CN101942677A - Heat-insulating coating material for aluminum electrolytic inert anode and use thereof - Google Patents
Heat-insulating coating material for aluminum electrolytic inert anode and use thereof Download PDFInfo
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- CN101942677A CN101942677A CN2010102987912A CN201010298791A CN101942677A CN 101942677 A CN101942677 A CN 101942677A CN 2010102987912 A CN2010102987912 A CN 2010102987912A CN 201010298791 A CN201010298791 A CN 201010298791A CN 101942677 A CN101942677 A CN 101942677A
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Abstract
The invention discloses a heat-insulating coating material for an aluminum electrolytic inert anode. The heat-insulating coating material consists of Me3AlF6 and Al2O3 fibers, wherein Me is at least one of Na, K and Li. The using method of the heat-insulating coating material comprises the following steps of: mixing materials according to the weight percentage of the components of the heat-insulating coating material for the aluminum electrolytic inert anode; coating the mixed material on the outer surface of the aluminum electrolytic inert anode or the inert anode set, wherein the coating thickness of the mixed material is between 1.5 and 5.0 centimeters; and then heating to 850 to1,010 DEG C and calcining for 4 to 24 hours to obtain the inert anode of inert anode set coated with the heat-insulating coating material. In the heat-insulating coating material, the polycrystalline Al2O3 fiber with high chemical stability, heat resistance and high anti-shock and toughening performance is used as one of the main raw materials, particles of the material are not independent but are connected with each other, and therefore the strength and the toughness of the heat-insulating coating material are effectively improved at high temperature and effective protection on the inert anode is realized. The composition of the heat-insulating coating material can be adjusted according to the components of the aluminum electrolyte without polluting the electrolyte.
Description
Technical field
The present invention relates to the used for aluminium electrolysis inert anode, be meant a kind of aluminum electrolysis inertia anode thermal insulation coating material and application thereof especially; Belong to technical field of electrochemistry.
Background technology
Hall-H é roult fused salt electrolysis process is unique up to now industrial metallurgy method for aluminum, adopts inert anode to replace the trend that existing carbon anode is the aluminium electrolytic industry development.For realizing the normal use of inert anode on aluminium cell, need at first adopt carbon anode that calcination is started, behind the electrolytic cell normal operation, use again through the inert anode of preheating carbon anode is changed, make electrolytic cell operation carry out the transition to the inert anode electrolysis by the carbon annode electrolysis; In addition, in the inert anode electrolysis running, the inert anode after also needing to adopt inert anode after the new preheating to the operation certain hour is changed, to guarantee the even running of inert anode aluminium cell.In the preheating-replacing process, inert anode will stand powerful thermal shocking, rush of current and gas corrosive nature, very easily causes the anodic broken invalid.
At the problems referred to above, the contriver once applied for a patent (patent No.: ZL 200710034822.1), had proposed a kind of aluminum electrolysis inertia anode preheating-replacing with thermal insulation coating material and preparation method.Although this material has good thermal shock resistance; can avoid in the inertia anode preheating-replacing process because thermal shock; rush of current and gas corrosiveness and the breakage that causes; but because coating the raw material of material, this kind insulation is powdered substance; material granule is each other relatively isolated behind the sintering; this not only easily causes in the material preparation process and cracking phenomena occurs; and the ability of material opposing external physical impact effect under the high temperature is on duty mutually; come from extraneous collision and very easily cause coming off of material, thereby can't effectively protect again inert anode or inert anode group.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art and a kind of heat-insulating coating material for aluminum electrolytic inert anode and application thereof are provided; this material can be kept out extraneous physical impacts effect and do not come off, do not ftracture under the condition of high temperature; avoid in preheating-transfer process; lose protective effect to inert anode owing to insulation coats coming off of material, realize smoothly the preheating-replacing of anode.
A kind of aluminum electrolysis inertia anode thermal insulation coating material of the present invention, form by following compositions in weight percentage:
Me
3AlF
6 60～90％，
Al
2O
3Fiber 10～40%,
Wherein Me is selected from least a among Na, K or the Li.
