CN102817044A - Aluminium electrolyte and using method thereof - Google Patents
Aluminium electrolyte and using method thereof Download PDFInfo
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- CN102817044A CN102817044A CN2012102621784A CN201210262178A CN102817044A CN 102817044 A CN102817044 A CN 102817044A CN 2012102621784 A CN2012102621784 A CN 2012102621784A CN 201210262178 A CN201210262178 A CN 201210262178A CN 102817044 A CN102817044 A CN 102817044A
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Abstract
The invention discloses aluminium electrolyte and a using method of the aluminium electrolyte and relates to a formula of an electrolyte fusing agent for production of aluminium electrolysis and a using method of the formula. The aluminium electrolyte is characterized in that the aluminium electrolyte in a fusion state comprises the following components by weight: 50%-56% of NaF, 0-3% of NaCl, 26%-30% of AlF3, 2%-4% of CaF2, 0-1% of CaCl2, 0-3% of MgF2, 1-6% of LiF, 0-3% of KF and 1%-3% of KCl. The electric conductivity of electrolyte fused salt is 2.30-2.65 S/cm; (2) the working temperature of the electrolyte is controlled to be 930-965 DEG C and the degree of superheat is 5-28 DEG C; and (3) the current intensity is improved, or the cathode-anode distance is increased or the heat insulation of a cell body is enhanced. By the aluminium electrolyte and the using method of the aluminium electrolyte, the voltage drop of the electrolyte of unit current is reduced, the productivity of an electrolytic cell is improved, the energy consumption of a unit product of the electrolytic cell is reduced, the addition volume for production of aluminum fluoride is lowered, and the aims of high efficiency, energy saving and consumption reduction in production of the electrolytic cell are realized.
Description
Technical field
A kind of aluminium relates to a kind of aluminum electrolysis with ionogen flux prescription and method of use thereof with ionogen and method of use thereof.
Background technology
Be used for Na in the industrial cell
3AlF
6-AlF
3-Al
2O
3The pure fluorine system electrolyte flux of base, its mol ratio (NaF and AlF
3The amount of substance ratio) generally is controlled between 2.2 ~ 2.6, is a kind of acidic flux, generally also contain LiF, MgF
2, CaF
2Deng.As aluminum oxide flux and main heating medium, therefore, electrolytical aluminum oxide melting performance and conductivity are its main electrolytic process parameters to ionogen flux in electrolysis.
Current, domestic Electrolytic Aluminum Series average anode current density 0.75A/cm
2About, actual current efficient is generally below 93%, and electrolysis temperature is at 930-960 ℃, and external advanced enterprise anodic current density has reached 0.9A/cm
2, potline current efficient is all between 94-96%.With comparing domestic main gap abroad is that current density and current efficiency are low, and electrolyzer unit surface output capacity is low, improves strength of current or improve current efficiency to have a high potential to improve output capacity.
It is that requirement production is steadily stable that aluminium cell is obtained its most important condition of better economic results, and electrolyzer is in material balance and heat balance preferably.Traditional conservation measures is mainly and reduces pole span or raising electrolytic cell currents intensity etc. between anode and the negative electrode; The former can cause electrolytic cell currents efficient and throughput to descend; The regular fluctuation of voltage; Groove condition instability and the increase of production operation difficulty etc. perhaps generally strengthen the heating region heat, and causing stove group to form difficulty influences electrolytic cell currents efficient and electrolytic bath life-span.
Summary of the invention
The object of the invention is exactly the deficiency that exists to above-mentioned prior art, proposes a kind ofly can effectively to reduce bath voltage, improves current efficiency, electrolyzer is moved at HCD, and the aluminium of raising production capacity and energy efficient is with ionogen and method of use thereof.
The objective of the invention is to realize through following technical scheme.
A kind of aluminium is used ionogen, it is characterized in that the weight ratio composition of its molten state comprises: NaF:50%～56%; NaCl:0 ~ 3%; AlF
3: 26%～30%; CaF
2: 2% ~ 4 %; CaCl
2: 0 ~ 1%; MgF
2: 0～3 %; LiF:1～6 %; KF:0～3 %; KCl:1% ~ 3%.
