CN109267108A - A kind of preparation method of aluminum chromium - Google Patents

A kind of preparation method of aluminum chromium Download PDF

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Publication number
CN109267108A
CN109267108A CN201811458465.6A CN201811458465A CN109267108A CN 109267108 A CN109267108 A CN 109267108A CN 201811458465 A CN201811458465 A CN 201811458465A CN 109267108 A CN109267108 A CN 109267108A
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chromium
oxide
aluminium
content
aluminum
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CN109267108B (en
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许晶
柴永成
于水
沈利
高宝堂
刘彬
赵云飞
夏增立
温瑞宇
谢长青
白洁
李超群
徐晓光
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Inner Mongolia Huayun New Materials Co Ltd
BAOTOU ALUMINUM Co Ltd
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Inner Mongolia Huayun New Materials Co Ltd
BAOTOU ALUMINUM Co Ltd
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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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • 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
    • C25C3/36—Alloys obtained by cathodic reduction of all their ions
    • 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
    • C25C7/02—Electrodes; Connections thereof
    • C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts

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  • 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 provide it is a kind of be electrolysed in aluminium cell using the oxide of chromium as primary raw material, obtain the preparation method of aluminum chromium.The present invention is merely with existing prebaked cell for aluminum-reduction, in the case where not increasing any equipment investment, realizes and uses aluminium cell industrial mass continuous production aluminum chromium.Electrolysis production process variation caused by this method reacts fierce after can effectively adding raw materials into controls in the reasonable scope, and the chromium content that can be precisely controlled in aluminum chromium.The oxide raw material utilization rate of chromium is high, and the aluminum chromium of acquisition has the characteristics that content is high, segregation is small, ingredient is uniform.

Description

A kind of preparation method of aluminum chromium
Technical field:
The present invention relates to a kind of preparation methods of aluminum chromium, prepare aluminum chromium with aluminium cell more particularly to a kind of Preparation method.
Background technique:
Currently, preparation of industrialization aluminum chromium is there are mainly two types of method, i.e., self- propagating thermit reduction, to the method for mixing.From climing Prolonging thermit reduction is that the principle to be reacted automatically at a certain temperature using chromium oxide and aluminium is produced, and this method lacks Point is: burning acutely in production process, the flue gas of generation has certain toxic action to human body；Meanwhile thermit reduction is Oxide using chromium is raw material, uses metallic aluminium as reducing agent, and reduction reaction occurs at high temperature and produces aluminum chromium, but The aluminium oxide that this method displaces is slag body, causes aluminium loss serious, while the difficulty that removes the gred, causes melt quality poor, produces Aluminum chromium defect it is serious.To the method for mixing there are two types of mode: first is that using containing chromium chrome additive and fine aluminium to mixing, chrome additive It is made of pure chromium and combustion adjuvant, the disadvantages of this method are: chrome additive can generate a large amount of flue gases during the addition process, pollutes Seriously, while chromium casting yield is low, higher cost；Second is that using pure chromium and fine aluminium to mixing, the disadvantages of the method are as follows chromium casting yield it is low, Component segregation is serious, and component content is not easily controlled.
In addition, fused salt electrolysis process realizes production aluminum chromium in laboratory.But laboratory is using crucible The small container of class, technology condition differ larger with industrialized environment, do not have the item being transplanted in industrialization electrolytic cell Part, and its aluminum chromium production capacity that can not form steady and continuous.
Patent CN201610104761 is disclosed produces alloy aluminum using aluminium reducing alloyed oxide in aluminium cell Technique is that required alloying element is added in the molten aluminum into aluminium cell across dielectric layer during aluminum electrolysis Oxide.Alloying element is the alloying element that oxidisability is better than aluminium；Method in the oxide investment molten aluminum of the alloying element It is: is added in change poles by the anode openings mentioned out, addition or separately opening addition from acute conjunctivitis mouth.
There are the problem of have: first is that oxidisability is better than in the alloying element of aluminium, if chromium is violent with reactive aluminum, excessive charging Amount be easy to cause electrolysis process technical conditions to change, and influences normal electrolysis production；Simultaneously because during electrolysis production, daily all It needs to extract certain raw aluminum liquid from the storage aluminium of electrolytic cell and be cast, be the process of a dynamic equilibrium, need to carry out Consider just the content of metallic element in storage aluminium can be made to obtain stable promotion comprehensively.For above situation, design science is needed Reasonable feeding quantity goes steady production process, while making the content of metallic element in storage aluminium it is anticipated that being promoted.And it is somebody's turn to do Do not have clearly to provide the control of feeding quantity and calculation method in patent, is not easy to realize purpose described in its patent with this method.
Second is that its oxide for mentioning alloying element needed for being added in the molten aluminum across dielectric layer into aluminium cell, and Actual conditions are that the upper surface of molten aluminum layer is electrolyte layer in a cell, which is flowing, while having temperature High, the features such as corrosivity is strong.It is able to achieve the stable electrolyte layer that can continuously pass through and is added to the anticorrosive, resistant to high temperatures of molten aluminum layer Device has no has been reported that at present content mentioned by the patent is not easy to realize.
Third is that for the time point of charging, due to requiring to extract certain raw aluminum liquid from the storage aluminium of electrolytic cell daily It is cast, is the process of a dynamic equilibrium, if feed time is improper, the metal oxides of addition can be not anti- It answers in complete situation, is extracted and gone in company with daily primary aluminum, caused the unnecessary consumption of raw material, lead to the pollution of raw aluminum liquid And the rising of cost.
Summary of the invention:
To overcome many deficiencies present in background technique, makes full use of and giving birth to the purpose of the present invention is to provide one kind The prebaked cell for aluminum-reduction of production, directly adds the oxide of chromium in aluminium electrolysis process, and realization is industrialized with aluminium cell and criticized The method for measuring continuous production aluminum chromium.This method has the advantages that production is stablized, low energy consumption, high-efficient, quality is high.
The purpose of the present invention is implemented by following technical solution: a kind of preparation method of aluminum chromium is carried out with aluminium cell Preparation comprising following steps: (1) in the aluminium cell that is producing, measure nNaF in the electrolyte of aluminium cell AlF3, n be 2.1~2.9 constant；KF；CaF2；MgF2；LiF；AL2O3Mass percentage content, wherein the nNaF AlF3It is 62~94%；KF is 0.1~8%；CaF2It is 1~8%；MgF2It is 1~8%；LiF is 1~8%；AL2O3For 2~ 7%, the sum of mass percentage of the above components is 100%；(2) when measured value within the above range when, the oxygen of chromium is added Compound, detect and maintain electrolysis process technical conditions: electrolysis temperature is 900~960 DEG C, and average voltage is 3.5~4.3V, is obtained Aluminum chromium.
Further, the oxide of chromium is added in aluminium cell according to the step (2), electrolytic process includes at least one Aluminum chromium electrolysing period, wherein one aluminum chromium electrolysing period includes: a chromium content rising stage and a chromium contain Measure balance period；Wherein the chromium content rising stage be chromium in aluminium cell amount of ram aluminium mass percentage content reach setting value before Electrolytic process, the mass percentage content of chromium persistently rises in the stage storage aluminium；Chromium content balance period is in aluminium cell The mass percentage content of chromium reaches the electrolytic process after setting value in storage aluminium, the quality percentage of chromium in the stage storage aluminium It is remained unchanged than content.
Further, the chromium content rising stage in electrolytic process, the oxide of chromium is added, specific steps include:
According to the content for testing and analyzing chromium in current electrolytic cell amount of ram aluminium, determine that chromium content day promotes rate；Calculate chromium The day feeding quantity of the oxide of content rising stage chromium
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
Wherein, WIt risesFor the day feeding quantity (kg) of the oxide of chromium content rising stage chromium, QDiskFor aluminium cell amount of ram aluminium Quality (kg), a1For the actually detected value (%) of the mass percentage content of chromium in same day aluminium cell amount of ram aluminium, a2It is second Chromium is expected by mass percentage content to be achieved (%), (a in its aluminium cell amount of ram aluminium2-a1) it is chromium content day to promote speed Rate (%), QIt producesFor the day aluminum yield (kg) of aluminium cell, P is the raw material availability (%) of the oxide of chromium, and C is the oxide of chromium Purity (%), m be chromium oxide in chromium mass percentage content (%).