A kind of heat-insulating coating material for aluminum electrolytic inert anode of the present invention also includes Al in its component
2O
3Powder or AlF
3In at least a, the each component percentage by weight is:
Me
3AlF
6 60～90％，
Al
2O
3Fiber 10～40%,
Al
2O
3Powder 0～20%,
AlF
30～30%, each component weight percent sum is 100%.
In a kind of heat-insulating coating material for aluminum electrolytic inert anode of the present invention, described Al
2O
3The diameter of fiber is 1.5～5.0 μ m, and length is 20～40mm;
In a kind of heat-insulating coating material for aluminum electrolytic inert anode of the present invention, described Al
2O
3Powder size is 30～60 μ m.
A kind of aluminum electrolysis inertia anode comprises the steps: with the application of thermal insulation coating material
The first step: batching
Aluminum electrolysis inertia anode by design is prepared burden with each composition weight percentage composition of thermal insulation coating material, mixes;
Second step: sintering
The first step gained compound is wrapped in aluminum electrolysis inertia anode or inert anode group outside surface, the coating thickness of described compound is 1.5cm～5.0cm, then, be heated to inert anode or the inert anode group that 850～1010 ℃ of calcinings promptly obtained being coated with thermal insulation coating material in 4～24 hours;
Described coating adopts the coating container to finish, the shape of described coating container is identical with inert anode or inert anode group, and described container height is more empty than described inert anode or the big 3～10cm of inert anode group appearance and size in the described container than described inert anode or the high 3～10cm of inert anode group; Described inert anode or inert anode group are placed described container center, and first step gained compound is filled up in the space between described inert anode or inert anode group and described container inner wall, and packed density is 0.36～3.00g/cm
3Then, carry out sintering, sintering is complete, with described container and inert anode or inert anode component from.
A kind of aluminum electrolysis inertia anode of the present invention is used in the application of thermal insulation coating material, the described thermal recovery high temperature resistance furnace that adds.
The present invention adopts the polymorph A l with good, the high temperature resistant and good antidetonation increasing tougheness energy of chemical stability
2O
3Fiber is as one of primary raw material, make in the material each particles no longer isolated and be connected with each other, thereby the Effective Raise insulation coats intensity and the toughness of material.
Simultaneously, can specifically form according to aluminium electrolyte, adjust aluminum electrolysis inertia anode and coat material Me with insulation
3AlF
6-Al
2O
3(fiber)-Al
2O
3The raw material of (powder)-AlF3 forms, and it is separated with inert anode behind preheating-replacing easily, and can not pollute or other adverse effect electrolyte; In thermal insulation coating material manufacturing process, by adjusting various raw material compositions, packed density, calcining heat and calcination time, can obtain aluminum electrolysis inertia anode is had the clad material of insulation effect.Owing to used Me
3AlF
6With fibrous Al
2O
3As primary raw material, the thermal insulation coating material that obtains not only has porous loose structure, and because Al
2O
3The effect of fiber, make in the material each particles no longer isolated and be connected with each other, this both had been conducive to improve the heat-insulating property of material, simultaneously under certain external influence power, thermal insulation coating material is difficult for coming off and keeps its integrality, avoid the inertia anode preheating-replacing process owing to thermal shock, rush of current and gas corrosiveness the problems such as broken invalid.Simultaneously, in raw material, add Al
2O
3Or AlF
3, not only can effectively reduce the sintering temperature of material preparation process, and because prepared insulation coats the material composition closer to the electrolyte ingredient in the aluminium cell, reduce the influence degree to composition of electrolyte in the groove.
Embodiment
Embodiment 1: a kind of Na
3AlF
6-Al
2O
3(fiber) thermal insulation coating material
Aluminum electrolysis inertia anode Na
3AlF
6-Al
2O
3(fiber) insulation coats material composition of raw materials (by the quality percentage composition): 90%Na
3AlF
610%Al
2O
3(fiber), its fibre diameter are 2.0～4.0 μ m, length 30-40mm.
