and the cracking of electrode.
The connection of electrode is relevant with the arrangement mode of electrode.The configuration of electrodes of noble electrode electrolyzer is nothing more than 3 kinds.A kind of is single-cell, has only a reaction plane that is the level of state, as Fig. 1.
Anode is hung in upper part of the electrolytic cell, and the negative electrode correspondence is placed on the electrolyzer bottom, and every anode all is state in parallel.Be similar to existing industrial aluminum electrolysis bath.Other two kinds is multicavity tray, and the reaction plane has a plurality of, in vertical state.A kind of is that negative electrode and anode are alternately arranged, and each tank room is state in parallel and (sees Fig. 2 a); Another kind is that two faces of every each battery lead plate are respectively negative electrode and anode, and each tank room is series connection (seeing Fig. 2 b).The characteristics of first kind of arrangement are, the bath voltage of each tank room is identical, but cell current is not necessarily identical, depends on the size of each tank room total electrical resistance.This arrangement simultaneously requires each electrode all must be connected with power supply.The characteristics of second kind of arrangement are, the cell current of each tank room is all identical, but bath voltage is not necessarily identical, also depends on the total electrical resistance of each tank room.The benefit of this arrangement is only need draw lead on the electrode of both sides, and the intermediary electrode does not need to connect lead.
2004, Northeastern University did the noble electrode multi-chamber electrolysis groove test of 3000A in the laboratory, what adopt is Fig. 2 (a) arrangement mode, the junction of electrode and power conductor is found in experiment, be subjected to electrolytical corrosion easily, cell resistance is changed, cause the distribution of current inequality of each electrolyzer, the distribution of current inequality can have influence on other connection again, has quickened the corrosion of junction.
Electrode among Fig. 2 (b) is the bipolar electrode that anode and negative electrode are combined with each other, and does not need to be connected with lead, only is fixed on the cell sidewall to get final product.There are problems such as by-pass current in the electrolyzer of certain this mode of connection, is soluble by design of electrolysis cells.
As far back as the sixties in last century, Italian Chinalco just begins to develop the bipolarity inert anode, and has designed one 8 Room electrolyzer, and the anode that is adopted is SnO
2Base anode and TiB
2Negative electrode compound inert anode, owing to some reasons such as anodic etching problems, test is not proceeded down.
1997, use Ni-Al-Cu-Fe series alloys such as J.A.Sekhar carried out electrolysis research as anode, the distribution of finding aluminium element in the corrosion layer seldom, and the phenomenon of the oriented electrode surface migration of aluminium element in the alloy.People such as Submarian have prepared the inert anode of Ni-Al-Cu-Fe-X metal ingredient, and wherein nickel content is 60-80wt%, and iron level is 3-10wt%, and aluminium content is 5-20wt%, and one or more metals in the chromium of 0-5wt%, magnesium, titanium, the molybdenum are formed in addition.In electrolytic process, anode surface forms the oxide film of one deck densification, has both had electroconductibility preferably, has good corrosion resistance nature again.Duruz and Nora study the corrosion layer structure; think that protective oxide film comprises that the blocking layer of a Sauerstoffatom and one keep chemically inert middle layer to nascent oxygen, and the electrochemical activity layer that can promote the oxonium ion generation oxidizing reaction on the anode interface.Hryn and Pellin have studied the formation and the dissolved dynamic process of metal-anodicoxide layer, think the oxidized formation aluminum oxide of aluminium, and aluminum oxide is dissolved by cryolite melts again, is the principal reaction of this dynamic process.
Summary of the invention
Weak point at existing used for aluminium electrolysis electrode the invention provides a kind of used for aluminium electrolysis bipolarity combined electrode.
Our main thought is to be combined with each other with metal anode and the wettable porous cathode of aluminium that this aluminium can move; because aluminium is fine to the wettability of porous cathode; can guarantee that the aluminium of separating out at negative electrode fully contacts with a face of anode alloy; one small part aluminium passes anode; move to the surface that anodic reaction takes place; form oxide film, the protection anode.
Two-layer compound electrode of the present invention is by being constituted by aluminium moistening cathode material and inert anode material, and wherein, wettable negative electrode is a vesicular structure, and aluminium liquid is full of the space and directly contacts with anode layer in the electrolytic process; Anode layer contains aluminium in the electrolytic process, and aluminium can arrive the anode working face of electrode from negative electrode process anode, and oxidized there formation oxide film; The formation speed of oxide film equates with dissolution rate in electrolytic process, thereby reaches the purpose of guard electrode.Combined electrode structure such as Fig. 3.Anode layer thickness 2～200mm, cathode layer thickness 2～200mm.Anode layer and cathode layer adopt overstocked or bonding method connects as one, and making electric current and aluminium element can be principle by the interface smoothly.Between 1mm～10mm, interstitial surface area accounts for 20～80% of electrode area according to the size of electrode size in the negative electrode aperture.
