CN108118203A - The method that thermal reduction prepares aluminium cerium intermediate alloy - Google Patents

The method that thermal reduction prepares aluminium cerium intermediate alloy Download PDF

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Publication number
CN108118203A
CN108118203A CN201711464006.4A CN201711464006A CN108118203A CN 108118203 A CN108118203 A CN 108118203A CN 201711464006 A CN201711464006 A CN 201711464006A CN 108118203 A CN108118203 A CN 108118203A
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CN
China
Prior art keywords
cerium
aluminium
intermediate alloy
thermal reduction
chloride
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Pending
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CN201711464006.4A
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Chinese (zh)
Inventor
贾锦玉
吴俊子
胡文鑫
王小青
姜佳鑫
王玮
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Baotou Rare Earth Research Institute
Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd
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Baotou Rare Earth Research Institute
Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd
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Application filed by Baotou Rare Earth Research Institute, Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd filed Critical Baotou Rare Earth Research Institute
Priority to CN201711464006.4A priority Critical patent/CN108118203A/en
Publication of CN108118203A publication Critical patent/CN108118203A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/04Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/026Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys

Abstract

The invention discloses a kind of method that thermal reduction prepares aluminium cerium intermediate alloy, including:It is calculated by the ingredient of aluminium cerium intermediate alloy and weighs aluminium, the oxide or halide of alkali halide and cerium;Aluminium is put into heating and is melted, is proportionally added into the oxide of cerium or halide and alkali halide;In 750~1500 DEG C of 0~200min of heat preservation hot reductase 12;It after the completion for the treatment of thermal reduction reaction, skims, cools to 700~850 DEG C and cast and cool down, obtain aluminium cerium intermediate alloy.The aluminium cerium intermediate alloy that the present invention obtains, Duration Ratio sodium salt degeneration agent of going bad is more permanent and has the shortcomings that better remelting stability, overcome current alterant.