Above-mentioned two kinds of raw materials are mixed in proportion, fill mixed raw material in a graphite crucible, making the thickness after its tamping is about 1.5cm, and inert anode is placed in the graphite crucible, fill all around and the mixing of the about 1.5cm thickness of tamping after raw material, its packed density is 1.60g/cm
3The graphite crucible that inert anode is housed is placed in the resistance furnace, be raised to 980 ℃ and be incubated 8 hours with the speed of 5 ℃ of per minutes, after the stove cooling, graphite crucible is removed, obtain being coated with Na
3AlF
6-Al
2O
3The inert anode of (fiber) material.
This insulation coats complete, the surperficial flawless of material profile, is that 4 times of 98 newton are impacted and do not come off at 1000 ℃ of lower active forces that come from the outside that can bear, and can be used for inert anode and contain Na in electrolyte
3AlF
6And Al
2O
3Aluminium cell on preheating-replacing.
Embodiment 2: a kind of Na
3AlF
6-Al
2O
3(fiber) thermal insulation coating material
Aluminum electrolysis inertia anode Na
3AlF
6-Al
2O
3(fiber) insulation coats material composition of raw materials (by the quality percentage composition): 80%Na
3AlF
620%Al
2O
3(fiber), its fibre diameter are 3.0～5.0 μ m, length 20-30mm.
Above-mentioned two kinds of raw materials are mixed in proportion, fill mixed raw material in a graphite crucible, making the thickness after its tamping is about 2.0cm, and inert anode is placed in the graphite crucible, fill all around and the mixing of the about 2.0cm thickness of tamping after raw material, its packed density is 1.90g/cm
3The graphite crucible that inert anode is housed is placed in the resistance furnace, be raised to 970 ℃ and be incubated 12 hours with the speed of 4 ℃ of per minutes, after the stove cooling, graphite crucible is removed, obtain being coated with Na
3AlF
6-Al
2O
3The inert anode of (fiber) material.
This insulation coats complete, the surperficial flawless of material profile, is that 4 times of 90 newton are impacted and do not come off at 1000 ℃ of lower active forces that come from the outside that can bear, and can be used for inert anode and contain Na in electrolyte
3AlF
6And Al
2O
3Aluminium cell on preheating-replacing.
Embodiment 3: a kind of Na
3AlF
6-Al
2O
3(fiber) thermal insulation coating material
Aluminum electrolysis inertia anode Na
3AlF
6-Al
2O
3(fiber) insulation coats material composition of raw materials (by the quality percentage composition): 60%Na
3AlF
640%Al
2O
3(fiber), its fibre diameter are 1.5～3.0 μ m, length 30-40mm.
Above-mentioned two kinds of raw materials are mixed in proportion, fill mixed raw material in a graphite crucible, making the thickness after its tamping is about 5.0cm, and inert anode is placed in the graphite crucible, fill all around and the mixing of the about 5.0cm thickness of tamping after raw material, its packed density is 2.80g/cm
3The graphite crucible that inert anode is housed is placed in the resistance furnace, be raised to 960 ℃ and be incubated 24 hours with the speed of 2.5 ℃ of per minutes, after the stove cooling, graphite crucible is removed, obtain being coated with Na
3AlF
6-Al
2O
3The inert anode of (fiber) material.
This insulation coats complete, the surperficial flawless of material profile, is that 4 times of 80 newton are impacted and do not come off at 1000 ℃ of lower active forces that come from the outside that can bear, and can be used for inert anode and contain Na in electrolyte
3AlF
6And Al
2O
3Aluminium cell on preheating-replacing.
