CN104736482B - 生产氧化铝的方法 - Google Patents

生产氧化铝的方法 Download PDF

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CN104736482B
CN104736482B CN201280074926.4A CN201280074926A CN104736482B CN 104736482 B CN104736482 B CN 104736482B CN 201280074926 A CN201280074926 A CN 201280074926A CN 104736482 B CN104736482 B CN 104736482B
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aluminium oxide
aluminium
chloride
chloride hexahydrate
crystallize
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CN104736482A (zh
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A·S·森尤塔
A·V·帕诺夫
A·G·萨斯
A·A·达马斯金
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Aluminum Engineering Technology Center Co., Ltd.
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
    • C01F7/22—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts with halides or halogen acids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • C01F7/306—Thermal decomposition of hydrated chlorides, e.g. of aluminium trichloride hexahydrate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/56—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/80—Compositional purity

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Abstract

本发明涉及冶金，具体而言涉及生产氧化铝的酸性方法，并可用于处理低级含铝原材料。生产氧化铝的方法包括：用盐酸处理含铝原材料；通过蒸发上层氯化物溶液而使六水合氯化铝结晶；并且将其热分解以形成氧化铝。为了提高氧化铝的品质并降低能耗，在平均粒度为250～500微米的六水合氯化铝种晶存在下添加氯化钙进行结晶，其中上层溶液中氯化钙总质量与计算的氧化铝质量的比等于2～4。

