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CN101842504B - 从铝土矿石中提取铝和铁的工艺 - Google Patents

从铝土矿石中提取铝和铁的工艺 Download PDF

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CN101842504B
CN101842504B CN2008800235902A CN200880023590A CN101842504B CN 101842504 B CN101842504 B CN 101842504B CN 2008800235902 A CN2008800235902 A CN 2008800235902A CN 200880023590 A CN200880023590 A CN 200880023590A CN 101842504 B CN101842504 B CN 101842504B
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CN101842504A (zh
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理查德·布德罗
瑟奇·艾里克斯
法比耶纳·比亚索托
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Abstract

本发明提供了由铝土矿石或其混合物提取铝和/或铁离子的几种工艺和组合物。一种工艺包括从含有所述铝离子、所述铁离子、有机溶剂和萃取剂的组合物中回收所述的铝离子,其中的萃取剂适合于基本上选择性地与铁离子或铝离子形成有机金属络合物,并可溶于有机溶剂中。另一种由矿石提取铝的工艺包括用酸浸提所述的矿石以获得浸出液和固体残渣,然后通过下述方法除去至少一部分包含在所述浸出液中的铁离子:在pH至少为10的碱性条件下,基本上选择性地沉淀所述的至少一部分铁离子;或者用适合于形成有机金属络合物的萃取剂基本上选择性地与所述的至少一部分铁离子络合。另一种将包含在组合物中的铝离子与铁离子至少部分地分离的工艺包括在pH至少为10的碱性条件下,基本上选择性地沉淀所述的至少一部分铁离子。

Description

从铝土矿石中提取铝和铁的工艺
技术领域
本发明涉及从铝土矿石(aluminous ores)中提取铝的化学工艺的改进。举例来说,这种工艺可用于从含有Fe、K、Mg、Na、Ca、Mn、Ba、Zn、Li、Sr、V、Ni、Cr、Pb、Cu、Co、Sb、As、B、Sn、Be、Mo等各类金属或其混合物的铝土矿石中提取铝。 
背景技术
全世界生产的氧化铝中,有96%以上是从铁铝氧石(bauxite)中提取的,而铁铝氧石是一种特别富含氧化铝(40-60%)的矿物,其主要供应商来自于牙买加、澳大利亚、巴西、非洲和俄罗斯。在世界上的某些地区存在大量的铝土矿石,这些铝土矿石属于氧化铝含量相对丰富(20-28%)的铝硅酸盐(例如,泥板岩、霞石等)。但迄今为止这些地区却几乎不受人们的关注,因为从此类矿石中提取铝的生产成本仍然太过高昂。与铁铝氧石相反,在这些铝土材料中,氧化铝与硅酸盐化或硫酸盐化状态的铝共同存在,因此无法采用拜耳精炼矾土法,这也就意味着必须采用或开发用于氧化铝生产的替代加工工艺。到目前为止,已经提出了各种各样的工艺用于从含有铝硅酸盐的这类铝土矿石中提取铝,但在改进现有工艺或开发其它工艺路线方面仍然存在空间。 
发明内容
从一个方面来说,本发明提供了一种从含有铝离子和铁离子的混合物中提取铝离子的工艺。这种工艺包括从含有铝离子、铁离子、有机溶剂和萃取剂的组合物中回收铝离子,其中的萃取剂适合于基本上选择性地与铁离子或铝离子形成有机金属络合物(organometalliccomplex),并可溶于有机溶剂中。 