A kind of aluminium of the present invention is used electrolytical method of use; It is characterized in that specific conductivity is 2.30 ~ 2.65S/cm under the aluminium use ionogen working order; The melt working temperature is 930 ~ 965 ℃, and its superheating temperature is controlled at 5 ~ 28 ℃, and it is 6.0 ~ 10.2% to the alumina dissolution degree.
A kind of aluminium of the present invention is used electrolytical method of use, it is characterized in that its anodic current density is 0.60 ~ 1.2A/cm
2, the electrolyte melt height is at 15 ~ 25cm.
A kind of aluminium of the present invention is used electrolytical method of use, it is characterized in that the electrolyzer grooved that uses is horizontal groove, vertical groove or is multicavity tray.
A kind of aluminium of the present invention is used electrolytical method of use, it is characterized in that the anode material that matches with its use can be expendable carbon anode or non-expendable inertia conductive anode.
A kind of aluminium of the present invention is used electrolytical method of use, it is characterized in that the cathode material that matches with its use can be full graphitization cathode or part graphite cathode material, also can be TiB
2/ C composite cathode material.
A kind of aluminium of the present invention is used electrolytical method of use, it is characterized in that the side wall composite material that matches with its use is common charcoal piece, or is silicon nitride combined silicon carbide, or be both compound side wall composite materials.
A kind of aluminium of the present invention is used ionogen, and (conductive carrier is Na more than 90% to its core in the ionogen for conductive carrier NaF content in the raising ionogen
+Ion).Major measure makes not improving under the liquidus temperature condition and improves Na
+Secondly the ion volumetric molar concentration adds a certain amount of LiF and KF raising NaF live volume activity at ionogen to improve live body quantity.Its purpose is for improving conductivity under the aluminium electrolyte molten state and to the melting ability of aluminum oxide, keeping existing superheating temperature condition of producing simultaneously, stablize electrolysis tank furnace group and heat radiation distribution.Use ionogen according to the invention, heating region resistance reduces, and can remedy through improving strength of current and increasing the pole span adding, and then can improve current efficiency and improve production capacity, reduction unit product production energy consumption.Therefore, ionogen of the present invention is compared the used ionogen of current industrial, has energy-efficient characteristics.
System component changes principle for passing through to optimize middle basic metal of ionogen and alkaline earth metal content proportioning; Keep the melt liquidus temperature after industrial electrolysis matter flux is replaced in the target electrolyzer constant; The raising electrolytic conductivity can improve the aluminum oxide melting performance more than 10% more than 20%, type in the high current efficient of maintenance electrolytic process and the better burner hearth; Simultaneously, this electrolyte system can also significantly reduce the daily ALUMNIUM FLUORIDE addition of electrolyzer.
The component specific aim is different in the prescription, but to different slots condition real-time monitoring.Can improve ionogen carbon slag separation performance like suitable raising Mg salt and Ca salts contg, mineralising suspension aluminum oxide improves alumina dissolution speed.Improving sylvite can promote and the aluminum oxide fusing speed.Improve lithium salts and can improve electric conductivity.
A kind of aluminium of the present invention is used ionogen, and its method of use can be divided into independent startup groove and the online groove replacement dual mode that do not stop.Wherein new independent startup groove can be used new the startup under the situation such as groove and electrolytic cell overhaul restarting groove.Calculate a certain amount of adjustment composition in advance like available original electrolyte flux in new startup and restarting groove; With packing electrolyzer into groove intensification fusing in the levigate back fusing back adding of both mixings electrolyzer or with solid-like, specifically look different the decision of startup methods and scheme.Be adjusted to the required solid matter of branch and mix, be generally yellow soda ash, Sodium Fluoride, sodium-chlor by oxide compound, carbonate and halogenide etc., Repone K, Quilonum Retard, magnesiumcarbonate, Calcium Fluoride (Fluorspan) and calcium chloride are formed.
The online groove that do not stop is adjusted into aluminium inlet and flue end and the adding of the anode bottom good adjustment material of calculating in advance, and the adding principle can be repeatedly progressively approaches on a small quantity, also can be disposable adding.Add-on is looked electrolyzer amount of ram ionogen and is decided, and generally is no more than 30% of the interior melt ionogen quality of groove.Add material and be generally oxide compound or halogenide, try not to add carbonate, produce the bottom land deposition in order to avoid react untimely, also can shorten the composition adjustment time simultaneously.
