由含金属氧化物材料获得的金属氯化物和金属 专利CN101448741AC类

基斯顿金属回收有限公司  2017-1-6 14:01
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用于由含金属氧化物材料制备至少一种金属氯化物的方法和设备,其包括在足以得到包含至少一种金属氧化物的煅烧产品的温度条件下煅烧含金属氧化物材料;并选择性地氯化(BB)该煅烧产品以形成至少一种金属氯化物(36B)。 说明

由含金属氧化物材料获得的金属氯化物和金属

相关申请的交叉引用

本申请要求2006年3月23日提交的美国专利申请序列号 11/386,852的优先权,将其内容以其整体在此引入。

技术领域

本发明涉及高温冶金术,其包括用于由具有金属氧化物成 分的材料例如煤层的相邻岩层,或从工业资源例如工厂的固体 副产品生产金属氯化物和金属的工艺和设备。

背景技术

历史上,由矿石生产用于金属加工工业的某些金属,该矿 石可包含高重量百分比的,例如高于50重量%的所关注的金属 氧化物(高等级来源)。铁通常由赤铁矿(Fe203)或磁铁矿(Fe304) 生产,铝由铝土矿(Al203)生产和钛由金红石(Ti02)或钛铁矿 (FeTi03)生产。它们的饱和含量和大部分这些矿石仅具有一种 金属氧化物的事实使得分离和纯化变得简单,使这些矿石成为 用于金属加工工业的首选来源。

然而,金属氧化物存在于所有种类的天然来源例如地质矿 产例如火成岩、沉积岩或变质岩材料或来自人造来源例如工业 废料。然而这些来源具有低于50重量。/。的金属氧化物含量,并 且经常以不同金属氧化物的混合形式存在。低金属氧化物含量 和高含量的不期望的硅酸盐和其它杂质导致其经济上定位为废 料。例如,在采煤时相邻岩层描述位于煤层之上或之下的材料; 通常由具有某些煤的岩石组成。在采煤期间,还挖掘出一些不 期望的相邻岩层。这种材料通常作为煤矿废料沉积在覆盖大面积地貌的地面上。典型地,煤矿废料包括含碳材料(煤、焦油等)

和含矿成分(metaliferous content)的岩石材料,根据相邻岩层的 地理特性,包括氧化铝、氧化铁、氧化钛和其它金属氧化物。 一般地,在煤矿废料中的金属氧化物的总重量百分比的范围在 煤矿废料的15至30重量%之间。在过去,这些量太低,以致不 会从经济上考虑将煤矿废料作为用于金属氯化物或元素金属的 来源。这同样适用于源自工业来源的含金属氧化物材料例如来 自燃煤电厂的灰烬,其由于地质成因,也具有在25%至35%之 间的金属氧化物重量百分比。

美国专利6,808,695B1公开了用于从粘土例如高岭石、伊利 石或硅质铝土矿中连续生产铝的工艺。美国专利4,349,420描述 了用于生产氯化铝的分级冷凝/蒸馏的工艺。

发明内容

本发明涉及用于生产金属氯化物和由这些金属氯化物生产 金属的方法和设备。对于这些产品的来源可为任意含金属氧化 物材料,该含金属氧化物材料还可优选含有可燃热源。此外, 能够将用于该方法和设备的能源保存和再循环,以将其用在整 个工艺和设备中的其它部分。

本发明涉及用于由含金属氧化物材料制备至少 一种金属氯 化物的方法,该方法包括在足以得到包含至少一种金属氧化物 的煅烧产物的温度条件下煅烧含金属氧化物材料,并选择性地 氯化该煅烧产物以形成至少 一种金属氯化物。

本发明进一步涉及在金属产生过程中保存能量的方法,其 包括燃烧热源以煅烧含金属氧化物材料,氯化至少 一 种金属氧 化物,并将能量从燃烧或氯化的至少之一转移到工艺的其它部此外本发明涉及一种设备,其包括用于氯化含金属氧化物 材料所构建和配置的氯化器,和用于再循环氯化器中释放的能 量所构建和配置的能量再循环器。