Embodiment 4: a kind of K
3AlF
6-Al
2O
3(fiber)-AlF
3Thermal insulation coating material
Aluminum electrolysis inertia anode K
3AlF
6-Al
2O
3(fiber)-AlF
3Insulation coats material composition of raw materials (by the quality percentage composition): 65%K
3AlF
625%Al
2O
3(fiber), its fibre diameter are 1.5～2.5 μ m, length 20-40mm; 10%AlF
3
Above-mentioned three kinds of raw materials are mixed in proportion, fill mixed raw material in a graphite crucible, making the thickness after its tamping is about 2.0cm, and the inertia utmost point is placed in the graphite crucible, fill all around and the thick mixing of the about 1.8cm of tamping after raw material, its packed density is 2.50g/cm
3The graphite crucible that inert anode is housed is placed in the resistance furnace, be raised to 940 ℃ and be incubated 12 hours with the speed of 4 ℃ of per minutes, after the stove cooling, graphite crucible is removed, obtain being coated with Na
3AlF
6-Al
2O
3(fiber)-AlF
3The inert anode of material.
Institute obtains insulation and coats complete, the surperficial flawless of material profile, comes from the outside 960 ℃ of lower can bearing that to act as be that 3 times of 120 newton are impacted and do not come off, and can be used for inert anode and contain K in electrolyte
3AlF
6, Al
2O
3And AlF
3Aluminium cell on preheating-replacing.
Embodiment 5: a kind of K
3AlF
6-Al
2O
3(fiber)-Al
2O
3(powder) thermal insulation coating material
Aluminum electrolysis inertia anode K
3AlF
6-Al
2O
3(fiber)-Al
2O
3(powder) insulation coats material composition of raw materials (by the quality percentage composition): 65%K
3AlF
625%Al
2O
3(fiber), its fibre diameter are 1.5～2.5 μ m, length 20-40mm; 10%Al
2O
3(powder), granularity are 30～40 μ m.
Above-mentioned three kinds of raw materials are mixed in proportion, fill mixed raw material in a graphite crucible, making the thickness after its tamping is about 2.0cm, and the inertia utmost point is placed in the graphite crucible, fill all around and the thick mixing of the about 1.8cm of tamping after raw material, its packed density is 2.50g/cm
3The graphite crucible that inert anode is housed is placed in the resistance furnace, be raised to 950 ℃ and be incubated 18 hours with the speed of 3 ℃ of per minutes, after the stove cooling, graphite crucible is removed, obtain being coated with Na
3AlF
6-Al
2O
3(fiber)-10%Al
2O
3The inert anode of (powder) material.
Institute obtains insulation and coats complete, the surperficial flawless of material profile, comes from the outside 960 ℃ of lower can bearing that to act as be that 3 times of 100 newton are impacted and do not come off, and can be used for inert anode and contain K in electrolyte
3AlF
6, Al
2O
3Aluminium cell on preheating-replacing.
Embodiment 6: a kind of Na
3AlF
6-K
3AlF
6-Al
2O
3(fiber)-Al
2O
3(powder)-AlF
3Thermal insulation coating material aluminum electrolysis inertia anode Na
3AlF
6-K
3AlF
6-Al
2O
3(fiber)-Al
2O
3(powder)-AlF
3Insulation coats material composition of raw materials (by the quality percentage composition): 45%K
3AlF
620%K
3AlF
615%Al
2O
3(fiber), its fibre diameter are 2.5～5.0 μ m, length 20-40mm; 5%Al
2O
3(powder), granularity are 50～60 μ m; 15%AlF
3
Above-mentioned five kinds of raw materials are mixed in proportion, fill mixed raw material in a graphite crucible, making the thickness after its tamping is about 3.0cm, and inert anode is placed in the graphite crucible, fill all around and the thick mixing of the about 3.0cm of tamping after raw material, its packed density is 1.80g/cm
3The graphite crucible that inert anode is housed is placed in the resistance furnace, be raised to 870 ℃ and be incubated 20 hours with the speed of 3 ℃ of per minutes, after the stove cooling, graphite crucible is removed, obtain being coated with Na
3AlF
6-K
3AlF
6-Al
2O
3(fiber)-Al
2O
3(powder)-AlF
3The inert anode of material.
