US20150122665A1 - Electrolyte used for aluminum electrolysis and electrolysis process using the electrolyte - Google Patents

Electrolyte used for aluminum electrolysis and electrolysis process using the electrolyte Download PDF

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Publication number
US20150122665A1
US20150122665A1 US14/407,314 US201314407314A US2015122665A1 US 20150122665 A1 US20150122665 A1 US 20150122665A1 US 201314407314 A US201314407314 A US 201314407314A US 2015122665 A1 US2015122665 A1 US 2015122665A1
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Prior art keywords
electrolyte
electrolysis
naf
alf
lif
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Abandoned
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US14/407,314
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English (en)
Inventor
Songtao Sun
Yulin Fang
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Inner Mongolia United Industrial Co Ltd
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Inner Mongolia United Industrial Co Ltd
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Priority claimed from CN201210188422.7A external-priority patent/CN103484897B/zh
Priority claimed from CN201310024018.0A external-priority patent/CN103938227A/zh
Application filed by Inner Mongolia United Industrial Co Ltd filed Critical Inner Mongolia United Industrial Co Ltd
Assigned to Inner Mongolia United Industrial Co., Ltd. reassignment Inner Mongolia United Industrial Co., Ltd. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FANG, Yulin, SUN, Songtao
Publication of US20150122665A1 publication Critical patent/US20150122665A1/en
Abandoned legal-status Critical Current

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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