根据一个实施方案,该组合物可以包含含有铝离子的酸性水相和含有与萃取剂络合的铁离子的有机相,其中的铝离子通过水相与有机相的分离加以回收。水相的pH值可以约为1-2.5或2。萃取剂可以选自磷酸及其衍生物,以及次膦酸及其衍生物。举例来说,萃取剂可以选自二(2-乙基己基)磷酸(HDEHP)、双(2,4,4-三甲基戊基)膦酸和单(2-乙基己基)-2-乙基己基膦酸酯中选择。萃取剂在有机相中的浓度可以约为0.5M-1.5M,或约为1M。该组合物中有机相与水相的体积比可以约为1∶1。提取(将组合物通过膜)后,水相可以与有机相 分离,铝离子能够回收到水相中,然后用碱(例如NaOH、KOH或其混合物)处理水相,以便使其pH值可以达到至少约为4。本工艺可以进一步包含用HCl处理有机相的步骤,分离出Fe3+形式的铁离子。 
根据另一个实施方案,该组合物中可以包含含有铁离子的酸性水相以及含有与萃取剂络合的铝离子的有机相,其中铝离子通过水相和有机相的分离加以回收。水相的pH值可以约为2.5-3.5。萃取剂可以为次膦酸或其衍生物。举例来说,萃取剂可以为双(2,4,4-三甲基戊基)次膦酸。萃取剂相对于有机溶剂的浓度可以约为10%-25%v/v或约为20%v/v。该组合物中水相与有机相的体积比可以约为1∶1-1∶3。在加工过程中,该组合物可以处于约30℃-约50℃的温度下,或处于约35℃-约45℃的温度下。通过膜进行提取后,水相可以与有机相分离,络合的铝离子可被回收到有机相中。随后有机相可以用HCl处理,以获得含有铝离子的含水的组合物。 
举例来说,有机溶剂可以选自烃类。例如,有机溶剂可以从C5-C12烷烃及其混合物中选择。有机溶剂还可以是己烷或庚烷。有机相和水相可以通过过滤膜(如中空纤维膜)的方式分离。这种膜可包括聚丙烯、聚偏二氟乙烯或其混合物的膜。水相可以用碱处理,以达到至少4的pH值。本工艺还可进一步包含过滤分离的步骤,以获得Al(OH)3。本工艺还可以包括清洗Al(OH)3的步骤。本工艺也可以还包含将Al(OH)3转化为Al2O3的步骤。从Al(OH)3到Al2O3的转化可以在约800℃-1200℃的温度下进行。 
从另一方面来说,本发明提供了一种含有铝离子、铁离子、有机溶剂和萃取剂的组合物,其中的萃取剂适合于基本上选择性地与铁离子或铝离子形成有机金属络合物,并可溶于有机溶剂中。 
从另一个方面来说,本发明提供了一种组合物,该组合物包含含有铝离子的酸性水相和含有与萃取剂络合的铁离子的有机相。 
从另一个方面来说,本发明提供了一种组合物,该组合物包含含有铁离子的酸性水相和含有与萃取剂络合的铝离子的有机相。 
上述关于本工艺的各种参数、实施方案和实施例在可能的情况下,也可以应用于这些组合物。 
从另一个方面来说,本发明提供了一种工艺,该工艺至少可以部分分离同一组合物中所含的铝离子和铁离子,该工艺包括在pH值至少为10的碱性条件下,基本上选择性地沉淀至少一部分铁离子。该铁离子可在含有NaOH或KOH的碱性含水组合物中沉淀出来。举例来说, 碱可以与该组合物发生反应,获得pH值至少为10的混合物,随后,至少一部分沉淀的铁离子可与混合物的其余部分分离。例如,沉淀的铁离子可以通过过滤、倾析、离心或其组合的技术与混合物的其余部分分离。本工艺可以还包括用碱性溶液清洗所获得的沉淀铁离子的步骤。碱性溶液的浓度可以约为0.01M-0.02M。pH值可以至少为11、至少为12、约为10.8-11.2,或约为11.5-12.5。本工艺还包含利用中空纤维膜对沉淀的铁离子进行提纯的步骤。 
从另一个方面来说,本发明提供了一种从铝矿石(aluminum ore)中提取铝的工艺,该工艺包含: 
-用酸浸提铝矿石,以获得浸出液和固体残渣; 
-通过以下工艺至少去除浸出液中所含的一部分铁离子: 
(i)在pH值至少为10的碱性条件下基本上选择性地沉淀至少一部分的铁离子,以获得富含铝的组合物;或 
(ii)使萃取剂基本上选择性地与至少一部分铁离子络合,以获得富含铝的组合物,该萃取剂适合于基本上选择性地与铁离子形成有机金属络合物。 
举例来说,所说的酸可以是HCl。可以用HCl在至少80℃、至少90℃,或约100℃-110℃的温度下浸提铝矿石。HCl的浓度可以约为6M。铝矿石重量与酸的体积比可以约为1/10。 