The too high mole of ionogen molecular ratio may anticathode and side wall composite material unfavorable to some extent; But find through experimental test; This influence is very limited and controlled, so electrolytic bath side part inner lining can continue to use with cathode material and have the electrolyzer material therefor now, also can use novel high performance material.For prebaked anode, its consumption is close with the existing ionogen of industry, and adapting to the anodic current density scope is 0.60 ~ 1.2A/cm
2
A kind of aluminium of the present invention is used ionogen, and the anode material that its use matches can be expendable carbon anode or non-expendable inertia conductive anode; The cathode material that matches with its use can be full graphitization cathode or part graphite cathode material, also can be TiB
2/ C composite cathode material; The side wall composite material that matches with its use can be common charcoal piece, also can be silicon nitride combined silicon carbide, also can be both compound side wall composite materials.
During use, strengthen potline current intensity, increase distance between used anode of electrolysis and the negative electrode, keep the interior type of existing groove thorax to distribute, reduce single groove ALUMNIUM FLUORIDE addition, can reach energy-conservation purpose through improving modes such as production capacity and current efficiency and reduction consumption with heat radiation.
During use, increase distance between the electrolytic tank electrode, keep the melt zone thermal value, keep the interior type of existing groove thorax to distribute, reduce single groove ALUMNIUM FLUORIDE addition, reach energy-conservation purpose through improving production capacity and current efficiency mode with heat radiation.
During use, strengthen electrolyzer cell body insulation design, reduce the electrolyzer heat lost by radiation, keep pole distance, reduce single groove ALUMNIUM FLUORIDE addition, reach energy-conservation purpose through reducing the electrolyzer average voltage.
A kind of aluminium of the present invention is with ionogen and method of use thereof; Can reduce the electrolytical volts lost of unitary current, improve electrolyzer unit's production capacity, reduce electrolyzer unit product energy expenditure; Reduce and produce the ALUMNIUM FLUORIDE addition, realize the purpose that electrolyzer is produced energy-efficient consumption reduction.
Embodiment
A kind of aluminium is used ionogen, and its composition comprises Sodium Fluoride, sodium-chlor, ALUMNIUM FLUORIDE, Calcium Fluoride (Fluorspan), calcium chloride, Sellaite, lithium fluoride, Potassium monofluoride and Repone K; Its molten state composition weight is formed and is comprised: NaF:50～56 wt.%; NaCl:0 ~ 3wt.%; AlF
3: 26～30 wt.%; CaF
2: 2 ~ 4 wt.%; CaCl
2: 0 ~ 1 wt.%; MgF
2: 0～3 wt.%; LiF:1～6 wt.%; KF:0～3 wt.%; KCl:1 ~ 3 wt.%.This prescription ionogen mole molecular ratio has been different from traditional acidic aluminum ionogen 3.20 ~ 4.30, is a kind of alkaline low-temperature ionogen.
A kind of aluminium of the present invention is used the ionogen method of use, and its aluminium uses that specific conductivity is 2.30 ~ 2.65S/cm under the electrolytical working order, and the melt working temperature is 930 ~ 965 ℃, and its superheating temperature is controlled at 5 ~ 28 ℃, and it is 6.02 ~ 10.20% to the alumina dissolution degree.
A kind of aluminium of the present invention is used the ionogen method of use, and it adapts to the anodic current density scope is 0.60 ~ 1.2A/cm
2, the electrolyte melt height is at 15 ~ 25cm.
A kind of aluminium of the present invention is used the ionogen method of use, and the electrolysis of aluminum grooved of use is horizontal groove or vertical groove, also can be multicavity tray.In new startup and restarting groove, calculate a certain amount of adjustment composition in advance with original electrolyte flux; With packing electrolyzer into groove intensification fusing in the levigate back fusing back adding of both mixings electrolyzer or with solid-like; Be adjusted to the required solid matter of branch and mix, be generally yellow soda ash, Sodium Fluoride, sodium-chlor, Repone K by oxide compound, carbonate and halogenide etc.; Quilonum Retard, magnesiumcarbonate, Calcium Fluoride (Fluorspan) and calcium chloride are formed.