Further, by percentage to the quality, when the chromium content of electrolytic cell amount of ram aluminium is less than 1.5%, the chromium content Day promotes rate≤0.3%/day；It is described when the chromium content of electrolytic cell amount of ram aluminium is more than or equal to 1.5% and when less than 2.8% Chromium content day promotes rate≤0.15%/day.
Further, the chromium content rising stage, oxide feeding quantity≤I/b of unit hour chromium；Wherein, I is series electricity It flows (kA), b is constant satisfaction: b=10kA/kg.
Further, the oxide of the chromium content rising stage in electrolytic process, chromium add the time are as follows: the oxide of chromium is daily The start time point of addition is after aluminium cell goes out aluminium.
Further, in chromium content balance period, the chromium content for controlling aluminium cell amount of ram aluminium is remained unchanged, specific steps packet It includes:
Calculate the daily feeding quantity of the oxide of chromium content balance period chromium
The day feeding quantity calculation formula of the oxide of chromium content balance period chromium is as follows:
Wherein, WIt is flatFor the day feeding quantity (kg) of the oxide of chromium content balance period chromium, QIt producesFor the day aluminum yield of aluminium cell (kg), aIt is flatFor the mass percentage content (%) of chromium in chromium content balance period aluminium cell amount of ram aluminium, P is the oxide of chromium Raw material availability (%), C are the purity (%) of the oxide of chromium, and m is the mass percentage content (%) of chromium in the oxide of chromium.
Further, the chromium content balance period, oxide feeding quantity≤I/b of unit hour chromium；Wherein, I is series electricity It flows (kA), b is constant satisfaction: b=10kA/kg.
Further, the oxide of the chromium content balance period in electrolytic process, chromium adds the time are as follows: the oxide of chromium is daily The start time point of addition is after aluminium cell goes out aluminium.
Further, the oxide of chromium is CrO2, Cr2O3Any one or two kinds of combinations.
Further, the aluminium cell is prebaked cell for aluminum-reduction.
The raw material availability of the oxide of chromium refers to the total amount of chromium in the aluminum chromium produced and is added to electrolytic cell The percentage of the total amount of chromium in the oxide of middle chromium.
The present invention has the advantages that in the aluminium cell produced be added chromium oxide, using electrolysis eutectoid and The principle continuous production aluminum chromium of aluminothermic reduction, major advantage are not generate excess byproduct, and significant loss is minimum, significantly Reduce production cost, aluminium cell can continuous production, product production capacity is high；The magnetic field of aluminium cell be again chromium in aluminium sufficiently more It dissipates and provides stirring power, aluminum chromium ingredient produced is uniform, and product quality is high；The present invention passes through the oxygen of strict control chromium The feeding quantity and feed way of compound avoid the oxide of chromium in aluminium cell and cause with aluminium generation thermite reaction fierceness Technology condition fluctuation is big, the problems such as being not normally functioning, so that aluminium cell technology condition is maintained reasonable model In enclosing, guarantee that aluminium cell in the stable operation of electrolytic preparation aluminum chromium process, prepares aluminum chromium by direct electrolysis method With the short characteristic of production procedure；
The present invention is merely with existing prebaked cell for aluminum-reduction, can be in the case where not increasing any equipment investment The chromium content being precisely controlled in aluminum chromium, Cr materials utilization rate is high, obtains the uniform aluminum chromium of ingredient.
Specific embodiment:
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's all other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
Embodiment 1: a kind of preparation method for the aluminum chromium that the mass percentage content of chromium is 1%, with aluminium cell into Prepared by row, electrolytic cell used in the present embodiment is prebaked cell for aluminum-reduction, and for the anode used for carbon anode, cathode is graphite yin Pole, electrolytic cell groove profile are cradle type groove, potline current 200KA；The oxide of chromium is Cr in the present embodiment2O3, purity is 99%.The technology condition of electrolytic cell are as follows: average voltage 3.642V, electrolysis temperature are 933 DEG C.
Preparation method specifically comprises the following steps:
Step 1: in the aluminium cell produced, measuring nNaFAlF in the electrolyte of aluminium cell3, n 2.1 ~2.9 constant；KF；CaF2；MgF2；LiF；AL2O3Mass percentage content, wherein KF be 0.8%；CaF2It is 5.1%； MgF2It is 2.1%；LiF is 5.5%；AL2O3It is 5.2%；Surplus is ice crystal nNaFAlF3, n 2.44, the above components The sum of mass percentage be 100%；
Step 2: the present embodiment electrolytic process includes an aluminum chromium electrolysing period, one of aluminum chromium electrolysis week Phase includes: a chromium content rising stage and a chromium content balance period；Wherein the chromium content rising stage is aluminium cell amount of ram aluminium The mass percentage content of middle chromium reach 1% before electrolytic process, the mass percentage content of chromium is held in the stage storage aluminium It is continuous to rise；Chromium content balance period is the electrolysis after the mass percentage content of chromium in aluminium cell amount of ram aluminium reaches 1% Journey, the mass percentage content of chromium remains unchanged in the stage storage aluminium.
2.1 in chromium content rising stage and balance period, oxide feeding quantity≤I/b of unit hour chromium；Wherein, I is series Electric current (kA), b are constant satisfaction: b=10kA/kg；In the present embodiment, be computed the oxide feeding quantity of unit hour chromium≤ 20kg；
The 2.2 chromium content rising stage in electrolytic process added the oxide of chromium, tested and analyzed current electrolytic cell amount of ram The content of chromium is 0 in aluminium, target content 1%, determines that promoting rate chromium content day is 0.1%/day.Specific steps include:
2.2.1 chromium content rising stage, the oxide feeding operation of chromium on the 1st
2.2.1.1 feeding quantity on the 1st of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
Wherein, WIt risesFor the day feeding quantity (kg) of the oxide of chromium content rising stage chromium, QDiskFor aluminium cell amount of ram aluminium Quality (kg), a1For the actually detected numerical value (%) of the mass percentage content of chromium in same day aluminium cell amount of ram aluminium, a2It is Chromium is expected by mass percentage content to be achieved (%), (a in two days aluminium cell amount of ram aluminium2-a1) it is to be promoted chromium content day Rate (%), QIt producesFor the day aluminum yield (kg) of aluminium cell, P is the raw material availability (%) of the oxide of chromium, and C is the oxidation of chromium The purity (%) of object, m are the mass percentage content (%) of chromium in the oxide of chromium.
In the present embodiment, QDiskFor 10500kg；a10% is detected as through spectrum analysis；Due to a2-a1=0.1%, determine a2For 0.1%；QIt producesFor 1460kg；P was set as 100% on 1st；C is 99%；M passes through Cr2O3Molecular formula is calculated as 68.42%；It utilizes W is calculated in formula (1)It risesFor 17.66kg.
2.2.1.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤20kg of unit hour chromium are pressed；This implementation Feeding quantity on the 1st is 17.66kg in example, and feeding operation can be completed in 1 hour；
2.2.1.3 when measured value, which meets step 1, to be required, by step 2.2.1.1 and 2.2.1.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 1st, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 0.0933%, determines that the raw material availability actual value of the oxide of chromium on the 1st is 93.3%.
2.2.2 chromium content rising stage, the oxide feeding operation of chromium on the 2nd
2.2.2.1 feeding quantity on the 2nd of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
In the present embodiment, QDiskFor 10500kg；a10.0933% is detected as through spectrum analysis；Due to a2-a1=0.1%, really Determine a2It is 0.1933%；QIt producesFor 1460kg；P on the 2nd use the raw material availability actual value of the oxide of chromium on the 1st for 93.3%；C is 99%；M passes through Cr2O3Molecular formula is calculated as 68.42%；W is calculated using formula (1)It risesFor 21.08kg.
2.2.2.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤20kg of unit hour chromium are pressed；This implementation The oxide feeding quantity of chromium on the 2nd is 21.08kg in example, and feeding operation needs are completed in 2 hours；
2.2.2.3 when measured value, which meets step 1, to be required, by step 2.2.2.1 and 2.2.2.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 2nd, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 0.1931%, determines that the raw material availability actual value of the oxide of chromium on the 2nd is 93.1%.
