CN106191927B - A kind of low-temperature molten salt system used for aluminium electrolysis and its application method - Google Patents

A kind of low-temperature molten salt system used for aluminium electrolysis and its application method Download PDF

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Publication number
CN106191927B
CN106191927B CN201610868647.5A CN201610868647A CN106191927B CN 106191927 B CN106191927 B CN 106191927B CN 201610868647 A CN201610868647 A CN 201610868647A CN 106191927 B CN106191927 B CN 106191927B
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molten salt
electrolytic
salt system
aluminium
temperature
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CN106191927A (en
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王维
李玉芝
刘海涛
李海涛
曲长兴
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Henan University of Science and Technology
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Henan University of Science and Technology
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    • 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
    • C25C3/18—Electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing

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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)
  • Electrolytic Production Of Metals (AREA)

Abstract

The present invention relates to a kind of low-temperature molten salt system used for aluminium electrolysis and its application method, molten salt system to be made up of the composition of following percentage by weight：Na3AlF645 50%, AlF315 20%, KAlF425 30%, NaAlO24 6%, Al2O36 9%, the liquidus temperature of the molten salt system is 885 905 DEG C, electrolytic condition：The degree of superheat is 6 10 DEG C, and carbon annode current density is 0.8 0.9A/cm2, electrolytic bath voltage is between 3.9 3.95V, under the electrolytic condition, the 2.7S cm of electrolytic conductivity 2.5‑1.The present invention is with NaAlO2As Al2O3Supplement raw material carry out aluminium electroloysis, dissolved with Al in electrolyte2O3、NaAlO2The alumina complex ion ionized out, NaAlO2There is very high alumina complex ion concentration under electrolysis conditions, ultra-voltage is very low in aluminium electrolysis cathode course of reaction, reduces aluminium electrolysis process middle-jiao yang, function of the spleen and stomach polar effect.