A kind of aluminium of the present invention is used the ionogen method of use; Its method of use is not stop bottom aluminium inlet and flue end and anode, adding under the groove state to calculate good adjustment material in advance; Add principle for repeatedly progressively approaching on a small quantity; Add-on is looked electrolyzer amount of ram ionogen and is decided, and general total add-on is no more than 30% of the interior melt ionogen quality of groove, adds material and is generally oxide compound or halogenide.
Embodiment 1
A kind of ionogen is prepared in the laboratory, and its solid consists of: NaF:56 wt.%; NaCl:1.0 wt.%; AlF
3: 26 wt.%; CaF
2: 4 wt.%; MgF
2: 1.0 wt.%; LiF:1 wt.%; KF:0 wt.%; KCl:3.0 wt.%.Testing its liquidus temperature is 928 ℃, and recording its specific conductivity under 940 ℃ is 2.60 S/cm, and conductivity lifting amplitude is 27% under the more industrial common electrolyte equal conditions, and the alumina dissolution degree is 7.81%.
Embodiment 2
A kind of ionogen is prepared in the laboratory, and its solid consists of: NaF:56 wt.%; NaCl:0.0 wt.%; AlF
3: 26 wt.%; CaF
2: 4 wt.%; MgF
2: 3.0 wt.%; LiF:6 wt.%; KF:0 wt.%; KCl:1.0 wt.%.Testing its liquidus temperature is 922 ℃, and recording its specific conductivity under 930 ℃ is 2.63 S/cm, and conductivity lifting amplitude is 28% under the more industrial common electrolyte equal conditions, and the alumina dissolution degree is 6.02%.
Embodiment 3
A kind of ionogen is prepared in the laboratory, and its solid consists of: NaF:56 wt.%; NaCl:1.0 wt.%; AlF
3: 26 wt.%; CaF
2: 2 wt.%; MgF
2: 0.0 wt.%; LiF:6 wt.%; KF:1 wt.%; KCl:1.0 wt.%.Testing its liquidus temperature is 924 ℃, and recording its specific conductivity under 935 ℃ is 2.65 S/cm, and conductivity lifting amplitude is 30% under the more industrial common electrolyte equal conditions, and the alumina dissolution degree is 7.43%.
Embodiment 4
A kind of ionogen is prepared in the laboratory, and its solid consists of: NaF:50 wt.%; NaCl:3 wt.%; AlF
3: 30wt.%; CaF
2: 2 wt.%; MgF
2: 0 wt.%; LiF:6 wt.%; KF:3 wt.%; KCl:1 wt.%.Testing its liquidus temperature is 944 ℃, and recording its specific conductivity under 960 ℃ is 2.42 S/cm, and conductivity lifting amplitude is 20% under the more industrial common electrolyte equal conditions, and the alumina dissolution degree is 9.27%.
Embodiment 5
A kind of ionogen is prepared in the laboratory, and its solid consists of: NaF:50 wt.%; NaCl:2 wt.%; AlF
3: 30wt.%; CaF
2: 4 wt.%; MgF
2: 1 wt.%; LiF:1wt.%; KF:3 wt.%; KCl:3 wt.%.Testing its liquidus temperature is 948 ℃, and recording its specific conductivity under 965 ℃ is 2.38 S/cm, and conductivity lifting amplitude is 19% under the more industrial common electrolyte equal conditions, and the alumina dissolution degree is 10.20%.
Embodiment 6
A kind of ionogen is prepared in the laboratory, and its solid consists of: NaF:50 wt.%; NaCl:3 wt.%; AlF
3: 30wt.%; CaF
2: 4 wt.%; MgF
2: 3wt.%; LiF:1 wt.%; KF:3 wt.%; KCl:3 wt.%.Testing its liquidus temperature is 938 ℃, and recording its specific conductivity under 950 ℃ is 2.30 S/cm, and conductivity lifting amplitude is 15% under the more industrial common electrolyte equal conditions, and the alumina dissolution degree is 8.56%.
