WO2014015596A1 - 一种生产铝锆硼合金并同步产生冰晶石的方法 - Google Patents

一种生产铝锆硼合金并同步产生冰晶石的方法 Download PDF

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WO2014015596A1
WO2014015596A1 PCT/CN2012/085285 CN2012085285W WO2014015596A1 WO 2014015596 A1 WO2014015596 A1 WO 2014015596A1 CN 2012085285 W CN2012085285 W CN 2012085285W WO 2014015596 A1 WO2014015596 A1 WO 2014015596A1
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cryolite
aluminum
boron alloy
fluoroborate
fluorozirconate
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PCT/CN2012/085285
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English (en)
French (fr)
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陈学敏
杨军
李志红
伍卫平
韦世铭
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深圳市新星轻合金材料股份有限公司
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Priority to ES12881623.8T priority Critical patent/ES2587534T3/es
Priority to US14/416,674 priority patent/US9546098B2/en
Priority to EP12881623.8A priority patent/EP2878690B1/en
Publication of WO2014015596A1 publication Critical patent/WO2014015596A1/zh

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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00Compounds of aluminium
    • C01F7/48Halides, with or without other cations besides aluminium
    • C01F7/50Fluorides
    • C01F7/54Double compounds containing both aluminium and alkali metals or alkaline-earth metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00Obtaining aluminium
    • C22B21/06Obtaining aluminium refining
    • C22B21/062Obtaining aluminium refining using salt or fluxing agents
    • 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
    • C22C21/00Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/18Electrolytes

Definitions

  • the present invention relates to a method for producing an aluminum zirconium boron alloy and simultaneously producing cryolite, and more particularly to a cryolite for producing an aluminum zirconium boron alloy and simultaneously producing an aluminum electrolytic industry and a preparation method thereof.
  • Aluminum intermediate alloy is mainly used to adjust the alloy composition of aluminum melt. It is a metal element with high melting temperature. It is produced by melting method and aluminum. The melting temperature of this intermediate is significantly reduced. Therefore, some metal elements with higher melting temperature can be added to the aluminum liquid at a lower temperature to adjust the element content of the aluminum melt.
  • Zirconium has a significant refinement effect on pure magnesium grains. Studies have shown that zirconium can effectively inhibit the growth of magnesium alloy grains, thereby refining grains and having homogeneous heterogeneous transformation. Moreover, in the alloy, the addition of boron can greatly improve the wear resistance, heat resistance and thermal shock resistance of the alloy.
  • the aluminum zirconium-boron alloy may improve the high-temperature properties and material properties of magnesium and its alloys, increase the yield of wrought magnesium alloys, and refine grains.
  • thermochemical synthesis is carried out by using a mixture of fluorozirconate and fluoroborate as raw materials.
  • the method of producing aluminum zirconium boron alloy has simple preparation method and high efficiency, and the low molecular weight sodium cryolite which is synchronously produced as the electrolyte of the aluminum electrolysis system can reduce the electrolysis temperature of the aluminum electrolysis industry, thereby reducing electric energy consumption and reducing the overall production cost.
  • the present invention provides a method for producing an aluminum zirconium boron alloy and simultaneously producing cryolite, comprising the following steps: Step A: placing aluminum in a reactor, raising the temperature to 700 to 850 ° C, and adding the amount of the substance to the reactor a mixture of fluorozirconate and fluoroborate of X:y; ⁇ Step B: After stirring for 4 to 6 hours, the upper molten liquid is extracted to obtain cryolite; the lower layer is an aluminum boron alloy;
  • zirconium 1-10% by weight
  • the fluorozirconate is potassium fluorozirconate
  • the fluoroborate is potassium fluoroborate
  • the fluorozirconate is sodium fluorozirconate
  • the fluoroborate is sodium fluoroborate
  • the cryolite obtained in the step B is potassium cryolite, and the molecular formula of the potassium cryolite is
  • the cryolite obtained in the step B is sodium cryolite, and the molecular formula of the sodium cryolite is
  • the ratio of X to y is 1:2.
  • the ratio of X to y is 1:1.
  • the method for preparing the aluminum zirconium boron alloy provided by the invention has mild reaction conditions, easy control, simple process flow, complete reaction, good product quality, and synchronous generation.
  • Low molecular weight cryolite KF * A1F3 and ⁇ NaF - A1F3) are used in the aluminum electrolysis industry, have suitable conductivity, improve the solubility of alumina, thereby reducing the electrolysis temperature, reducing the power consumption, and improving Electrolysis efficiency and reduced overall production costs. detailed description

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Ceramic Products (AREA)

