CN104087974A - Box-type zirconium boride inert anode for aluminium electrolysis, preparation method and aluminium electrolysis system - Google Patents
Box-type zirconium boride inert anode for aluminium electrolysis, preparation method and aluminium electrolysis system Download PDFInfo
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- CN104087974A CN104087974A CN201410361441.4A CN201410361441A CN104087974A CN 104087974 A CN104087974 A CN 104087974A CN 201410361441 A CN201410361441 A CN 201410361441A CN 104087974 A CN104087974 A CN 104087974A
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- zirconium boride
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Abstract
The invention provides a box-type zirconium boride inert anode for aluminium electrolysis. The box-type zirconium boride inert anode comprises a plurality of panels, wherein the plurality of panels are fixedly connected through connectors to form a hollow polyhedron; the panels are made of a zirconium boride material; a zircon skeleton is internally arranged inside each panel; the connectors are made of a zircon material or zirconium boride material. The invention provides a preparation method of the box-type zirconium boride inert anode for aluminium electrolysis. The method comprises the following steps: preparing skeletons and the connectors; burying the skeletons into zirconium boride particles, and forming boards in high-pressure molding and high-temperature sintering manners; connecting the plurality of boards through the connectors to form the hollow polyhedron. The invention provides an aluminium electrolysis system. The aluminium electrolysis system comprises the box-type zirconium boride inert anode for aluminium electrolysis and electrolyte. The box-type zirconium boride inert anode for aluminium electrolysis has the beneficial effects that the box-type electrode is mainly made of the zirconium boride material, is of a hollow structure, and is large in superficial area; the electrical efficiency is apparently higher than that of the existing solid carbon electrode; meanwhile, the problem that a lot of CO and CO2 are discharged because of the carbon anode used in the existing aluminium electrolysis process can be thoroughly changed.
Description
Technical field
The present invention relates to electrolysis of aluminum electrode, particularly a kind of box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode, preparation method and electrolysis of aluminum system.
Background technology
Aluminum current electrolytic industry still adopts traditional Hall-Heroult method, and ionogen be take sodium aluminum fluoride-aluminum oxide as primary structure always, and existing prebaked-anode type cell mainly adopts carbon annode.So-called inert anode material, refer to and in general sodium aluminum fluoride-alumina molten salt electrolysis, do not consume or the micro-anode consuming, recently twenty or thirty is over year, and the research data of inert anode material that had a lot of bibliographical informations is intended to replace general carbon anode (being active anode) now.
When using carbon anode to carry out electrolysis, the reaction formula of electrolysis of aluminum is:
Existing zirconium boride 99.5004323A8ure industrial production is mainly by zirconium and pure boron direct reaction and obtaining at high temperature.Because industrial production yield not high (often lower than 90%) and the production cost of pure boron are high, the expensive of pure boron caused the expensive of zirconium boride 99.5004323A8ure, thereby limited the large-scale commercial production of zirconium boride 99.5004323A8ure.
Summary of the invention
In order to solve above-mentioned existing technical problem, the invention provides a kind of box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode, its electrical efficiency increases substantially than existing electrode.
The present invention solves above-mentioned existing technical problem, and a kind of box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode is provided, and comprises polylith panel and web member, and described panel is zirconium boride 99.5004323A8ure material, and built-in zirconium matter skeleton; Described web member is zirconium material or zirconium boride 99.5004323A8ure material.
Further improvement of the present invention is as described below.
Between described polylith panel, through described web member, be fixedly connected with and form a hollow polyhedron.
Described web member is zirconium boride 99.5004323A8ure material, also built-in zirconium matter skeleton.
Described web member comprises connection piece and screw.
The cross section of described connection piece is a type, L-type or V-type.
Described connection piece has through hole, and corresponding described panel also has through hole, and described screw correspondence is placed in the through hole of described connection piece and the through hole of described panel.
Described panel is the veneer of integral type, or the plurality of plates being spliced.
Described skeleton is zirconium net.
Described polyhedron is hexahedron.