Description

A kind of low-temperature molten salt system used for aluminium electrolysis and its application method
Technical field
The present invention relates to technical field of aluminum electrolysis, and in particular to a kind of low-temperature molten salt system used for aluminium electrolysis and its user Method.
Background technology
With developing rapidly for national economy, aluminium electrolytic industry technology achieves huge progress.Current efficiency is brought up to 93%-95%, direct current consumption have been lowered to 12500kW h/t-Al or so.Nevertheless, at present also exist capacity usage ratio it is low, The shortcomings of specific investment cost is higher and unit equipment yield is relatively low.Low temperature low-voltage aluminium electroloysis is always the heat of field of aluminum electrolysis research One of door topic.The realization of low temperature is realized often through adjustment fused salt composition, increases AlF in electrolyte3Content or addition LiF、KF、CaF2With the alkali metal such as NaCl or the halide and fluoride of alkaline-earth metal.Remaining is equal in addition to KF in these additives Aluminum oxide solubility in the electrolyte is reduced, causes the precipitation increase of aluminium electrolysis process bracket groove bottom, tank voltage rise.But KF pairs The damage capability of carbon anode/cathode is ten times of sodium salt or so.Low-voltage is realized often through pole span is reduced, in normally production bar Under part, the reduction of pole span is generally accompanied with the decline of current efficiency and electrolytic cell stability, while comprehensive energy consumption raises.Therefore such as What ensures that aluminum oxide in the electrolyte as the technique realize by solubility and current efficiency in low temperature low-voltage aluminium electrolysis process Key factor.However, the voltage drop of electrolyte, close to the 1/2 of whole tank voltage, the electrical conductivity for improving electrolyte is low-voltage Can the realization of aluminium electroloysis creates good condition, therefore search out with liquidus temperature, the raising electrolysis for reducing electrolyte The electrical conductivity and increase aluminum oxide of matter turn into what low temperature low-voltage aluminum electrolysis process was realized in the additive of the solubility of electrolyte It is crucial.
The content of the invention
The purpose of the present invention be for solve above-mentioned technical problem deficiency, there is provided a kind of low-temperature molten salt system used for aluminium electrolysis and Its application method, low temperature and low-voltage can realize solve using sodium cryolite as main component simultaneously in aluminium electrolysis process Electrolytic conductivity is low, the low problem of alumina dissolution degree, reaches the mesh for improving current efficiency, reducing aluminium electroloysis power consumption 's.
To solve the deficiency of above-mentioned technical problem, used technical scheme is the present invention：A kind of low temperature used for aluminium electrolysis melts Salt system, molten salt system are made up of the composition of following percentage by weight：Na3AlF645-50%, AlF315-20%, KAlF4 25- 30%, NaAlO24-6%, Al2O36-9%, the liquidus temperature of the molten salt system is 885-905 DEG C, electrolytic condition：The degree of superheat is 6- 10 DEG C, carbon annode current density is 0.8-0.9A/cm2, electrolytic bath voltage is between 3.9-3.95V, in the electrolytic condition Under, electrolytic conductivity 2.5-2.7S cm-1
The application method of above-mentioned low-temperature molten salt system used for aluminium electrolysis：Aluminium electroloysis operation is carried out in aluminium cell, work bar Part is：891-915 DEG C of electrolysis temperature, carbon annode current density are 0.8-0.9A/cm2, electrolysis time 10-22h, electrolytic bath Voltage is controlled between 3.9-3.95V, and upper part of the electrolytic cell spreads 11-13cm thickness mulches, and the thermal window filling outside corner is protected Adiabator, aluminium cell reinforced bottom during operation are incubated, cell lining surface and bottom cathode carbon block design temperature point Wei not be 640-780 DEG C and 790-915 DEG C.
Beneficial effect
The present invention is with NaAlO2As Al2O3Supplement raw material carry out aluminium electroloysis, dissolved with Al in electrolyte2O3、NaAlO2Electricity The alumina complex ion separated out, NaAlO2There is very high alumina complex ion concentration under electrolysis conditions, in aluminium electrolysis cathode Ultra-voltage is very low in course of reaction, reduces aluminium electrolysis process middle-jiao yang, function of the spleen and stomach polar effect.CF is reduced in electrolytic process4And C2F6Fluorine The discharge of compound.On the other hand, 25% or so KAlF is added in electrolyte molten salt system of the invention4Additive, it is and existing Electrolyte primary crystal temperature compared to reducing 15 ~ 20 DEG C, alumina dissolution degree improves 1.5%, and the electrical conductivity of electrolyte improves 0.05 S•cm-1, NaAlO2The alumina complex ion ionized out can be equivalent to Al2O3In the dissolving of electrolyte, current efficiency can carry It is high by 1% or so.
Embodiment
Liquidus temperature is measured using thermal analysis system in the examples below, and electrolyte constant temperature 4 at 400 DEG C of Muffle furnace is small When, when stove furnace temperature to be measured reaches 50 DEG C or so of pre-estimation liquidus temperature, the sealing of electrolyte will be placed with, be put in measurement stove. After matter melt temperature to be electrolysed is stable, cooled down with 2 DEG C/min speed, recording instrument without paper obtains electricity with 1 second record, 1 data Matter cooling curve is solved, gradient maxima point is electrolyte primary crystal temperature on cooling curve.Graphite crucible aluminum oxide saturation dissolves Degree is using oxidation al rotary disc weight method measure, i.e., after melt temperature is heated to certain value, sintering oxidation aluminium flake is in melt In rotated with 100r/min speed, by corundum piece with hot AlCl after rotation3Electrolyte on solution cleaning corundum piece, according to corundum piece Weight difference, calculate aluminum oxide saturation solubility.Electrolytic conductivity is measured using CVCC methods, and device mainly includes constant potential Instrument（PGSTAT30）With current expansion instrument（Booster20A）.
Embodiment 1
A kind of low-temperature molten salt system used for aluminium electrolysis, molten salt system are made up of the composition of following percentage by weight：Na3AlF6 50%, AlF3 15%, KAlF420%, NaAlO26%, Al2O3 9%。
The application method of above-mentioned low-temperature molten salt system：Above-mentioned composition electrolyte is placed in 400kA electrolytic cells and carries out aluminium electricity Solution, condition of work are：910 DEG C of electrolysis temperature, the A/cm of carbon annode current density 0.92Electrolysis time 14 hours, electricity 12 cm thickness mulches are spread on solution groove top, and bottom of electrolytic tank cathode carbon pieces temperature is 890 DEG C, and cell lining surface temperature is 790 DEG C, electrolytic bath voltage 3.91V.KW h/t-the Al of direct current consumption 11840 of the heat, current efficiency 94%, electrolysis The S cm of matter electrical conductivity 2.58-1。
Embodiment 2
A kind of low-temperature molten salt system used for aluminium electrolysis, molten salt system are made up of the composition of following percentage by weight：Na3AlF6 48%, AlF3 13%, KAlF424%, NaAlO27%, Al2O3 8%。
The application method of above-mentioned low-temperature molten salt system：Above-mentioned composition electrolyte is placed in 400kA electrolytic cells and carries out aluminium electricity Solution, condition of work are：903 DEG C of electrolysis temperature, the A/cm of carbon annode current density 0.92Electrolysis time 12 hours, electricity 13 cm thickness mulches are spread on solution groove top, and bottom of electrolytic tank cathode carbon pieces temperature is 885 DEG C, and cell lining surface temperature is 785 DEG C, electrolytic bath voltage 3.90V.KW h/t-the Al of direct current consumption 11820 of the heat, current efficiency 94%, electrolysis The S cm of matter electrical conductivity 2.62-1。
Embodiment 3
A kind of low-temperature molten salt system used for aluminium electrolysis, molten salt system are made up of the composition of following percentage by weight：Na3AlF6 46%, AlF3 17%, KAlF426%, NaAlO25%, Al2O3 6%。
The application method of above-mentioned low-temperature molten salt system：Above-mentioned composition electrolyte is placed in 400kA electrolytic cells and carries out aluminium electricity Solution, condition of work are：890 DEG C of electrolysis temperature, the A/cm of carbon annode current density 0.82Electrolysis time 16 hours, electrolysis 13 cm thickness mulches are spread on groove top, and bottom of electrolytic tank cathode carbon pieces temperature is 885 DEG C, and cell lining surface temperature is 785 DEG C, electrolytic bath voltage 3.90V.KW h/t-the Al of direct current consumption 11820 of the heat, current efficiency 94%, electrolysis The S cm of matter electrical conductivity 2.64-1。
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, though So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make out a little change or repair The equivalent embodiment for equivalent variations is adornd, as long as being the technical spirit according to the present invention without departing from technical solution of the present invention content Any simple modification, equivalent change and modification made to above example, in the range of still falling within technical solution of the present invention.

