CN1514044A - Method of producing aluminium zirconium alloy by hydrolysis - Google Patents

Method of producing aluminium zirconium alloy by hydrolysis Download PDF

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Publication number
CN1514044A
CN1514044A CNA031537871A CN03153787A CN1514044A CN 1514044 A CN1514044 A CN 1514044A CN A031537871 A CNA031537871 A CN A031537871A CN 03153787 A CN03153787 A CN 03153787A CN 1514044 A CN1514044 A CN 1514044A
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aluminium
zirconium
weight percent
fluoride
alloy
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CN1236108C (en
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N 杨
杨昇
顾松青
刘凤琴
李强
罗丽芬
赵淋
徐建华
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Aluminum Corp of China Ltd
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Aluminum Corp of China Ltd
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Abstract

A process for preparing Al-Zr alloy by electrolyzing features that the oxides of aluminium and zirconium are used as its raw materials and the fused salt electrolysis is used to educe Al and Zr to obtain Al-Zr alloy. Its advantages are no need of high purity Zr, simple process, high output rate and low cost.

Description

A kind of method of electrolytic production of aluminum zirconium alloy
Technical field
A kind of method of electrolytic production of aluminum zirconium alloy, relating to a kind of oxide compound with aluminium and zirconium is raw material, adopts electrolytic process that aluminium and zirconium electrolysis are simultaneously separated out the formation alloy, the method for direct production aluminium zirconium alloy.
Background technology
At present, the production method of aluminium zirconium alloy is now more to be adopted to melt and joins method, is that employing high pure metal zirconium is cooperated in fusion with aluminium, and this method is not easy to operate, scaling loss is serious, the production process complexity of the easy segregation of alloying constituent and pure metal zirconium, the metal yield is low, involves great expense.Also useful in addition potassium fluozirconate thermit reduction, the used potassium fluozirconate Production Flow Chart of this method is long and the metal yield is low, the cost height, and remain in the performance that fluorochemical in the alloy also has a strong impact on alloy.
Summary of the invention
The objective of the invention is deficiency, provide a kind of and can effectively simplify Production Flow Chart, improve the yield of expensive metal zirconium, the method for the electrolytic production of aluminum zirconium alloy that reduces energy consumption and production costs at above-mentioned prior art.
Method of the present invention is achieved through the following technical solutions.
A kind of method of electrolytic production of aluminum zirconium alloy, it is characterized in that the oxide compound with aluminium and zirconium is a raw material, adopt fused salt electrolysis process that aluminium and zirconium electrolysis are separated out the formation alloy, processing condition are: the weight percent composition of control ionogen molten cryolitic system is: aluminium oxide Al 2O 3: 1%-10%; Zirconium white ZrO 2: 0.1%-2%, all the other are sodium aluminum fluoride nNaFAlF 3And unavoidable impurities, and Sodium Fluoride NaF and aluminum fluoride AlF 3Ratio be: 2-3; Electrolysis temperature: 900 ℃-990 ℃; Electric tank working voltage: 3.0V-6.5V; Electrode distance: 2.0cm-7.0cm; Contain zirconium white ZrO in the raw material that adds in the continuous electrolysis process 2: 0.1%-3%, surplus is an aluminium oxide Al 2O 3And unavoidable impurities, wherein igloss＜1%, ferric oxide Fe 2O 3＜0.2%, silicon oxide sio 2＜0.2%, other impurity summation＜0.2%.
A kind of method of electrolytic production of aluminum zirconium alloy is characterized in that containing in the weight percent composition of ionogen molten cryolitic system the lithium fluoride LiF less than 25%.
A kind of method of electrolytic production of aluminum zirconium alloy is characterized in that containing in the weight percent composition of ionogen molten cryolitic system the Calcium Fluoride (Fluorspan) CaF2 less than 10%.
