CN1092822A - Composite for oxidation and corrosion protection of anode nipples - Google Patents
Composite for oxidation and corrosion protection of anode nipples Download PDFInfo
- Publication number
- CN1092822A CN1092822A CN94103148A CN94103148A CN1092822A CN 1092822 A CN1092822 A CN 1092822A CN 94103148 A CN94103148 A CN 94103148A CN 94103148 A CN94103148 A CN 94103148A CN 1092822 A CN1092822 A CN 1092822A
- Authority
- CN
- China
- Prior art keywords
- matrix material
- guard ring
- dry weight
- waste product
- cement
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
- C25C3/125—Anodes based on carbon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Prevention Of Electric Corrosion (AREA)
- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention relates to when the Hall-Hcroult cell operation, have in the one or more anode suspension bracket joints of protection and avoid oxidation and corrosive matrix material, comprising the base mateiral, aluminous cement, catalyzer and the water that exist with particulate form that come from the anode waste product that in aluminium electrolysis cell, consumes.The material such as the polyaromatic of insalubrity have been removed in the matrix material.This matrix material is characterised in that a material material accounts for more than 80% of matrix material, and its particle diameter is between 1 and 2000 μ m, and cement accounts for the matrix material ratio and is no more than 15%, and catalyzer accounts for 0.6%, and the water of adding then accounts for 28% of amount of solid.
Description
The present invention relates to a kind of matrix material; this matrix material can protect one or more anode suspension bracket joints (to call joint in the following text) to avoid oxidation and corrosion when Hall-Heroult aluminium electrolysis cell operation operation, and it comprises anodic waste product pellet, aluminous cement, catalyzer and the water that consumes when coming from electrolysis of aluminum.Around being contained in joint, pretreated matrix material formed guard ring.
Used in this article mainly is two kinds of dissimilar matrix materials:
Protection anode suspension bracket joint is avoided normally first type of oxidation and corrosive material when cell operation is moved for many years, and it is by petroleum coke and/or come from the anodic waste product that is consumed as base mateiral, and pitch is agent as sticking.The shortcoming of this material is the material that pitch contains insalubrity, for example electrolyzer processing high temperature is the PAH(polyaromatic that will discharge), simultaneously the patience of corrosive gases is lower during joint, this be because since particle bounding force between protective ring and joint and contractility too a little less than, protective ring can only cover whole joint one section operation working time, and it will corrosion fall a part then.
Second type is that mixture with petroleum coke, graphite, schungite and depleted electrode materials is as base mateiral, the cement admixture that is aided with a kind of special use is as tackiness agent, add water and make it reach certain rigidity, thereby obtain having the matrix material of suitable solidness.The shortcoming of such matrix material is, not only contains the waste prods of carbon and electrolytic process in the base mateiral but also used starting material such as petroleum coke, graphite and schungite, and its each all is factors that the production cost of matrix material is risen.
European patent application described for No. 269534 with back one type coating obtain matrix material with the protection joint avoid oxidation and corrosion.Based on the argumentation of this application, its new feature that presents seemingly is to add the antioxidant of 0.01 to 0.5% particle diameter that exists with the aluminium powder form of passivation less than 0.1mm in matrix material, and the impurity in the aluminous cement should be not more than 2% simultaneously.
A shortcoming of this method is that base mateiral must be a powder, be that its particle dia must be between 1 to 1000 μ m, this just makes must carry out complicated and high pulverizing and the screening that expends in the technology, to add more aluminous cement simultaneously with adhesive powder shape particle, make that intergranular combination is more all even good in the matrix material.Another condition is that base mateiral is to select for use as second type above-mentioned matrix material.These shortcomings make final matrix material price rise significantly.Owing to do not add catalyzer, all material during the result gathers materials powder because of surface tension cement is very difficult are all together compound, thereby the indivedual positions that cause coating in conjunction with must than by a little less than the position of cementing some, do not add catalyzer and also can make the expansionary force between joint and the protective ring inconsistent.Thereby the be full of cracks at indivedual coatings position makes joint suffer erosion when causing the electrolyzer operation.
The objective of the invention is to overcome the shortcoming of above-mentioned materials, antianode suspension bracket joint provides better protection in order to avoid oxidated and corrosion during the electrolyzer operation.