Definitions

  • the present invention relates to an electrolyte for aluminum electrolysis and an electrolysis process using the electrolyte, belonging to non-ferrous metal smelting industry.
  • Aluminum electrolysis refers to acquisition of aluminum by means of an electrolysis method.
  • a traditional Hall-Heroult molten salt aluminum electrolysis process is typically adopted for aluminum electrolysis.
  • This process is featured by use of a cryolite-alumina molten salt electrolysis method in which cryolite Na 3 AlF 6 fluoride salt melt is taken as flux, Al 2 O 3 is dissolved in fluoride salt, carbon body is taken as an anode, aluminum liquid is taken as a cathode, and electrolytic aluminum is obtained by performing electrochemical reaction at the anode and cathode of the electrolytic cell at a high temperature ranging from 940 to 960° C. after a strong direct current is introduced. Due to high electrolysis temperature, the traditional aluminum electrolysis process has such characteristics as large volatilization amount of electrolyte, large oxidization loss of a carbon anode, large energy consumption, large thermal loss and poor electrolysis working environment.
  • the molten salt composition of the system includes AlF 3 , Al 2 O 3 and one or more salts selected from the group consisting of KF, NaF, MgF 2 , CaF 2 , NaCl, LiF, and BaF 2 , wherein according to mole percentage, the content of AlF 3 is 22-50%, the content of Al 2 O 3 is 1-25% and the content of the rest components is 25-77%.
  • the electrolysis temperature of the electrolyte can be lowered to be within a wide area from 680° C. to 900° C. for the purpose of operations.
  • an electrolyte can be successfully applied to industrial production is based on comprehensive consideration for many factors like its liquidus temperature, volatility, electric conductivity, alumina solubility, preparation environment and whether stable electrolysis process can be guaranteed, however, due to the above problems in the prior art, industrial application of the electrolyte is significantly limited, and it is an unsolved problem in the prior art to find a way of avoiding corrosion to electrolysis devices and damage to human body and ensuring proper electric conductivity and alumina solubility as well as no ‘crusting’ phenomenon of the prepared electrolyte while the liquidus temperature of the electrolyte is further lowered.
  • the technical problem to be solved by the present invention is that, the prior art is incapable of avoiding corrosion to electrolysis devices and damage to human body and ensuring proper electric conductivity and alumina solubility as well as no ‘crusting’ phenomenon of the prepared electrolyte while the liquidus temperature of the electrolyte is further lowered.
  • the present invention provides an electrolyte for aluminum electrolysis, which is low in liquidus temperature, free from corrosion to an electrolytic cell, not liable to volatilization, proper in electric conductivity and alumina solubility and free from ‘crusting’ phenomenon, and an electrolysis process using the electrolyte.
  • An electrolyte for aluminum electrolysis is composed of the following components by mass percent: 20-29.9% of NaF, 60.1-66% of AlF3, 3-10% of LiF, 4-13.9% of KF and 3-6% of Al 2 O 3 , wherein the molar ratio of NaF to AlF 3 is 0.6-0.995;
  • the molar ratio of NaF to AlF 3 is 0.6-0.7 or 1.12-1.52.
  • the liquidus temperature of the electrolyte ranges from 620 to 670° C.
  • the liquidus temperature of the electrolyte ranges from 640 to 670° C.
  • the electrolysis temperature of the electrolyte ranges from 720 to 760° C.
  • An electrolysis process using the electrolyte for aluminum electrolysis comprises the steps of:
  • step (2) heating up the melt prepared in step (1) to 720-760° C. and then carrying out electrolysis.
  • the melt prepared in step (1) is electrolyzed at 730-750° C.
  • Al 2 O 3 is quantitatively supplied in the electrolysis process.
  • the electrolyte for aluminum electrolysis in the present invention employs a pure fluoride system and is composed of the following components by mass percent: 20-29.9% of NaF, 60.1-66% of AlF 3 , 3-10% of LiF, 4-13.9% of KF and 3-6% of Al 2 O 3 , wherein the molar ratio of NaF to AlF 3 is 0.6-0.995; or the electrolyte is composed of the following components by mass percent: 30-38% of NaF, 49-60% of AlF 3 , 1-5% of LiF, 1-6% of KF and 3-6% of Al 2 O 3 , wherein the molar ratio of NaF to AlF 3 is 1.0-1.52.
  • the electrolysis process which reduces volatilization loss of fluoride salt, avoids corrosion to electrolysis device and damage to human body, improves working environment, greatly reduces energy consumption in the electrolysis process and achieves the aims of energy saving and emission reduction; and meanwhile, in the present invention, proper amounts of LiF and KF are added and can be combined with sodium ions and aluminum ions in the electrolyte to form lithium cryolite and potassium cryolite with low melting points, thus ensuring no crusting phenomenon in the electrolysis process.
  • the electrolyte for aluminum electrolysis in the present invention has no CaF 2 and MgF 2 added therein, instead, KF in an appropriate proportion, which has the function of increasing alumina solubility and dissolution velocity, is added to a system in which the molar ratio of NaF to AlF 3 is 0.6-0.995 or 1.0-1.52, and therefore, the shortcoming of low alumina solubility in the low-molar-ratio electrolyte is improved.
  • the electric conductivity of the electrolyte decreases as the temperature decreases, so typically, the electric conductivity at a low electrolysis temperature hardly meets the demand in a normal electrolysis process; the electrolysis temperature is lowered by lowering the liquidus temperature of the electrolyte in the present invention, however, the electric conductivity of the electrolyte at a low temperature can still meet the demand in the electrolysis process because LiF with a larger electric conductivity is added and component proportions in the electrolyte are optimized, thus enhancing the current efficiency in the electrolysis process.
  • the content of LiF is defined as 3-10% or 1-5% in the electrolyte system, this is because too low content of LiF fails to improve electric conductivity and to prevent crusting, and too high content of LiF results in decrease of the alumina solubility, and the above two situations are effectively avoided by defining the content of LiF in the present invention.
  • Electrolysis temperature is directly associated with volatilization of the electrolyte, energy consumption of the process, electric conductivity and alumina solubility, and the inventor of the present invention, by long research, set the electrolysis temperature within a range from 720° C. to 760° C.
  • the electrolysis temperature is further set within a range from 730 to 750° C. in the present invention.
  • the components of the electrolyte in this embodiment are as follows: 20% of NaF, 65.98% of AlF 3 , 5.01% of LiF, 6.01% of KF and 3% of Al 2 O 3 , wherein the molar ratio of NaF to aluminum fluoride AlF 3 is 0.6.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 640° C.
  • step (2) raising the temperature of the melt prepared in step (1) to 720° C. and then carrying out electrolysis, and quantitatively supplying Al 2 O 3 in the electrolysis process, wherein in the electrolysis process, the electric conductivity of the electrolyte is about 1.75 ⁇ ⁇ 1 •cm ⁇ 1 , the density is about 2.03 g/cm 3 and the saturation concentration of alumina is 5%.
  • the components of the electrolyte in this embodiment are as follows: 29.9% of NaF, 60.1% of AlF3, 3% of LiF, 4% of KF and 3% of Al2O3, wherein the molar ratio of NaF to aluminum fluoride AlF3 is 0.995.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 670° C.