Description

The method that thermal reduction prepares aluminium cerium intermediate alloy
Technical field
The present invention relates to a kind of rare earth aluminium intermediate alloy technologies of preparing, specifically, are related to a kind of thermal reduction and prepare aluminium cerium The method of intermediate alloy.
Background technology
Aluminium and its alloy are current most widely used non-ferrous metal and alloy, in modern industry, space flight, building traffic fortune The fields such as defeated, packing and decorating, daily necessities have become indispensable important materials.The addition of rare earth element causes rare earth Aluminium alloy becomes a kind of function admirable, widely used new material.Therefore the development speed of rare earth aluminium alloy is quite surprising, mesh The annual output of preceding rare earth aluminium alloy has been more than the 1/10 of primary aluminum annual output, from deformation is casted into, from 1 system to 7 systems, from high-precision Guided missile aluminium alloy to common daily aluminum product, from tonne aluminium cable that weighs, aluminium bus array to gently to aluminium foil, it may be said that rare earth is Penetrate into aluminium and aluminium alloy every field.However the extensive developing of aluminium and aluminium alloy application field and grow rapidly in the past 30 years The research and use of alterant are undivided.
Nineteen twenty is it is found that Na has metamorphism, and confirms that Na is most suitably adapted for making the element of alterant, still Significant drawbacks with Na Metamorphism treatments are that effective time is short, and Na is oxidizable, and consumption is fast, easily and crucible reaction, reduce making for crucible With the service life, the cleaning of corrosion product is also extremely difficult and environmental condition is poor.
It thus finds the stronger alterant of new comprehensive performance to be never interrupted, rare earth is that most promising aluminium and its alloy become Matter agent.There are advantageous rare earth resources in China, selects Aluminum and rare-earth industry of the rare earth as alterant for development China There is important realistic meaning.People studied active Sr goes bad since 1977, and the 1980s is by studying rank Section enters the practical stage.Sr modification effects are good, and with long-term effect.However, when individually making alterant with Sr, discovery has air-breathing to incline To, and cost is higher, easily causes shrinkage cavity defect, makes the reduction of alloy consistency, Sr is combined with the oxide constituent phases in melt Can hinder dehydrogenation, and to do not remove be mingled with (oxide) Al melts in plus Sr, casting generates loose.
The content of the invention
Technical problem solved by the invention is to provide a kind of method that thermal reduction prepares aluminium cerium intermediate alloy, obtains Aluminium cerium intermediate alloy goes bad the agent of Duration Ratio sodium salt degeneration more for a long time and with better remelting stability, overcomes current change The shortcomings that matter agent.
Technical solution is as follows:
A kind of method that thermal reduction prepares aluminium cerium intermediate alloy, including:
It is calculated by the ingredient of aluminium cerium intermediate alloy and weighs aluminium, the oxide or halogenation of alkali halide and cerium Object;
Aluminium is put into heating and is melted, is proportionally added into the oxide of cerium or halide and alkali halide;
In 750~1500 DEG C of 0~200min of heat preservation hot reductase 12;
It after the completion for the treatment of thermal reduction reaction, skims, cools to 700~850 DEG C and cast and cool down, obtain aluminium cerium intermediate alloy.
Further:The oxide of cerium selects cerium oxide, and the halide of cerium selects cerium chloride, cerium fluoride, bromination cerium or iodine Change cerium.
Further:Alkali halide selects sodium chloride, potassium chloride, calcium chloride, magnesium chloride, lithium chloride, manganese chloride, fluorination Sodium, potassium fluoride, calcirm-fluoride, magnesium fluoride, lithium fluoride, manganous fluoride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, lithium bromide, bromination Manganese, sodium iodide, potassium iodide, calcium iodide, magnesium iodide, lithium iodide, manganese iodide, cryolite or potassium fluoroaluminate.
Further:The type of cooling is air-cooled or water cooling.
Further:Aluminium selects commercial-purity aluminium or refined aluminium.
Further:Heating furnace selects induction furnace, resistance furnace, gas furnace or electric arc furnaces.
Compared with prior art, the technology of the present invention effect includes:
Gone bad using aluminium cerium intermediate alloy to Al, good modification effect can be obtained when adding in appropriate.Due to dilute Earth elements chemical property is more active, oxidizable, and scaling loss is serious, and the present invention is added in the form of intermediate alloy.Aluminium cerium intermediate alloy makes It is at low cost with simple process, pollution-free, reactionless slag, easily storage, synthesis, Duration Ratio sodium salt degeneration agent of going bad it is more permanent and With better remelting stability, the shortcomings that overcoming current alterant, have broad application prospects.
Specific embodiment
It elaborates below with reference to example embodiment to technical solution of the present invention.However, example embodiment can Implement in a variety of forms, and be not understood as limited to embodiment set forth herein;On the contrary, it theses embodiments are provided so that The design of example embodiment more comprehensively and completely, and is comprehensively communicated to those skilled in the art by the present invention.