2.2.3 chromium content rising stage, the oxide feeding operation of chromium on the 3rd
2.2.3.1 feeding quantity on the 3rd of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
In the present embodiment, QDiskFor 10500kg；a10.1931% is detected as through spectrum analysis；Due to a2-a1=0.1%, really Determine a2It is 0.2931%；QIt producesFor 1460kg；P on the 3rd was using the 1st day, the raw material availability actual value of the oxide of chromium on the 2nd Average value is 93.2%；C is 99%；M passes through Cr2O3Molecular formula is calculated as 68.42%；W is calculated using formula (1)It risesFor 23.41kg。
2.2.3.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤20kg of unit hour chromium are pressed；This implementation The oxide feeding quantity of chromium on the 3rd is 23.41kg in example, and feeding operation needs are completed in 2 hours；
2.2.3.3 when measured value, which meets step 1, to be required, by step 2.2.3.1 and 2.2.3.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 3rd, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 0.2931%, determines that the raw material availability actual value of the oxide of chromium on the 3rd is 93.2%.
It is calculated and is fed by third day method daily later, detailed process repeats no more, until aluminium cell memory The mass percentage content of chromium reaches 1% in amount aluminium.In the present embodiment, chromium content rising stage in electrolytic process, the oxygen of chromium The average value of the actual value of the raw material availability of compound is 93.2%.
2.3, when the mass percentage content of chromium in aluminium cell amount of ram aluminium reaches 1%, start by chromium content balance period Charging.Chromium content balance period in electrolytic process, adds the oxide of chromium, and specific steps include:
2.3.1 the daily feeding quantity of the oxide of chromium content balance period chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content balance period chromium is as follows:
Wherein, WIt is flatFor the day feeding quantity (kg) of the oxide of chromium content balance period chromium, QIt producesFor the day aluminum yield of aluminium cell (kg), aIt is flatFor the mass percentage content (%) of chromium in chromium content balance period aluminium cell amount of ram aluminium, P is the oxide of chromium Raw material availability (%), C are the purity (%) of the oxide of chromium, and m is the mass percentage content (%) of chromium in the oxide of chromium.
In the present embodiment, QIt producesFor 1460kg；aIt is flatIt is 1%；P was used in the chromium content rising stage, the raw material of the oxide of chromium The average value of the actual value of utilization rate is 93.2%；C is 99%；M passes through Cr2O3Molecular formula is calculated as 68.42%；Utilize formula (2) W is calculatedIt is flatFor 23.13kg.
2.3.2 step 2.1 is pressed, in chromium content balance period, oxide feeding quantity≤20kg of unit hour chromium；The present embodiment The oxide feeding quantity of the middle daily chromium of balance period is 23.13kg, and feeding operation needs are completed in 2 hours；
2.3.3 when measured value, which meets step 1, to be required, by step 2.3.1 and 2.3.2 calculated result, to prebaked anode aluminium The oxide of chromium is added in electrolytic cell, and the start time point that the oxide of chromium adds daily is after aluminium cell goes out aluminium.
The aluminum chromium of electrolytic preparation is carried out using the present embodiment, the aluminium chromium that separate unit electrolytic cell can produce 1460kg daily closes Gold, the mass percentage of chromium is 1% in aluminum chromium；For the mass percentage deviation of chromium less than 0.01%, ingredient is uniform；Chromium The average value of actual value of raw material availability of oxide reach 93.2%, raw material availability is high；Current efficiency of aluminium cell It is 91.2%；In aluminum chromium production process, electrolysis main technique technical conditions are held essentially constant, and smooth production process connects It is continuous.
Embodiment 2: a kind of preparation method for the aluminum chromium that the mass percentage content of chromium is 1%, with aluminium cell into Prepared by row, electrolytic cell used in the present embodiment is prebaked cell for aluminum-reduction, and for the anode used for carbon anode, cathode is graphite yin Pole, electrolytic cell groove profile are cradle type groove, potline current 200KA；The oxide of chromium is Cr in the present embodiment2O3, purity is 99%.The technology condition of electrolytic cell are as follows: average voltage 3.642V, electrolysis temperature are 933 DEG C.
Preparation method specifically comprises the following steps:
Step 1: in the aluminium cell produced, measuring nNaFAlF in the electrolyte of aluminium cell3；KF；CaF2； MgF2；LiF；AL2O3Mass percentage content, wherein KF be 4.1%；CaF2It is 2.1%；MgF2It is 4.8%；LiF is 2.5%；AL2O3It is 2.2%；Surplus is ice crystal nNaFAlF3, n 2.77, the sum of mass percentage of the above components It is 100%；
Other steps are same as Example 1.
The aluminum chromium of electrolytic preparation is carried out using the present embodiment, for chromium content deviation less than 0.01%, ingredient is uniform；It is practical The raw material availability of the oxide of chromium reaches 93.2%；Current efficiency is 91.3%；Separate unit electrolytic cell can produce 1460kg daily Aluminum chromium, the mass percentage content of chromium is 1% in aluminum chromium.
Embodiment 3: a kind of preparation method for the aluminum chromium that the mass percentage content of chromium is 1%, with aluminium cell into Prepared by row, electrolytic cell used in the present embodiment is prebaked cell for aluminum-reduction, and for the anode used for carbon anode, cathode is graphite yin Pole, electrolytic cell groove profile are cradle type groove, potline current 200KA；The oxide of chromium is Cr in the present embodiment2O3, purity is 99%.The technology condition of electrolytic cell are as follows: average voltage 4.028V, electrolysis temperature are 948 DEG C.
Specific process step is same as Example 1.
The aluminum chromium of electrolytic preparation is carried out using the present embodiment, for chromium content deviation less than 0.01%, ingredient is uniform；It is practical The raw material availability of the oxide of chromium reaches 93.1%；Current efficiency is 91.2%；Separate unit electrolytic cell can produce 1460kg daily Aluminum chromium, the mass percentage content of chromium is 1% in aluminum chromium.
Embodiment 4: a kind of preparation method for the aluminum chromium that the mass percentage content of chromium is 1.5% uses aluminium cell It is prepared, electrolytic cell used in the present embodiment is prebaked cell for aluminum-reduction, and for the anode used for carbon anode, cathode is half stone Black cathode, electrolytic cell groove profile are rectangular slot, and potline current 320KA, the oxide of chromium is CrO in the present embodiment2, purity It is 99%.The technology condition of electrolytic cell are as follows: when average voltage 3.998V, electrolysis temperature are 918 DEG C.
Preparation method specifically comprises the following steps:
Step 1: in the aluminium cell produced, measuring nNaFAlF in the electrolyte of aluminium cell3, n 2.1 ~2.9 constant；KF；CaF2；MgF2；LiF；AL2O3Mass percentage content, wherein KF be 5.1%；CaF2It is 2.1%； MgF2It is 3.1%；LiF is 4.5%；AL2O3It is 2.2%；Surplus is ice crystal nNaFAlF3, n 2.73, the above components The sum of mass percentage be 100%；
Step 2: the present embodiment electrolytic process includes an aluminum chromium electrolysing period, one of aluminum chromium electrolysis week Phase includes: a chromium content rising stage and a chromium content balance period；Wherein the chromium content rising stage is aluminium cell amount of ram aluminium The mass percentage content of middle chromium reach 1.5% before electrolytic process, the mass percentage content of chromium in the stage storage aluminium It is lasting to rise；Chromium content balance period is the electricity after the mass percentage content of chromium in aluminium cell amount of ram aluminium reaches 1.5% Solution preocess, the mass percentage content of chromium remains unchanged in the stage storage aluminium.
2.1 in chromium content rising stage and balance period, oxide feeding quantity≤I/b of unit hour chromium；Wherein, I is series Electric current (kA), b are constant satisfaction: b=10kA/kg；In the present embodiment, be computed the oxide feeding quantity of unit hour chromium≤ 32kg；
The 2.2 chromium content rising stage in electrolytic process added the oxide of chromium, tested and analyzed current electrolytic cell amount of ram The content of chromium is 0 in aluminium, target content 1.5%, determines that promoting rate chromium content day is 0.2%/day.Specific steps include:
2.2.1 chromium content rising stage, the oxide feeding operation of chromium on the 1st
2.2.1.1 feeding quantity on the 1st of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
Wherein, WIt risesFor the day feeding quantity (kg) of the oxide of chromium content rising stage chromium, QDiskFor aluminium cell amount of ram aluminium Quality (kg), a1For the actually detected numerical value (%) of the mass percentage content of chromium in same day aluminium cell amount of ram aluminium, a2It is Chromium is expected by mass percentage content to be achieved (%), (a in two days aluminium cell amount of ram aluminium2-a1) it is to be promoted chromium content day Rate (%), QIt producesFor the day aluminum yield (kg) of aluminium cell, P is the raw material availability (%) of the oxide of chromium, and C is the oxidation of chromium The purity (%) of object, m are the mass percentage content (%) of chromium in the oxide of chromium.