The present invention solves above-mentioned existing technical problem, and a kind of preparation method of box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode is provided, and comprises the steps: to prepare skeleton, web member; In zirconium boride 99.5004323A8ure particle, bury skeleton underground, through high-pressure molding, high temperature sintering, form sheet material; Multi-sheets forms a hollow polyhedron through web member.
Further improvement of the present invention is as described below.
Described skeleton is zirconium material, and described web member is zirconium material or zirconium boride 99.5004323A8ure material.
Described multi-sheets forms in a hollow polyhedron step through web member, and sheet material is first made panel through web member, and panel is made polyhedron through web member again.
The present invention solves above-mentioned existing technical problem, and a kind of electrolysis of aluminum system is provided, and comprises electrode and ionogen, and described electrode is the box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode described in claim 1 to 7 any one; Described ionogen is Na
3alF
6-AlF
3-mKFAlF
3-Al
2o
3mixed system,, m is 1.0～3.0.
Further improvement of the present invention is as described below.
In described ionogen, the content of the weight percent of potassium element is 3%～10%.
Described m is 1.0,1.2,1.5 or 3.0.
Compared to prior art, the invention has the beneficial effects as follows: this chest electrode is mainly zirconium boride 99.5004323A8ure material, for hollow structure, surface-area are large, meanwhile, electrical efficiency, apparently higher than existing solid carbon pole, can improve 30-50%.
Accompanying drawing explanation
Fig. 1 is the box used for aluminium electrolysis zirconium boride 99.5004323A8ure of the present invention inert anode one structural representation.
Fig. 2 is Fig. 1 two panels connection diagram.
Fig. 3 is the decomposing state schematic diagram of Fig. 2.
Fig. 4 is that a panel is the connection diagram of plurality of plates.
Fig. 5 is the decomposing schematic representation of Fig. 4.
Fig. 6 is preparation method's schema of box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode.
| Panel 11 | Web member 12 |
| Connection piece 121 | Screw 122 |
Embodiment
Below in conjunction with accompanying drawing explanation and embodiment, the present invention is further described.
As shown in Figures 1 to 5, a kind of box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode, comprises polylith panel 11, between polylith panel 11, through web member 12, is fixedly connected with and forms a hollow polyhedron; Panel 11 is zirconium boride 99.5004323A8ure material, and built-in zirconium matter skeleton; Web member 12 is zirconium material or zirconium boride 99.5004323A8ure material.Box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode of the present invention, is formed through high pressure and high temperature sintering by the zirconium boride 99.5004323A8ure of excellent electric conductivity, has electroconductibility, and the advantage such as resistance is less.
When described web member 12 is zirconium boride 99.5004323A8ure material, also built-in zirconium matter skeleton; When being zirconium material, can omitting skeleton is set.
Web member 12 comprises connection piece 121 and screw 122, and this web member 12 is zirconium material.The cross section of connection piece 121 is a type, L-type or V-type.Connection piece 121 has through hole, and corresponding panel 11 also has through hole, and screw 122 correspondences are placed in the through hole of connection piece 121 and the through hole of panel 11.
The veneer that panel 11 is integral type, or the plurality of plates being spliced, polyhedron is hexahedron, or the polyhedron of other shape.
Skeleton is zirconium net.The zirconium rod that this zirconium net is array distribution; For example, or centered by a zirconium rod, all the other zirconium rods distribute along this zirconium rod left and right: fish-bone.
Box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode of the present invention, it has following characteristics as inert anode: 1), inertia, no matter low temperature or hot environment, not can with oxygen generation chemical reaction; 2) can resist thermal shocking, under high temperature, possess certain intensity and rigidity, can reach the state of ceramic metal oxide; 3) cost has the feasibility of actual use, and one ton of aluminium of every production consumes zirconium boride 99.5004323A8ure cost and uses carbon element suitable.Also owing to being inert anode, when electrolysis, it occurs in the surface of anode, so make casing anode, can reduce the manufacturing cost of electrode.Electrolysis equation is:
As shown in Figure 6, a kind of preparation method of box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode, comprises the steps:
Prepare skeleton, web member 12;
In zirconium boride 99.5004323A8ure particle, bury skeleton underground, through high-pressure molding, high temperature sintering, form sheet material;
Multi-sheets forms a hollow polyhedron through web member 12.