  • step (2) raising the temperature of the melt prepared in step (1) to 760° C. and then carrying out electrolysis, wherein in the electrolysis process, the electric conductivity of the electrolyte is about 1.8 ⁇ ⁇ 1 •cm ⁇ 1 , the density is about 2.05 g/cm 3 and the saturation concentration of alumina is 6%.
  • the components of the electrolyte in this embodiment are as follows: 20% of NaF, 66% of AlF 3 , 4% of LiF, 4% of KF and 6% of Al 2 O 3 , wherein the molar ratio of NaF to aluminum fluoride AlF 3 is 0.6.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 640° C.
  • step (2) raising the temperature of the melt prepared in step (1) to 730° C. and then carrying out electrolysis, and quantitatively supplying Al 2 O 3 in the electrolysis process, wherein in the electrolysis process, the electric conductivity of the electrolyte is about 1.6 ⁇ ⁇ 1 •cm ⁇ 1 , the density is about 2.03 g/cm 3 and the saturation concentration of alumina is 5%.
  • the components of the electrolyte in this embodiment are as follows: 21% of NaF, 60.1% of AlF 3 , 10% of LiF, 5.9% of KF and 3% of Al 2 O 3 , wherein the molar ratio of NaF to aluminum fluoride AlF 3 is 0.7.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 640° C.
  • step (2) raising the temperature of the melt prepared in step (1) to 750° C. and then carrying out electrolysis, and quantitatively supplying Al 2 O 3 in the electrolysis process, wherein in the electrolysis process, the electric conductivity of the electrolyte is about 1.8 ⁇ ⁇ 1 •cm ⁇ 1 , the density is about 2.04 g/cm 3 and the saturation concentration of alumina is 6%.
  • the components of the electrolyte in this embodiment are as follows: 20 % of NaF, 60 . 1 % of AlF 3 , 3% of LiF, 13.9% of KF and 3% of Al 2 O 3 , wherein the molar ratio of NaF to aluminum fluoride AlF 3 is 0.67.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 620° C.
  • step (2) raising the temperature of the melt prepared in step (1) to 720° C. and then carrying out electrolysis, and quantitatively supplying Al 2 O 3 in the electrolysis process, wherein in the electrolysis process, the electric conductivity of the electrolyte is about 1.6 ⁇ ⁇ 1 •cm ⁇ 1 , the density is about 2.03 g/cm 3 and the saturation concentration of alumina is 5%.
  • the components of the electrolyte in this embodiment are as follows: 20% of NaF, 61% of AlF 3 , 9% of LiF, 4% of KF and 6% of Al 2 O 3 , wherein the molar ratio of NaF to aluminum fluoride AlF 3 is 0.65.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 670° C.
  • step (2) raising the temperature of the melt prepared in step (1) to 760° C. and then carrying out electrolysis, and quantitatively supplying Al 2 O 3 in the electrolysis process, wherein in the electrolysis process, the electric conductivity of the electrolyte is about 1.8 ⁇ ⁇ 1 •cm ⁇ 1 , the density is about 2.05 g/cm 3 and the saturation concentration of alumina is 6%.
  • the components of the electrolyte in this embodiment are as follows: 13% of NaF, 60% of AlF 3 , 10% of LiF, 12% of KF and 5% of Al 2 O 3 , wherein the molar ratio of NaF to aluminum fluoride AlF 3 is 0.43.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 660° C.
  • step (2) raising the temperature of the melt prepared in step (1) to 760° C. and then carrying out electrolysis, and quantitatively supplying Al 2 O 3 in the electrolysis process, wherein in the electrolysis process, the electric conductivity of the electrolyte is about 1.8 ⁇ ⁇ 1 •cm ⁇ 1 , the density is about 2.05 g/cm 3 and the saturation concentration of alumina is 6%.
  • the components of the electrolyte in this embodiment are as follows: 32% of NaF, 57% of AlF 3 , 3% of LiF, 4% of KF and 4% of Al 2 O 3 , wherein the molar ratio of NaF to aluminum fluoride AlF 3 is 1.12.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 640° C.
  • step (2) raising the temperature of the melt prepared in step (1) to 720° C. and then carrying out electrolysis, and quantitatively supplying Al 2 O 3 in the electrolysis process, wherein in the electrolysis process, the electric conductivity of the electrolyte is about 1.7 ⁇ ⁇ 1 •cm ⁇ 1 , the density is about 2.03 g/cm 3 and the saturation concentration of alumina is 5%.
  • the components of the electrolyte in this embodiment are as follows: 38% of NaF, 50% of AlF 3 , 2% of LiF, 5% of KF and 5% of Al 2 O 3 , wherein the molar ratio of NaF to aluminum fluoride AlF 3 is 1.52.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 670° C.
  • step (2) raising the temperature of the melt prepared in step (1) to 760° C. and then carrying out electrolysis, wherein in the electrolysis process, the electric conductivity of the electrolyte is about 1.8 ⁇ ⁇ 1 •cm ⁇ 1 , the density is about 2.05 g/cm 3 and the saturation concentration of alumina is 6%.
  • the components of the electrolyte in this embodiment are as follows: 32% of NaF, 57% of AlF 3 , 3% of LiF, 4% of KF and 4% of Al 2 O 3 , wherein the molar ratio of NaF to aluminum fluoride AlF 3 is 1.12.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 640° C.
  • the components of the electrolyte in this embodiment are as follows: 32% of NaF, 57% of AlF3, 3% of LiF, 4% of KF and 4% of Al2O3, wherein the molar ratio of NaF to aluminum fluoride AlF3 is 1.12.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 640° C.
  • step (2) raising the temperature of the melt prepared in step (1) to 750° C. and then carrying out electrolysis, and quantitatively supplying Al 2 O 3 in the electrolysis process, wherein in the electrolysis process, the electric conductivity of the electrolyte is about 1.8 ⁇ ⁇ 1 •cm ⁇ 1 , the density is about 2.04 g/cm 3 and the saturation concentration of alumina is 6%.
  • the components of the electrolyte in this embodiment are as follows: 30% of NaF, 60% of AlF3, 1% of LiF, 6% of KF and 3% of Al 2 O 3 , wherein the molar ratio of NaF to aluminum fluoride AlF3 is 1.0.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that: the liquidus temperature of the electrolyte in this embodiment is 620° C.
  • step (2) raising the temperature of the melt prepared in step (1) to 720° C. and then carrying out electrolysis, and quantitatively supplying Al 2 O 3 in the electrolysis process, wherein in the electrolysis process, the electric conductivity of the electrolyte is about 1.6 ⁇ ⁇ 1 •cm ⁇ 1 , the density is about 2.03 g/cm 3 and the saturation concentration of alumina is 5%.
  • the components of the electrolyte in this embodiment are as follows: 38% of NaF, 54% of AlF 3 , 4% of LiF, 1% of KF and 3% of Al 2 O 3 , wherein the molar ratio of NaF to aluminum fluoride AlF 3 is 1.4.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 670° C.
  • step (2) raising the temperature of the melt prepared in step (1) to 760° C. and then carrying out electrolysis, and quantitatively supplying Al 2 O 3 in the electrolysis process, wherein in the electrolysis process, the electric conductivity of the electrolyte is about 1.8 ⁇ ⁇ 1 •cm ⁇ 1 , the density is about 2.05 g/cm 3 and the saturation concentration of alumina is 6%.
  • the components of the electrolyte in this embodiment are as follows: 34% of NaF, 49% of AlF 3 , 5% of LiF, 6% of KF and 6% of Al 2 O 3 , wherein the molar ratio of NaF to aluminum fluoride AlF3 is 1.39.
  • the performances of the electrolyte in this embodiment are measured and the measurement result is that the liquidus temperature of the electrolyte in this embodiment is 660° C.
  • the electrolytic cells used in the electrolysis processes in the aforementioned embodiments are continuous pre-baked anode electrolytic cells having an anode current density of 0.8A•cm 2 .
  • the electrolyte described in the present invention is applicable to any electrolytic cell in the prior art.