Another object of the present invention is to eliminate the component of insalubrity, uses the waste product in the processing treatment process, can avoid the storage of waste product on the one hand, can produce the cheap goods that butt junction effectively provides protection on the other hand.
According to the present invention, by using the matrix material of mentioning in the introduction just can achieve the above object, this matrix material is characterised in that the anode waste product grain diameter that comes from consumption between 1 to 2000 μ m, and these particles account for more than 80% of matrix material dry substance mixture.Also have, as defined in claim 1, matrix material comprises the aluminous cement that accounts for dry weight to 15% and accounts for the water of dry weight to 28% and account for the catalyzer of dry weight 0.6%.In addition, as defined in claim 7, the present invention includes the removal of the material of insalubrity, as the removal of PAH.Other concrete advantage of the present invention is as described in the claim 2-6.
To carry out more detailed description to the present invention by an example with reference to accompanying drawing now.Shown in the accompanying drawing is perspective sketch map with the anode suspension bracket 1 of three joints, and three joints insert in three holes of carbon anodes 4, all extrusion is arranged on each joint 2 guard ring 3 of matrix material avoid oxidation and corrosion with the protection joint.With the ring circle that fills up cast iron joint is fixed on the carbon between joint and carbon, its fixed form mode does not here describe in further detail.When the operation operation, positive current is down conducted, by anode suspension bracket and joint, and carbon anode, oxide compound/sodium aluminum fluoride body lotion and liquid aluminium body lotion arrive carbon cathode.Because conduction of current carries out under high resistance, thereby discharge heat-flash and make battery temperature reach Celsius approximately 960 to spend.High temperature causes oxide compound and sodium aluminum fluoride, adds other component generation reaction generation liquid aluminium.When reaction was progressively carried out, high chemically reactive gas discharged continuously and corrodes especially anode suspension bracket joint of each parts, disengages iron and enters in electrolytic solution and the aluminium, has greatly reduced the quality of product aluminium.The guard ring of compacting all can effectively have the protection joint in entire operation when no matter being ready-formed or installation in the time.Thereby product aluminium high purity and high price have been guaranteed.
As mentioned in the introduction, this matrix material comprises the particulate material that comes from the anodic waste product that consumes in electrolyzer, jointing material, catalyzer and the cement that aluminous cement forms.Under 60-90 degree Celsius, matrix material is compressed and harden, make the tool resistance to compression emphasize to reach 1MPa.It is that carbon anode and anode suspension bracket connect the position that guard ring preferably makes and be contained in the plunger position in advance.
The aluminous cement of avoiding being used as in oxidation and the corrosive matrix material tackiness agent in the protection positive contact has a large amount of different models on market.Impurity such as Fe in the aluminous cement that different manufacturers is produced
2O
3, SiO
2, Na
2O, Cr
2O and K
2O etc., its content has very big-difference, but its total amount can not surpass 7 percent of dry weight in the present invention.
Embodiment
Produced 60 cover carbon anode/anode hanger devices in this experiment, wherein 40 covers are equipped with card board kai around anode suspension bracket joint.Find that there were significant differences (in 5% conspicuous level) being with or without between the device of card board kai.Be the prescription of matrix material below:
From anodic waste product 〉=80% that consumes
Aluminous cement≤15%
Catalyzer=0.6%
Water about 28%
Produce the 20Kg mixture.Before adding water, solid matter is mixed.Measure the water (28%) of aequum to be added, and water with before solid matter mixes with catalyst dissolution in water.By electric mixer mixing water and solid matter.On joint, put a ring-like mould, matrix material is toppled over into, strike tightly with hammer and rammer.Subsequently, guard ring is hardened under 60-90 degree Celsius.To go out utmost point device is installed in 6 electrolyzers.Examine guard ring and anodic situation by measuring gas, temperature and density at the electrolyzer run duration.After using in electrolyzer, that stays a large amount of matrix materials on the joint still can cover whole joint, and the cladding thickness of guard ring is much bigger when using traditional matrix material simultaneously.In 60 days, do not find the vicissitudinous trend of iron level in the aluminum metal.
