CN109970438A - A kind of side-wall material - Google Patents
A kind of side-wall material Download PDFInfo
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- CN109970438A CN109970438A CN201910348176.9A CN201910348176A CN109970438A CN 109970438 A CN109970438 A CN 109970438A CN 201910348176 A CN201910348176 A CN 201910348176A CN 109970438 A CN109970438 A CN 109970438A
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Abstract
The invention discloses a kind of side-wall materials applied to aluminium electroloysis industry, the side-wall material especially to match with low-temperature electrolytes, the chemical composition of the material includes: zinc oxide, chromium oxide as basic raw material, the total composition of the two is 100%, on this basis, a kind of additive of magnesia, titanium oxide, iron oxide, silica, aluminium oxide or several as additive of certain content is additionally added.The present invention selects above-mentioned basic raw material and additive, and prepared product sintering character is preferable, and material structure is fine and close, no obvious macrostructure cracking and microstructural defects.By Dynamic Corrosion and static corrosion experiment test, the result shows that, this material has extremely low solubility and corrosion rate in low-temperature electrolytes, can satisfy the requirement of novel side wall material.
Description
Technical field
The invention belongs to field of aluminum electrolysis, are related to a kind of novel side wall material, especially with the matched side of low-temperature electrolytes
Wall material.
Background technique
Due to having many advantages, such as lower energy consumption, oxygen is discharged, novel green aluminium cell is considered as Aluminium Industry
Developing direction.Side-wall material is as one important component part of aluminium cell, electrolyte-resistant corrosivity and thermal shock resistance
The stability and service life that electrolytic cell uses can be largely fixed.Traditional side-wall material such as Si3N4 combination SiC material and carbon
Material is due to its poor inoxidizability, poor corrosion resistance, and be electrolysed out the disadvantages of molten aluminum is reacted, be unable to satisfy novel
Side-wall material requirement.Therefore, it is badly in need of developing one kind with good inoxidizability and corrosion proof material, to meet newly
The requirement of profile material service performance.
Up to the present, scholars have carried out some researchs to novel side wall material, and research direction is concentrated mainly on iron
Two aspects of spinel systems and aluminate system, form several documents and patent.
102603341 B of patent CN invented a kind of founding corundum-spinel brick for aluminium cell side wall and its
Preparation method, with the industrial alumina powder of 79~91wt%, the work of the light-magnesite powder of 5~14wt% and 4~10wt%
Industry soda ash is raw material, and the ferrous acid nickel fine powder of the additional 2~12wt% of raw material stirs evenly；It is put into electric arc furnaces, is warming up to
1850~1880 DEG C, 80~100 minutes are kept the temperature, then furnace temperature is risen to 2250~2290 DEG C, 30~40 minutes is kept the temperature, successively carries out
Oxygen blast twice, oxygen blown time interval is 20~30 minutes twice；Then furnace temperature is down to 1860~1890 DEG C to cast, is mended
It pours；It finally anneals 9~13 days in tunnel oven, in 30~70 DEG C of kiln discharges to get the founding corundum-for aluminium cell side wall
Spinel brick.Have apparent porosity low, anti-for founding corundum-spinel brick of aluminium cell side wall prepared by the present invention
Oxidation susceptibility and the excellent feature of potential resistance to electrolyte contamination erosion performance.
102674857 B of patent CN has invented a kind of preparation method of aluminum electrolysis cell upper part side wall magnesia composite material,
Its technical solution be using the light calcined magnesia fine powder of the magnesia particle of 60~80wt% and 20~40wt% as raw material, it is additional described
The polyvinyl alcohol of 1.5~5.0wt% of raw material and the oxide addition fine powder of 2~20wt% are uniformly mixed, compression moulding,
3~9h is kept the temperature under the conditions of 300~600 DEG C, and 2~8h is kept the temperature under conditions of 1350~1750 DEG C, it is cooling；Then firing is made
Product are machined to get aluminum electrolysis cell upper part side wall magnesia composite material.Aluminum electrolysis cell upper part prepared by the present invention
Side wall is with magnesia composite material with low in cost, thermal coefficient is lower, antioxygenic property and potential resistance to electrolyte contamination erosion performance are excellent
The characteristics of.