A kind of method of electrolytic production of aluminum zirconium alloy is characterized in that containing in the weight percent composition of ionogen molten cryolitic system the fluorine magnesium fluoride MgF2 less than 10%.
The weight percent chemical constitution of the aluminium zirconium alloy of producing with method of the present invention is: zirconium: 0.1%-3%, all the other are aluminium and unavoidable impurities, wherein iron Fe＜0.5%, silicon Si＜0.5%, other impurity summation＜0.5%.
The present invention adopts electrolytic method, adds the oxide compound of zirconium in existing aluminium electrolysis process, by electrolysis aluminium and zirconium is separated out jointly, obtains the aluminium zirconium alloy.This method need not to use the high pure metal zirconium, and technical process shortens greatly than traditional method, metal yield height, thus can reduce the cost of producing the aluminium zirconium alloy significantly, help applying of aluminium zirconium alloy.
Embodiment
A kind of method of electrolytic production of aluminum zirconium alloy is a raw material with the oxide compound of aluminium and zirconium, adopts fused salt electrolysis process that aluminium and zirconium electrolysis are separated out the formation alloy, and processing condition are: the weight percent composition of control ionogen molten cryolitic system is an aluminium oxide Al 2O 3: 1%-10%; Zirconium white ZrO 2: 0.1%-2%, all the other are sodium aluminum fluoride nNaFAlF 3And unavoidable impurities, and Sodium Fluoride NaF and aluminum fluoride AlF 3Ratio be 2-3; Electrolysis temperature: 900 ℃-990 ℃; Electric tank working voltage: 3.0V-6.5V; Electrode distance: 2.0cm-7.0cm.Contain zirconium white ZrO in the raw material that adds in the continuous electrolysis process 2: 0.1%-3%, surplus is an aluminium oxide Al 2O 3And unavoidable impurities, wherein igloss＜1%, ferric oxide Fe 2O 3＜0.2%, silicon oxide sio 2＜0.2%, other impurity summation＜0.2%.The weight percent chemical constitution of the aluminium zirconium alloy of producing with method of the present invention is: zirconium: 0.1%-3%, all the other are aluminium and unavoidable impurities, wherein iron Fe＜0.5%, silicon Si＜0.5%, other impurity summation＜0.5%.
Embodiment 1
The weight percent composition of control ionogen molten cryolitic system is Calcium Fluoride (Fluorspan) CaF 2: 2%, magnesium fluoride MgF 2: 4%, aluminium oxide Al 2O 3: 7%, zirconium white ZrO 2: 1%, surplus is a sodium aluminum fluoride; Electrolysis temperature is 950 ℃; Electric tank working voltage is 4.0V; Electrode distance is 4.0cm; The sodium aluminum fluoride molecular ratio is 2.4.The weight percent that adds the electrolysis raw material during electrolysis continuously consists of: zirconium white ZrO 2: 1.5%, other is an aluminium oxide Al 2O 3And unavoidable impurities, wherein: igloss＜1%, ferric oxide Fe 2O 3＜0.2%, silicon oxide sio 2＜0.2%, other impurity summation＜0.2%.
The weight percent chemical constitution of the aluminium zirconium alloy of producing is: zirconium 1.5%, all the other are aluminium and unavoidable impurities, wherein iron Fe＜0.15%, silicon Si＜0.12%, other impurity trace.
Embodiment 2
The weight percent composition of control ionogen molten cryolitic system is an aluminium oxide Al 2O 3: 1.5%, zirconium white ZrO 2: 2%, surplus is a sodium aluminum fluoride: electrolysis temperature is 980 ℃, and electric tank working voltage is 6.5V, and electrode distance is 6.0cm; The sodium aluminum fluoride molecular ratio is 3.The weight percent that adds the electrolysis raw material during electrolysis continuously consists of: zirconium white ZrO 23%, other is an aluminium oxide Al 2O 3And unavoidable impurities, wherein igloss＜1%, ferric oxide Fe 2O 3＜0.2%, silicon oxide sio 2＜0.2%, other impurity summation＜0.2%.
The weight percent chemical constitution of the aluminium zirconium alloy of producing is: zirconium 3%, all the other are aluminium and unavoidable impurities, wherein: iron Fe＜0.15%, silicon Si＜0.12%, other impurity trace.
Embodiment 3