用于由含金属氧化物材料制备至少 一 种金属氯化物的方法 可进一步包含干燥含金属氧化物材料。

该至少 一种金属氧化物包括含以下的金属的至少 一种氧化

物:碱金属和碱土金属、除硼之外的第III主族、除碳和硅之外 的第IV主族、全部过渡金属、全部镧系元素和锕系元素。

含金属氧化物材料的煅烧可在1450和1750。F之间的温度下进行。

含金属氧化物材料可具有焓(heat content),并且该用于煅 烧的热可由存在于含金属氧化物材料中的焓提供。 煅烧可包括添加热源。

选择性氯化可包含碳氯化(carbochlorination)。 选择性氯化可包括确定在含金属氧化物材料中金属氧化物 的含量,和基于该确定在选择性氯化时使用氯源的量和来自碳 源的碳量。氯源的量可包括0.1至2重量%的过量,基于金属氧 化物含量。

所述至少一种金属氯化物可包含至少两种金属氯化物并将 该至少两种金属氯化物分离。该分离可包括在分级分离该至少 两种金属氯化物的压力和温度下分级冷凝/蒸馏该至少两种金 属氯化物。

该至少 一 种含金属氧化物材料可包括煤矿废料和/或固体 工业副产品。

该方法和设备可进一步包括:来自含金属氧化物材料的至 少一种金属氯化物可进一步包括从气体分离固体和通过分级冷 凝/蒸馏分离气态金属氯化物。从气体分离固体可包括从固体分离液体。而且,该分离包括从气体分离液体。此外,分级冷凝/

蒸馏可包括在大气压力和60psig之间的压力下的金属氯化物的 冷凝和蒸馏。

所述方法包括由金属氯化物形成金属。

该方法可进一步包括使用来自该工艺中的煅烧和选择性氯 化的至少之一的过量的热。

所述方法和设备可进一步包含发电。 可使用来自所述工艺和设备的能量。

所述方法和设备可进一步包含为俘获来自氯化器释放的能 量而构建和配置并将热转移至发电机组的热交换器。

所述方法和设备可进一步包含构建和配置以由来自氯化器 的至少 一种金属氯化物形成至少 一种金属的金属生产部。

所述方法和设备可进一步将来自发电机组的电力提供给金 属生产部。

附图说明

参考所提到的多个本发明的示例性实施方案的非限定性实 例,以下以详细的描述进一步描述本发明,其中全部几张-现图 中,同样的附图标记表示相同部分,其中:

图1为说明煤和煤矿废料干燥部的装置图的一部分;

图2为说明还描述为煅烧炉的流化床燃烧器装置图的一部

分;

图3为说明氯化系统的装置图的一部分;

图4为说明初级分离系统的装置图的一部分;

图5为说明第二分离系统和铝生产系统的装置图的一部分;

图6为说明TiCU分离系统和钛生产系统的示例性装置图;

和图7为说明氯化和分离工艺的实验室规模的实验的图。 具体实施方式

示于此处的细节作为实例和仅出于本发明实施方案的说明 性讨论的目的,并且为了提供认为是最有用和易于理解本发明 的原则和概念方面的描述而提出。在这方面,没有进行以与比 用于本发明的基本理解所必须的更加详细地示出本发明的结构 细节的尝试,使用图的描述使本领域技术人员显而易见本发明 的几种形式如何在实践中具体化。

除非另有说明,提及的化合物或组分包括化合物或组分本 身,以及与其它化合物或组分的组合,例如化合物的混合物。

如此处使用的,单数形式包括复数参照,除非上下文另有 清楚地说明。

除非另有说明的情况,将用于说明书和权利要求书中表达 成分数量、反应条件等的所有数字理解为在所有例子中由词语 "约,,修饰。所以,除非表明相反,在以下说明书和所附的权利 要求书中所述的数值参数为近似值,其根据本发明要获得的所 期望的性质而变化。至少,并且不作为用与权利要求书范围等 同的学说限定申请的目的,各数值参数应根据有效数字的数值 和普通的四舍五入的方法解释。

另外,认为在本说明书内的数值范围的叙述是在该范围之

内的所有数值的公开。例如,如果范围为1至约50,则它被认为 包括例如l、 7、 34、 46.1、 23.7,或任何其它在该范围内的值。 术语金属氧化物描述可由金属和含氧化合物如氧,化学产 生的化合物。以下元素周期表的族为所考虑的金属:碱金属和 碱土金属族、除硼之外的第III主族、除碳和硅之外的第IV主族、 所有过渡金属、所有镧系元素和锕系元素。所有其它元素,包括硼、碳和硅为所考虑的非金属。术语氧化物还包括化合物的 任何中间形式例如,但不限定于,过氧化物、超氧化物和低氧 化物。