Institute obtains insulation and coats complete, the surperficial flawless of material profile, can bear down at 920 ℃ and coming from the outside that to act as be that 3 times of 120 newton are impacted and do not come off, and can be used for inert anode and contain Na in ionogen
3AlF
6, K
3AlF
6, Al
2O
3And AlF
3Aluminium cell on preheating-replacing.
Claims (6)
1. aluminum electrolysis inertia anode thermal insulation coating material, form by following compositions in weight percentage:
Me
3AlF
6 60～90％，
Al
2O
3Fiber 10～40%,
Wherein Me is selected from least a among Na, K or the Li.
2. a kind of heat-insulating coating material for aluminum electrolytic inert anode according to claim 1 also includes Al in its component
2O
3Powder or AlF
3In at least a, the each component percentage by weight is:
Me
3AlF
6 60～90％，
Al
2O
3Fiber 10～40%,
Al
2O
3Powder 0～20%,
AlF
30～30%, each component weight percent sum is 100%.
3. a kind of heat-insulating coating material for aluminum electrolytic inert anode according to claim 2 is characterized in that: described Al
2O
3The diameter of fiber is 1.5～5.0 μ m, and length is 20～40mm.
4. a kind of heat-insulating coating material for aluminum electrolytic inert anode according to claim 3 is characterized in that: described Al
2O
3Powder size is 30～60 μ m.
5. the application of an aluminum electrolysis inertia anode usefulness thermal insulation coating material comprises the steps:
The first step: batching
Aluminum electrolysis inertia anode by design is prepared burden with each composition weight percentage composition of thermal insulation coating material, mixes;
Second step: sintering
The first step gained compound is wrapped in aluminum electrolysis inertia anode or inert anode group outside surface, the coating thickness of described compound is 1.5cm～5.0cm, then, be heated to inert anode or the inert anode group that 850～1010 ℃ of calcinings promptly obtained being coated with thermal insulation coating material in 4～24 hours;
Described coating adopts the coating container to finish, the shape of described coating container is identical with inert anode or inert anode group, and described container height is more empty than described inert anode or the big 3～10cm of inert anode group appearance and size in the described container than described inert anode or the high 3～10cm of inert anode group; Described inert anode or inert anode group are placed described container, and first step gained compound is filled up in the space between described inert anode or inert anode group and described container inner wall, and packed density is 0.36～3.00g/cm
3Then, carry out sintering, sintering is complete, with described container and inert anode or inert anode component from.
6. a kind of aluminum electrolysis inertia anode according to claim 5 is characterized in that: the described thermal recovery high temperature resistance furnace that adds with the application of thermal insulation coating material.
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|---|---|---|---|
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|---|---|---|---|
| CN2010102987912A CN101942677A (en) | 2010-09-30 | 2010-09-30 | Heat-insulating coating material for aluminum electrolytic inert anode and use thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106894051A (en) * | 2017-01-23 | 2017-06-27 | 中南大学 | A kind of preparation of aluminium cell artificial hearth material and described artificial hearth |
| CN109763146A (en) * | 2019-03-27 | 2019-05-17 | 贵州省过程工业技术研究中心 | A kind of titanium composite material anode preparation method used for aluminium electrolysis |
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| CN106894051A (en) * | 2017-01-23 | 2017-06-27 | 中南大学 | A kind of preparation of aluminium cell artificial hearth material and described artificial hearth |
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| CN109763146A (en) * | 2019-03-27 | 2019-05-17 | 贵州省过程工业技术研究中心 | A kind of titanium composite material anode preparation method used for aluminium electrolysis |
| CN109763146B (en) * | 2019-03-27 | 2021-03-26 | 贵州省过程工业技术研究中心 | Preparation method of titanium-based composite material anode for aluminum electrolysis |
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Application publication date: 20110112 |