In the present embodiment, QDiskFor 16200kg；a10% is detected as through spectrum analysis；Due to a2-a1=0.2%, determine a2For 0.2%；QIt producesFor 2355kg；P was set as 100% on 1st；C is 99%；M passes through CrO2Molecular formula is calculated as 61.9%；It utilizes W is calculated in formula (1)It risesFor 60.56kg.
2.2.1.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤32kg of unit hour chromium are pressed；This implementation Oxide feeding quantity on the 1st is 60.56kg in example, and feeding operation needs are completed in 2 hours；
2.2.1.3 when measured value, which meets step 1, to be required, by step 2.2.1.1 and 2.2.1.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 1st, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 0.185%, determines that the raw material availability actual value of the oxide of chromium on the 1st is 92.5%.
2.2.2 chromium content rising stage, the oxide feeding operation of chromium on the 2nd
2.2.2.1 feeding quantity on the 2nd of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
In the present embodiment, QDiskFor 16200kg；a10.185% is detected as through spectrum analysis；Due to a2-a1=0.2%, it determines a2It is 0.385%；QIt producesFor 2355kg；P used the raw material availability actual value of the oxide of chromium on the 1st for 92.5% on 2nd；C It is 99%；M passes through CrO2Molecular formula is calculated as 61.9%；W is calculated using formula (1)It risesFor 73.15kg.
2.2.2.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤32kg of unit hour chromium are pressed；This implementation The oxide feeding quantity of chromium on the 2nd is 73.15kg in example, and feeding operation needs are completed in 3 hours；
2.2.2.3 when measured value, which meets step 1, to be required, by step 2.2.2.1 and 2.2.2.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 2nd, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 0.386%, determines that the raw material availability actual value of the oxide of chromium on the 2nd is 92.9%.
2.2.3 chromium content rising stage, the oxide feeding operation of chromium on the 3rd
2.2.3.1 feeding quantity on the 3rd of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
In the present embodiment, QDiskFor 16200kg；a10.386% is detected as through spectrum analysis；Due to a2-a1=0.2%, it determines A2 is 0.586%；QIt producesFor 2355kg；P on the 3rd using the 1st day, the raw material availability actual value of the oxide of chromium on the 2nd it is flat Mean value is 92.7%；C is 99%；M passes through CrO2Molecular formula is calculated as 61.9%；W is calculated using formula (1)It risesFor 81.33kg。
2.2.3.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤32kg of unit hour chromium are pressed；This implementation The oxide feeding quantity of chromium on the 3rd is 81.33kg in example, and feeding operation needs are completed in 3 hours；
2.2.3.3 when measured value, which meets step 1, to be required, by step 2.2.3.1 and 2.2.3.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 3rd, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 0.587%, determines that the raw material availability actual value on the 3rd of the oxide of chromium is 92.9%.
It is calculated and is fed by third day method daily later, detailed process repeats no more, until aluminium cell memory The mass percentage content of chromium reaches 1.5% in amount aluminium.In the present embodiment, chromium content rising stage in electrolytic process, chromium The average value of the actual value of the raw material availability of oxide is 92.8%.
2.3, when the mass percentage content of chromium in aluminium cell amount of ram aluminium reaches 1.5%, start to balance by chromium content Phase charging.Chromium content balance period in electrolytic process, adds the oxide of chromium, and specific steps include:
2.3.1 the daily feeding quantity of the oxide of chromium content balance period chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content balance period chromium is as follows:
Wherein, WIt is flatFor the day feeding quantity (kg) of the oxide of chromium content balance period chromium, QIt producesFor the day aluminum yield of aluminium cell (kg), aIt is flatFor the mass percentage content (%) of chromium in chromium content balance period aluminium cell amount of ram aluminium, P is the oxide of chromium Raw material availability (%), C are the purity (%) of the oxide of chromium, and m is the mass percentage content (%) of chromium in the oxide of chromium.
In the present embodiment, QIt producesFor 2355kg；aIt is flatIt is 1.5%；P was used in the chromium content rising stage, the original of the oxide of chromium The average value for expecting the actual value of utilization rate is 92.8%；C is 99%；M passes through CrO2Molecular formula is calculated as 61.9%；Utilize formula (2) W is calculatedIt is flatFor 62.12kg.
2.3.2 step 2.1 is pressed, in chromium content balance period, oxide feeding quantity≤32kg of unit hour chromium；The present embodiment The oxide feeding quantity of the middle daily chromium of balance period is 62.12kg, and feeding operation needs are completed in 2 hours；
2.3.3 when measured value, which meets step 1, to be required, by step 2.3.1 and 2.3.2 calculated result, to prebaked anode aluminium The oxide of chromium is added in electrolytic cell, and the start time point that the oxide of chromium adds daily is after aluminium cell goes out aluminium.
The aluminum chromium of electrolytic preparation is carried out using the present embodiment, the aluminium chromium that separate unit electrolytic cell can produce 2355kg daily closes Gold, the mass percentage of chromium is 1.5% in aluminum chromium；For the mass percentage deviation of chromium less than 0.02%, ingredient is uniform； The average value of the actual value of the raw material availability of the oxide of chromium reaches 92.8%, and raw material availability is high；Aluminum cell current effect Rate is 91.4%；In aluminum chromium production process, electrolysis main technique technical conditions are held essentially constant, and smooth production process connects It is continuous.
Embodiment 5: a kind of preparation method for the aluminum chromium that the mass percentage content of chromium is 1.5% uses aluminium cell It is prepared, electrolytic cell used in the present embodiment is prebaked cell for aluminum-reduction, and for the anode used for carbon anode, cathode is half stone Black cathode, electrolytic cell groove profile are rectangular slot, and potline current 320KA, the oxide of chromium is CrO in the present embodiment2, purity It is 99%.The technology condition of electrolytic cell are as follows: when average voltage 3.998V, electrolysis temperature are 918 DEG C.
Preparation method specifically comprises the following steps:
Step 1: in the aluminium cell produced, measuring nNaFAlF in the electrolyte of aluminium cell3, n 2.1 ~2.9 constant；KF；CaF2；MgF2；LiF；AL2O3Mass percentage content, wherein KF be 1.8%；CaF2It is 3.1%； MgF2It is 4.7%；LiF is 5.2%；AL2O3It is 4.6%；Surplus is ice crystal nNaFAlF3, n 2.28, the above components The sum of mass percentage be 100%.
Other steps are same as Example 4.
The aluminum chromium of electrolytic preparation is carried out using the present embodiment, the aluminium chromium that separate unit electrolytic cell can produce 2355kg daily closes Gold, the mass percentage of chromium is 1.5% in aluminum chromium；For the mass percentage deviation of chromium less than 0.02%, ingredient is uniform； The average value of the actual value of the raw material availability of the oxide of chromium reaches 92.9%, and raw material availability is high；Aluminum cell current effect Rate is 91.4%；In aluminum chromium production process, electrolysis main technique technical conditions are held essentially constant, and smooth production process connects It is continuous.
Embodiment 6: a kind of preparation method for the aluminum chromium that the mass percentage content of chromium is 1.5% uses aluminium cell It is prepared, electrolytic cell used in the present embodiment is prebaked cell for aluminum-reduction, and for the anode used for carbon anode, cathode is half stone Black cathode, electrolytic cell groove profile are rectangular slot, and potline current 320KA, the oxide of chromium is CrO in the present embodiment2, purity It is 99%.The technology condition of electrolytic cell are as follows: when average voltage 3.451V, electrolysis temperature are 948 DEG C.
It is other same as Example 4.
The aluminum chromium of electrolytic preparation is carried out using the present embodiment, the aluminium chromium that separate unit electrolytic cell can produce 2355kg daily closes Gold, the mass percentage of chromium is 1.5% in aluminum chromium；For the mass percentage deviation of chromium less than 0.02%, ingredient is uniform； The average value of the actual value of the raw material availability of the oxide of chromium reaches 92.6%, and raw material availability is high；Aluminum cell current effect Rate is 91.4%；In aluminum chromium production process, electrolysis main technique technical conditions are held essentially constant, and smooth production process connects It is continuous.
Embodiment 7: a kind of preparation method for the aluminum chromium that the mass percentage content of chromium is 2.8% uses aluminium cell It is prepared, electrolytic cell used in the present embodiment is prebaked cell for aluminum-reduction, and for the anode used for carbon anode, cathode is graphite Cathode, electrolytic cell groove profile are cradle type groove, and the potline current of electrolytic cell is 600KA；The oxide of chromium is Cr in the present embodiment2O3, Its purity is 99%.Electrolytic cell main technique technical conditions: average voltage 3.625V, electrolysis temperature are 915 DEG C.
Preparation method specifically comprises the following steps:
Step 1: in the aluminium cell produced, measuring nNaFAlF in the electrolyte of aluminium cell3, n 2.1 ~2.9 constant；KF；CaF2；MgF2；LiF；AL2O3Mass percentage content, wherein KF be 4.1%；CaF2It is 1.7%； MgF2It is 2.1%；LiF is 5.3%；AL2O3It is 2.6%；Surplus is ice crystal nNaFAlF3, n 2.82, the above components The sum of mass percentage be 100%；
Step 2: the present embodiment electrolytic process includes two aluminum chromium electrolysing periods, one of aluminum chromium electrolysis week Phase includes: a chromium content rising stage and a chromium content balance period；In first aluminum chromium electrolysing period, chromium content rises Phase is the electrolytic process before the mass percentage content of chromium in aluminium cell storage aluminium reaches 1.5%, in the stage storage aluminium The mass percentage content of chromium persistently rises；Chromium content balance period is that the mass percentage content of chromium in aluminium cell storage aluminium reaches Electrolytic process after to 1.5%, the mass percentage content of chromium remains unchanged in the stage storage aluminium；First aluminum chromium In electrolysing period, the duration of chromium content balance period is 10 electrolysis working days；In second aluminum chromium electrolysing period, chromium The content rising stage is that the mass percentage content of chromium in aluminium cell storage aluminium reaches electrolytic process between 2.8% from 1.5%, The mass percentage content of chromium persistently rises in the stage storage aluminium；Chromium content balance period is the matter of chromium in aluminium cell storage aluminium The electrolytic process after degree reaches 2.8% is measured, the mass percentage content of chromium remains unchanged in the stage storage aluminium；
2.1 in chromium content rising stage and balance period, oxide feeding quantity≤I/b of unit hour chromium；Wherein, I is series Electric current (kA), b are constant satisfaction: b=10kA/kg；In the present embodiment, be computed the oxide feeding quantity of unit hour chromium≤ 60kg；
2.2 first chromium content rising stage in electrolytic process, the mass percentage of chromium in aluminium cell storage aluminium Electrolytic process between from 0 to 1.5% adds the oxide of chromium, tests and analyzes the content of chromium in current electrolytic cell amount of ram aluminium It is 0, target content 1.5% determines that promoting rate chromium content day is 0.3%/day.Specific steps include:
2.2.1 chromium content rising stage, the oxide feeding operation of chromium on the 1st
2.2.1.1 feeding quantity on the 1st of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
Wherein, WIt risesFor the day feeding quantity (kg) of the oxide of chromium content rising stage chromium, QDiskFor aluminium cell amount of ram aluminium Quality (kg), a1For the actually detected numerical value (%) of the mass percentage content of chromium in same day aluminium cell amount of ram aluminium, a2It is Chromium is expected by mass percentage content to be achieved (%), (a in two days aluminium cell amount of ram aluminium2-a1) it is to be promoted chromium content day Rate (%), QIt producesFor the day aluminum yield (kg) of aluminium cell, P is the raw material availability (%) of the oxide of chromium, and C is the oxidation of chromium The purity (%) of object, m are the mass percentage content (%) of chromium in the oxide of chromium.
In the present embodiment, QDiskFor 40200kg；a10% is detected as through spectrum analysis；Due to a2-a1=0.3%, determine a2For 0.3%；QIt producesFor 4410kg；P was set as 100% on 1st；C is 99%；M passes through Cr2O3Molecular formula is calculated as 68.42%；It utilizes W is calculated in formula (1)It risesFor 197.58kg.
2.2.1.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤60kg of unit hour chromium are pressed；This implementation Feeding quantity on the 1st is 197.58kg in example, and feeding operation can be completed in 4 hours；
2.2.1.3 when measured value, which meets step 1, to be required, by step 2.2.1.1 and 2.2.1.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 1st, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 0.2763%, determines that the raw material availability actual value of the oxide of chromium on the 1st is 92.1%.
2.2.2 chromium content rising stage, the oxide feeding operation of chromium on the 2nd
2.2.2.1 feeding quantity on the 2nd of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
In the present embodiment, QDiskFor 40200kg；a10.2763% is detected as through spectrum analysis；Due to a2-a1=0.3%, really Determine a2It is 0.5763%；QIt producesFor 4410kg；P on the 2nd use the raw material availability actual value of the oxide of chromium on the 1st for 92.1%；C is 99%；M passes through Cr2O3Molecular formula is calculated as 68.42%；W is calculated using formula (1)It risesFor 234.06kg.
2.2.2.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤60kg of unit hour chromium are pressed；This implementation The oxide feeding quantity of chromium on the 2nd is 234.06kg in example, and feeding operation needs are completed in 4 hours；
2.2.2.3 when measured value, which meets step 1, to be required, by step 2.2.2.1 and 2.2.2.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 2nd, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 0.5777%, determines that the raw material availability actual value of the oxide of chromium on the 2nd is 92.5%.
2.2.3 chromium content rising stage, the oxide feeding operation of chromium on the 3rd
2.2.3.1 feeding quantity on the 3rd of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
In the present embodiment, QDiskFor 40200kg；a10.5777% is detected as through spectrum analysis；Due to a2-a1=0.3%, really Determine a2It is 0.8777%；QIt producesFor 4410kg；P on the 3rd was using the 1st day, the raw material availability actual value of the oxide of chromium on the 2nd Average value is 92.3%；C is 99%；M passes through Cr2O3Molecular formula is calculated as 68.42%；W is calculated using formula (1)It risesFor 254.81kg。
2.2.3.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤60kg of unit hour chromium are pressed；This implementation The oxide feeding quantity of chromium on the 3rd is 254.81kg in example, and feeding operation needs are completed in 5 hours；
2.2.3.3 when measured value, which meets step 1, to be required, by step 2.2.3.1 and 2.2.3.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 3rd, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 0.8773%, determines that the raw material availability actual value of the oxide of chromium on the 3rd is 92.2%.
It is calculated and is fed by third day method daily later, detailed process repeats no more, until aluminium cell memory The mass percentage content of chromium reaches 1.5% in amount aluminium.In the present embodiment, chromium content rising stage in electrolytic process, chromium The average value of the actual value of the raw material availability of oxide is 92.2%.
2.3, when the mass percentage content of chromium in aluminium cell amount of ram aluminium reaches 1.5%, start to balance by chromium content Phase charging.Chromium content balance period in electrolytic process, adds the oxide of chromium, and specific steps include:
2.3.1 the daily feeding quantity of the oxide of chromium content balance period chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content balance period chromium is as follows:
Wherein, WIt is flatFor the day feeding quantity (kg) of the oxide of chromium content balance period chromium, QIt producesFor the day aluminum yield of aluminium cell (kg), aIt is flatFor the mass percentage content (%) of chromium in chromium content balance period aluminium cell amount of ram aluminium, P is the oxide of chromium Raw material availability (%), C are the purity (%) of the oxide of chromium, and m is the mass percentage content (%) of chromium in the oxide of chromium.
In the present embodiment, QIt producesFor 4410kg；aIt is flatIt is 1.5%；P uses the raw material of the oxide of chromium in the chromium content rising stage The average value of the actual value of utilization rate is 92.2%；C is 99%；M passes through Cr2O3Molecular formula is calculated as 68.42%；Utilize formula (2) W is calculatedIt is flatFor 105.92kg.
2.3.2 step 2.1 is pressed, in chromium content balance period, oxide feeding quantity≤60kg of unit hour chromium；The present embodiment The oxide feeding quantity of the middle daily chromium of balance period is 105.92kg, and feeding operation needs are completed in 2 hours；
2.3.3 when measured value, which meets step 1, to be required, by step 2.3.1 and 2.3.2 calculated result, to prebaked anode aluminium The oxide of chromium is added in electrolytic cell, and the start time point that the oxide of chromium adds daily is after aluminium cell goes out aluminium.First The duration of a chromium content balance period is 10 electrolysis working days, then begins to second aluminum chromium electrolysing period.