Abstract

一种生产铝锆硼合金并同步产生冰晶石的方法,包括如下步骤:步骤A:将铝置于反应器中,升温至700至850°C,向反应器中加入物质的量比为x:y的氟锆酸盐与氟硼酸盐的混合物;步骤B:搅拌4至6小时后,将上层熔融的液体抽出,得到冰晶石;下层为铝锆硼合金;其中,所述铝过量加入。该方法反应条件温和,容易控制,工艺流程简单,并且能够同步产生出可用于铝电解工业的低分子比冰晶石。

Description

一种生产铝锆硼合金并同步产生冰晶石的方法
技术领域
本发明涉及一种生产铝锆硼合金并同步产生冰晶石的方法, 尤其涉及一种用于 生产铝锆硼合金并同步产生铝电解工业用的冰晶石及其制备方法。
背景技术
铝中间合金主要是用来调整铝熔体中合金成份的一种传统产品, 它是一些融化温 度较高的金属元素,用熔融法和铝生产成中间体,这种中间体的熔化温度显著降低, 从而能使一些熔解温度较高的金属元素在较低的温度下加入到铝液当中, 以调解铝 熔体的元素含量。 锆对纯镁晶粒有明显细化效果, 有研究表明锆能有效抑制镁合金 晶粒的生长, 从而细化晶粒, 且有同质异晶转变。 并且, 在合金中, 硼的加入能大 幅提高合金耐磨性、 耐热性、 抗热冲击性。
因此, 铝锆硼合金可能改善镁及其合金的高温性能和材料性能, 提高变形镁合金 的成材率, 并使其晶粒细化。
发明内容
为解决现有技术中存在的问题, 发明人在电解质的选择以及制备方法方面进行 了大量的探索, 预料不到地发现, 以氟锆酸盐和氟硼酸盐的混合物为原料通过热化 学合成法生产铝锆硼合金, 制备方法简单, 效率高, 并且同步产生的低分子比钠冰 晶石作为铝电解体系的电解质,可降低铝电解工业的电解温度,从而降低电能消耗, 降低综合生产成本。
本发明提供一种生产铝锆硼合金并同步产生冰晶石的方法, 包括如下步骤: 步骤 A: 将铝置于反应器中, 升温至 700至 850°C, 往反应器中再加入物质的量 比为 X: y的氟锆酸盐与氟硼酸盐的混合物; ^骤 B: 搅拌 4至 6小时后, 将上层熔融的液体抽出, 得到冰晶石; 下层为铝 硼合金;
其中, 所述铝过量加入:
优选的, 所述铝锆硼合金中, 按重量百分比计, 锆: 1-10%;
Figure imgf000003_0001
优选的, 所述氟锆酸盐为氟锆酸钾, 所述氟硼酸盐采用氟硼酸钾。
优选的, 所述氟锆酸盐为氟锆酸钠, 所述氟硼酸盐采用氟硼酸钠。
优选的, 所述步骤 B 中得到的冰晶石为钾冰晶石, 所述钾冰晶石的分子式为
- KF · A1F3的钾冰晶石。
X
优选的, 所述步骤 B 中得到的冰晶石为钠冰晶石, 所述钠冰晶石的分子式为
3y+6x
NaF · A1F3的钠冰晶石,
3y+4x 优选的, 所述 X与 y之比为 1: 2。 优选的, 所述 X与 y之比为 1: 1。 所涉及到的化学反应式:
^Θ Α Λ 3y+6x
Al (过量) +x K2ZrF6+y KBF4→A1 · Zr · B (合金) + ^— - KF · A1F3
3y+4x
^Θ A Λ 3y+6x
Al (过量) +x Na2ZrF6+y NaBF4→Al · Zr · B (合金) NaF · A1F3
3y+4x 现有技术相比, 本发明的有益效果是: 本发明提供的制备铝锆硼合金的方法反 应条件温和, 容易控制, 工艺流程简单, 反应完全, 产物质量好, 并且同步产生的
3v+6x 3v+6x
低分子比冰晶石 KF * A1F3和^^ NaF - A1F3)用于铝电解工业, 具有合适 的电导率, 提高了氧化铝的溶解度, 从而降低了电解温度, 降低电能消耗, 提高了 电解效率, 并且降低了综合生产成本。 具体实施方式
下面通过具体实施例对本发明做进一步详细说明。
实施例 1
称取 100kg铝置于反应器中, 升温至 750 °C, 往反应器中再加入 141. 5kg氟锆酸 钾与 62. 5kg氟硼酸钾的混合物; 搅拌 4小时后, 将上层熔融的液体为 171kg钾冰晶 石 ( KF * A1F3), 用虹吸泵抽出后, 下层为铝锆硼合金 1 33kg。 实施例 2
称取 100kg铝置于反应器中, 升温至 700 °C, 往反应器中再加入 125. 5kg氟锆酸 钠与 54. 5kg氟硼酸钠的混合物; 搅拌 6小时后, 将上层熔融的液体抽出 151. 5kg钠 冰晶石 ( NaF · A1F3 ) 后, 下层为 128. 5kg铝锆硼合金。 实施例 3
称取 200kg铝置于反应器中, 升温至 800 °C, 往反应器中再加入 141. 5kg氟锆酸 钾与 62. 5kg氟硼酸钾的混合物; 搅拌 6小时后, 将上层熔融的液体抽出钾冰晶石 ( F · A1 F3) 后, 下层为 312kg铝锆硼合金。 实施例 4
称取 200kg铝置于反应器中, 升温至 850 °C, 往反应器中再加入 125. 5kg氟锆酸 钠与 109kg氟硼酸钠的混合物; 搅拌 5小时后, 将上层熔融的液体抽出钠晶石 ή NaF . AlF3) 后, 下层为铝锆硼合金 300. lkg。 以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明, 不能认 定本发明的具体实施只局限于这些说明。 对于本发明所属技术领域的普通技术人员 来说, 在不脱离本发明构思的前提下, 还可以做出若干简单推演或替换, 都应当视 为属于本发明的保护范围。