此外,应理解:还考虑将能够分解为金属氧化物和其它材

料的化合物看作含金属氧化物材料。例如,不限制本发明的范 围,可将金属碳酸盐看作含金属氧化物材料,这是因为在处理 如加热时,它分解为金属氧化物和二氧化石友。相似地,将由金 属氧化物和非金属氧化物产生的化合物也看作是含金属氧化物 材料。例如,铝硅酸盐为含金属氧化物材料,这是因为它们可 由氧化铝(金属氧化物)和二氧化硅(非金属氧化物)产生。所述方 法和设备涉及由含金属氧化物材料生产金属氯化物。含金属氧 化物材料可包括具有金属氧化物成分的任何材料以及此种材料 的混合物。因而,本发明的工艺和设备能够利用任何含金属氧 化物的材料。

含金属氧化物材料还可包含通常不被看作是用于获得金属 氯化物或金属的经济的和/或有用的来源的含金属氧化物材料。 因此,含金属氧化物材料可用于本发明的工艺和设备,这些含 金属氧化物材料具有低含量的至少 一 种金属氧化物,例如以致 于不被认为对于金属氯化物和/或金属的生产是经济的和/或有 用的低含量的金属氧化物。不限制本发明的范围,在根据本发 明的方法和设备中使用的材料包括废料例如煤矿废料、焦油、 炼油厂废料、燃煤电厂固体副产品、沥青混凝土废料,优选煤 矿废料和/或电厂固体副产品。

例如,根据本发明利用的材料可具有低金属氧化物含量,

例如金属氧化物含量低于约50重量%,且包括5至40重量%、 10 至35重量%和15至30重量%的范围。

优选含金属氧化物材料包含可燃成分,该可燃成分可以提供尽可能多的能量,优选在50至100%之间,更优选在60至100% 之间,最优选在80至100%之间,基于用于本工艺所需能量要求, 该工艺包括至少形成一种或多种金属氯化物,以及最优选形成 元素金属。理想地,含金属氧化物材料内在的焓足以提供对于 从形成一种或多种金属氯化物以及由此生产金属的工艺的全部 能量要求。

所述方法和设备包括氯化含金属氧化物材料的以形成可以 转化为元素金属的金属氯化物。优选地,所述氯化包括选择性 氯化。选择性氯化描述为由含金属氧化物材料产生金属氯化物。 选择该方法的条件和氯化剂的量以形成金属氯化物而基本不形 成非金属氯化物。例如,不限定方法和设备,如果将燃煤电厂 煤灰用作含金属氧化物材料,该含金属氧化物材料具有作为成 分的含硅材料例如二氧化硅和硅酸盐,此外还有氧化铝和氧化 钠,根据本发明的选择性氯化将提供氯化铝和氯化钠,而基本 不包含氯化硅。此外,应了解根据本发明的用于选择性氯化的 方法和设备不使用也不需要除氯化剂之外的任何催化剂,例如 含硫化合物。生产的非金属氯化物的量理想地为零,或基本上 低于约10重量%,更优选低于约5重量%,最优选低于约1重量%, 基于初始材料的总重量。

氯化剂包括氯源和还原剂。氯源可包括氯气和/或任何提供 元素氯的化合物。还原剂可包括能够还原包含在金属氧化物中 的氧的任何化合物,例如含碳化合物,包括碳、煤、有机化合 物,和天然气; 一氧化碳;还可考虑将其它金属例如铁作为还 原剂。氯源和还原剂可存在于混合物中和/或可包含相同的化合 物,举例如氯化有机材料,例如光气或氯化脂族化合物,例如 氯仿或四氯化碳或氯化芳香族化合物例如氯苯。优选地,氯化 剂不包含水分。元素氯源和/或还原剂可以任何方式干燥,例如还原剂能够以与用于含金属氧化物材料描述的干燥工艺相同的 方式干燥。而且,氯化剂可包含氯化氢。

此外,本发明提供用于由含金属氧化物材料制备金属氯化 物的方法和设备,其中氯化包含碳氯化,优选使用选择性氯化, 因而提供选择性碳氯化。在这方面,碳氯化描述了用于由金属 氧化物产生金属氯化物的方法,该方法使用如上所述的氯化剂, 优选氯气和含碳还原剂,优选碳源如煤。而且,氯源可包括氯 化有机材料。可使用这些材料的任意组合。在所述方法中氯和 含碳还原剂的组合导致由金属氧化物形成金属氯化物。因而,