Skeleton is zirconium material, and web member 12 is zirconium material or zirconium boride 99.5004323A8ure material.Multi-sheets forms in a hollow polyhedron step through web member 12, and sheet material is first made panel 11 through web member 12, and panel 11 is made polyhedron through web member 12 again.
The preparation method of zirconium boride 99.5004323A8ure panel comprises the steps:
According to different specification requirements, in mould, put into the zirconium matter skeleton of setting size, in being housed, the mould of skeleton adds zirconium boride 99.5004323A8ure powder, adopt large hydraulic equipment high-pressure molding, obtain zirconium boride 99.5004323A8ure panel.Again gained panel is adopted to vacuum sintering mode, be placed on high temperature sintering in vacuum sintering furnace, obtain zirconium boride 99.5004323A8ure panel.
This chest electrode of the present invention is mainly zirconium boride 99.5004323A8ure material, is hollow structure, and surface-area is large, and electrical efficiency is compared with solid carbon pole and wanted high, can improve 30-50%.For the chest electrode of hollow, inside and outside it, be connected state, inside and outside facilitating electrolytic solution, circulate.Also can make the structure of inside and outside isolation.
The preparation method of zirconium boride 99.5004323A8ure of the present invention is:
Potassium fluoborate and potassium fluozirconate are put into reactor with 2:1 mol ratio, after vacuumizing, pass into rare gas element, be warming up to 700～800 ℃, add aluminium, rapid stirring, reaction 4～6h, generates zirconium boride 99.5004323A8ure and potassium cryolite; Or aluminium is put into reactor, after vacuumizing, pass into rare gas element, be warming up to 700～800 ℃, add potassium fluoborate, the potassium fluozirconate of mol ratio 2:1, rapid stirring, reaction 4～6h, generates zirconium boride 99.5004323A8ure and potassium cryolite; Potassium cryolite is extracted out, after zirconium boride 99.5004323A8ure is purified, is can be used in and prepare inert anode.
The invention provides a kind of electrolysis of aluminum system, comprise electrode and ionogen, electrode is above-mentioned box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode; Ionogen is Na
3alF
6-AlF
3-mKFAlF
3-Al
2o
3mixed system, m is 1.0～3.0.
In ionogen, the weight percent content of potassium element is 3%～10%.
The operation of this electrolyte system comprises following step:
Steps A: by electrolyzer Na
3alF
6-Al
2o
3system fluting starts, and operation continuously, with Na
3alF
6-AlF
3as ionogen, supplement system until burner hearth is regular;
Step B: the ionogen added body using potassium cryolite in aluminium electrolysis process is tied to form one of part, and synchronously adds AlF
3and Na
3alF
6or employing AlF
3, Na
3alF
6after mixing with potassium cryolite, as the ionogen system of supplementing, add;
Step C: use potassium cryolite to supplement in the electrolytical process of system as electrolysis of aluminum, the content of controlling potassium weight percent in the ionogen in electrolyzer is 3%-5%-10%.
Above-mentioned supplementary system also comprises directly mixes potassium cryolite and sodium cryolite rear and Al according to a certain percentage
2o
3forming an individual system directly drops in electrolyzer for starting the process of electrolyzer.
Wherein, in steps A, by electrolyzer Na
3alF
6– Al
2o
3after system fluting starts, operation continuously, with Na
3alF
6– AlF
3as ionogen, supplement system until burner hearth is regular; But, by electrolyzer Na
3alF
6-mKFAlF
3(m=1.0-1.5)-Al
2o
3the system startup of also can slotting, this start-up mode should be noted, Na
3alF
6with mKFAlF
3ratio, general recommendations is in the scope of 7:3-9:1-10.5:0.5.