Embodiment 7
A kind of ionogen is prepared in the laboratory, and its solid consists of: NaF:53 wt.%; NaCl:2 wt.%; AlF
3: 28wt.%; CaF
2: 3wt.%; MgF
2: 2wt.%; LiF:4 wt.%; KF:2 wt.%; KCl:2 wt.%.Testing its liquidus temperature is 935 ℃, and recording its specific conductivity under 945 ℃ is 2.53S/cm, and conductivity lifting amplitude is 24% under the more industrial common electrolyte equal conditions, and the alumina dissolution degree is 8.09%.
Embodiment 8
Certain 20 kA independence adjustable current intensity electrolytic trial groove, grooved is horizontal, and anode adopts carbon anode, and negative electrode adopts TiB
2/ C composite cathode material, groove average voltage are 3.98V, and electrolysis temperature is about 950 ℃, and initial stage strength of current is 20KA, and current density is 0.70A/cm through measuring and calculating
2, pole span is about 4.5cm through field measurement.Ionogen consists of in the groove: NaF:50 wt.%; NaCl:1 wt.%; AlF
3: 30wt.%; CaF
2: 4 wt.%; MgF
2: 2wt.%; LiF:1 wt.%; KF:2 wt.%; KCl:3 wt.%.Instantaneous current efficiency reaches 92.15%, and electrolysis ton aluminium direct current consumption is 12870KWh.
Change test conditions, strength of current is promoted to 22KA by 20KA, and the reinforcement ratio is 10%, corresponding 0.77 A/cm that brings up to of current density
2, change the interior ionogen of groove and consist of NaF:56 wt.%; NaCl:1.0 wt.%; AlF
3: 26 wt.%; CaF
2: 4 wt.%; MgF
2: 1.0 wt.%; LiF:1 wt.%; KF:1 wt.%; KCl:3.0 wt.%.Electrolyte temperature is reduced to about 940 ℃, and the groove average voltage will be 3.92V, and instantaneous current efficiency reaches 92.86%, and electrolysis ton aluminium direct current consumption is 12580KWh.。
Embodiment 9
Certain 200 kA series actual current intensity 217kA, the groove average voltage is 4.02V, and electrolysis temperature is 940 ℃, and measuring and calculating is 0.73A/cm to current density through the scene
2, pole span is about 4.3cm through field measurement.Actual current efficient is 91.92% through taking inventory analysis.Because of its current density is in domestic medium level, therefore the supporting height of corresponding selection is led the ionogen composition, and ionogen finally consists of in the groove: NaF:50～52wt.%; NaCl:0 ~ 0.8wt.%; AlF
3: 29～30wt.%; CaF
2: 3 ~ 4 wt.%; CaCl
2: 0.5 ~ 1 wt.%; MgF
2: 2.5～3 wt.%; LiF:4～6 wt.%; KF:2～3 wt.%.Specific conductivity gradually becomes 2.17S/cm by 2.04S/cm, again to 2.40 S/cm, finally adjusts to 2.52 S/cm, and conductivity lifting amplitude is 23%, the at interval reinforced and feeding quantity in simultaneously corresponding adjustment back.Strength of current is promoted to 233KA by 217KA, and the reinforcement ratio is 8%, corresponding 0.83 A/cm that brings up to of current density
2Electrolysis temperature progressively is reduced to 933 ℃ by 944 ℃, and single groove ton aluminium ALUMNIUM FLUORIDE addition is reduced to 19kg by 25kg, and current efficiency remains on about 92%; Bath voltage is reduced to 3.98V, and ton aluminium direct current consumption is reduced to 12900kWh by 13020kWh, decreases owing to share power consumption; Ton aluminium Integrated Exchange power consumption is reduced to 13800kWh by 14470kWh; Single groove production capacity is increased to 653 tons/year by 578 tons/year, and single groove reduces cost about 18.1 ten thousand yuan because of reducing unit power consumption every year, because of raising the output increases about 520,000 yuan of economic benefit; Reduce 1.8 ten thousand yuan of costs because of reducing the ALUMNIUM FLUORIDE addition, add up to 71.9 ten thousand yuan of single groove economic benefits.