金属氧化物的氧化物阴离子(oxide anions)可形成一氧化碳和/ 或优选二氧化碳。

本发明还提供用于通过分级冷凝/蒸馏分离气态金属氯化 物的方法和设备。优选在高于大气压下,将热气态金属氯化物 的混合物逐渐冷却。根据多种金属氯化物的压力/温度相图,提 高的压力导致金属氯化物的冷凝(气-液转化)而非发生在通常 大气压下的凝华(气-固转化)。优选金属氯化物的冷凝,这是因 为,与凝华相比,它使金属氯化物混合物更有效地分离。所以,

本发明优选通过利用从气态至液态的分级冷凝/蒸馏实现金属 氯化物的高纯度分离。

所述方法和设备还可以提供热源的积极有效的使用,使该 工艺经济上可行。可将在该工艺中释放的热/能量转移,以供能 给工艺的其它部分。例如,在煅烧炉或氯化器中产生的热可用 于干燥含金属氧化物材料的供给进料以除去水分和湿气。而且, 对于该工艺可外部使用来自煅烧炉或氯化器的热,或还可将其 用于例如发电,可将该电力随后在金属产生部中外部使用和/ 或内部使用,从而将分离的金属氯化物还原为元素金属。

此外,在积极有效地使用热的范围内,所述方法和设备可包括使用含金属氧化物材料的焓。优选地,对于该工艺,不需 要焓的外部来源。例如,不限定本发明的范围,当将煤矿废料 用作含金属氧化物材料时,优选不外加能量例如添加煤加入到 该工艺中,且利用煤矿废料的焓以提供全部或基本全部的工艺 能量要求。然而,根据工艺的能量要求,可添加高达10重量%,

高达20重量%,高达30重量%的煤矿废料总重量的添加煤。可 将天然气用作用于煅烧炉的防止灭焰源。

根据本发明的工艺和设备可为全部位于一个地方的系统的 一部分,或者可包含能够位于彼此附近或位于相对于彼此遥远 的各种工艺步骤和设备。优选地,出于经济的和/或加工效率的 目的,将用于将金属氧化物加工为金属的工艺和设备在一个地 方进行和放置。因此,当该工艺的各部分可在不同的位置进行, 且设备可放置在不同位置时,优选用于使含金属氧化物材料加 工成金属的设备包括位于同 一位置的系统。

本发明可提供一种装置,其包括用于干燥材料如含金属氧 化物材料和/或含碳材料以去除水分和湿气的干燥部。干燥部可 拥有输送设备,例如输送机或带,以输送干燥的材料至煅烧部, 在煅烧部中可煅烧干燥的进料。

煅烧部可进 一 步包括输送组件以输送热煤灰至氯化部。氯 化部可包括为了氯化,优选选择性氯化,和最优选选择性碳氯 化而构建和配置的反应室。例如,反应室可包括适合的入口, 以使干燥的含碳材料如干燥的煤、天然气或油与氯源如氯和来 自煅烧部的热固体产品组合。此外,反应室可包括用于气体如 氮气的入口。氯化部用于由热固体产品形成金属氯化物,然后 将金属氯化物输送或转移至分离部。氯化部的压力可高于在分 离部第一阶段分级冷凝/蒸馏单元中的压力。

干燥部、煅烧部和氯化部可包括足以得到干燥、煅烧和氯化的任何设备。此种设备可为固定床或流化床结构,并可包括 各种流动介质例如惰性气体如氮气或空气和烟气。

分离部可包括将固体从液体分离和将固体从气体分离的分 离器,例如旋风分离器,以及将液体从气体分离的分离器。此 外,分离部可包括对于各期望的金属氯化物产品的至少 一 种分 级冷凝/蒸馏单元,其中不同物理性质的气态金属氯化物可有效 地分离。为了进一步加工和处理,分离部可进一步包括输送已 分离金属氯化物的输送设备,例如所述方法和设备可以包括金 属生产系统,该金属生产系统包含反应室,在该反应室中,金 属可通过例如电解工艺或通过使用还原剂如石威金属和;威土金 属,由获得的金属氯化物产生。分离部可包括用于实现分离的 任意设备,且优选包括至少一种用于分离气态金属氯化物的分 级冷凝/蒸馏单元,且优选多个冷凝/蒸馏单元。