Claims (7)
1, when the Hall-Heroult cell operation, protect one or more anode suspension bracket joints to avoid oxidation and corrosive matrix material; particulate material and aluminous cement, catalyzer and water comprising the anodic waste product that in electrolysis of aluminum, comes from consumption; the particle diameter that it is characterized in that waste product is between 1 and 2000 μ m; simultaneously these particles account for the matrix material dry weight 80% or more; in addition; comprise the aluminous cement that is no more than 15% dry weight in the matrix material, be no more than the water of 28% waste product and cement dry weight and be no more than the catalyzer of 0.6% dry weight.
2,, it is characterized in that containing in the cement aluminium that is no more than 70% weight according to the matrix material of claim 1.
3,, it is characterized in that containing in the particulate material ash of at least 1% dry weight according to the matrix material of claim 1.
4, according to the matrix material of claim 1, it is characterized in that this matrix material can be processed into prefabricated guard ring, also can form guard ring around the positive contact compacting.
5,, it is characterized in that guard ring hardened 60 minutes down at 60-90 degree centigrade, made ultimate compression strength reach 1MPa according to the matrix material of claim 1.
6,, it is characterized in that and to inject a kind of non-oxidizing middle layer closely and paper material layer between protective ring and the joint to prevent under the positive contact situation different, making guard ring break with the guard ring bulging force according to the matrix material of claim 1.
7,, it is characterized in that removing unwholesome material such as polyaromatic in the waste product used in particulate material by processing according to the matrix material of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO930957 | 1993-03-17 | ||
| NO930957A NO930957L (en) | 1993-03-17 | 1993-03-17 | Marterial composite for oxidation and corrosion protection of anode nipples |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1092822A true CN1092822A (en) | 1994-09-28 |
Family
ID=19895934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94103148A Pending CN1092822A (en) | 1993-03-17 | 1994-03-17 | Composite for oxidation and corrosion protection of anode nipples |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0627505A1 (en) |
| CN (1) | CN1092822A (en) |
| AU (1) | AU5769494A (en) |
| BR (1) | BR9401181A (en) |
| CA (1) | CA2119084A1 (en) |
| NO (1) | NO930957L (en) |
| NZ (1) | NZ260060A (en) |
| ZA (1) | ZA941615B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896555A (en) * | 2014-03-25 | 2014-07-02 | 湖南创元铝业有限公司 | Production method of anode steel pawl protection ring |
| CN104005056A (en) * | 2014-05-28 | 2014-08-27 | 沈阳化工大学 | Method for preparing electrolytic aluminium carbon anode protective coating |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2606796B1 (en) * | 1986-11-14 | 1989-02-03 | Savoie Electrodes Refract | PROTECTIVE COATING FOR PRE-COOKED ANODE ROUND |
| IN169360B (en) * | 1987-12-22 | 1991-09-28 | Savoie Electrodes Refract |
-
1993
- 1993-03-17 NO NO930957A patent/NO930957L/en unknown
-
1994
- 1994-03-08 ZA ZA941615A patent/ZA941615B/en unknown
- 1994-03-09 AU AU57694/94A patent/AU5769494A/en not_active Abandoned
- 1994-03-10 NZ NZ260060A patent/NZ260060A/en unknown
- 1994-03-15 EP EP94200655A patent/EP0627505A1/en not_active Withdrawn
- 1994-03-15 CA CA002119084A patent/CA2119084A1/en not_active Abandoned
- 1994-03-16 BR BR9401181A patent/BR9401181A/en not_active Application Discontinuation
- 1994-03-17 CN CN94103148A patent/CN1092822A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896555A (en) * | 2014-03-25 | 2014-07-02 | 湖南创元铝业有限公司 | Production method of anode steel pawl protection ring |
| CN103896555B (en) * | 2014-03-25 | 2015-12-09 | 湖南创元铝业有限公司 | Anode steel claw protection ring production method |
| CN104005056A (en) * | 2014-05-28 | 2014-08-27 | 沈阳化工大学 | Method for preparing electrolytic aluminium carbon anode protective coating |
Also Published As
| Publication number | Publication date |
|---|---|
| NZ260060A (en) | 1994-12-22 |
| AU5769494A (en) | 1994-09-22 |
| EP0627505A1 (en) | 1994-12-07 |
| CA2119084A1 (en) | 1994-09-18 |
| ZA941615B (en) | 1994-10-12 |
| NO930957D0 (en) | 1993-03-17 |
| NO930957L (en) | 1994-09-19 |
| BR9401181A (en) | 1994-10-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |