CN101709488B - Method for producing aluminum manganese alloy through direct electrolysis of manganese oxide containing carbon anode - Google Patents

Method for producing aluminum manganese alloy through direct electrolysis of manganese oxide containing carbon anode Download PDF

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CN101709488B
CN101709488B CN2009102194157A CN200910219415A CN101709488B CN 101709488 B CN101709488 B CN 101709488B CN 2009102194157 A CN2009102194157 A CN 2009102194157A CN 200910219415 A CN200910219415 A CN 200910219415A CN 101709488 B CN101709488 B CN 101709488B
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manganese oxide
carbon anode
manganese
oxide containing
electrolysis
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CN101709488A (en
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崔雅茹
马绍良
李小明
刘环
李凯茂
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Xian University of Architecture and Technology
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Abstract

The invention provides a method for producing an aluminum manganese alloy through direct electrolysis of a manganese oxide containing carbon anode. The method comprises the following steps: mixing sintered petroleum coke, coal tar pitch and manganese oxide powder in percentage by weight; heating and kneading the mixed material in a kneading pot to prepare paste; processing the obtained paste into a manganese oxide containing prebaked carbon anode raw block with a required specification; baking the obtained manganese oxide containing prebaked carbon anode raw block according to a conventional process for baking the prebaked carbon anode raw block into a qualified manganese oxide containing carbon anode baked block; assembling the obtained qualified manganese oxide containing carbon anode baked block; and finally mounting the assembled manganese oxide containing carbon anode baked block on an aluminium cell, and producing the aluminum manganese alloy through the direct electrolysis. The method solves the technical problems of easy loss of metal and high energy consumption in the electrolysis process of the conventional electrolysis method, and has the advantages of energy saving, low cost and the like.

Description

A kind of method with producing aluminum manganese alloy through direct electrolysis of manganese oxide containing carbon anode
Technical field
The present invention relates to look metallurgical technical field of aluminum electrolysis, be specifically related to a kind of method with producing aluminum manganese alloy through direct electrolysis of manganese oxide containing carbon anode.
Background technology
The industrial aluminum electrolysis production generally is under 920-970 ℃, adopts sodium aluminum fluoride (Na 3AlF 6) be solvent and AlF 3, MgF 2, CaF 2Etc. the electrolyte system of multiple additives, realize through dissolving and electrolytic oxidation aluminium powder.
Produce aluminium intermediate alloy, extensively adopt the method for mixing, promptly produce through the method that directly in molten aluminum, adds alloying element, this method is prone to cause the scaling loss of metal, and wherein the damage of aluminium is for losing 5-10 ‰, and the loss of the alloying element of interpolation is up to 25%; And produced higher energy expenditure.In addition, the alloy of this method preparation exists grain fineness number bigger, and alloying element is prone to defectives such as segregation.
Manganese (Mn) is a kind of transition metal, silvery white metal, and matter is hard and crisp, and chemical property is more active.Manganese element has 25 electronics, and electronics is arranged as 1S 22S 22P 63S 23P 63D 54S 2Its density is 7.20 gram/cubic centimetres; Fusing point is 1244 ℃; Boiling point is 2097 ℃; Valency is+2 ,+3 ,+4 ,+6 and+7.Wherein with+2 (Mn 2+Compound) ,+4 (Manganse Dioxide is natural mineral) and+7 (permanganate is like KMnO 4) ,+6 (manganate is like K 2MnO 4) be stable oxidation state.It exists with four kinds of allotropic substances when solid, that is: α manganese (body-centered cubic), β manganese (cubes), γ manganese (F.C.C.), δ manganese (body-centered cubic).Ionization energy is 7.435 electron-volts.In air, be prone to oxidation, generate the oxide cover layer of brown; Also be prone to oxidation when heating up.When oxidation, form stratiform oxidation scale, the zone of oxidation near metal is MnO, and skin is Mn 3O 4During oxidation, the thickness of MnO increases gradually under being higher than 800 ℃ temperature, and Mn 3O 4The thickness of layer reduces.The third zone of oxidation Mn appears below 800 degree 2O 2At about outmost the 4th layer of oxide M nO below 450 ℃ 2Be stable.The ability water of decomposition is soluble in diluted acid, and has hydrogen to emit, and generates divalent manganesetion.Manganese is the crystal grain of refinement alloy consumingly, can significantly improve the recrystallization temperature of alloy, and strongly inhibited improves the intensity of alloy along brilliant fracture tendency, plasticity and fracture toughness property, so alumal has purposes widely.Because this type alloy can not be heat-treated reinforcement, Main Feature is to have good corrosion resistance, thereby the rust-preventing aluminum alloy of gaining the name.Corrosion-resisting aluminium manganese alloy commonly used is the LF21 alloy, contains manganese 1.0-1.6%, and microstructure is the MnAl that manganiferous αGu Rongti and disperse distribute 6Particle has higher intensity and good plasticity.LF21 alloy solidity to corrosion with fine aluminium in atmosphere and seawater is suitable, and the favorable manufacturability ability is arranged, and in aircraft industry, is used to bear deep-draw processing and stressed little part, like parts such as fuel tank, grease conduits, rivets, and building slab.
Manganese is again the high transition metal of chemically reactive, fusing point higher (1224 ℃ ± 3 ℃), and the fusing point of aluminium very low (660 ℃), and this brings very big difficulty for melting and manufacturing alumal.And manganese metal costs an arm and a leg, and adopts the direct manganese metal that adds to produce to the method in the molten aluminum, and energy consumption is high, and raw materials cost is high, and the alloy grain degree that obtains is bigger, is easy to generate component segregation, and alloy strength is lower.Therefore become the research focus with electrolytic process direct production alumal.
The patent No. is the method for manufacture that direct electrolysis production rare-earth-Al-Mn alloy contains the multicomponent microalloying aluminium alloy of rare earth, manganese, aluminium for " ZL96100980.2 " disclosed technical scheme; And be raw material with the oxide compound of rare earth and manganese; The method of direct production aluminium rare earth manganese alloy, it mainly adopts electrolytic process that rare earth and manganese electrolysis are simultaneously separated out the formation alloy.But this kind method loses manganese oxide in electrolytic process easily, thereby causes the recovery lower.
Summary of the invention
In order to solve existing easy loss, the energy expenditure big technical problem that make metal of electrolysis process in electrolytic process, the present invention provides a kind of method with producing aluminum manganese alloy through direct electrolysis of manganese oxide containing carbon anode.
Technical scheme of the present invention is following:
Steps A: with after-smithing petroleum coke, coal-tar pitch, and the oxidation manganese powder is prepared burden by weight percentage;
Step B: the batching that steps A is configured is placed on to mix and pinches in the pot heating and mix and pinch, and after mixed pinching, processes thickener;
Step C: the manganese oxide pre-baking carbon anode block that the thickener of step B acquisition is processed into required specification;
Step D: the manganese oxide pre-baking carbon anode block that step C is obtained carries out roasting according to the processing condition of conventional roasting pre-baking carbon anode block, forms ripe of qualified manganese oxide pre-baked carbon anode;
Step e: step D is obtained ripe qualified of manganese oxide pre-baked carbon anode assemble;
Step F: ripe of the manganese oxide pre-baked carbon anode that step e is assembled is installed on the aluminium cell, again through directly carrying out producing alumal after the electrolysis.
Batching mixture ratio by weight percent in the said steps A is: after-smithing petroleum coke 70-82%, coal-tar pitch 15-28%, oxidation manganese powder≤10%.
Pinch to mixing that the after-smithing petroleum coke thickener must be made as pasty state 80-200 ℃ of mixed down 20-100 minute of pinching with manganese oxide powder and coal pitch of agglomerant mixture in the pot among the said step B, again thickener to be processed into the manganese oxide pre-baking carbon anode block of required specification.
Among the said step D, to the manganese oxide pre-baking carbon anode block roasting be 900 ℃-1350 ℃ roasting temperature 600-800 hour.
Roasting becomes ripe qualified of manganese oxide pre-baked carbon anode to produce the pre-baked anode block that satisfies containing of different needs of different manganese oxide content according to the ratio of producing the required adjustment manganese oxide of alumal among the said step D.
Aluminium cell in the said step F is for being electrolytical aluminium cell with sodium cryolite.
Said alumal is to adopt steps A-step F direct production to form with the aluminium liquid that contains manganese.
The raw material of said alumal is manganese oxide or manganous fluoride or Manganous chloride tetrahydrate;
The ratio of said adjustment manganese oxide can not surpass the ratio upper limit.
The method with producing aluminum manganese alloy through direct electrolysis of manganese oxide containing carbon anode of embodiment of the present invention has following beneficial effect:
1. only utilize the electrolyzer of fine aluminium; Under the prerequisite that not increase equipment drops into basically, adopt the electrolysis process and the parameter of fine aluminium, through the MOX of in aluminium cell, correcting than aluminium deposition potential; And do not influence under the prerequisite of main electrolysis index; The direct aluminium base master alloy of electrolysis production, thus energy consumption reduced, also reduce its cost by a relatively large margin.
2. to satisfy the Gibbs free energy of thermite reduction reaction be negative value to the fused salt electrolysis duraluminum, deposition potential less than or approach the aluminium deposition potential and all can carry out electrolysis and produce duraluminum.Producing metal and master alloy through direct electrolysis method, to have a Production Flow Chart short, the characteristic that cost and comprehensive energy consumption are lower.
3. manganese oxide is added in the carbon anode, the anode physical and chemical index is constant basically, and the recovery of manganese improves.
4. the alumal with direct electrolysis of manganese oxide containing carbon anode production has the purity height, advantages such as performance is more superior than the alloy that mix-melting method is produced, more refinement of crystal grain, component segregation is little and alloying element and aluminium consistency be good.
Embodiment:
The present invention's one specific embodiment, realize through following steps with the method for producing aluminum manganese alloy through direct electrolysis of manganese oxide containing carbon anode:
At first after-smithing petroleum coke, coal-tar pitch and oxidation manganese powder are prepared burden by weight percentage; Wherein, after-smithing petroleum coke 70-82%, coal-tar pitch 15-28%, oxidation manganese powder≤10%, for guaranteeing anode quality conformance with standard, strictness is controlled to partition ratio.Batching is placed on mixed pinching in the pot was made as thickener in 20-100 minute 80-200 ℃ of mixed down pinching; Mixing and pinching pot interior after-smithing petroleum coke thickener and manganese oxide powder and coal pitch of agglomerant blended Heating temperature is optimum temps with 120 ℃-160 ℃, is Best Times with 30-50 minute.
Secondly thickener is processed into the manganese oxide pre-baking carbon anode block of required specification.
Then according to the processing condition of conventional roasting pre-baking carbon anode block 900 ℃-1350 ℃ roasting temperature 600-800 hour, 680 hours be the best with 1250 ℃ of temperature roastings.It is ripe of qualified manganese oxide pre-baked carbon anode that roasting becomes by quality standard YS/T285-2007; Also can be according to the ratio of producing the required adjustment manganese oxide of alumal; Maximum ratio can be 8-10%; But this ratio can not surpass the ratio upper limit, produces the pre-baked anode block that different needs contains different manganese oxide content.
Be on the electrolytical aluminium cell with ripe of qualified manganese oxide pre-baked carbon anode according to being installed in sodium cryolite after the assembling of electrolysis of aluminum industry internal standard at last, (and being not other aluminium cells), thus directly carry out producing alumal after the electrolysis.Alumal is to form with the aluminium liquid direct production that contains manganese.The raw material of this alumal can be manganese oxide, manganous fluoride, Manganous chloride tetrahydrate, but is mainly manganese oxide.
Wherein ripe of qualified manganese oxide pre-baked carbon anode being carried out electrolytic technical qualification is:
Electrolysis temperature 900-990 ℃; Molecular ratio 2.0-2.8; Alumina concentration 1.5-5.0%; Manganese oxide concentration 0-5%; Bath voltage 3.8-5.0V; Pole span 3.0-5.0 centimetre; Calcium Fluoride (Fluorspan) 0-6%; Sellaite 0-6%; Lithium fluoride 0-6%.
Wherein ripe physical and chemical index of manganese oxide pre-baked carbon anode is:
Figure GSB00000439776100041
Embodiment 1
1. by ingredients by weight per-cent be: after-smithing petroleum coke 82%, coal-tar pitch 17%, oxidation manganese powder 1%; Go up the groove test after being mixed and made into pre-baked anode block; The pre-baked anode block physical and chemical index is:
Ash % 0.4 resistivity Ω mm/m 55
Compressive strength N/mm 232 volume density g/cm 31.55
Void content %＜26 true density g/cm 32.05
2. electrolysis technology condition is:
Electrolysis temperature 950-960 ℃ of molecular ratio 2.35-2.45 alumina concentration 1.5-3.5%
4.7 centimetres of bath voltage 4.155V pole spans
Calcium Fluoride (Fluorspan) 4-5% Sellaite 2-3% lithium fluoride 1.5-2%
The chemical constitution of the alumal of 3. producing is (weight percent): manganese 0.22%; All the other are aluminium and unavoidable impurities, iron Fe＜0.095% wherein, silicon Si＜0.082%, other impurity trace.The recovery 80.3% of manganese.
Embodiment 2
1. by ingredients by weight per-cent be: after-smithing petroleum coke 80%, coal-tar pitch 17%, oxidation manganese powder 3%; Go up the groove test after being mixed and made into pre-baked anode block; The pre-baked anode block physical and chemical index is:
Ash % 0.5 resistivity Ω mm/m 56
Compressive strength N/mm 231 volume density g/cm 31.56
Void content %＜26 true density g/cm 32.06
2. electrolysis technology condition is:
Electrolysis temperature 950-960 ℃ of molecular ratio 2.40-2.50 alumina concentration 1.5-3.5%
4.7 centimetres of bath voltage 4.165 pole spans
Calcium Fluoride (Fluorspan) 4-5% Sellaite 2-3% lithium fluoride 1.5-2%
The chemical constitution of the alumal of 3. producing be (weight percent): all the other are aluminium and unavoidable impurities for manganese 0.61%, iron Fe＜0.095% wherein, and Si＜0.082%, other impurity is micro-.The recovery 74.2% of manganese.
Embodiment 3
1. by ingredients by weight per-cent be: after-smithing petroleum coke 78%, coal-tar pitch 17%, oxidation manganese powder 5%; Go up the groove test after being mixed and made into pre-baked anode block; The pre-baked anode block physical and chemical index is:
Ash % 1.0 resistivity Ω mm/m 60
Compressive strength N/mm 230 volume density g/cm 31.57
Void content %＜26 true density g/cm 32.07
2. electrolysis technology condition is:
Electrolysis temperature 950-960 ℃ of molecular ratio 2.45-2.55 alumina concentration 1.5-3.5%
4.7 centimetres of bath voltage 4.175 pole spans
Calcium Fluoride (Fluorspan) 4-5% Sellaite 2-3% lithium fluoride 1.5-2%
The chemical constitution of the alumal of 3. producing be (weight percent): manganese 1.01%, and all the other are aluminium and unavoidable impurities, iron Fe＜0.095% wherein, Si＜0.082%, other impurity is micro-.The recovery 73.7% of manganese.
Embodiment 4
1. by ingredients by weight per-cent be: after-smithing petroleum coke 76%, coal-tar pitch 16%, oxidation manganese powder 8%; Go up the groove test after being mixed and made into pre-baked anode block; The pre-baked anode block physical and chemical index is:
Ash % 0.6 resistivity Ω mm/m 59
Compressive strength N/mm 231 volume density g/cm 31.54
Void content %＜26 true density g/cm 32.03
2. electrolysis technology condition is:
Electrolysis temperature 950-970 ℃ of molecular ratio 2.35-2.55 alumina concentration 1.5-3.5%
4.8 centimetres of bath voltage 4.195V pole spans
Calcium Fluoride (Fluorspan) 4-5% Sellaite 2-3% lithium fluoride 1.5-2%
The chemical constitution of the alumal of 3. producing is (weight percent):
Manganese 1.57%, all the other are aluminium and unavoidable impurities, iron Fe＜0.095% wherein, other impurity trace of silicon Si＜0.082%.The recovery of manganese is 71.9%.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area need not creative work and just can design according to the present invention make many modifications and variation.Therefore, all technician in the art all should be in claim protection domain of the present invention under this invention's idea on the basis of existing technology through the available technical scheme of logical analysis, reasoning, or a limited experiment.

Claims (5)

1. method with producing aluminum manganese alloy through direct electrolysis of manganese oxide containing carbon anode, it is characterized in that: said method may further comprise the steps at least:
Steps A: with after-smithing petroleum coke, coal-tar pitch, and the oxidation manganese powder is prepared burden by weight percentage;
Step B: the batching that steps A is configured is placed on to mix and pinches in the pot heating and mix and pinch, and after mixed pinching, processes thickener;
Step C: the manganese oxide pre-baking carbon anode block that the thickener of step B acquisition is processed into required specification;
Step D: the manganese oxide pre-baking carbon anode block that step C is obtained carries out roasting according to the processing condition of conventional roasting pre-baking carbon anode block, forms ripe of qualified manganese oxide pre-baked carbon anode;
Step e: step D is obtained ripe qualified of manganese oxide pre-baked carbon anode assemble;
Step F: ripe of the manganese oxide pre-baked carbon anode that step e is assembled is installed on the aluminium cell, again through directly carrying out producing alumal after the electrolysis;
Batching mixture ratio by weight percent in the said steps A is: after-smithing petroleum coke 70-82%, coal-tar pitch 15-28%, oxidation manganese powder≤10%.
2. preparation method according to claim 1; It is characterized in that: pinch to mixing that the after-smithing petroleum coke thickener must be made as pasty state in 20-100 minute 80-200 ℃ of mixed down pinching with manganese oxide powder and coal pitch of agglomerant mixture in the pot among the said step B, again thickener to be processed into the manganese oxide pre-baking carbon anode block of required specification.
3. the method with producing aluminum manganese alloy through direct electrolysis of manganese oxide containing carbon anode according to claim 2 is characterized in that: among the said step D, to the manganese oxide pre-baking carbon anode block roasting be 900 ℃-1350 ℃ roasting temperature 600-800 hour.
4. the method with producing aluminum manganese alloy through direct electrolysis of manganese oxide containing carbon anode according to claim 3 is characterized in that: to become ripe qualified of manganese oxide pre-baked carbon anode be to produce the pre-baked anode block that satisfies containing of different needs of different manganese oxide content according to the ratio of producing the required adjustment manganese oxide of alumal in roasting among the said step D.
5. the method with producing aluminum manganese alloy through direct electrolysis of manganese oxide containing carbon anode according to claim 4 is characterized in that: the aluminium cell in the said step F is for being electrolytical aluminium cell with sodium cryolite.
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