Wherein, supplementary system also comprises the content of potassium in ionogen in electrolyzer is risen to the scope of 5-15% or higher scope by 3%-5%, the lifting of potassium content can cause aluminium electrolytic temperature further to decline, but electrolysis temperature can not be down to below 750 ℃, otherwise cannot normally produce (because the fusing point of liquid aluminium is 660 ℃).
The elementary composition of the potassium cryolite of this lower molecular ratio belongs to following category: K content 28-38%, Al content 13-21%, F content 38-52%.
Adding ionogen is advisable with the mass concentration lifting 0.2% to 0.3% of every batch of potassium.
The mass concentration of controlling potassium element in ionogen in whole step is between 3%-5%-10%.
In electrolysis of aluminum system operational process, ionogen supplements the preparation method of system, comprises the steps:
Steps A: aluminium is placed in to reactor, passes into rare gas element after vacuumizing, be warming up to 700-850 ℃, add one or more in potassium fluotitanate, potassium fluoborate, potassium fluozirconate;
Step B: stir after 4-6h, the liquid of upper strata melting is extracted out, the ionogen obtaining in aluminium electrolysis process supplements system.
The chemical equation relating to comprises:
KBF
4+Al＝B+KF·AlF
3
(aluminium excessive and x, y can not be 0) simultaneously
(aluminium excessive and x, y can not be 0) simultaneously
This electrolysis of aluminum system response mild condition, easily controls, and technical process is simple, react completely, and good product quality.
Lower molecular ratio potassium cryolite provided by the invention supplements system for aluminium electrolytic industry as ionogen, there is following advantage: 1. without changing existing cell construction, electrolysis process, all kinds of consumable materials etc., but can obviously reduce the electrolysis temperature (average 10 ℃) in aluminium electrolysis process.With traditional aluminium electrolytic industry comparison: current efficiency promotes approximately 1%, and one ton of aluminium ingot of every output can be saved power consumption 500-700 degree.2. adding of lower molecular ratio potassium cryolite, can obviously improve Al
2o
3solubleness in ionogen and dissolution rate, the various compositions that can reduce aluminium electrolytic temperature that in the past had been found that or used are as CaF
2, MgF
2, LiF
2, Li
3alF
6deng, be all obvious reduction Al
2o
3solubleness in ionogen; Al
2o
3in ionogen, the raising of solubleness can obviously promote the production capacity of aluminium cell, and the lifting of traditional its production capacity of situation comparison is about between 5-30%.
Under temperature 1300K, Al
2o
3decomposition voltage be 1.18V, theoretical carbon consumption 0.333kg/kg (Al) (calculating by current efficiency 100%), actual carbon consumption is 0.45-0.55kg/kg (Al).Due to the purity needs of aluminium, with oil coke, make anode, its theoretical consumption is 6.32KWh/kg (Al) (calculating by current efficiency 100%); The actual new-type large-scale groove of energy expenditure is 13.5KWh/kg (Al).If use inert anode instead, electrolytic reaction formula is:
Under 1300K, Al
2o
3decomposition voltage be 2.2V, this is because anode has neither part nor lot in reaction and energy is not provided.Therefore theoretical amount consumption is up to 9.2KWh/kg (Al), in theory, and inert anode and active anode Al between the two
2o
3the poor 1V of decomposition voltage left and right, electrisity consumption differs about 3KWh/kg (Al).
Aluminium industry member research now replaces carbon anode with inert anode, has started one upsurge.This be because: (1), in application during carbon anode, on anode, bubble is large, and anodic overvoltage reaches 0.4V-0.6V; And application is during inert anode, on anode, bubble is little, and anodic overvoltage only has 0.2V, and this just can give 0.3V for change.(2) owing to accounting for the project of largest component in bath voltage, be that negative electrode-anode spacing is from 4-5cm, its volts lost reaches 1.6-1.8V, if application inert anode matches with inert cathode, form novel electrolytic bath, pole distance can shrink, from 4-5cm, shorten to 3cm, this is equivalent to reduce bath voltage 0.5V; (3) anode needn't often be changed, so process cost is low; (4) on anode, produce O2 gas, rather than CO2 and CO gas, be conducive to environment protection.
To the preparation of inert anode material, must reach following requirement:
(1) material solubleness in sodium aluminum fluoride-aluminum oxide liquation is little;
(2) material is little to the response capacity of the oxygen producing in aluminium liquid or anodic gas [O];
(3) material manufacturing price is cheaper and easily obtain;
(4) material is easily processed into relatively large inert anode, and is easily connected with wire;
(5) material is moistening good to cryolite melt, is difficult for occurring anode effect.
Experiment discovery, the zirconium boride 99.5004323A8ure material after high-pressure molding high temperature sintering can meet above-mentioned 5 requirements substantially.But existing zirconium boride 99.5004323A8ure industrial production is mainly by metal zirconium and pure boron direct reaction and obtaining at high temperature.Because industrial production yield not high (often lower than 90%) and the production cost of pure boron are high, the expensive of pure boron caused the expensive of zirconium boride 99.5004323A8ure, thereby limited the large-scale commercial production of zirconium boride 99.5004323A8ure.
From Hall-heroult in 1886, (Hall--Ai Lu), since aluminium reduction process comes out, the ionogen of industrial aluminum production process was always with sodium aluminum fluoride (Na
3alF
6)--commercial alumina (Al
2o
3) be primary structure, in electrolytic process, add aluminum fluoride (AlF
3thereby) to adjust the molecular ratio of electrolytic solution, reduce electrolysis temperature, increase conductivity to produce fine aluminium (≤99.7%).How further effectively reducing the electrolysis temperature of aluminium electrolysis process or effectively improve the current efficiency of aluminium electrolysis process, is the problem of nearly 100 years whole world aluminium industry primary studies.That is, how to find that some additive (salts substances) is the global aluminium industrial science man problem of primary study for a long time further to improve the physicochemical property of aluminium electrolyte and to improve electrolysis production index.This class additive (salts substances) must possess the following performance: it can not decompose (1) in aluminium electrolysis process, thereby can guarantee quality and the current efficiency of aluminium; (2) can improve sodium aluminum fluoride adding of additive--the physicochemical property of alumina solution, for example, reduce electrolytical fusing point (primary crystal point), or improve electrolytical specific conductivity.(3) for aluminum oxide, the solubleness in cryolite melt and dissolution rate do not have large impact.(4) wide material sources of additive and cheap.
Since half a century, people have studied adding electrolytical physicochemical property impact of the additives such as Calcium Fluoride (Fluorspan) (CaF2), magnesium fluoride (MgF2), lithium fluoride (LiF2), Potassium monofluoride (KF) and sodium-chlor (NaCl), find can reduce adding of these additives the primary crystal point of ionogen liquation, and lithium fluoride has the greatest impact to primary crystal point reduction value, reach 7.8 ℃ (every 1% additions).But defect of existence without exception of adding of these additives is exactly that the melting degree of commercial alumina in cryolite melt that cause more or less declines to some extent.And lithium compound price is very expensive, and it is larger that actual industrial is applied resistance.
In year in 2013, research through nearly 3 years: contriver finds in the process that with potassium base (sodium base) zirconium boron villiaumite mixture is intermediate raw material production zirconium boride 99.5004323A8ure and all kinds of alloys: if the potassium cryolite of this lower molecular ratio of the synchronous output of production process is meticulously controlled in process of production technical process and added critical anti-polymerizing agent, can substitute or part substitution of Al electrolysis production process in the fusing assistant aluminum fluoride that must add, this substitute or the alternative work of part can impel the current efficiency of Aluminium Electrolysis process at least to improve 2% left and right, the raising of current efficiency causes the production of aluminium per ton and traditional simple use aluminum fluoride fusing assistant to be spent than more electricity saving at least 500, generally, economize on electricity 700 degree left and right.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (15)
1. a box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode, is characterized in that: comprise polylith panel and web member, described panel is zirconium boride 99.5004323A8ure material, and built-in zirconium matter skeleton; Described web member is zirconium material or zirconium boride 99.5004323A8ure material.