Embodiment 10
Certain 200 kA series actual current intensity 222kA, the groove average voltage is 3.96V, and electrolysis temperature is 930 ℃, and measuring and calculating is 0.75A/cm to current density through the scene
2, pole span is about 4.0cm through field measurement.Actual current efficient is 91.03% through taking inventory analysis.Because of its current density is in domestic medium level, therefore the supporting height of corresponding selection is led the ionogen composition,, ionogen finally consists of in the groove: NaF:54～56 wt.%; NaCl:1.2 ~ 1.5wt.%; AlF
3: 26～27 wt.%; CaF
2: 4 ~ 5 wt.%; MgF
2: 0.8～1.0 wt.%; LiF:2～3 wt.%; KF:1～2 wt.%; KCl:1.0 ~ 1.5 wt.%.Specific conductivity gradually becomes 2.23S/cm by 2.02S/cm, again to 2.46 S/cm, finally adjusts to 2.65 S/cm, and conductivity lifting amplitude is 30%, obtains energy-saving effect through drawing high pole span with the reduction bath voltage.The electrolyzer average voltage is reduced to 3.88V, and single groove ton aluminium ALUMNIUM FLUORIDE addition is reduced to 17kg by 25kg, and current efficiency remains on about 93%;, ton aluminium direct current consumption is reduced to 12460kWh by 12970kWh, decreases owing to share power consumption; Ton aluminium Integrated Exchange power consumption is reduced to 13200kWh by 13800kWh; Single groove production capacity is increased to 596 tons/year by 587 tons/year, and single groove reduces cost about 14.3 ten thousand yuan because of reducing unit power consumption every year, because of raising the output increases about 20,000 yuan of economic benefit; Reduce 2.8 ten thousand yuan of costs because of reducing the ALUMNIUM FLUORIDE addition, add up to 19.1 ten thousand yuan of single groove economic benefits.
Above-mentioned embodiment only is that exemplary embodiment of the present invention is described; Do not breaking away under the design concept prerequisite of the present invention; Engineering technical personnel make technical scheme of the present invention in this area various modification and improvement; All should be in protection scope of the present invention, the technology contents that the present invention asks for protection all is documented in claims.
Claims (7)
1. an aluminium is used ionogen, it is characterized in that the weight ratio composition of its molten state comprises: NaF:50%～56%; NaCl:0 ~ 3%; AlF
3: 26%～30%; CaF
2: 2% ~ 4 %; CaCl
2: 0 ~ 1%; MgF
2: 0～3 %; LiF:1～6 %; KF:0～3 %; KCl:1% ~ 3%.
2. a kind of aluminium according to claim 1 is used electrolytical method of use; It is characterized in that specific conductivity is 2.30 ~ 2.65S/cm under the aluminium use ionogen working order; The melt working temperature is 930 ~ 965 ℃, and its superheating temperature is controlled at 5 ~ 28 ℃, and it is 6.02 ~ 10.20% to the alumina dissolution degree.
3. a kind of aluminium according to claim 1 is used electrolytical method of use, it is characterized in that its anodic current density is 0.60 ~ 1.2A/cm
2, the electrolyte melt height is at 15 ~ 25cm.
4. a kind of aluminium according to claim 1 is used electrolytical method of use, it is characterized in that the electrolyzer grooved that uses is horizontal groove, vertical groove or is multicavity tray.
5. a kind of aluminium according to claim 1 is used electrolytical method of use, it is characterized in that the anode material that matches with its use can be expendable carbon anode or non-expendable inertia conductive anode.
6. a kind of aluminium according to claim 1 is used electrolytical method of use, it is characterized in that the cathode material that matches with its use can be full graphitization cathode or part graphite cathode material, also can be TiB
2/ C composite cathode material.
7. a kind of aluminium according to claim 1 is used electrolytical method of use, it is characterized in that the side wall composite material that matches with its use is common charcoal piece, or is silicon nitride combined silicon carbide, or be both compound side wall composite materials.
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| CN105473766B (en) * | 2013-07-09 | 2018-02-02 | 俄铝工程技术中心有限责任公司 | For obtaining the electrolyte of melt using aluminium electroloysis device |
| CN103849898A (en) * | 2014-02-28 | 2014-06-11 | 云南云铝涌鑫铝业有限公司 | Aluminum electrolysis production method |
| CN104313642A (en) * | 2014-11-17 | 2015-01-28 | 中南大学 | Method for reducing voltage drop of aluminum electrolysis anode gas film |
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