In the present embodiment, first chromium content rising stage and balance period in electrolytic process, the raw material of the oxide of chromium The average value of the actual value of utilization rate is 92.2%.
2.4 second chromium content rising stage in electrolytic process, the mass percentage of chromium in aluminium cell storage aluminium Electrolytic process between from 1.5% to 2.8% adds the oxide of chromium, tests and analyzes chromium in current electrolytic cell amount of ram aluminium Content is 1.5%, target content 2.8%, determines that promoting rate chromium content day is 0.1%/day.Specific steps include:
2.4.1 chromium content rising stage, the oxide feeding operation of chromium on the 1st
2.4.1.1 feeding quantity on the 1st of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
Wherein, WIt risesFor the day feeding quantity (kg) of the oxide of chromium content rising stage chromium, QDiskFor aluminium cell amount of ram aluminium Quality (kg), a1For the actually detected numerical value (%) of the mass percentage content of chromium in same day aluminium cell amount of ram aluminium, a2It is Chromium is expected by mass percentage content to be achieved (%), (a in two days aluminium cell amount of ram aluminium2-a1) it is to be promoted chromium content day Rate (%), QIt producesFor the day aluminum yield (kg) of aluminium cell, P is the raw material availability (%) of the oxide of chromium, and C is the oxidation of chromium The purity (%) of object, m are the mass percentage content (%) of chromium in the oxide of chromium.
In the calculating on the 1st of the present embodiment, QDiskFor 40200kg；a11.5% is detected as through spectrum analysis；Due to a2-a1 =0.1%, determine a2It is 1.6%；QIt producesFor 4410kg；P uses first chromium content rising stage and balance period in electrolytic process, The average value of the actual value of the raw material availability of the oxide of chromium is 92.2%；C is 98%；M passes through Cr2O3Molecular formula is calculated as 68.42%；W is calculated using formula (1)It risesFor 177.35kg.
2.4.1.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤60kg of unit hour chromium are pressed；This implementation The oxide feeding quantity of chromium on the 1st is 177.35kg in example, and feeding operation needs complete for 3 hours；
2.4.1.3 when measured value, which meets step 1, to be required, by step 2.4.1.1 and 2.4.1.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 1st, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 1.6%, determines that the raw material availability actual value of the oxide of chromium on the 1st is 92.2%.
It is calculated and is fed by method on the 1st daily later, detailed process repeats no more, until aluminium cell amount of ram The mass percentage content of chromium reaches 2.8% in aluminium.In the present embodiment, in first chromium content rising stage and balance period and electricity Second chromium content rising stage in solution preocess, the average value of the actual value of the raw material availability of the oxide of chromium are 92.2%.
2.5, when the mass percentage content of chromium in aluminium cell amount of ram aluminium reaches 2.8%, start to balance by chromium content Phase charging.First chromium content balance period in electrolytic process, adds the oxide of chromium, specific steps include:
2.5.1 the daily feeding quantity of the oxide of chromium content balance period chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content balance period chromium is as follows:
Wherein, WIt is flatFor the day feeding quantity (kg) of the oxide of chromium content balance period chromium, QIt producesFor the day aluminum yield of aluminium cell (kg), aIt is flatFor the mass percentage content (%) of chromium in chromium content balance period aluminium cell amount of ram aluminium, P is the oxide of chromium Raw material availability (%), C are the purity (%) of the oxide of chromium, and m is the mass percentage content (%) of chromium in the oxide of chromium.
In the present embodiment, QIt producesFor 4410kg；aIt is flatIt is 2.8%；P is using numerical value obtained in above-mentioned accumulation 92.2%；C is 98%；M passes through Cr2O3Molecular formula is calculated as 68.42%；W is calculated using formula (2)It is flatFor 105.92kg.
2.5.2 step 2.1 is pressed, in chromium content balance period, oxide feeding quantity≤60kg of unit hour chromium；The present embodiment The oxide feeding quantity of the middle daily chromium of balance period is 105.92kg, and feeding operation needs complete for 2 hours；
2.5.3 when measured value, which meets step 1, to be required, by step 2.5.1 and 2.5.2 calculated result, to prebaked anode aluminium The oxide of chromium is added in electrolytic cell, and the start time point that the oxide of chromium adds daily is after aluminium cell goes out aluminium.
The aluminum chromium of electrolytic preparation is carried out using the present embodiment, the aluminium chromium that separate unit electrolytic cell can produce 4410kg daily closes Gold, the mass percentage of chromium is 2.8% in aluminum chromium；For the mass percentage deviation of chromium less than 0.03%, ingredient is uniform； The average value of the actual value of the raw material availability of the oxide of chromium reaches 92.2%, and raw material availability is high；Aluminum cell current effect Rate is 91.2%；In aluminum chromium production process, electrolysis main technique technical conditions are held essentially constant, and smooth production process connects It is continuous.
Embodiment 8: a kind of preparation method for the aluminum chromium that the mass percentage content of chromium is 2.8% uses aluminium cell It is prepared, electrolytic cell used in the present embodiment is prebaked cell for aluminum-reduction, and for the anode used for carbon anode, cathode is graphite Cathode, electrolytic cell groove profile are cradle type groove, and the potline current of electrolytic cell is 600KA；The oxide of chromium is Cr in the present embodiment2O3, Its purity is 99%.Electrolytic cell main technique technical conditions: average voltage 3.625V, electrolysis temperature are 915 DEG C.
Preparation method specifically comprises the following steps:
Step 1: in the aluminium cell produced, measuring nNaFAlF in the electrolyte of aluminium cell3, n 2.1 ~2.9 constant；KF；CaF2；MgF2；LiF；AL2O3Mass percentage content, wherein KF be 4.1%；CaF2It is 1.7%； MgF2It is 2.1%；LiF is 5.3%；AL2O3It is 2.6%；Surplus is ice crystal nNaFAlF3, n 2.82, the above components The sum of mass percentage be 100%；
Step 2: the present embodiment electrolytic process includes two aluminum chromium electrolysing periods, one of aluminum chromium electrolysis week Phase includes: a chromium content rising stage and a chromium content balance period；In first aluminum chromium electrolysing period, chromium content rises Phase is the electrolytic process before the mass percentage content of chromium in aluminium cell storage aluminium reaches 1.5%, in the stage storage aluminium The mass percentage content of chromium persistently rises；Chromium content balance period is that the mass percentage content of chromium in aluminium cell storage aluminium reaches Electrolytic process after to 1.5%, the mass percentage content of chromium remains unchanged in the stage storage aluminium；First aluminum chromium In electrolysing period, the duration of chromium content balance period is 10 electrolysis working days；In second aluminum chromium electrolysing period, chromium The content rising stage is that the mass percentage content of chromium in aluminium cell storage aluminium reaches electrolytic process between 2.8% from 1.5%, The mass percentage content of chromium persistently rises in the stage storage aluminium；Chromium content balance period is the matter of chromium in aluminium cell storage aluminium The electrolytic process after degree reaches 2.8% is measured, the mass percentage content of chromium remains unchanged in the stage storage aluminium；
2.1 in chromium content rising stage and balance period, oxide feeding quantity≤I/b of unit hour chromium；Wherein, I is series Electric current (kA), b are constant satisfaction: b=10kA/kg；In the present embodiment, be computed the oxide feeding quantity of unit hour chromium≤ 60kg；
2.2 first chromium content rising stage in electrolytic process, the mass percentage of chromium in aluminium cell storage aluminium Electrolytic process between from 0 to 1.5% adds the oxide of chromium, tests and analyzes the content of chromium in current electrolytic cell amount of ram aluminium It is 0, target content 1.5% determines that promoting rate chromium content day is 0.3%/day.Specific steps include:
2.2.1 chromium content rising stage, the oxide feeding operation of chromium on the 1st
2.2.1.1 feeding quantity on the 1st of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
Wherein, WIt risesFor the day feeding quantity (kg) of the oxide of chromium content rising stage chromium, QDiskFor aluminium cell amount of ram aluminium Quality (kg), a1For the actually detected numerical value (%) of the mass percentage content of chromium in same day aluminium cell amount of ram aluminium, a2It is Chromium is expected by mass percentage content to be achieved (%), (a in two days aluminium cell amount of ram aluminium2-a1) it is to be promoted chromium content day Rate (%), QIt producesFor the day aluminum yield (kg) of aluminium cell, P is the raw material availability (%) of the oxide of chromium, and C is the oxidation of chromium The purity (%) of object, m are the mass percentage content (%) of chromium in the oxide of chromium.