The weight percent composition of control ionogen molten cryolitic system is an aluminium oxide Al 2O 3: 9%, zirconium white ZrO 2: 0.5%, lithium fluoride 5%, surplus is a sodium aluminum fluoride: electrolysis temperature is 930 ℃, and electric tank working voltage is 3.0V, and electrode distance is 2.5cm; The sodium aluminum fluoride molecular ratio is 2.6.The weight percent that adds the electrolysis raw material during electrolysis continuously consists of: zirconium white ZrO 20.1%, other is an aluminium oxide Al 2O 3And unavoidable impurities, wherein igloss＜1%, ferric oxide Fe 2O 3＜0.2%, silicon oxide sio 2＜0.2%, other impurity summation＜0.2%.
The weight percent chemical constitution of the aluminium zirconium alloy of producing is: zirconium 0.1%, all the other are aluminium and unavoidable impurities, wherein: iron Fe＜0.15%, silicon Si＜0.12%, other impurity trace.
Embodiment 4
The weight percent composition of control ionogen molten cryolitic system is an aluminium oxide Al 2O 3: 1.5%, zirconium white ZrO 2: 0.5%, lithium fluoride 22% surplus is a sodium aluminum fluoride: electrolysis temperature is 900 ℃, and electric tank working voltage is 4.0V, and electrode distance is 7.0cm; The sodium aluminum fluoride molecular ratio is 2.1.The weight percent that adds the electrolysis raw material during electrolysis continuously consists of: zirconium white ZrO 20.5%, other is an aluminium oxide Al 2O 3And unavoidable impurities, wherein igloss＜1%, ferric oxide Fe 2O 3＜0.2%, silicon oxide sio 2＜0.2%, other impurity summation＜0.2%.
The weight percent chemical constitution of the aluminium zirconium alloy of producing is: zirconium 0.5%, all the other are aluminium and unavoidable impurities, wherein: iron Fe＜0.15%, silicon Si＜0.12%, other impurity trace.
Embodiment 5
The weight percent composition of control ionogen molten cryolitic system is an aluminium oxide Al 2O 3: 1.5%, zirconium white ZrO 2: 1%, magnesium fluoride 8% surplus is a sodium aluminum fluoride: electrolysis temperature is 960 ℃, and electric tank working voltage is 4.0V, and electrode distance is 4.0cm; The sodium aluminum fluoride molecular ratio is 2.6.The weight percent that adds the electrolysis raw material during electrolysis continuously consists of: zirconium white ZrO 22%, other is an aluminium oxide Al 2O 3And unavoidable impurities, wherein igloss＜1%, ferric oxide Fe 2O 3＜0.2%, silicon oxide sio 2＜0.2%, other impurity summation＜0.2%.
The weight percent chemical constitution of the aluminium zirconium alloy of producing is: zirconium 2%, all the other are aluminium and unavoidable impurities, wherein: iron Fe＜0.15%, silicon Si＜0.12%, other impurity trace.
Embodiment 6
The weight percent composition of control ionogen molten cryolitic system is an aluminium oxide Al 2O 3: 1.5%, zirconium white ZrO 2: 2%, Calcium Fluoride (Fluorspan) 9%, surplus is a sodium aluminum fluoride: electrolysis temperature is 970 ℃, and electric tank working voltage is 4.5V, and electrode distance is 3.5cm; The sodium aluminum fluoride molecular ratio is 2.6.The weight percent that adds the electrolysis raw material during electrolysis continuously consists of: zirconium white ZrO 21.5%, other is an aluminium oxide Al 2O 3And unavoidable impurities, wherein igloss＜1%, ferric oxide Fe 2O 3＜0.2%, silicon oxide sio 2＜0.2%, other impurity summation＜0.2%.
The weight percent chemical constitution of the aluminium zirconium alloy of producing is: zirconium 1.5%, all the other are aluminium and unavoidable impurities, wherein: iron Fe＜0.15%, silicon Si＜0.12%, other impurity trace.
Embodiment 7
The weight percent composition of control ionogen molten cryolitic system is an aluminium oxide Al 2O 3: 2.0%, zirconium white ZrO 2: 2%, magnesium fluoride 1%, Calcium Fluoride (Fluorspan) 2%, surplus is a sodium aluminum fluoride: electrolysis temperature is 950 ℃, and electric tank working voltage is 4.3V, and electrode distance is 4.0cm; The sodium aluminum fluoride molecular ratio is 2.4.The weight percent that adds the electrolysis raw material during electrolysis continuously consists of: zirconium white ZrO 21.5%, other is an aluminium oxide Al 2O 3And unavoidable impurities, wherein igloss＜1%, ferric oxide Fe 2O 3＜0.2%, silicon oxide sio 2＜0.2%, other impurity summation＜0.2%.
The weight percent chemical constitution of the aluminium zirconium alloy of producing is: zirconium 1.5%, all the other are aluminium and unavoidable impurities, wherein: iron Fe＜0.15%, silicon Si＜0.12%, other impurity trace.