此外,基于以上扩展,可将含金属氧化物材料干燥至其变 为适合燃烧的足够程度。材料的干燥可用于除去游离水例如在 材料中的水分和湿气。优选干燥的材料,以避免在工艺中任何 非常不期望的蒸气产生。优选地,在装入煅烧炉之前,在材料 中不包含游离水。然而,基于含金属氧化物材料的总重量,范 围在0至10重量%之间的游离水是可接受的,不会对工艺造成损 害,例如由于不必要的水气产生导致热的过度浪费。优选连续 干燥直至废料没有水分、湿气或非结合水。

将干燥的材料输送至煅烧炉,在煅烧炉中,将其在1450至 1750。F之间,优选在1500至1600。F之间,最优选在1550至1570°F 之间的温度下煅烧。煅烧是将材料加热至一高温而不导致材料 熔合,镏出挥发性成分或导致变化如粉碎的作用或工艺。非可 燃材料可包括具有多种化学式例如MgAl2(Si04)3的各种铝硅酸 盐。这种非可燃材料的煅烧通过破坏铝硅酸盐(alumosilicate)骨架中的键和导致铝硅酸盐分解为氧化铝、氧化镁和二氧化硅造 成结构中的变化。煅烧材料用作用于该工艺的中间材料。

可将煅烧在氧化气氛如空气和/或再循环的烟气中进行。存 在于含金属氧化物材料中的可燃材料可在氧化气氛中燃烧,从 而提供能够用于该工艺的热。例如,当使用煤矿废料时,在煅 烧期间的燃烧可通过存在于含金属氧化物材料的焓提供燃料。 因此,例如,碳材料如存在于煤矿废料中的残余煤可作为热源。 如果要求,可添加可燃材料的补充源例如煤、天然气或油等。

燃烧之后,将热固体产品输送至氯化室,在氯化室中,利 用氯化,优选选择性氯化和更优选选择性碳氯化形成金属氯化 物。可将热固体产品与氯化剂,优选干燥的氯化剂混合。

此外,氯源例如氯气可由来自金属车间的再循环工艺供给。 例如,氯气可由来自金属车间和/或来自氯贮存单元的再循环工 艺供给。还原剂可由干燥器供给。在要求选择性氯化的情况下, 可控制加入的还原剂量和氯量,以产生金属氧化物的氯化。测 量的量可通过分析方法确定,以给出存在于含金属氧化物材料 中的金属氧化物的含量,例如存在与煤矿废料中或煤灰中的金 属氧化物的重量百分比。然后,可计算还原剂和氯的测量量以 满足如此处所示的对于铝、铁和钛的化学反应式。

A1203 + 3C12 + 3C -> 2A1C13 + 3CO A1203 + 3C12 + 1.5C 2A1C13 + 1.5C02 Fe203 + 3C12 + 3C今2FeCl3 + 3CO Fe203 + 3C12 + 1.5C 2FeCl3 + 1.5C02 Ti02 + 2C12 + 2C + TiCl4 + 2CO Ti02 + 2C12 + C + TiCl4 + C02

限定氯和还原剂的量以及省略催化剂如含硫化合物,例如 硫化氢,可避免氧化硅的氯化。因此,可将不期望的副产品的形成最小化。选择性氯化之后,可将主要包含氧化硅的未氯化 的剩余物与形成的金属氯化物分离,该金属氯化物以液态熔体

形式存在,例如NaCl或MgCl2,或以气体形式存在,例如AlCl3、 FeCl3。在工艺中形成的一氧化碳可再循环,以进一步燃烧为二 氧化碳。例如,可使用基于金属氧化物成分的氯的化学计量量。 而且,可将基于金属氧化物成分达到约10重量%、优选达到约5 重量%、更优选达到约2重量%、最优选在0.1至2重量%之间过 量的氯直接导入氯化器中,以实现金属氯化物的最大产率。此 外,可使用达到约10重量%、优选在约5至约10重量%之间、最 优选在约7重量%至约10重量%之间的过量的还原剂,基于金属 氧化物成分。