102267815 B of patent CN has invented a kind of refractory material for side wall and preparation method thereof of aluminium cell.Its skill
Art scheme is: with the corundum in granules of 60~72wt%, the magnesium aluminate spinel fine powder of 22~35wt% and the α-of 2~10wt%
Al2O3 micro mist is raw material, the TiO2 micro mist of additional 0.5~4.0wt% and the polyvinyl alcohol of 0.5~2.0wt%, is uniformly mixed,
Compression moulding handles 4~8h under the conditions of 400~600 DEG C, is then burnt under conditions of 1350~1650 DEG C, and heat preservation 3~
6h to get aluminium cell refractory material for side wall.The refractory material for side wall of aluminium cell prepared by the present invention has excellent
The characteristics of good antioxygenic property and potential resistance to electrolyte contamination erosion performance.
In foregoing invention patent, aluminium oxide, magnesia and its additive are capable of forming complex phase spinelle, and the ingredient is inhibited to exist
Dissolution in electrolyte, but since the solubility of both ingredients in the electrolyte is higher by (Al2O3 :~6wt.%；MgO:
1wt.%), it is difficult to ensure and is on active service for a long time in the electrolyte.And nickel and ferro element in NiFe_2O_4 spinel system, although being formed
Spinel structure be able to suppress the corrosion rate of two kinds of elements in the electrolyte, but two kinds of elements corrode in electrolyte chemical
With the lower easily formation Ni-Fe alloy of low oxygen partial pressure effect, the corrosion rate of accelerated material in the electrolyte, after causing " calamity "
Fruit.
The present invention passes through for deficiency existing for the above side-wall material from material Corrosion Resistant Mechanism and Service Environment
The other chemical attack of laboratory level and electrochemical corrosion experimental detection, determine two kinds of ingredients of ZnO and Cr2O3 not only in the electrolyte
With lower solubility (ZnO:0.017wt.%；Cr2O3:0.011wt.%), and the ZnCr2O4 spinelle that synthesizes exists
There is good thermal stability and chemical inertness in electrolyte.In order to make spinel consistency with higher, pass through
Additive is introduced, makes it have higher bulk density, it is ensured that when not influencing material corrosion performance, further increase it
Physical property.It is tested by a series of across comparisons, the results showed that novel side wall material prepared by the present invention, corrosion resistance
Better than the side-wall material referred in the above patent, there is apparent novelty and creativeness.
Summary of the invention
The raw material sources that the present invention selects are extensive, low in cost, and material preparation process is simple and easily implements.By rationally setting
Meter formula, prepared side-wall material not only has good corrosion resistance in low-temperature electrolytes, but also has anti-oxidant
Property, meet novel side wall materials'use performance requirement.
The present invention is achieved by the following technical solutions.
A kind of side-wall material, it is basic raw material, the total composition ratio of the two that the component of the material, which includes: zinc oxide, chromium oxide,
Example is 100%, and on this basis, magnesia, titanium oxide, iron oxide, silica, the aluminium oxide for additionally adding certain content are a kind of
Additive or the compound additive of several formation, the basic raw material uniformly mix according to a certain percentage with above-mentioned additive
It closes.
Further, zinc oxide mass fraction is 15wt.%-45wt.%, and chromium oxide mass fraction is 85wt.%-
55wt.%, formation base raw material, the additive amount of additive account for the quality hundred of basic raw material to two kinds of materials according to a certain percentage
Score are as follows: magnesia 0wt.%-20wt.%, titanium oxide 0wt.%-20wt.%, iron oxide 0wt.%-20wt.%, silica
0wt.%-20wt.%, aluminium oxide 0wt.%-20wt.%.