Description

生产氧化铝的方法
本发明涉及冶金，具体而言涉及生产氧化铝的酸性方法，并可用于处理低级含铝原材料。
已知一种通过盐酸浸取由高二氧化硅矾土生产氧化铝的方法，所述方法涉及：在至多700℃的温度煅烧含铝原材料；将其用盐酸进行处理；通过用气态氯化氢使澄清的氯化物溶液饱和而使氯化铝盐析；煅烧氯化铝以生产氧化铝；并且在酸处理和盐析步骤中进行母液热水解并回收氯化氢(Elsner D.,Jenkins D.H.和Sinha H.N.Alumina viahydrochloric acid leaching of high silica bauxites-process development.Light metals,1984,411-426页)。
根据所述方法，六水合氯化铝由于用气态氯化氢盐析而从溶液中分离；但是最终产物中的磷含量超出了冶炼级氧化铝允许限度1.5倍。
所述方法的缺陷还包括需要在后续技术处理阶段中生产干燥的氯化氢气体以便将其循环用于盐析处理阶段，在某些情况下，所述缺陷使过程过于复杂且增加热能消耗。
与所要求保护的方法最接近的是盐酸氧化铝生产方法，其包括：对预煅烧的原材料进行酸处理，蒸发澄清氯化物溶液同时使六水合氯化铝(AlCl3·6H2O)结晶，然后将其煅烧为氧化物，其被作者称为“粗氧化铝”(有色金属冶金学家手册：氧化铝生产工艺[俄罗斯].Metallurgiya:Moscow,1970,236-237页)，因为铁和其他杂质(除硅之外)的含量高。此中间材料随后通过常规的碱拜耳法处理以去除铁、磷和其他杂质，从而生产冶炼级氧化铝。
但是，几乎不可能确保在从含有氯化铁和其他杂质金属以及磷的溶液中结晶AlCl3·6H2O期间的高纯度目标产物。因此，必需将六水合氯化铝溶解于水中然后将其再沉淀；这导致为了蒸发额外引入循环中的水而不可避免的热能消耗。
所述方法的其他缺陷还包括工艺设计过于复杂、其实现期间的总能耗高、从酸循环至碱循环的氯迁移以及与其相关的额外碱损耗(多至36～37kg/吨氧化铝)。这些是所述方法没有工业应用的原因。
本发明基于包括以下的目的：开发一种由低级原材料生产冶炼级氧化铝的方法，其允许处理低级的高二氧化硅矿和废物。
技术结果是改进氧化铝品质和减少能量使用。
以上技术结果如下实现：在氧化铝生产方法中，包括：用盐酸处理含铝原材料；通过将澄清的氯化物溶液蒸发而使六水合氯化铝结晶；并且将六水合氯化铝热分解以生产氧化铝；在平均粒度为250μm～500μm的六水合氯化铝种晶存在下添加氯化钙(其中澄清溶液中氯化钙总重量与估算的氧化铝重量的比为2～4)而进行结晶。
在平均粒度为250μm～500μm的六水合氯化铝种晶存在下添加氯化钙(其中澄清溶液中氯化钙总重量与估算的氧化铝重量的比为2～4)而进行结晶使得能够控制晶体生长并且防止磷进入六水合氯化铝进而进入氧化铝。
所述氧化铝生产方法如下进行：
将用盐酸浸取天然含铝原材料、分离不溶性残渣并预蒸发至饱和点之后的澄清氯化铝溶液(以AlCl3计的浓度约为30％)与50％～70％的СаCl2溶液(700g/L～900g/L)混合(基于其在混合溶液中的浓度进一步降低到30％～40％以下)。在粒度为250μm～500μm的六水合氯化铝种晶存在下进行结晶，继续蒸发并维持盐沉淀速率以提供期望粒度的产品晶体。一旦母液中的СаCl2浓度上升至高达700g/L～900g/L的初始水平，结晶过程结束，同时Al2O3含量降至5g/L～10g/L。此时，进入所述过程的超过90％的Al2O3与盐一起析出。分离所得浆料；回收母液至所述过程的初始阶段，并且利用热分解将六水合氯化铝晶体用于氧化铝生产。
通过具体实施例进一步阐明所述氧化铝生产方法。
实施例1.用20％盐酸溶液以L:S＝4:1的液固比处理高岭土，同时在110℃～115℃搅拌3小时，所述高岭土中主要成分的含量(％)如下：Al2O336.4；SiO245.3；Fe2O30.78；TiO20.51；CaO 0.96；MgO 0.49；和P2O50.12。在该过程完成后，过滤浆料。将澄清氯化物在烧瓶中蒸发至AlCl3浓度为31％，之后逐步加入热的60％氯化钙溶液直至六水合氯化铝晶体开始被分离，然后以两倍于AlCl3·6H2O估算量的量添加粒度为250μm～500μm的氯化铝种晶(来自先前的试验)，将其与通过澄清氯化物溶液一起引入所述过程，并且继续蒸发1小时。将所得晶体在过滤器上用38％盐酸洗涤并在1000℃煅烧。所得氧化铝中P2O5含量低于0.001％，产物的平均粒度为82.3μm。所述值完全符合冶炼级氧化铝标准。
实施例2.在相同条件下重复所述实验，不同在于省略了氯化钙。所得氧化铝中P2O5含量为0.004％，产物的平均粒度为71.2μm；即，在杂质含量方面不符合要求。
实施例3.在实施例1的条件下重复所述实验，不同在于添加粒度为100μm～250μm的六水合氯化铝种晶。所得氧化铝中P2O5含量低于0.002％，产物的平均粒度为52.2μm；即，在粒度分布方面不符合要求。
比较评价表明，与现有技术相比，要求保护的方法能够节约多达36％的热能。

Claims (1)

1.一种生产氧化铝的方法，其包括：用盐酸处理含铝原材料；通过将澄清的氯化物溶液蒸发而使六水合氯化铝结晶；并且将六水合氯化铝热分解以生产氧化铝；所述方法的特征在于，在平均粒度为250μm～500μm的六水合氯化铝种晶存在下添加氯化钙而进行结晶，其中澄清溶液中氯化钙总重量与估算的氧化铝重量之比为2～4。
CN201280074926.4A 2012-08-01 2012-08-01 生产氧化铝的方法 Expired - Fee Related CN104736482B (zh)

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RU2705071C1 (ru) * 2018-11-07 2019-11-01 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" Способ получения металлургического глинозема кислотно-щелочным способом
BR112022004017A2 (pt) * 2019-09-06 2022-05-31 Alcoa Australia Processo para preparação de alumina
CN117321003A (zh) * 2021-03-05 2023-12-29 美铝澳大利亚有限公司 制备氧化铝的方法

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CA2877653C (en) 2016-07-12
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