氯化之后,将固体从气体和如果存在的液体中分离,并将 气体和如果存在的液体进行分离技术处理。优选地,将金属氯 化物的气体混合物使用分级冷凝/蒸馏分离。

例如,气态金属氯化物可直接导入分离部,在分离部中, 气体通过在升高的压力下逐渐冷却而分级冷凝和蒸馏。将在分 离部中的压力升高,范围从大气压(〜14.7psig)至80psig、优选在 20psig至70psig之间、最优选在40至60psig之间。在升高的压力 下,将气体分级冷却,导致一种金属氯化物接着另一种金属氯 化物冷凝和蒸馏。冷凝和蒸馏温度依赖于升高的压力,并可处 于100。F至1000。F之间的任何位置。然而,不限定所述方法和所 述工艺的范围,如果升高的压力选择在50psig下,包含金属组 (metal group)铝、钬和铁的金属氯化物的冷凝和蒸馏温度可在 275至675。F之间。冷凝和蒸馏温度可由本技术领域中已知的各 种物质的相图推导出。此外,除金属氯化物气体的分级冷却之 外,该方法还使如果需要的冷却工艺期间所升高的压力改变, 从而得到金属氯化物种类之间的最大分离。应了解:由于液态或气态的氯化剂和金属氯化物的腐蚀特 性,该方法和设备可包括惰性和防腐蚀材料,以避免在产生的 金属氯化物或未反应的氯化剂和设备之间的任何反应。这些防 护措施包括利用防腐蚀材料。例如,不限制本发明的范围,氯 化器的壁可内衬有包含高二氧化硅酸性砖或碳化硅结合砖的耐

火内衬;和出口和输送金属氯化物和其它腐蚀性反应产品的管 道可以包含陶资内衬管或耐腐蚀高镍合金管。对于400。F以下的 温度,可以考虑聚四氟乙烯(tetrafl丽inated polyethylene)内衬。 对于本发明的以下非限定实施方案,将给出图的参考,在 该实施方案中,将煤矿废料或电厂的固体副产品用作含金属氧 化物材料,并对用于金属氯化物和金属生产的示例性工艺和设 备进行讨论。例如,煤矿废料可具有含量为5-35重量%的碳、 0.25-0.75重量%的氢、10-12重量%的水、35-45重量%的二氧化 硅、15-25重量%的氧化铝、1-3重量%的氧化铁、0.5-1.5重量% 的氧化钛和痕量的其它金属氧化物。尽管,所述方法发现使用 上述组成的煤矿废料的应用,但还可考虑其它组成的煤矿废料。 因此,不限定在其它实施方案中考虑到的金属氧化物的范围, 煤矿废料可以以变动的浓度包含例如以下金属的氧化物:镓、 铟、锗、锡、铅、锑、铋、钒、铬、铍、锰、钴、镍、铜、锌、 锆、釕、锇、铑、铱或铀。相似地,电厂煤灰可包含不同量的 金属氧化物。

在图l中,将废料(1)和/或原煤(1,)使用带或螺杆驱动的输 送机输送至压;争才几O中,并压碎为具有尺寸在约l至约20mm之 间,更优选在约3至约6mm之间,最优选约4mm的细颗粒,输送 至干燥器(A)中。将破碎的材料经管线2输送至干燥器A中。冷 却水管(14)从冷却塔(K)和冷却水泵(I)通过蒸汽冷凝器(G)进给 冷却水。G冷凝来自汽轮机(D1和D2)的蒸汽(9),因而将冷却水由约环境温度加热至约212。F,优选在约80至约180。F之间,最 优选在约IOO至约140。F之间。将冷凝物(7a),现在为锅炉进给 水直接导入用作贮存罐的锅炉水进给罐(F)中。然后将水用锅炉 进给泵(E)泵至锅炉/煅烧炉(B),并重复此循环。然后使用来自 蒸汽冷凝器的温冷却水流(11A),以在加热器H中将来自鼓风机 J的环境空气从环境温度加热至约212。F ,优选在约80至约180°F 之间、最优选在约95至约105。F之间。还使用温冷却水(ll)在流 化床干燥器(A)中加热煤。将H的排水经管线13 A和13返回至冷 却塔K。使用加热空气(12)干燥材料干燥器A以及循环水(11)流 经干燥器内的热交换器管,以提供干燥材料所需的大部分能量。 干燥材料随空气经管线17离开干燥器。使用在干燥工艺中产生 的一些温热空气(12A)和水(11B)干燥用于氯化反应的煤,如图3 所示。在煤干燥器中所用的水(11B)经管线13B返回至冷却塔。 在图2中,将已干燥的材料经管线17投入大型进料机(P), 并将废料和热源的混合物经管线18放出,用输送机(Q,管线19) 进给到流化床煅烧炉(B)中。加入热源以增加用于添加蒸汽和电 力生产的锅炉的煃。例如为了保持该方法和装置自身电力充足, 可利用相对于煤矿废料给料范围为直至约30重量%的煤添加。 将经管线2 0提供的天然气用作防灭焰源和/或燃料补充。将锅炉 内容物在约1450至约1750。F之间、优选在约1475至约1650。F之 间、最优选在1550至1570。F之间的控制温度范围内燃烧。将燃 气随同从管线(25)再循环的 一 些燃料气体,经管线26通过设计 为使固体均匀地提升和流化的分布喷水管,加入到锅炉的底部。 控制空气流量和速度,以维持规定的床高度和提及的温度范围。 煤灰内部的内键被破坏,且各个单独的氧化物不具有任何化学 结合水键。例如,煤矿废料灰的典型的组成为约55至65%氧化 硅、约25至35%氧化铝、约2至4%氧化铁、约1至2%氧化钛和余量的各种痕量材料。随同碳一起,将夹带的氢气燃烧,贡献焓。 将夹带的水蒸发,并经管线6随燃料气体放出。将大多数固体(煤 灰)随送入包括至少一个旋风分离器(S)的气/固分离系统燃料气

体放出。将剩余的煤灰经管线27落入至锅炉底部,并经输送机 R与来自旋风分离器后的管线28的经分离固体再会合。在通过 传输机如螺杆驱动的输送机系统U输送至氯化系统之前,液流 2 7和2 8落入贮存设备例如料斗(T)。这里将金属氧化物与碳源例 如煤(还原剂)和氯源例如氯气混合,以生产金属氧化物的氯化 物。煤灰中的氧化物成分不限于所列举的化合物。煤灰可以包 含任何中间氧化物,例如过氧化物和超氧化物(superoxides)。 以下描述氯化过程。

仍参考图2,从鼓风机W经管线24鼓入的燃烧空气通过(旋 风分离器后)燃料气体(22)在加热器V中预热到约275至约325。F 之间,优选约300。F。预热空气后,将现在约1300。F的冷却的燃 料气体(23)进一步在下游(见图3)使用,例如用于蒸发和加热来 自再循环单元或中间贝i存单元如有轨车的氯源例如氯气。热空

气还辅助加热铝生产池和钛生产池中的熔融盐电解质。在锅炉 的超级加热器中生产的蒸汽在经管线6送入至汽轮机(Dl和D2) 之前,达到约500psi和约800。F以上。将来自氯化器的蒸汽(39) 在进入D1和D2之前与液流6结合。可将来自汽轮机的低压蒸汽 在返回锅炉作为进给水(7b)之前,用于加热或冷却其它工艺的 液流,最合适的是在铝池中的盐电解质。将后汽轮机蒸汽的剩 余物直接送入冷凝器G,以将其冷凝并作为进给水流10泵送返 回至锅炉/煅烧炉。

在图3中,将还原剂例如含碳材料如煤(碳还原剂)在碳氯化 工艺之前干燥,从而避免在该工艺期间腐蚀性氯化氢的形成。 如上所述,这可在图1中的废料干燥器系统的小规模复制中实现。将煤经管线30输送至干燥器X的顶部。加热的空气(12A)使 煤流化,且当温水(11B)经过内部热交换器管时,将温水(11B) 作为初级传热流体使用。水从干燥器经管线13B放出并返回至 冷却塔(K,图l)。流化空气随同温热干燥的煤一起经31离开干 燥器X的顶部,且经过旋风分离器(Y)和/或袋式过滤器(Z)以使 煤(33)从空气(32)分离。将分离的煤压碎至颗粒尺寸在约l至 20mm之间,优选在约3至6mm之间,最优选约4mm,并将其通 过输送机A A经管线3 4进给至氯化器。将过滤后空气(15 B)排入 大气。