举例来说,可以通过从碱性含水组合物中沉淀出铁离子来除去至少一部分铁离子。该组合物可以含有NaOH或KOH。 
举例来说,可以通过使浸出液与碱发生反应以达到至少为10的pH值,并使铁离子发生沉淀来除去至少一部分铁离子。 
举例来说,可以通过过滤、倾析、离心或其组合的技术使沉淀的铁离子与浸出液的其余部分分离。 
本工艺还可以包含用碱性溶液对所得沉淀的铁离子进行清洗的步骤。碱性溶液的浓度可以约为0.01M-0.02M。其pH值可以至少为11、至少为12、约为10.8-11.2,或约为11.5-12.5。本工艺可以进一步包含利用中空纤维膜纯化沉淀的铁离子的步骤。 
通过在酸性条件下,使浸出液与萃取剂和有机溶剂反应,以获得包含含有铝离子的酸性水相和含有与萃取剂络合的铁离子的有机相的组合物,可以除去至少一部分铁离子。通过水相和有机相的分离可以获得富含铝的组合物。水相的pH值可以约为1-2.5,或约为2。萃取 剂可以选自二(2-乙基己基)磷酸(HDEHP)、双(2,4,4-三甲基戊基)膦酸和单(2-乙基己基)-2-乙基己基膦酸酯)。萃取剂在有机相中的浓度可以约为0.5M-1.5M或约为1M。 
举例来说,有机溶剂可以选自C5-C12烷烃及其混合物。有机溶剂可以是庚烷。该组合物中有机相与水相的体积比约为1∶1。有机相和水相可以利用过滤膜分离。这种膜可以是中空纤维膜。该膜可包括聚丙烯、聚偏二氟乙烯或其混合物的膜。 
将组合物通过膜之后,水相即可与有机相分离。铝离子可以被回收到水相中,然后用碱(如NaOH或KOH)处理水相。该水相可以用碱处理,以使其pH值达到至少约为4。本工艺还可以包含过滤分离以获得Al(OH)3的步骤,最终可以对Al(OH)3进行清洗。 
举例来说,在浸提之前可以对铝矿石进行粉碎和煅烧。 
举例来说,在去除铁离子之前,可以用碱处理浸出液。 
举例来说,在去除铁离子之前,可以对浸出液进行蒸馏,以减少其体积。 
举例来说,本工艺还可包含至少回收一部分存在于富含铝的组合物中的铝离子的步骤。 
举例来说,可以在有机溶剂和酸性溶液存在的情况下,用萃取剂对富含铝的组合物进行处理,以形成一种包含含有杂质的酸性水相和含有与萃取剂络合的铝离子的有机相的组合物,其中的萃取剂适合于基本上选择性地与铝离子形成有机金属络合物 
通过分离水相和有机相,可以回收铝离子。举例来说,水相的pH值可以约为2.5-3.5。萃取剂可以为亚膦酸或其衍生物。萃取剂可以为双(2,4,4-三甲基戊基)膦酸。萃取剂相对于有机溶剂的浓度可以约为10%-25%v/v或约为20%v/v。有机溶剂可以选自C5-C12烷烃及其混合物。有机溶剂可以为庚烷。该组合物中水相与有机相的体积比约为1∶1-1∶3。有机相和水相的分离可以利用膜(例如中空纤维膜)来实现。这种膜可以是聚丙烯、聚偏二氟乙烯或其混合物的膜。该组合物可以处于约30℃-50℃,或者约35℃-45℃的温度下。在组合物通过膜之后,水相可以与有机相分离。络合的铝离子可以被回收到有机相中。随后可以用HCl处理该有机相以获得含有铝离子的含水组合物。该铝离子可以通过与碱接触转化为Al(OH)3。随后Al(OH)3可以转化为Al2O3。从Al(OH)3到Al2O3的转化可以在约800℃-1200℃的温度下进行。 
附图说明
以下附图仅作为实施例来表示本发明的各种实施方案: 
图1给出了基于从铝土矿中提取铝的工艺的一个实施方案的工艺总图。 
具体实施方式
如在附图中仅作为实施例的说明,由以下不同实施例的描述,将会使本发明特征和优势变得更为显而易见,其中: 
如图1所示,这种工艺可能包含多个步骤,其中每个步骤最终都可以单独视为一个工艺。 
泥质板岩样品的制备 