Further, it is 0.3-100 μm that the material particle size of the component, which is respectively as follows: zinc oxide D50,；Chromium oxide D50 is
0.3-100μm；Magnesia D50 is 0.3-100 μm；Titanium oxide D50 is 0.3-100 μm；Iron oxide D50 is 0.3-100 μm；Oxidation
Silicon D50 is 0.3-100 μm；Aluminium oxide D50 is 0.3-100 μm.
Further, the synthesis of the side-wall material uses two kinds of basic raw materials of zinc oxide and chromium oxide according to a certain ratio
ZnCr2O4 intermediate products are first synthesized, the mode of above-mentioned additive is still further introduced.
Further, the synthesis of the side-wall material is using two kinds of basic raw materials together with one or more compound additives
The mode of synthesis.
Further, the synthesis sintering temperature of side-wall material is between 1500 DEG C to 1650 DEG C, soaking time 3h-6h it
Between, cooling rate controls between 2-6 DEG C/min.
Further, in the preparation link of material, binder used is one of PVA, CMC, PEG, mass fraction
It accounts between two kinds of raw material and the 0.5-2wt.% of additive gross mass.
Further, the density for being sintered out material is between 3.0-5.5g/cm3, and flexural strength is in 70MPa-
Between 300MPa, linear shrinkage ratio≤20%.
The preparation method of side-wall material, comprising the following steps:
Using zinc oxide, chromium oxide as indispensable raw material, magnesia, titanium oxide, chromium oxide, silica, aluminium oxide conduct
Additive first synthesizes ZnCr according to by two kinds of basic raw materials of zinc oxide and chromium oxide according to a certain ratio2O4Intermediate products, then
In addition it introduces the mode of above-mentioned additive or synthesizes two kinds of basic raw materials together with one or more compound additives
Mode, the intermediate products or raw material are uniformly mixed with additive respectively, add binder, and are carried out wet ball grinding, dried
Dry, manual granulating working procedure, it is dry-pressing formed to certain shapes green compact, it is subsequently placed in high temperature furnace and is calcined, finally obtain finished product.
Further, it is described it is dry-pressing formed be that primary dry-pressing formed or isostatic cool pressing is dry-pressing formed, or it is first dry-pressing formed, then
Carry out isostatic cool pressing dry-pressing processing.
The shape of side-wall material finished product of the invention is one of cuboid, square, cylindrical body.Side wall of the invention
Material is mainly used for aluminium electroloysis industry.
Advantageous effects of the invention:
The present invention not only solves the problems, such as that existing novel side wall material itself decomposes during military service, and is being electrolysed
Also there is extremely low corrosion rate in matter, thus there is good corrosion resistance.
Detailed description of the invention
Fig. 1 is the microstructure figure of side-wall material of the invention；
Fig. 2 is side-wall material product schematic diagram of the invention.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
Embodiment 1
15wt.% zinc oxide (D50=1 μm), the basic raw material of (D50=2 μm) of 85wt.% chromium oxide conduct are chosen, to
It is additive that it, which introduces (D50=2 μm) of 4.5wt.% magnesia, with the PVA for the 1wt.% that mass fraction is the material gross mass
For binder, by wet ball grinding, the processes such as dry are dry-pressing formed on 500t hydraulic press, are placed in 1600 DEG C of high temperature sintering furnaces
In calcined, with 2 DEG C/min rate cooling, finally obtain finished product, bulk density 4.15g/cm3, flexural strength are
250MPa。
Embodiment 2
It is former based on selection raw material 20wt.% zinc oxide (D50=1.5 μm), 80wt.% chromium oxide (D50=1 μm)
Material, it is the material gross mass with mass fraction that introducing (D50=2 μm) of 4.5wt.% titanium oxide to it, which is additive,
The PVA of 1wt.% is binder, dry-pressing formed on 500t hydraulic press by processes such as wet ball grinding, dryings, is placed in 1650 DEG C
It is calcined in high temperature sintering furnace, with the cooling of 3 DEG C/min rate, finally obtains finished product, density 4.2g/cm3, intensity are
260MPa。
Embodiment 3
It is former based on selection raw material 20wt.% zinc oxide (D50=1.5 μm), 80wt.% chromium oxide (D50=1 μm)
Two kinds of materials are uniformly mixed, are sintered, is broken by material, then introducing (D50=2 μm) of 4.5wt.% titanium oxide to it is additive,
Using the PEG for the 1.5wt.% that mass fraction is the material gross mass as binder, by processes such as wet ball grinding, dryings,
It is dry-pressing formed on 500t hydraulic press, it is placed in 1550 DEG C of high temperature sintering furnaces and is calcined, with the cooling of 5 DEG C/min rate, finally obtained
Obtain finished product, density 4.4g/cm3, intensity 300MPa.