Claims

权利要求书
1.一种生产铝锆硼合金并同步产生冰晶石的方法,其特征在于,包括如下步骤: 步骤 A : 将铝置于反应器中, 升温至 700至 850 °C, 往反应器中再加入物质的: 比为 X: y的氟锆酸盐与氟硼酸盐的混合物;
^骤 B: 搅拌 4至 6小时后, 将上层熔融的液体抽出, 得到冰晶石; 下层为铝 硼合金; 其中, 所述铝过量加入。
2.如权利要求 1 所述的方法, 其特征在于, 所述铝锆硼合金中, 按重量百分比
Figure imgf000006_0001
3.如权利要求 2 所述的方法, 其特征在于, 所述氟锆酸盐为氟锆酸钾, 所述氟 硼酸盐采用氟硼酸钾。
4.如权利要求 2 所述的方法, 其特征在于, 所述氟锆酸盐为氟锆酸钠, 所述氟 硼酸盐采用氟硼酸钠。
5.如权利要求 3所述的方法, 其特征在于, 所述步骤 B中得到的冰晶石为钾冰 晶石, 所述钾冰晶石的分子式为^ KF · A 1 F 3的钾冰晶石。
6.如权利要求 4所述的方法, 其特征在于, 所述步骤 B中得到的冰晶石为钠冰
3v+6x
晶石, 所述钠冰晶石的分子式为^^ NaF · A 1 F 3的钠冰晶石。
7.如权利要求 1至 6任一项所述的方法,其特征在于,所述 X与 y之比为 1 : 2。
8.如权利要求 1至 6任一项所述的方法,其特征在于,所述 X与 y之比为 1 : 1。
PCT/CN2012/085285 2012-07-25 2012-11-26 一种生产铝锆硼合金并同步产生冰晶石的方法 WO2014015596A1 (zh)

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ES12881623.8T ES2587534T3 (es) 2012-07-25 2012-11-26 Procedimientos para la producción de una aleación de aluminio-zirconio-boro y para la producción simultánea de criolita
US14/416,674 US9546098B2 (en) 2012-07-25 2012-11-26 Method for preparing aluminum-zirconium-boron alloy and synchronously preparing crylite
EP12881623.8A EP2878690B1 (en) 2012-07-25 2012-11-26 Method for producing aluminum-zirconium-boron alloy and for simultaneously producing cryolite

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CN201210259144XA CN102747253A (zh) 2012-07-25 2012-07-25 一种生产铝锆硼合金并同步产生冰晶石的方法

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CN102732914A (zh) * 2012-07-25 2012-10-17 深圳市新星轻合金材料股份有限公司 铝电解过程中的电解质及其补充体系的制备方法
CN102745704A (zh) * 2012-07-25 2012-10-24 深圳市新星轻合金材料股份有限公司 一种生产硼化锆并同步产出冰晶石的方法
CN102747253A (zh) * 2012-07-25 2012-10-24 深圳市新星轻合金材料股份有限公司 一种生产铝锆硼合金并同步产生冰晶石的方法
CN107098371A (zh) * 2016-02-23 2017-08-29 达州励志环保科技有限公司 一种利用氟化铝生产废水制备钾冰晶石的方法
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US9546098B2 (en) 2017-01-17
EP2878690B1 (en) 2016-05-18
ES2587534T3 (es) 2016-10-25
EP2878690A1 (en) 2015-06-03
EP2878690A4 (en) 2015-07-22
CN102747253A (zh) 2012-10-24

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