In the present embodiment, QDiskFor 40200kg；a10% is detected as through spectrum analysis；Due to a2-a1=0.3%, determine a2For 0.3%；QIt producesFor 4410kg；P was set as 100% on 1st；C is 99%；M passes through Cr2O3Molecular formula is calculated as 68.42%；It utilizes W is calculated in formula (1)It risesFor 197.58kg.
2.2.1.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤60kg of unit hour chromium are pressed；This implementation Feeding quantity on the 1st is 197.58kg in example, and feeding operation can be completed in 4 hours；
2.2.1.3 when measured value, which meets step 1, to be required, by step 2.2.1.1 and 2.2.1.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 1st, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 0.2763%, determines that the raw material availability actual value of the oxide of chromium on the 1st is 92.1%.
2.2.2 chromium content rising stage, the oxide feeding operation of chromium on the 2nd
2.2.2.1 feeding quantity on the 2nd of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
In the present embodiment, QDiskFor 40200kg；a10.2763% is detected as through spectrum analysis；Due to a2-a1=0.3%, really Determine a2It is 0.5763%；QIt producesFor 4410kg；P on the 2nd use the raw material availability actual value of the oxide of chromium on the 1st for 92.1%；C is 99%；M passes through Cr2O3Molecular formula is calculated as 68.42%；W is calculated using formula (1)It risesFor 234.06kg.
2.2.2.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤60kg of unit hour chromium are pressed；This implementation The oxide feeding quantity of chromium on the 2nd is 234.06kg in example, and feeding operation needs are completed in 4 hours；
2.2.2.3 when measured value, which meets step 1, to be required, by step 2.2.2.1 and 2.2.2.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 2nd, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 0.5777%, determines that the raw material availability actual value of the oxide of chromium on the 2nd is 92.5%.
2.2.3 chromium content rising stage, the oxide feeding operation of chromium on the 3rd
2.2.3.1 feeding quantity on the 3rd of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
In the present embodiment, QDiskFor 40200kg；a10.5777% is detected as through spectrum analysis；Due to a2-a1=0.3%, really Determine a2It is 0.8777%；QIt producesFor 4410kg；P on the 3rd was using the 1st day, the raw material availability actual value of the oxide of chromium on the 2nd Average value is 92.3%；C is 99%；M passes through Cr2O3Molecular formula is calculated as 68.42%；W is calculated using formula (1)It risesFor 254.81kg。
2.2.3.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤60kg of unit hour chromium are pressed；This implementation The oxide feeding quantity of chromium on the 3rd is 254.81kg in example, and feeding operation needs are completed in 5 hours；
2.2.3.3 when measured value, which meets step 1, to be required, by step 2.2.3.1 and 2.2.3.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 3rd, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 0.8773%, determines that the raw material availability actual value of the oxide of chromium on the 3rd is 92.2%.
It is calculated and is fed by third day method daily later, detailed process repeats no more, until aluminium cell memory The mass percentage content of chromium reaches 1.5% in amount aluminium.In the present embodiment, chromium content rising stage in electrolytic process, chromium The average value of the actual value of the raw material availability of oxide is 92.2%.
2.3, when the mass percentage content of chromium in aluminium cell amount of ram aluminium reaches 1.5%, start to balance by chromium content Phase charging.Chromium content balance period in electrolytic process, adds the oxide of chromium, and specific steps include:
2.3.1 the daily feeding quantity of the oxide of chromium content balance period chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content balance period chromium is as follows:
Wherein, WIt is flatFor the day feeding quantity (kg) of the oxide of chromium content balance period chromium, QIt producesFor the day aluminum yield of aluminium cell (kg), aIt is flatFor the mass percentage content (%) of chromium in chromium content balance period aluminium cell amount of ram aluminium, P is the oxide of chromium Raw material availability (%), C are the purity (%) of the oxide of chromium, and m is the mass percentage content (%) of chromium in the oxide of chromium.
In the present embodiment, QIt producesFor 4410kg；aIt is flatIt is 1.5%；P uses the raw material of the oxide of chromium in the chromium content rising stage The average value of the actual value of utilization rate is 92.2%；C is 99%；M passes through Cr2O3Molecular formula is calculated as 68.42%；Utilize formula (2) W is calculatedIt is flatFor 105.92kg.
2.3.2 step 2.1 is pressed, in chromium content balance period, oxide feeding quantity≤60kg of unit hour chromium；The present embodiment The oxide feeding quantity of the middle daily chromium of balance period is 105.92kg, and feeding operation needs are completed in 2 hours；
2.3.3 when measured value, which meets step 1, to be required, by step 2.3.1 and 2.3.2 calculated result, to prebaked anode aluminium The oxide of chromium is added in electrolytic cell, and the start time point that the oxide of chromium adds daily is after aluminium cell goes out aluminium.First The duration of a chromium content balance period is 10 electrolysis working days, then begins to second aluminum chromium electrolysing period.
In the present embodiment, first chromium content rising stage and balance period in electrolytic process, the raw material of the oxide of chromium The average value of the actual value of utilization rate is 92.2%.
2.4 second chromium content rising stage in electrolytic process, the mass percentage of chromium in aluminium cell storage aluminium Electrolytic process between from 1.5% to 2.8% adds the oxide of chromium, tests and analyzes chromium in current electrolytic cell amount of ram aluminium Content is 1.5%, target content 2.8%, determines that promoting rate chromium content day is 0.15%/day.Specific steps include:
2.4.1 chromium content rising stage, the oxide feeding operation of chromium on the 1st
2.4.1.1 feeding quantity on the 1st of the oxide of chromium content rising stage chromium is calculated
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
Wherein, WIt risesFor the day feeding quantity (kg) of the oxide of chromium content rising stage chromium, QDiskFor aluminium cell amount of ram aluminium Quality (kg), a1For the actually detected numerical value (%) of the mass percentage content of chromium in same day aluminium cell amount of ram aluminium, a2It is Chromium is expected by mass percentage content to be achieved (%), (a in two days aluminium cell amount of ram aluminium2-a1) it is to be promoted chromium content day Rate (%), QIt producesFor the day aluminum yield (kg) of aluminium cell, P is the raw material availability (%) of the oxide of chromium, and C is the oxidation of chromium The purity (%) of object, m are the mass percentage content (%) of chromium in the oxide of chromium.
In the calculating on the 1st of the present embodiment, QDiskFor 40200kg；a11.5% is detected as through spectrum analysis；Due to a2-a1 =0.15%, determine a2It is 1.65%；QIt producesFor 4410kg；P uses first chromium content rising stage and balance in electrolytic process Phase, the average value of the actual value of the raw material availability of the oxide of chromium are 92.2%；C is 98%；M passes through Cr2O3Molecular formula, meter Calculate is 68.42%；W is calculated using formula (1)It risesFor 213.07kg.
2.4.1.2 step 2.1, in the chromium content rising stage, oxide feeding quantity≤60kg of unit hour chromium are pressed；This implementation The oxide feeding quantity of chromium on the 1st is 177.35kg in example, and feeding operation needs complete for 4 hours；
2.4.1.3 when measured value, which meets step 1, to be required, by step 2.4.1.1 and 2.4.1.2 calculated result, to prebake The oxide of chromium is added in anode aluminium cell, and the start time point that the oxide of chromium adds daily is that aluminium cell goes out aluminium Afterwards.
It after the completion of charging on the 1st, is detected through spectrum analysis, the mass percentage content of chromium is real in aluminium cell amount of ram aluminium Border is 1.65%, determines that the raw material availability actual value of the oxide of chromium on the 1st is 92.2%.
It is calculated and is fed by method on the 1st daily later, detailed process repeats no more, until aluminium cell amount of ram The mass percentage content of chromium reaches 2.8% in aluminium.In the present embodiment, in first chromium content rising stage and balance period and electricity Second chromium content rising stage in solution preocess, the average value of the actual value of the raw material availability of the oxide of chromium are 92.2%.