为了有助于所有后续步骤的进行,可以对泥质板岩进行微细粉碎处理。举例来说,微粉化处理可以使反应时间缩短数小时(约2-3小时)。为了去除大部分的铁,在室温下的浸提步骤是粉碎步骤和煅烧步骤之间的可选步骤(参见选项1)。举例来说,这一操作是使用盐酸HCl(12M)进行的,而所采用的泥质板岩的重量与酸的体积比为1∶5。根据实验条件(颗粒粒度、处理时间、搅拌系统),约65%到约93%的铁随后会被去除。尽管如此,这一浸提步骤也可能带入一定比例的铝(0-5%)。泥质板岩制备的最后一步是对经过预处理的泥质板岩进行煅烧。这一步可以在高于550℃的温度下完成,煅烧时间约为1-2小时。举例来说,在相同的时间内,热处理可能使所提取到的铝的数量增加了约30%-约40%。换句话说,所提取的铝的数量翻了一番。在室温下浸提时,在煅烧前可以进行相分离,以回收酸并降低加热成本。 
酸浸提 
酸浸提是指使经过粉碎和煅烧的泥质板岩与盐酸溶液在高温下反应一段给定的时间。举例来说,泥质板岩/酸的比可以约为1∶10(重量/体积),HCl的浓度可以约为6M,温度可以约为100℃-110℃,反应时间可以约为5-7小时。在这种条件下,除了杂质之外,可以提取约90%以上的铝和约100%的铁。 
在上述处理工艺的后半部分(例如最后的2或3个小时),可以通过浓缩回收一部分的酸。提取过程一旦结束,可以通过倾析或过滤实现固(耗竭其金属成分的泥质板岩)液分离,随后对其进行清洗。残留的浸出液和清洗水可能被完全蒸发。随后,相应所得的残渣可以用水多次清洗,以降低酸度,并减少在去除铁的过程中调节pH值所需的氢氧化钠(NaOH)数量。最终体积占初始体积的10%-20%。所回收的酸在通过添加气态HCl或添加浓HCl(12M)调节其浓度之后,可以重新加以利用。反应后,酸的浓度可以根据实验条件而有所不同,约为4M到6M。至于固体,它占泥质板岩初始质量的约65%-75%,可以经过稳定化处理后再用作离子交换树脂或吸附剂。 
铁的去除 
通过在,例如pH值至少为10,或pH值约为11.5-12.5的碱性介质中使铁沉淀,可以将铁去除。这一步骤可以通过添加NaOH,例如以10M的浓度来进行。同样也可以使用其它碱,如KOH。随后,所需的就是通过过滤、倾析或离心来分离固体和液体部分,并用如NaOH溶液(例如浓度为0.01M-0.02M的NaOH)这样的稀碱液对固体进行清洗。接着,用蒸馏水清洗固体。液体部分含有铝和碱土金属。从而可以实现铁以及几乎所有杂质(其它金属)的基本上完全去除。作为一个可选步骤,可以利用通过中空纤维膜进行液-液萃取的提纯步骤来回收铁(参见选项2)。 
作为另一种选择(参见选项3),可以使用萃取剂和中空纤维膜来实现铁的去除。各种能够基本上选择性地与铁离子络合超过与铝离子络合(或选择性地与铝离子络合超过与铁离子络合)的萃取剂可以根据铝/铁的比例用于这一步骤中。举例来说,可以使用适合于与铁离子络合的HDEHP(2-乙基己基磷酸)作为萃取剂来进行萃取。浓度约为1M的HDEHP可以用于像庚烷这样的有机溶剂或任何烃类溶剂中。这种萃取可以只需要相对较短的接触时间(数分钟)。例如,可以采用数量级为2的pH值,而液相与有机相的比例可约为1∶1。据观察在这样的条件下可以提取86%-98%的铁。在本例子中,人们可知铁被捕集在有机相中。为了将铁回收到水相中,随后可以采用盐酸(2M或6M)和约为1∶0.5的有机相/酸性相比进行反向萃取。在这种情况下,所得到的水相富含Fe3+离子。 
铝的回收 
由上述采用沉淀或萃取技术的步骤获得的溶液较为清洁,其中主要含铝,例如,铝的含量约为90%-95%(在沉淀的情况下不含碱土金属)。铝的回收例如,可以采用同样的中空纤维膜以及萃取剂通过液-液萃取来实现,该萃取剂适合于至少基本上选择性地与铝的络合胜过与其它金属或残余物的络合。例如,双(2,4,4-三甲基戊基)膦酸(如以CyanexTM272的名称销售的产品)可以作为铝的专用萃取剂。举例来说,这种萃取剂在像庚烷这样的有机溶剂中的使用浓度可以约为20%v/v。水相与有机相之间的比例可以约为1∶1-1∶3。举例来说,萃取温度可以约为40℃,pH值可以保持在约2.5-3.5。据观察这种技术有可能提取70-90%以上的铝。当铝被捕获在有机相中之后,可以采用反萃取以Al3+离子浓缩液的形式回收。举例来说,反萃取可以在温度约为40℃的情况下使用盐酸(例如,以6M的浓度)进行。在这种条件下,可以回收90%以上的铝。随后,Al3+可以通过添加NaOH转化为氢氧化铝Al(OH)3。最后,通过在约800℃-1200℃的温度下煅烧Al(OH)3的方法,可将Al(OH)3转化为氧化铝(氧化铝Al2O3)。 
以下非限制性的实施例进一步对本发明进行说明。 
实施例1 
泥质板岩样品的制备 
泥石岩的粉碎:检测所采用的微粉化颗粒平均粒径范围在10-50微米之间。 
煅烧:经过粉碎的泥石岩在600℃的温度下煅烧至少1小时。其平均组分为: 
Al2O3                    21.0% 
Fe2O3                    8.0% 
K2O                      1.5% 
Na2O                     0.9% 
TiO2                     0.9% 
CaO                      0.08% 
ZnO                      0.06% 
SiO2                     51.0% 
酸浸提 
将500g经过粉碎和煅烧的泥质板岩加入5升的6M盐酸中。随后将混合物在100℃-110℃下加热7小时。 
反应后,通过过滤实现固液分离。用蒸馏水对固体进行清洗,并将清洗液加入液体部分中。这种清洗可以回收被捕集在固体中的一部分铝。这种固体的干物量为345±-5g,相应的损失约为30%-32%。 
含有铝、铁和最初存在于泥石岩中的大部分杂质的剩余液体部分,在100℃下蒸发,使其体积减少到其初始体积的90%。残留的体积则为50mL。蒸发前后的液体组成为: 
Figure G2008800235902D00071
所有离子种类似乎仍然可溶。 
铁的去除 
残留物略经稀释(+25%),加入浓的氢氧化钠(10M),直至pH值达到11.5以上为止。所形成的沉淀物通过一般的过滤从溶液中分离出来,并用稀NaOH和热的超纯水多次清洗。沉淀物中含有所有的铁和大部分的金属杂质。除了Al3+离子以外,滤出液中主要含有碱土金属和部分下列杂质: 
    主要的滤出液杂质(%)
 铁   0.14
 钠   94.13
 碱土金属  (Mg,K,Ca)   5.71
 其它金属   0.02
Na+来自于苏打,也是Al(OH)4 -的抗衡离子。 
铝的回收 
通过添加6M的HCl将滤出液的pH值调节至2.5-3.5,所得到的溶液利用络合剂Cyanex272,按照其在有机溶剂中的20%VN的浓度和1∶1的体积比来萃取。萃取在采用中空纤维的膜接触器中、40℃的温度下进行。在不到30-60分钟的时间内,可以提取85%以上的铝。通过控制NaOH(10M)添加的调节回路来调节pH值。随后,在40℃下,以1∶0.5的有机相/酸性相体积比,用HCl(6M)进行反萃取以回收与Cyanex络合的Al3+。在反萃取之后, 所回收的酸性相的组成为: 
    组成(%)
 铝   92.81
 铁   0
 碱土金属  (Na,Mg,K,Ca)   7.14
 其它金属   0.05
为了提高纯度的百分比,使Al3+离子以Al(OH)3氢氧化物的形式沉淀,随后用超纯水清洗多次。这种氢氧化物的组成变为: 
    组成(%)
 铝   99.09
 铁   0
 碱土金属  (Na,Mg,K,Ca)   0.88
 其它金属   0.03
进一步的纯化可通过再结晶进行。 
虽然是特别针对具体的实施方案来进行描述的,但应当理解,本领域的技术人员会对其进行各种修改。因此,上述描述和附图应视为具体的实施例,而不是限制的含义。 

Claims (99)

1.一种从含有铁离子和铝离子的混合物中提取铝离子的工艺,所述工艺包括从含有所述铝离子、所述铁离子、酸、有机溶剂以及萃取剂的组合物中回收所述铝离子,该萃取剂适合于选择性地与所述铁离子或所述铝离子形成一种有机金属络合物,该萃取剂可溶于所述的有机溶剂中,其中当所述的萃取剂适合于与所述的铁离子形成有机金属络合物时,所述的组合物包含含有所述的铝离子和所述酸的酸性水相,以及含有所述的有机溶剂和与所述的萃取剂络合的铁离子的有机相,通过使用中空纤维膜使所述的水相与所述的有机相分离,并使所分离的水相与碱反应,即可回收所述的铝离子,以及其中当所述的萃取剂适合于与所述的铝离子形成有机金属络合物时,所述的组合物包含含有所述的铁离子和所述酸的酸性水相,以及含有所述的有机溶剂和与所述的萃取剂络合的铝离子的有机相,通过使用中空纤维膜使所述的水相与所述的有机相分离,并使所述分离的有机相与HCl反应,以便得到另一个含有铝离子的水相和另一个有机相,通过使该另一个水相与碱反应,即可使所述的另一水相与所述的另一有机相分离并以Al(OH)3的形式回收所述的铝离子。
2.权利要求1所述的工艺,其中所述的萃取剂适合于选择性地与所述铁离子形成一种有机金属络合物。
3.权利要求2所述的工艺,其中所述酸性水相的pH值为1-2.5。
4.权利要求2所述的工艺,其中所述酸性水相的pH值为2。
5.权利要求2-4任何一项所述的工艺,其中所述的萃取剂选自二(2-乙基己基)磷酸(HDEHP)、双(2,4,4-三甲基戊基)膦酸和单(2-乙基己基)-2-乙基己基膦酸酯。
6.权利要求2-4任何一项所述的工艺,其中所述的萃取剂在所述有机相中的浓度为0.5M-1.5M。
7.权利要求2-4任何一项所述的工艺,其中所述的萃取剂在所述有机相中的浓度为1M。
8.权利要求2-4任何一项所述的工艺,其中所述的有机溶剂选自C5-C12烷烃及其混合物。
9.权利要求2-4任何一项所述的工艺,其中所述的有机溶剂为庚烷。
10.权利要求2-4任何一项所述的工艺,其中所述的组合物中有机相与水相的体积比为1∶1。
11.权利要求2-4任何一项所述的工艺,其中所述的膜包括聚丙烯、聚偏二氟乙烯或其混合物的膜。
12.权利要求2-4任何一项所述的工艺,其中所述的膜包括聚丙烯膜。
13.权利要求2-4任何一项所述的工艺,其中所述分离的水相与碱反应,所述的碱选自NaOH、KOH,及其混合物。
14.权利要求2-4任何一项所述的工艺,其中所述分离的水相与碱反应,所述的碱选自NaOH。
15.权利要求2-4任何一项所述的工艺,其中所述的水相与所述的碱反应,以达到至少为4的pH值。
16.权利要求2-4任何一项所述的工艺,还包括通过过滤分离以回收Al(OH)3形式的所述铝离子的步骤。
17.权利要求16所述的工艺,还包括清洗所述的Al(OH)3的步骤。
18.权利要求17所述的工艺,还包括将Al(OH)3转化为Al2O3的步骤。
19.权利要求18所述的工艺,其中Al(OH)3转化为Al2O3在800℃-1200℃的温度下进行。
20.权利要求2-4,17-19任何一项所述的工艺,还包括用HCl处理所述分离的有机相,并以Fe3+的形式分离出所述的铁离子。
21.权利要求1所述的工艺,其中所述的萃取剂适合于选择性地与所述的铝离子形成有机金属络合物。
22.权利要求21所述的工艺,其中所述水相的pH为2.5-3.5。
23.权利要求21或22所述的工艺,其中所述的萃取剂为次膦酸或其衍生物。
24.权利要求21或22所述的工艺,其中所述的萃取剂为双(2,4,4-三甲基戊基)膦酸。
25.权利要求21或22所述的工艺,其中所述的萃取剂相对于所述有机溶剂的浓度为10%-25%v/v。
26.权利要求21或22所述的工艺,其中所述的萃取剂相对于所述有机溶剂的浓度为20%v/v。
27.权利要求21或22所述的工艺,其中所述的有机溶剂选自C5-C12烷烃及其混合物。
28.权利要求21或22所述的工艺,其中所述的有机溶剂为庚烷。
29.权利要求21或22所述的工艺,其中所述的组合物中水相与有机相的体积比为1∶1-1∶3。
30.权利要求21或22所述的工艺,其中所述的膜包括聚丙烯、聚偏二氟乙烯或其混合物的膜。
31.权利要求21或22所述的工艺,其中所述的膜包括聚丙烯膜。
32.权利要求21或22所述的工艺,其中所述的组合物处于30℃-50℃的温度下。
33.权利要求21或22所述的工艺,其中所述的组合物处于35℃-45℃的温度下。
34.权利要求21或22所述的工艺,其中所述的碱包括NaOH、KOH或其混合物。
35.权利要求21或22所述的工艺,其中所述的碱包括NaOH。