Embodiment 4
It is former based on selection raw material 40wt.% zinc oxide (D50=1.5 μm), 60wt.% chromium oxide (D50=1 μm)
Two kinds of materials are uniformly mixed, are sintered, is broken by material, then introducing total amount to it is 8wt.% compound additive (4.0wt.% oxygen
Change titanium, D50=1 μm；4.0wt.% magnesia, D50=2 μm), with the PEG for the 2wt.% that mass fraction is the material gross mass
It is dry-pressing formed on 500t hydraulic press by processes such as wet ball grinding, dryings for binder, it is placed in 1600 DEG C of high temperature sintering furnaces
In calcined, with 5 DEG C/min rate cooling, finally obtain finished product, density 4.1g/cm3, intensity 270MPa.
Embodiment 5
It is former based on selection raw material 30wt.% zinc oxide (D50=1.5 μm), 70wt.% chromium oxide (D50=1 μm)
Two kinds of materials are uniformly mixed, are sintered, is broken by material, then introducing total amount to it is 8wt.% compound additive (4.0wt.% oxygen
Change titanium, D50=1 μm；4.0wt.% magnesia, D50=2 μm), with 1.5wt.%'s that mass fraction is the material gross mass
PEG is binder, dry-pressing formed on 500t hydraulic press by processes such as wet ball grinding, dryings, is placed in 1550 DEG C of high temperature sinterings
It is calcined in furnace, with the cooling of 5 DEG C/min rate, finally obtains finished product, density 4.7g/cm3, intensity 250MPa.
Embodiment 6
It is former based on selection raw material 30wt.% zinc oxide (D50=1.5 μm), 70wt.% chromium oxide (D50=1 μm)
Two kinds of materials are uniformly mixed, are sintered, is broken by material, then introducing (D50=2 μm) of 4.5wt.% magnesia to it is additive,
Using the PEG for the 2wt.% that mass fraction is the material gross mass as binder, by processes such as wet ball grinding, dryings, in 500t
It is dry-pressing formed on hydraulic press, it is placed in 1550 DEG C of high temperature sintering furnaces and is calcined, with the cooling of 5 DEG C/min rate, finally obtained into
Product, density 4.2g/cm3, intensity 280MPa.
Embodiment 7
It is former based on selection raw material 45wt.% zinc oxide (D50=1.5 μm), 55wt.% chromium oxide (D50=1 μm)
Two kinds of materials are uniformly mixed, are sintered, is broken by material, then introducing (D50=2 μm) of 4.5wt.% titanium oxide to it is additive,
Using the PEG for the 1.5wt.% that mass fraction is the material gross mass as binder, by processes such as wet ball grinding, dryings,
It is dry-pressing formed on 500t hydraulic press, it is placed in 1550 DEG C of high temperature sintering furnaces and is calcined, with the cooling of 5 DEG C/min rate, finally obtained
Obtain finished product, density 4.4g/cm3, intensity 240MPa.
Embodiment 8
It is former based on selection raw material 40wt.% zinc oxide (D50=1.5 μm), 60wt.% chromium oxide (D50=1 μm)
Two kinds of materials are uniformly mixed, are sintered, is broken by material, then introducing total amount to it is 10wt.% compound additive (5wt.% oxygen
Change magnesium, D50=1 μm；5wt.% silica, D50=1 μm), with the PEG for the 1.0wt.% that mass fraction is the material gross mass
It is dry-pressing formed on 500t hydraulic press by processes such as wet ball grinding, dryings for binder, it is placed in 1650 DEG C of high temperature sintering furnaces
In calcined, with 5 DEG C/min rate cooling, finally obtain finished product, density 5.0g/cm3, intensity 290MPa.