Claims (5)

1. the method for an electrolytic production of aluminum zirconium alloy, it is characterized in that the oxide compound with aluminium and zirconium is a raw material, adopt fused salt electrolysis process that aluminium and zirconium electrolysis are separated out the formation alloy, processing condition are: the weight percent composition of control ionogen molten cryolitic system is: aluminium oxide Al 2O 3: 1%-10%; Zirconium white ZrO 2: 0.1%-2%, all the other are sodium aluminum fluoride nNaFAlF 3And unavoidable impurities, and Sodium Fluoride NaF and aluminum fluoride AlF 3Ratio be: 2-3; Electrolysis temperature: 900 ℃-990 ℃; Electric tank working voltage: 3.0V-6.5V; Electrode distance: 2.0cm-7.0cm; Contain zirconium white ZrO in the raw material that adds in the continuous electrolysis process 2: 0.1%-3%, surplus is an aluminium oxide Al 2O 3And unavoidable impurities, wherein igloss＜1%, ferric oxide Fe 2O 3＜0.2%, silicon oxide sio 2＜0.2%, other impurity summation＜0.2%.
2. according to the method for the described a kind of electrolytic production of aluminum zirconium alloy of claim 1, it is characterized in that containing in the weight percent composition of ionogen molten cryolitic system lithium fluoride LiF less than 25%.
3. according to the method for the described a kind of electrolytic production of aluminum zirconium alloy of claim 1, it is characterized in that containing in the weight percent composition of ionogen molten cryolitic system Calcium Fluoride (Fluorspan) CaF2 less than 10%.
4. according to the method for the described a kind of electrolytic production of aluminum zirconium alloy of claim 1, it is characterized in that containing in the weight percent composition of ionogen molten cryolitic system fluorine magnesium fluoride MgF2 less than 10%.
5. according to the method for the described a kind of electrolytic production of aluminum zirconium alloy of claim 1, the weight percent chemical constitution that it is characterized in that the aluminium zirconium alloy produced is: zirconium: 0.1%-3%, all the other are aluminium and unavoidable impurities, wherein iron Fe＜0.5%, silicon Si＜0.5%, other impurity summation＜0.5%.
CN 03153787 2003-08-21 2003-08-21 Method of producing aluminium zirconium alloy by hydrolysis Expired - Lifetime CN1236108C (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100415941C (en) * 2005-10-13 2008-09-03 郑州大学 Preparation method of multicomponent microalloying aluminium alloy containing titanium, zirconium and scandium
CN101967573A (en) * 2010-11-15 2011-02-09 湖南金联星冶金材料技术有限公司 Method for manufacturing aluminum zirconium intermediate alloy by alloying zirconium crumbs and aluminum at low temperature
CN102634821A (en) * 2012-05-15 2012-08-15 山东滨州渤海活塞股份有限公司 Electrolytic production process of aluminum-zirconium-titanium alloy
CN103741171A (en) * 2014-01-24 2014-04-23 东北大学 Method for producing aluminum zirconium alloy by aluminum liquid-molten salt method
CN105132953A (en) * 2015-07-24 2015-12-09 中国原子能科学研究院 Spent fuel dry reprocessing method for directly obtaining zirconium alloy fuel
CN105154725A (en) * 2015-09-28 2015-12-16 河北四通新型金属材料股份有限公司 High-end Al-Zr intermediate alloy and industrial preparation method
CN109055997A (en) * 2018-10-09 2018-12-21 东北大学 Fused salt electrolysis process prepares ultra-fine Al3The method of Zr intermetallic compound particle
CN109267108A (en) * 2018-11-30 2019-01-25 包头铝业有限公司 A kind of preparation method of aluminum chromium
CN110820017A (en) * 2019-12-10 2020-02-21 中南大学 Preparation method of aluminum-manganese alloy
CN114196841A (en) * 2022-01-05 2022-03-18 东北大学 Molten salt system for promoting zircon sand decomposition and method for decomposing zircon sand