Wettable cathode layer is by Ti, the boride of Zr and based on their Composite Preparation, as TiB
2, ZrB
2, TiB
2-C (mass percent TiB
230～90%), ZrB
2-C (mass percent ZrB
230～90%) material etc.The inert anode layer is by metal matrix or ceramic-metal composite preparation.As Ni-Fe-Al-Me alloy (Me=Cu, Zn, Pb, Ag, Ti, Zr, Ce, La etc.), NiMe
2O
4(Me=Fe, Al, Ce, Cr, Nd etc.) base metal-ceramic material, the metal of interpolation have (Al, Ni, Cu, Ag, etc.).Electrode preparation method adopts smelting process or powder metallurgy process commonly used.It is that the alloy of Ni50～70%, Fe 10～30%, Al 4～10%, Cu 8～12% is as anode material that general the present invention adopts composition by mass percentage.
The structure of the aluminium cell that the two-layer compound electrode is used has the multicell structure, each chamber series connection, and electrode incline is fixed in the electrolyzer, does not need to connect lead, and the electrolyzer two ends connect the positive and negative electrode of power supply respectively.Electrolyzer is closed structure, and oxygen is discharged on top, and aluminium liquid is discharged in the bottom.An aluminum oxide self-feeding mouth is all arranged at each tank room top.Cell construction synoptic diagram such as Fig. 4.
Used for aluminium electrolysis bipolarity combined electrode of the present invention; be characterized in and move to the anode working face slightly at the aluminium that negative electrode is separated out, form dense oxidation film there, the protection anode; the dissolution rate of oxide film equates with formation speed, slows down the corrosion of anode working face.This electrode is arranged in series in electrolyzer, do not need to connect lead, has solved the difficulty that noble electrode connects.Cell construction is simple, and is easy to operate, can reduce the production cost of aluminium.
Description of drawings
Fig. 1 is that single chamber inert anode electrolytic tank electrode is arranged synoptic diagram;
Fig. 2 is that multicell noble electrode electrolytic tank electrode is arranged synoptic diagram, wherein (a) each tank room parallel-connection structure, (b) each tank room cascaded structure;
Fig. 3 is the combined electrode structure synoptic diagram, and wherein (a) cathode aperture is arranged synoptic diagram, (b) negative electrode, anode composite structure synoptic diagram;
Fig. 4 is a noble electrode multicell aluminium cell synoptic diagram;
Among the figure: 1 graphite, 2 aluminium liquid, 3 anodes; 4 porous cathodes; 5 cathode apertures, 6 anodes, 7 bipolarity combined electrodes, 8 negative electrodes, 9 ionogen.
Embodiment
Embodiment 1
Combined electrode structure such as Fig. 3.Anode layer thickness 50mm, cathode layer thickness 50mm.Anode layer adopts overstocked with cathode layer or bonding method is connected, and the negative electrode aperture is 5mm, and interstitial surface area accounts for 50% of electrode area.Wettable cathode layer is by TiB
2Preparation, the inert anode layer is by the alloy preparation of Ni 60%, Fe 22%, Al 8%, Cu 10% by mass percentage.
Combined electrode structure such as Fig. 3.Anode layer thickness 5mm, cathode layer thickness 5mm.Anode layer adopts overstocked with cathode layer or bonding method is connected, negative electrode aperture 10mm, and interstitial surface area accounts for 80% of electrode area.Wettable cathode layer is by ZrB
2Preparation, the inert anode layer is by the alloy preparation of Ni 52%, Fe 30%, Al 10%, Cu 8% by mass percentage.
Combined electrode structure such as Fig. 3.Anode layer thickness 200mm, cathode layer thickness 200mm.Anode layer adopts overstocked with cathode layer or bonding method is connected, negative electrode aperture 1mm, and interstitial surface area accounts for 20% of electrode area.Wettable cathode layer is by TiB
2-C (mass percent TiB
255%) Composite Preparation, the inert anode layer is by the alloy preparation of Ni 70%, Fe 10%, Al 10%, Cu 10% by mass percentage.
Embodiment 4
Combined electrode structure such as Fig. 3.Anode layer thickness 100mm, cathode layer thickness 150mm.Anode layer adopts overstocked with cathode layer or bonding method is connected, negative electrode aperture 3mm, and interstitial surface area accounts for 60% of electrode area.Wettable cathode layer is by ZrB
2-C (mass percent ZrB
248%) Composite Preparation, the inert anode layer is by the alloy preparation of Ni 70%, Fe 14%, Al 4%, Cu 12% by mass percentage.
Combined electrode structure such as Fig. 3.Anode layer thickness 100mm, cathode layer thickness 80mm.Anode layer adopts overstocked with cathode layer or bonding method is connected, negative electrode aperture 6mm, and interstitial surface area accounts for 35% of electrode area.Wettable cathode layer is by TiB
2-C (mass percent TiB
290%) Composite Preparation, the inert anode layer is by the alloy preparation of Ni 66%, Fe 19%, Al 7%, Cu 8% by mass percentage.
Combined electrode structure such as Fig. 3.Anode layer thickness 30mm, cathode layer thickness 60mm.Anode layer adopts overstocked with cathode layer or bonding method is connected, negative electrode aperture 5mm, and interstitial surface area accounts for 45% of electrode area.Wettable cathode layer is by ZrB
2-C (mass percent ZrB
290%) Composite Preparation, the inert anode layer is by the alloy preparation of Ni 50%, Fe 30%, Al 10%, Cu 10% by mass percentage.
Combined electrode structure such as Fig. 3.Anode layer thickness 60mm, cathode layer thickness 150mm.Anode layer adopts overstocked with cathode layer or bonding method is connected, negative electrode aperture 2mm, and interstitial surface area accounts for 65% of electrode area.Wettable cathode layer is by TiB
2-C (mass percent TiB
233%) Composite Preparation, the inert anode layer is by the alloy preparation of Ni 65%, Fe 18%, Al 9%, Cu 8% by mass percentage.
Combined electrode structure such as Fig. 3.Anode layer thickness 200mm, cathode layer thickness 50mm.Anode layer adopts overstocked with cathode layer or bonding method is connected, negative electrode aperture 30mm, and interstitial surface area accounts for 40% of electrode area.Wettable cathode layer is by ZrB
2-C (mass percent ZrB
233%) Composite Preparation, the inert anode layer is by the alloy preparation of Ni 55%, Fe 20%, Al 5%, Cu 10% by mass percentage.
Combined electrode structure such as Fig. 3.Anode layer thickness 2mm, cathode layer thickness 2mm.Anode layer adopts overstocked with cathode layer or bonding method is connected, negative electrode aperture 10mm, and interstitial surface area accounts for 80% of electrode area.Wettable cathode layer is by ZrB
2Preparation, the inert anode layer is by the alloy preparation of Ni 52%, Fe 30%, Al 10%, Cu 8% by mass percentage.
Claims (2)
1, a kind of used for aluminium electrolysis bipolarity combined electrode, it is characterized in that by being constituted by aluminium moistening cathode material and inert anode material, anode layer and cathode layer adopt overstocked or bonding method connects as one, anode layer thickness 2～200mm, cathode layer thickness 2～200mm, wettable negative electrode is a vesicular structure, and between the 1mm～10mm of negative electrode aperture, interstitial surface area accounts for 20～80% of electrode area.
2, according to the described used for aluminium electrolysis bipolarity of claim 1 combined electrode, it is characterized in that wettable cathode layer by Ti, the boride of Zr and based on their Composite Preparation comprises TiB
2, ZrB
2And mass percent TiB
230～90% TiB
2-C matrix material, mass percent ZrB
230～90% ZrB
2-C matrix material, inert anode layer are the alloy of Ni 50～70%, Fe 10～30%, Al 4～10%, Cu 8～12% by mass percentage.
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|---|---|---|---|
| CNB2006100469823A CN100552091C (en) | 2006-06-20 | 2006-06-20 | A kind of used for aluminium electrolysis bipolarity combined electrode |
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|---|---|---|---|
| CNB2006100469823A CN100552091C (en) | 2006-06-20 | 2006-06-20 | A kind of used for aluminium electrolysis bipolarity combined electrode |
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| CN1896327A true CN1896327A (en) | 2007-01-17 |
| CN100552091C CN100552091C (en) | 2009-10-21 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011144A (en) * | 2010-12-15 | 2011-04-13 | 中国铝业股份有限公司 | Nickel-based alloy material suitable for inert anode of metal molten salt electrolyzer |
| CN102703925A (en) * | 2012-04-23 | 2012-10-03 | 江阴安凯特电化学设备有限公司 | Production process of double-coating combined electrode |
| CN102703924A (en) * | 2012-04-23 | 2012-10-03 | 江阴安凯特电化学设备有限公司 | Electrolytic cell employing composite electrode with coating on two sides |
| CN103108997A (en) * | 2010-08-11 | 2013-05-15 | 奥图泰有限公司 | Apparatus for use in electrorefining and electrowinning |
-
2006
- 2006-06-20 CN CNB2006100469823A patent/CN100552091C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103108997A (en) * | 2010-08-11 | 2013-05-15 | 奥图泰有限公司 | Apparatus for use in electrorefining and electrowinning |
| US9783900B2 (en) | 2010-08-11 | 2017-10-10 | Outotec (Finland) Oy | Apparatus for use in electrorefining and electrowinning |
| CN102011144A (en) * | 2010-12-15 | 2011-04-13 | 中国铝业股份有限公司 | Nickel-based alloy material suitable for inert anode of metal molten salt electrolyzer |
| CN102703925A (en) * | 2012-04-23 | 2012-10-03 | 江阴安凯特电化学设备有限公司 | Production process of double-coating combined electrode |
| CN102703924A (en) * | 2012-04-23 | 2012-10-03 | 江阴安凯特电化学设备有限公司 | Electrolytic cell employing composite electrode with coating on two sides |
| CN102703925B (en) * | 2012-04-23 | 2014-12-17 | 江阴安凯特电化学设备有限公司 | Production process of double-coating combined electrode |
| CN102703924B (en) * | 2012-04-23 | 2015-05-20 | 江阴安凯特电化学设备有限公司 | Electrolytic cell employing composite electrode with coating on two sides |
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| CN100552091C (en) | 2009-10-21 |
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Granted publication date: 20091021 Termination date: 20110620 |