Embodiment 9
It is former based on selection raw material 40wt.% zinc oxide (D50=1.5 μm), 60wt.% chromium oxide (D50=1 μm)
Two kinds of materials are uniformly mixed, are sintered, is broken by material, then introducing total amount to it is 20wt.% compound additive (15wt.% oxygen
Change aluminium, D50=2 μm；5wt.% iron oxide, D50=3 μm), with the PVA for the 2.0wt.% that mass fraction is the material gross mass
It is dry-pressing formed on 500t hydraulic press by processes such as wet ball grinding, dryings for binder, it is placed in 1500 DEG C of high temperature sintering furnaces
In calcined, with 5 DEG C/min rate cooling, finally obtain finished product, density 4.8g/cm3, intensity 290MPa.
Embodiment 10
It is former based on selection raw material 30wt.% zinc oxide (D50=1.5 μm), 70wt.% chromium oxide (D50=1 μm)
Two kinds of materials are uniformly mixed, are sintered, is broken by material, then introduce the aluminium oxide (D50=2 μm) that total amount is 20wt.% to it,
Using the PEG for the 2.0wt.% that mass fraction is the material gross mass as binder, by processes such as wet ball grinding, dryings,
It is dry-pressing formed on 500t hydraulic press, it is placed in 1600 DEG C of high temperature sintering furnaces and is calcined, with the cooling of 5 DEG C/min rate, finally obtained
Obtain finished product, density 4.5g/cm3, intensity 280MPa.
Above-described is only presently preferred embodiments of the present invention, not limitation invention.It should be understood that for the general of this field
For logical technical staff, under technical inspiration provided by the present invention, other equivalent improvement can also be made, this may be implemented
The purpose of invention, is regarded as protection scope of the present invention.
Claims (10)
1. a kind of side-wall material, which is characterized in that it is basic raw material, the two that the component of the material, which includes: zinc oxide, chromium oxide,
Total composition is 100%, on this basis, additionally adds magnesia, titanium oxide, iron oxide, silica, the oxygen of certain content
Change the compound additive of a kind of additive of aluminium or several formation, the basic raw material and above-mentioned additive are according to a certain percentage
Uniformly mixing.
2. side-wall material according to claim 1, which is characterized in that zinc oxide mass fraction is 15wt.%-45wt.%,
Chromium oxide mass fraction is 85wt.%-55wt.%, and formation base raw material, additive add two kinds of materials according to a certain percentage
Dosage accounts for the mass percent of basic raw material are as follows: magnesia 0wt.%-20wt.%, titanium oxide 0wt.%-20wt.%, oxidation
Iron 0wt.%-20wt.%, silica 0wt.%-20wt.%, aluminium oxide 0wt.%-20wt.%.
3. side-wall material according to claim 2, which is characterized in that the material particle size of the component is respectively as follows: zinc oxide
D50 is 0.3-100 μm；Chromium oxide D50 is 0.3-100 μm；Magnesia D50 is 0.3-100 μm；Titanium oxide D50 is 0.3-100 μ
m；Iron oxide D50 is 0.3-100 μm；Silica D50 is 0.3-100 μm；Aluminium oxide D50 is 0.3-100 μm.
4. side-wall material according to claim 2, which is characterized in that the synthesis of the side-wall material uses zinc oxide and oxidation
Two kinds of basic raw materials of chromium first synthesize ZnCr2O4 intermediate products according to a certain ratio, still further introduce the mode of above-mentioned additive.
5. side-wall material according to claim 2, which is characterized in that the synthesis of the side-wall material is using two kinds of basic former materials
Expect the mode synthesized together with one or more compound additives.