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100415941C (en) * 2005-10-13 2008-09-03 郑州大学 Preparation method of multicomponent microalloying aluminium alloy containing titanium, zirconium and scandium
CN101967573A (en) * 2010-11-15 2011-02-09 湖南金联星冶金材料技术有限公司 Method for manufacturing aluminum zirconium intermediate alloy by alloying zirconium crumbs and aluminum at low temperature
CN102634821A (en) * 2012-05-15 2012-08-15 山东滨州渤海活塞股份有限公司 Electrolytic production process of aluminum-zirconium-titanium alloy
CN102634821B (en) * 2012-05-15 2014-12-24 山东滨州渤海活塞股份有限公司 Electrolytic production process of aluminum-zirconium-titanium alloy
CN103741171B (en) * 2014-01-24 2016-01-20 东北大学 A kind of aluminium liquid-molten-salt growth method produces the method for aluminium zirconium alloy
CN103741171A (en) * 2014-01-24 2014-04-23 东北大学 Method for producing aluminum zirconium alloy by aluminum liquid-molten salt method
CN105132953A (en) * 2015-07-24 2015-12-09 中国原子能科学研究院 Spent fuel dry reprocessing method for directly obtaining zirconium alloy fuel
CN105154725B (en) * 2015-09-28 2017-03-22 河北四通新型金属材料股份有限公司 High-end Al-Zr intermediate alloy and industrial preparation method
CN105154725A (en) * 2015-09-28 2015-12-16 河北四通新型金属材料股份有限公司 High-end Al-Zr intermediate alloy and industrial preparation method
CN109055997A (en) * 2018-10-09 2018-12-21 东北大学 Fused salt electrolysis process prepares ultra-fine Al3The method of Zr intermetallic compound particle
CN109055997B (en) * 2018-10-09 2020-01-10 东北大学 Preparation of superfine Al by fused salt electrolysis method3Method for producing Zr intermetallic compound particles
CN109267108A (en) * 2018-11-30 2019-01-25 包头铝业有限公司 A kind of preparation method of aluminum chromium
CN109267108B (en) * 2018-11-30 2021-02-26 包头铝业有限公司 Preparation method of aluminum-chromium alloy
CN110820017A (en) * 2019-12-10 2020-02-21 中南大学 Preparation method of aluminum-manganese alloy
CN110820017B (en) * 2019-12-10 2020-11-20 中南大学 Preparation method of aluminum-manganese alloy
CN114196841A (en) * 2022-01-05 2022-03-18 东北大学 Molten salt system for promoting zircon sand decomposition and method for decomposing zircon sand
CN114196841B (en) * 2022-01-05 2023-03-10 东北大学 Molten salt system for promoting zircon sand decomposition and method for decomposing zircon sand

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