36.权利要求21或22所述的工艺,其中所述的另一水相用所述的碱处理,以达到至少为4的pH值。
37.权利要求21或22所述的工艺,还包含通过过滤分离获得Al(OH)3的步骤。
38.权利要求37所述的工艺,还包含清洗所述Al(OH)3的步骤。
39.权利要求21-22,38任何一项所述的工艺,还包括将Al(OH)3转化为Al2O3的步骤。
40.权利要求39所述的工艺,其中Al(OH)3转化为Al2O3在为800℃-1200℃的温度下进行。
41.一种将铝离子与组合物中所含的铁离子至少部分分离的工艺,所述工艺包括在pH至少为10的碱性条件下,选择性地沉淀至少一部分所述的铁离子,以及用中空纤维膜纯化沉淀的铁离子。
42.权利要求41所述的工艺,其中所述的铁离子从含有NaOH的碱性水性组合物中沉淀出来。
43.权利要求41所述的工艺,其中所述的铁离子从含有KOH的碱性的水性组合物中沉淀出来。
44.权利要求41所述的工艺,其中碱与所述组合物发生反应,以获得pH值至少为10的混合物,随后,将至少一部分所述的沉淀铁离子与所述混合物的其余部分分离。
45.权利要求44所述的工艺,其中通过过滤、倾析、离心或其组合的技术,使所述沉淀的铁离子与混合物的其余部分分离。
46.权利要求44或45所述的工艺,其中所述的碱选自KOH、NaOH及其混合物。
47.权利要求44或45所述的工艺,其中所述的碱为NaOH。
48.权利要求44或45所述的工艺,其中所述碱为KOH。
49.权利要求44或45所述的工艺,还包含用碱性溶液对所获得的沉淀的铁离子进行清洗的步骤。
50.权利要求49所述的工艺,其中碱性溶液为NaOH或KOH,其浓度为0.01M-0.02M。
51.权利要求44-45,50任何一项所述的工艺,其中所述的pH值至少为11。
52.权利要求44-45,50任何一项所述的工艺,其中所述的pH值至少为12。
53.权利要求44-45,50任何一项所述的工艺,其中所述的pH值为10.8-11.2。
54.权利要求44-45,50任何一项所述的工艺,其中所述的pH值为11.5-12.5。
55.一种从铝矿石中提取铝的工艺,所述工艺包含:
-用酸浸提所述的铝矿石以获得浸出液和固体残渣;
-通过以下方式去除所述浸出液中所含的至少一部分铁离子:使所述浸出液与碱反应,以达到至少为10的pH值并选择性地沉淀出至少一部分所述的铁离子,然后使所述沉淀出的至少一部分该铁离子与所述的浸出液分离,以获得富含铝的组合物。
56.权利要求55所述的工艺,其中所述的酸为HCl。
57.权利要求55所述的工艺,其中在至少80℃的温度下用HCl浸提铝矿石。
58.权利要求55所述的工艺,其中在至少90℃的温度下用HCl浸提铝矿石。
59.权利要求55所述的工艺,其中在100-110℃的温度下用HCl浸提铝矿石。
60.权利要求56-59任何一项所述的工艺,其中所述HCl的浓度为6M。
61.权利要求55-59任何一项所述的工艺,其中铝矿石的重量与酸的体积比为1/10。
62.权利要求55-59任何一项所述的工艺,其中至少一部分所述铁离子的去除是通过选择性地从含有NaOH的碱性水性组合物中沉淀出所述铁离子来完成的。
63.权利要求55-59任何一项所述的工艺,其中至少一部分所述铁离子的去除是通过选择性地从含有KOH的碱性水性组合物中沉淀出所述铁离子来完成的。
64.权利要求55-59任何一项所述的工艺,其中所述的碱选自KOH、NaOH及其混合物。
65.权利要求64所述的工艺,其中所述的碱为NaOH。
66.权利要求64所述的工艺,其中所述的碱为KOH。
67.权利要求55-59,65,66任何一项所述的工艺,其中通过过滤、倾析、离心或其组合的技术使所述沉淀的至少一部分铁离子与所述浸出液分离。
68.权利要求55-59,65,66任何一项所述的工艺,还包括用碱性溶液对所获得的沉淀的至少一部分铁离子进行清洗的步骤。
69.权利要求68所述的工艺,其中碱性溶液为浓度为0.01M-0.02M的NaOH或KOH。
70.权利要求55-59,65,66,69任何一项所述的工艺,其中所述的pH值至少为11。