6. side-wall material according to claim 4 or 5, which is characterized in that the synthesis sintering temperature of side-wall material is 1500
DEG C between 1650 DEG C, between 3h-6h, cooling rate controls between 2-6 DEG C/min soaking time.
7. side-wall material according to claim 4 or 5, which is characterized in that in the preparation link of material, binder used
It is one of PVA, CMC, PEG, mass fraction accounts between two kinds of raw material and the 0.5-2wt.% of additive gross mass.
8. side-wall material according to claim 6, which is characterized in that the density for being sintered out material is in 3.0-5.5g/
Between cm3, flexural strength is between 70MPa-300MPa, linear shrinkage ratio≤20%.
9. such as the preparation method of the described in any item side-wall materials of claim 1-8, which comprises the following steps:
Using zinc oxide, chromium oxide as indispensable raw material, magnesia, titanium oxide, chromium oxide, silica, aluminium oxide are as addition
Agent first synthesizes ZnCr according to by two kinds of basic raw materials of zinc oxide and chromium oxide centainly to match2O4Intermediate products still further draw
The mode system for entering the mode of above-mentioned additive or synthesizing two kinds of basic raw materials together with one or more compound additives
Standby, the intermediate products or raw material are uniformly mixed with additive respectively, add binder, and carry out wet ball grinding, drying,
Manual granulating working procedure, it is dry-pressing formed to certain shapes green compact, it is subsequently placed in high temperature furnace and is calcined, finally obtain finished product.
10. side-wall material according to claim 9, which is characterized in that it is described it is dry-pressing formed be primary dry-pressing formed or cold
Equal static pressure are dry-pressing formed, or first dry-pressing formed, then carry out isostatic cool pressing dry-pressing processing.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548141A (en) * | 2020-04-09 | 2020-08-18 | 中国铝业股份有限公司 | Strong corrosion-resistant material and preparation method thereof |
| CN113999044A (en) * | 2021-11-12 | 2022-02-01 | 郑州磨料磨具磨削研究所有限公司 | Porous ceramic plate and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58157982A (en) * | 1982-03-11 | 1983-09-20 | Nippon Ferrite Ltd | Sintered metallic oxide electrode |
| CN1180679A (en) * | 1996-10-24 | 1998-05-06 | 周季楠 | Antierosion fireproof material for aluminium electrolyzer |
| CN101255570A (en) * | 2007-12-07 | 2008-09-03 | 东北大学 | Inert anode material for aluminium electrolysis and method for manufacturing same |
| CN102010193A (en) * | 2010-12-15 | 2011-04-13 | 中国铝业股份有限公司 | Corrosion resistant protection material for fusedsaltelectrolysis and preparation method thereof |
-
2019
- 2019-04-28 CN CN201910348176.9A patent/CN109970438A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58157982A (en) * | 1982-03-11 | 1983-09-20 | Nippon Ferrite Ltd | Sintered metallic oxide electrode |
| CN1180679A (en) * | 1996-10-24 | 1998-05-06 | 周季楠 | Antierosion fireproof material for aluminium electrolyzer |
| CN101255570A (en) * | 2007-12-07 | 2008-09-03 | 东北大学 | Inert anode material for aluminium electrolysis and method for manufacturing same |
| CN102010193A (en) * | 2010-12-15 | 2011-04-13 | 中国铝业股份有限公司 | Corrosion resistant protection material for fusedsaltelectrolysis and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 蒋官澄等: "《海洋设备腐蚀与保护》", 31 March 2011, 中国石油大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548141A (en) * | 2020-04-09 | 2020-08-18 | 中国铝业股份有限公司 | Strong corrosion-resistant material and preparation method thereof |
| CN113999044A (en) * | 2021-11-12 | 2022-02-01 | 郑州磨料磨具磨削研究所有限公司 | Porous ceramic plate and preparation method thereof |
| CN113999044B (en) * | 2021-11-12 | 2022-08-26 | 郑州磨料磨具磨削研究所有限公司 | Porous ceramic plate and preparation method thereof |
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Application publication date: 20190705 |