Claims (2)

  1. A kind of 1. low-temperature molten salt system used for aluminium electrolysis, it is characterised in that：Molten salt system is made up of the composition of following percentage by weight： Na3AlF645-50%, AlF315-20%, KAlF425-30%, NaAlO24-6%, Al2O36-9%, the primary crystal of the molten salt system Temperature is 885-905 DEG C, electrolytic condition：The degree of superheat is 6-10 DEG C, and carbon annode current density is 0.8-0.9A/cm2, electrolytic cell Tank voltage is between 3.9-3.95V, under the electrolytic condition, electrolytic conductivity 2.5-2.7S cm-1。
  2. A kind of 2. application method of low-temperature molten salt system used for aluminium electrolysis as claimed in claim 1, it is characterised in that：In aluminium cell Middle progress aluminium electroloysis operation, condition of work are：891-915 DEG C of electrolysis temperature, carbon annode current density are 0.8-0.9A/cm2, Electrolysis time 10-22h, electrolytic bath voltage are controlled between 3.9-3.95V, and upper part of the electrolytic cell spreads 11-13cm thickness mulches, Outside corner thermal window filling insulation material, aluminium cell during operation reinforced bottom be incubated, cell lining surface and Bottom cathode carbon block design temperature is respectively 640-780 DEG C and 790-915 DEG C.
CN201610868647.5A 2016-09-30 2016-09-30 A kind of low-temperature molten salt system used for aluminium electrolysis and its application method Expired - Fee Related CN106191927B (en)

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CN108118366A (en) * 2018-01-04 2018-06-05 昆明理工大学 A kind of method of alumina dissolution speed in quickening aluminium cell
CN110938838B (en) * 2019-11-06 2021-12-31 东北大学 Method for treating anode carbon slag of aluminum electrolysis cell by using NaCl molten salt extraction method
CN111710368A (en) * 2020-07-02 2020-09-25 神华准能资源综合开发有限公司 Method for calculating conductivity of aluminum electrolyte system

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