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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)
  • Conductive Materials (AREA)
US14/407,314 2012-06-11 2013-05-30 Electrolyte used for aluminum electrolysis and electrolysis process using the electrolyte Abandoned US20150122665A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
CN201210188422.7 2012-06-11
CN201210188422.7A CN103484897B (zh) 2012-06-11 2012-06-11 一种电解铝用电解质以及使用该电解质的电解工艺
CN201310024018.0 2013-01-23
CN201310024018.0A CN103938227A (zh) 2013-01-23 2013-01-23 电解铝用电解质以及使用该电解质的电解工艺
PCT/CN2013/076442 WO2013185540A1 (zh) 2012-06-11 2013-05-30 一种电解铝用电解质以及使用该电解质的电解工艺

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EP (1) EP2862962A4 (ja)
KR (1) KR101801453B1 (ja)
AP (1) AP2015008185A0 (ja)
AU (1) AU2013275997B2 (ja)
CA (1) CA2876345C (ja)
EA (1) EA032047B1 (ja)
IN (1) IN2015DN00211A (ja)
WO (1) WO2013185540A1 (ja)
ZA (1) ZA201409514B (ja)

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BR112020005885A2 (pt) 2017-09-26 2020-09-29 Ecolab Usa Inc. composições antimicrobiana, virucida, antimicrobiana sólida e virucida sólida, e, métodos para uso de uma composição antimicrobiana e para inativar um vírus.

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EA032047B1 (ru) 2019-03-29
EA201492228A1 (ru) 2015-05-29
WO2013185540A1 (zh) 2013-12-19
CA2876345C (en) 2017-03-14
AP2015008185A0 (en) 2015-01-31
EP2862962A1 (en) 2015-04-22
IN2015DN00211A (ja) 2015-06-12
KR101801453B1 (ko) 2017-11-24
KR20150022995A (ko) 2015-03-04
CA2876345A1 (en) 2013-12-19
AU2013275997A1 (en) 2015-01-22
EP2862962A4 (en) 2015-12-09
ZA201409514B (en) 2016-06-29

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