The method that thermal reduction prepares aluminium cerium intermediate alloy, including:
Step 1:It is calculated by the ingredient (by weight percentage) of aluminium cerium intermediate alloy and weighs commercial-purity aluminium or refined aluminium, alkali The oxide or halide of metal halide and cerium;
The oxide of cerium is cerium oxide, and the halide of cerium is cerium chloride, cerium fluoride, bromination cerium or cerous iodide.
Alkali halide is sodium chloride, potassium chloride, calcium chloride, magnesium chloride, lithium chloride, manganese chloride, sodium fluoride, fluorination Potassium, calcirm-fluoride, magnesium fluoride, lithium fluoride, manganous fluoride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, lithium bromide, manganous bromide, iodate Sodium, potassium iodide, calcium iodide, magnesium iodide, lithium iodide, manganese iodide, cryolite, potassium fluoroaluminate.
Step 2:Commercial-purity aluminium or refined aluminium are put into induction furnace, resistance furnace, gas furnace or electric arc furnaces and melted, is added in proportion Enter the oxide of cerium or halide and alkali halide;
Step 3:In 750~1500 DEG C of 0~200min of heat preservation hot reductase 12;
Step 4:It after the completion for the treatment of thermal reduction reaction, skims, cools to 700~850 DEG C and cast and cool down, obtain among aluminium cerium Alloy.
The type of cooling is air-cooled or water cooling.
Embodiment 1
(1) calculated by the ingredient (by weight percentage) of aluminium cerium intermediate alloy and weigh commercial-purity aluminium, cerium chloride, chlorination Sodium, potassium chloride, magnesium chloride;
(2) commercial-purity aluminium is put into after being melted in induction furnace, is proportionally added into cerium chloride, sodium chloride, potassium chloride, magnesium chloride To fusing;
(3) in 750 DEG C of heat preservation hot reductase 12 00min;
(4) 700 DEG C of air-cooled, acquisition aluminium cerium intermediate alloys of casting and carry out are cooled to.
Embodiment 2
(1) calculated by the ingredient (by weight percentage) of aluminium cerium intermediate alloy and weigh commercial-purity aluminium, cerium fluoride, fluorination Calcium, lithium fluoride;
(2) commercial-purity aluminium is put into after being melted in resistance furnace, is proportionally added into cerium fluoride, calcirm-fluoride, lithium fluoride to fusing;
(3) in 900 DEG C of heat preservation thermal reduction 180min;
(4) after the completion for the treatment of thermal reduction reaction, skim, cool to 750 DEG C of water coolings of casting and carry out, obtain and closed among aluminium cerium Gold.
Embodiment 3
(1) calculated by the ingredient (by weight percentage) of aluminium cerium intermediate alloy and weigh refined aluminium, bromination cerium, manganous bromide;
(2) refined aluminium is put into after being melted in gas furnace, is proportionally added into bromination cerium, manganous bromide to fusing;
(3) in 1050 DEG C of heat preservation thermal reduction 150min;
(4) after the completion for the treatment of thermal reduction reaction, skim, cool to 800 DEG C of air-cooled, conjunctions among acquisition aluminium cerium of casting and carry out Gold.
Embodiment 4
(1) calculated by the ingredient (by weight percentage) of aluminium cerium intermediate alloy and weigh refined aluminium, cerous iodide and lithium iodide;
(2) refined aluminium is put into after being melted in electric arc furnaces, is proportionally added into cerous iodide and lithium iodide to fusing;
(3) in 1200 DEG C of heat preservation thermal reduction 120min;
(4) after the completion for the treatment of thermal reduction reaction, skim, cool to 850 DEG C of water coolings of casting and carry out, obtain and closed among aluminium cerium Gold.
Embodiment 5
(1) calculated by the ingredient (by weight percentage) of aluminium cerium intermediate alloy and weigh commercial-purity aluminium, cerium oxide, fluorine aluminium Sour sodium, sodium chloride, potassium chloride;
(2) commercial-purity aluminium is put into after being melted in induction furnace, is proportionally added into cerium oxide, cryolite, sodium chloride, chlorination Potassium extremely melts;
(3) in 1350 DEG C of heat preservation thermal reduction 60min;
(4) after the completion for the treatment of thermal reduction reaction, skim, cool to 700 DEG C of air-cooled, conjunctions among acquisition aluminium cerium of casting and carry out Gold.
Embodiment 6
(1) calculated by the ingredient (by weight percentage) of aluminium cerium intermediate alloy and weigh refined aluminium, cerium fluoride, fluoaluminic acid Potassium, magnesium fluoride, lithium fluoride;
(2) refined aluminium is put into after being melted in electric arc furnaces, is proportionally added into cerium fluoride, potassium fluoroaluminate, magnesium fluoride, lithium fluoride extremely Fusing;
(3) in 1500 DEG C of heat preservation hot reductase 12 0min;
(4) after the completion for the treatment of thermal reduction reaction, skim, cool to 700 DEG C of air-cooled, conjunctions among acquisition aluminium cerium of casting and carry out Gold.
Term used herein is explanation and term exemplary, and not restrictive.Since the present invention can be with a variety of Form specific implementation without departing from the spiritual or substantive of invention, it should therefore be appreciated that above-described embodiment be not limited to it is any foregoing Details, and should widely being explained in the spirit and scope that appended claims are limited, thus fall into claim or its etc. Whole variations and remodeling in the range of effect all should be appended claims and covered.

Claims (6)

1. a kind of method that thermal reduction prepares aluminium cerium intermediate alloy, including:
It is calculated by the ingredient of aluminium cerium intermediate alloy and weighs aluminium, the oxide or halide of alkali halide and cerium;
Aluminium is put into heating and is melted, is proportionally added into the oxide of cerium or halide and alkali halide;
In 750~1500 DEG C of 0~200min of heat preservation hot reductase 12;
It after the completion for the treatment of thermal reduction reaction, skims, cools to 700~850 DEG C and cast and cool down, obtain aluminium cerium intermediate alloy.
2. the method that thermal reduction as described in claim 1 prepares aluminium cerium intermediate alloy, it is characterised in that:The oxide of cerium is selected Cerium oxide, the halide of cerium select cerium chloride, cerium fluoride, bromination cerium or cerous iodide.
3. the method that thermal reduction as described in claim 1 prepares aluminium cerium intermediate alloy, it is characterised in that:Alkali halide selects With sodium chloride, potassium chloride, calcium chloride, magnesium chloride, lithium chloride, manganese chloride, sodium fluoride, potassium fluoride, calcirm-fluoride, magnesium fluoride, fluorination Lithium, manganous fluoride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, lithium bromide, manganous bromide, sodium iodide, potassium iodide, calcium iodide, iodate Magnesium, lithium iodide, manganese iodide, cryolite or potassium fluoroaluminate.
4. the method that thermal reduction as described in claim 1 prepares aluminium cerium intermediate alloy, it is characterised in that:The type of cooling is air-cooled Or water cooling.
5. the method that thermal reduction as described in claim 1 prepares aluminium cerium intermediate alloy, it is characterised in that:Aluminium selects technical pure Aluminium or refined aluminium.
6. the method that thermal reduction as described in claim 1 prepares aluminium cerium intermediate alloy, it is characterised in that:Heating furnace selects sensing Stove, resistance furnace, gas furnace or electric arc furnaces.
CN201711464006.4A 2017-12-28 2017-12-28 The method that thermal reduction prepares aluminium cerium intermediate alloy Pending CN108118203A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003171724A (en) * 2001-12-07 2003-06-20 Aomori Prefecture METHOD OF PRODUCING Al-Sc MASTER ALLOY, AND Al-Sc MASTER ALLOY OBTAINED BY THE METHOD
CN1605641A (en) * 2004-11-09 2005-04-13 湖南稀土金属材料研究院 Method for preparation of aluminum scandium alloy by alumino-thermic reduction method
CN102220503A (en) * 2011-05-26 2011-10-19 中国地质科学院矿产综合利用研究所 Method for preparing aluminum-scandium intermediate alloy by calcium thermal reduction method
CN102220502A (en) * 2011-05-26 2011-10-19 中国地质科学院矿产综合利用研究所 Method for preparing aluminum-scandium intermediate alloy by thermal reduction of aluminum-calcium alloy

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003171724A (en) * 2001-12-07 2003-06-20 Aomori Prefecture METHOD OF PRODUCING Al-Sc MASTER ALLOY, AND Al-Sc MASTER ALLOY OBTAINED BY THE METHOD
CN1605641A (en) * 2004-11-09 2005-04-13 湖南稀土金属材料研究院 Method for preparation of aluminum scandium alloy by alumino-thermic reduction method
CN102220503A (en) * 2011-05-26 2011-10-19 中国地质科学院矿产综合利用研究所 Method for preparing aluminum-scandium intermediate alloy by calcium thermal reduction method
CN102220502A (en) * 2011-05-26 2011-10-19 中国地质科学院矿产综合利用研究所 Method for preparing aluminum-scandium intermediate alloy by thermal reduction of aluminum-calcium alloy

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