The aluminum chromium of electrolytic preparation is carried out using the present embodiment, the aluminium chromium that separate unit electrolytic cell can produce 4410kg daily closes Gold, the mass percentage of chromium is 2.8% in aluminum chromium；For the mass percentage deviation of chromium less than 0.03%, ingredient is uniform； The average value of the actual value of the raw material availability of the oxide of chromium reaches 92.2%, and raw material availability is high；Aluminum cell current effect Rate is 91.2%；In aluminum chromium production process, electrolysis main technique technical conditions are held essentially constant, and smooth production process connects It is continuous.
Embodiment 9: a kind of preparation method for the aluminum chromium that the mass percentage content of chromium is 2.8% uses aluminium cell It is prepared, electrolytic cell used in the present embodiment is prebaked cell for aluminum-reduction, and for the anode used for carbon anode, cathode is graphite Cathode, electrolytic cell groove profile are cradle type groove, and the potline current of electrolytic cell is 600KA；The oxide of chromium is Cr in the present embodiment2O3, Its purity is 99%.Electrolytic cell main technique technical conditions: average voltage 3.625V, electrolysis temperature are 915 DEG C.
Preparation method specifically comprises the following steps:
Step 1: in the aluminium cell produced, measuring nNaFAlF in the electrolyte of aluminium cell3, n 2.1 ~2.9 constant；KF；CaF2；MgF2；LiF；AL2O3Mass percentage content, wherein KF be 1.1%；CaF2It is 3.7%； MgF2It is 3.6%；LiF is 2.3%；AL2O3It is 4.6%；Surplus is ice crystal nNaFAlF3, n 2.48, the above components The sum of mass percentage be 100%；
Other steps are same as Example 7.
The aluminum chromium of electrolytic preparation is carried out using the present embodiment, the aluminium chromium that separate unit electrolytic cell can produce 4410kg daily closes Gold, the mass percentage of chromium is 2.8% in aluminum chromium；For the mass percentage deviation of chromium less than 0.03%, ingredient is uniform； The average value of the actual value of the raw material availability of the oxide of chromium reaches 92.2%, and raw material availability is high；Aluminum cell current effect Rate is 91.3%；In aluminum chromium production process, electrolysis main technique technical conditions are held essentially constant, and smooth production process connects It is continuous.
Embodiment 10: a kind of preparation method for the aluminum chromium that the mass percentage content of chromium is 2.8% uses aluminium cell It is prepared, electrolytic cell used in the present embodiment is prebaked cell for aluminum-reduction, and for the anode used for carbon anode, cathode is graphite Cathode, electrolytic cell groove profile are cradle type groove, and the potline current of electrolytic cell is 600KA；The oxide of chromium is Cr in the present embodiment2O3, Its purity is 99%.Electrolytic cell main technique technical conditions: average voltage 3.771V, electrolysis temperature are 932 DEG C.
It is other same as Example 7.
The aluminum chromium of electrolytic preparation is carried out using the present embodiment, the aluminium chromium that separate unit electrolytic cell can produce 4410kg daily closes Gold, the mass percentage of chromium is 2.8% in aluminum chromium；For the mass percentage deviation of chromium less than 0.03%, ingredient is uniform； The average value of the actual value of the raw material availability of the oxide of chromium reaches 92.1%, and raw material availability is high；Aluminum cell current effect Rate is 91.3%；In aluminum chromium production process, electrolysis main technique technical conditions are held essentially constant, and smooth production process connects It is continuous.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (11)

1. a kind of preparation method of aluminum chromium, which is characterized in that prepared with aluminium cell comprising following steps: (1) In the aluminium cell produced, nNaFAlF in the electrolyte of aluminium cell is measured3, n be 2.1~2.9 constant；KF； CaF2；MgF2；LiF；AL2O3Mass percentage content, wherein the nNaFAlF3It is 62~94%；KF is 0.1~8%； CaF2It is 1~8%；MgF2It is 1~8%；LiF is 1~8%；AL2O3Be 2~7%, the mass percentages of the above components it Be 100%；(2) when measured value within the above range when, the oxide of chromium is added, detects and maintains electrolysis process technology item Part: electrolysis temperature is 900~960 DEG C, and average voltage is 3.5~4.3V, obtains aluminum chromium.
2. a kind of preparation method of aluminum chromium according to claim 1, which is characterized in that existed according to the step (2) The oxide of chromium is added in aluminium cell, electrolytic process includes at least one aluminum chromium electrolysing period, wherein one aluminium Evanohm electrolysing period includes: a chromium content rising stage and a chromium content balance period；Wherein the chromium content rising stage is aluminium electricity The mass percentage content of chromium reaches the electrolytic process before setting value in solution slot amount of ram aluminium, the matter of chromium in the stage storage aluminium Amount degree persistently rises；Chromium content balance period reaches for the mass percentage content of chromium in aluminium cell amount of ram aluminium to be set Electrolytic process after definite value, the mass percentage content of chromium remains unchanged in the stage storage aluminium.
3. a kind of preparation method of aluminum chromium according to claim 2, which is characterized in that the chromium in electrolytic process contains The rising stage is measured, adds the oxide of chromium, specific steps include:
According to the content for testing and analyzing chromium in current electrolytic cell amount of ram aluminium, determine that chromium content day promotes rate；Calculate chromium content The day feeding quantity of the oxide of rising stage chromium
The day feeding quantity calculation formula of the oxide of chromium content rising stage chromium is as follows:
Wherein, WIt risesFor the day feeding quantity (kg) of the oxide of chromium content rising stage chromium, QDiskFor the quality of aluminium cell amount of ram aluminium (kg), a1For the actually detected value (%) of the mass percentage content of chromium in same day aluminium cell amount of ram aluminium, a2For second day aluminium Chromium is expected by mass percentage content to be achieved (%), (a in electrolytic cell amount of ram aluminium2-a1) it is chromium content day to promote rate (%), QIt producesFor the day aluminum yield (kg) of aluminium cell, P is the raw material availability (%) of the oxide of chromium, and C is the oxide of chromium Purity (%), m are the mass percentage content (%) of chromium in the oxide of chromium.
4. a kind of preparation method of aluminum chromium according to claim 3, which is characterized in that by percentage to the quality, when When the chromium content of electrolytic cell amount of ram aluminium is less than 1.5%, the chromium content day promotes rate≤0.3%/day；When electrolytic cell memory The chromium content for measuring aluminium is more than or equal to 1.5% and when less than 2.8%, and the chromium content day promotes rate≤0.15%/day.
5. a kind of preparation method of aluminum chromium according to claim 4, which is characterized in that the chromium content rising stage, Oxide feeding quantity≤I/b of unit hour chromium；Wherein, I is potline current (kA), and b is constant satisfaction: b=10kA/kg.
6. a kind of preparation method of aluminum chromium according to claim 3, which is characterized in that the chromium in electrolytic process contains It measures the rising stage, the oxide of chromium adds the time are as follows:
The start time point that the oxide of chromium adds daily is after aluminium cell goes out aluminium.
7. a kind of preparation method of aluminum chromium according to claim 2, which is characterized in that in chromium content balance period, control The chromium content of aluminium cell amount of ram aluminium processed remains unchanged, and specific steps include:
Calculate the daily feeding quantity of the oxide of chromium content balance period chromium
The day feeding quantity calculation formula of the oxide of chromium content balance period chromium is as follows:
Wherein, WIt is flatFor the day feeding quantity (kg) of the oxide of chromium content balance period chromium, QIt producesFor the day aluminum yield (kg) of aluminium cell, aIt is flatFor the mass percentage content (%) of chromium in chromium content balance period aluminium cell amount of ram aluminium, P is the raw material of the oxide of chromium Utilization rate (%), C are the purity (%) of the oxide of chromium, and m is the mass percentage content (%) of chromium in the oxide of chromium.
8. a kind of preparation method of aluminum chromium according to claim 7, which is characterized in that the chromium content balance period, Oxide feeding quantity≤I/b of unit hour chromium；Wherein, I is potline current (kA), and b is constant satisfaction: b=10kA/kg.
9. a kind of preparation method of aluminum chromium according to claim 7, which is characterized in that the chromium in electrolytic process contains Balance period is measured, the oxide of chromium adds the time are as follows:
The start time point that the oxide of chromium adds daily is after aluminium cell goes out aluminium.
10. the preparation method of any a kind of aluminum chromium according to claim 1-9, which is characterized in that the oxide of chromium For CrO2, Cr2O3Any one or two kinds of combinations.
11. the preparation method of any a kind of aluminum chromium according to claim 1-9, which is characterized in that the aluminium electroloysis Slot is prebaked cell for aluminum-reduction.
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