71.权利要求55-59,65,66,69任何一项所述的工艺,其中所述的pH值至少为12。
72.权利要求55-59,65,66,69任何一项所述的工艺,其中所述的pH值为10.8-11.2。
73.权利55-59,65,66,69任何一项所述的工艺中,其中所述的pH值为11.5-12.5。
74.权利要求55-59,65,66,69任何一项所述的工艺中,其中所述的pH值为10-11。
75.权利要求55-59,65,66,69任何一项所述的工艺,还包括使用中空纤维膜纯化沉淀的铁离子的步骤。
76.权利要求55-59,65,66,69任何一项所述的工艺,其中所述的铝矿石在浸提处理之前进行粉碎和煅烧。
77.权利要求55-59,65,66,69任何一项所述的工艺,其中在去除所述的铁离子之前,使所述的浸出液与碱反应以提高该浸出液的pH值。
78.权利要求55-59,65,66,69任何一项所述的工艺,其中在去除所述的铁离子之前,对所述浸出液进行蒸馏以减小其体积。
79.权利要求55-59,65,66,69任何一项所述的工艺,还包含至少部分回收存在于所述富含铝的组合物中的铝离子的步骤。
80.权利要求79所述的工艺,其中在有机溶剂和酸溶液存在的条件下,用萃取剂对所述富含铝的组合物进行处理,以形成包含含有杂质的酸性水相和含有与所述萃取剂络合的铝离子的有机相的组合物,其中所说的萃取剂适合于选择性地与所述铝离子形成有机金属络合物,以及其中所述的铝离子通过使所述水相和所述有机相分离来回收。
81.权利要求80所述的工艺,其中所述酸性水相的pH值为2.5-3.5。
82.权利要求80或81所述的工艺,其中所述的萃取剂为次膦酸或其衍生物。
83.权利要求80或81所述的工艺,其中所述的萃取剂为双(2,4,4-三甲基戊基)膦酸。
84.权利要求80或81所述的工艺,其中所述的萃取剂相对于所述有机溶剂的浓度为10%-25%v/v。
85.权利要求80或81所述的工艺,其中所述的萃取剂相对于所述有机溶剂的浓度为20%v/v。
86.权利要求80或81所述的工艺,其中所述的有机溶剂选自C5-C12烷烃及其混合物。
87.权利要求80或81所述的工艺,其中所述的有机溶剂为庚烷。
88.权利要求80或81所述的工艺,其中所述的组合物中水相与有机相的体积比为1∶1-1∶3。
89.权利要求80或81所述的工艺,其中所述的有机相与所述的水相通过膜进行分离。
90.权利要求89所述的工艺,其中所述的膜为中空纤维膜。
91.权利要求90所述的工艺,其中所述的膜包括聚丙烯、聚偏二氟乙烯或其混合物的膜。
92.权利要求90所述的工艺,其中所述的膜包括聚丙烯膜。
93.权利要求80-81,90-92任何一项所述的工艺,其中所述的组合物处于30℃-50℃的温度下。
94.权利要求80-81,90-92任何一项所述的工艺,其中所述的组合物处于35℃-45℃的温度下。
95.权利要求80-81,90-92任何一项所述的工艺,其中当所述组合物通过所述的膜后,所述水相即与所述有机相分离,所述络合的铝离子被回收到有机相中,随后用HCl处理所述的有机相,以获得含有所述铝离子的水性组合物。
96.权利要求95所述的工艺,其中铝离子通过与碱接触而转化为Al(OH)3
97.权利要求96所述的工艺,还包括将Al(OH)3转化为Al2O3的步骤。
98.权利要求97所述的工艺,其中Al(OH)3转化为Al2O3是在800℃-1200℃的温度下进行的。
99.权利要求55-59,80-81,90-92,96-98任何一项所述的工艺,其中所述铝矿石是泥质板岩。
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US20130052103A1 (en) 2013-02-28
US20100150799A1 (en) 2010-06-17
US8337789B2 (en) 2012-12-25
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