2. box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode according to claim 1, is characterized in that: between described polylith panel, through described web member, be fixedly connected with and form a hollow polyhedron.
3. box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode according to claim 1, is characterized in that: described web member is zirconium boride 99.5004323A8ure material, also built-in zirconium matter skeleton.
4. box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode according to claim 1, is characterized in that: described web member comprises connection piece and screw.
5. box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode according to claim 4, is characterized in that: the cross section of described connection piece is a type, L-type or V-type.
6. box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode according to claim 5, is characterized in that: described connection piece has through hole, and corresponding described panel also has through hole, and described screw correspondence is placed in the through hole of described connection piece and the through hole of described panel.
7. box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode according to claim 1, is characterized in that: the veneer that described panel is integral type, or the plurality of plates being spliced.
8. box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode according to claim 1, is characterized in that: described skeleton is zirconium net.
9. box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode according to claim 2, is characterized in that: described polyhedron is hexahedron.
10. a preparation method for box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode, is characterized in that, comprises the steps:
Prepare skeleton, web member;
In zirconium boride 99.5004323A8ure particle, bury skeleton underground, through high-pressure molding, high temperature sintering, form sheet material;
Multi-sheets forms a hollow polyhedron through web member.
The preparation method of 11. box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anodes according to claim 10, is characterized in that: described skeleton is zirconium material, and described web member is zirconium material or zirconium boride 99.5004323A8ure material.
The preparation method of 12. box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anodes according to claim 10, it is characterized in that: described multi-sheets forms in a hollow polyhedron step through web member, sheet material is first made panel through web member, and panel is made polyhedron through web member again.
13. 1 kinds of electrolysis of aluminum systems, comprise electrode and ionogen, it is characterized in that, described electrode is the box used for aluminium electrolysis zirconium boride 99.5004323A8ure inert anode described in claim 1 to 9 any one; Described ionogen is the mixed system of Na3AlF6-AlF3-mKFAlF3-Al2O3, and m is 1.0～3.0.
14. electrolysis of aluminum systems according to claim 13, is characterized in that, in described ionogen, the content of the weight percent of potassium element is 3%～10%.
15. electrolysis of aluminum systems according to claim 13, is characterized in that, described m is 1.0,1.2,1.5 or 3.0.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5316718A (en) * | 1991-06-14 | 1994-05-31 | Moltech Invent S.A. | Composite electrode for electrochemical processing having improved high temperature properties and method for preparation by combustion synthesis |
| CN101186503A (en) * | 2007-12-03 | 2008-05-28 | 中国科学院上海硅酸盐研究所 | Zirconium boride-zirconium carbide composite diphase material and use thereof |
| CN102745703A (en) * | 2012-07-25 | 2012-10-24 | 深圳市新星轻合金材料股份有限公司 | Process for preparing aluminum electrolysis inert anode material or aluminum electrolysis inert cathode coating material |
| CN102745704A (en) * | 2012-07-25 | 2012-10-24 | 深圳市新星轻合金材料股份有限公司 | Method for producing zirconium boride and synchronously outputting cryolite |
-
2014
- 2014-07-25 CN CN201410361441.4A patent/CN104087974B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5316718A (en) * | 1991-06-14 | 1994-05-31 | Moltech Invent S.A. | Composite electrode for electrochemical processing having improved high temperature properties and method for preparation by combustion synthesis |
| CN101186503A (en) * | 2007-12-03 | 2008-05-28 | 中国科学院上海硅酸盐研究所 | Zirconium boride-zirconium carbide composite diphase material and use thereof |
| CN102745703A (en) * | 2012-07-25 | 2012-10-24 | 深圳市新星轻合金材料股份有限公司 | Process for preparing aluminum electrolysis inert anode material or aluminum electrolysis inert cathode coating material |
| CN102745704A (en) * | 2012-07-25 | 2012-10-24 | 深圳市新星轻合金材料股份有限公司 | Method for producing zirconium boride and synchronously outputting cryolite |
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