仍参考图3,将来自旋风分离器S的煤灰通过输送设备U例 如螺杆驱动输送机系统(管线29)输送至氯化器(BB)中,并与干 燥的碳源和氯源如氯气在氯化器BB的流化床反应器中混合。将 热煤灰金属氧化物通过氯源氯化,产生金属氯化物和氧气。将 氧气通过碳源还原,即,热氧气燃烧碳产生C0和C02混合物。 氯来自两个供应源:大部分是从金属装置再循环(42)直接进入 反应器和通过有轨车以液化的方式引入(40)的任何必要的补 充。液态氯用空气或氮气直接填塞(44)在有轨车(GG)外至气化 室(FF)中,在气化室中液态氯通过来自锅炉的热燃料气体(23) 气化。使有轨车出口(45)通到作为安全机构的洗涤器。然后输 送燃料气体(43)通过一 系列分离器以尝试分离各种气体用于进 一步加工。随后将氯气(41)进给到反应器中。如上所述,必需 氯量通过对于在含金属氧化物起始材料中或在来自锅炉B中的 热煤灰中的金属氧化物的重量百分比的分析确定。优选地,将 达到约5重量%、更优选达到约2重量%、最优选在约0.1至约2 重量%之间的过量氯导入氯化器中,以得到金属氯化物的最大 产率。相似地,经管线34进给到反应器中的干燥的还原剂(煤) 还具有达到约10重量%、优选约5重量%至约10重量%、最优选约7重量%至约10重量%之间的过量,以达到金属氯化物的最大 产率而不产生不期望的副产品。为了在氯化器内得到理想的流

化床,将干燥惰性气体如氮气(44B)加入到BB的底部。能够将 氯化器内部的压力维持在不同的水平,优选压力高于在分离单 元的第一阶段。

将主要由二氧化硅组成的非氯化固体随同金属氯化物、过 量氯和其它气体在约2000。F下经管线35排出反应器。排出温度 取决于液流29的组成,该组成是经常变化的。反应器直接卸料 到至少包含旋风分离器CC的分离系统中,在分离系统中,通过 管线38排出的固体从通过管线36排出的液/气混合物中分离。分 离器DD使经管线36B的液体碱金属/碱土金属氯化物从直接通 过管线36A的气体分离。可将液流36A输送经过另外的分离设备 (旋风分离器、离心分离机或过滤器),以将剩余的液体和固体 从气体分离。将从气体分离的所有固体使用输送机EE经管线38 输送至固体加工装置。然后将来自D D经管线3 6 A的无液体的气 体冷却,使用其能量以在锅炉HH中使由管线10A(图l)供给的水 流沸腾,从而产生过热蒸汽,将该过热蒸汽经管线39送至汽轮 机D1和D2(图l)用于发电。锅炉HH接收来自锅炉进给水泵E(图 l)的进给水。然后将在约500至1000。F之间、更优选在约615至 约630之间、最优选约620。F的近似温度下的大部分冷却气体 (37A)输送至初级分离系统,但是一些能够再循环(37B)返回至 氯化器中。

在图4中,来自HH的气体流(37A)进入初级吸收器(II)的中 部,并通过要描述的再循环液体冷却。当向上流动的气体与向 下流动的液体接触时,气体冷却至约330至约370。F之间,优选 约350。F(在吸收器的底部),以冷凝FeCl3。初级吸收器的底部(重 关键部分(heavy key))液流(49A)包括冷凝的FeCl3,气态A1C13 、TiCU和其它痕量金属氯化物。将一些重关键组分液流再循环 (49B)返回至初级吸收器的入口 ,以获得最佳吸收。初级分离容 器的顶部液流(45)包括气态A1C13 、 TiCU和其它痕量金属氯化 物。将该液流通过冷凝器(JJ和KK)输送,以冷却和冷凝AlCl3 和TiCU。在约210至约220。F、优选约215。F温度下,将包含液 态A1C13和气态TiCU和其它痕量金属氯化物的初级冷凝器(JJ)的 冷凝物(46B)返回至初级吸收器中,以将其用作液体进料的主要 部分。将未冷凝的气体(46A)通入副冷凝器(sub-condenser) (KK),以除去温度在0。F以下作为冷液体的TiCU。需要已冷的 制冷系统来实现此副冷凝。冷凝物(47A)返回初级分离容器,以 用作液体进料的一部分,未冷凝的气体(47B)输送至TiCU冷凝 系统(图5)中以用于进一步加工。

仍参考图4,将来自初级吸收器的底部的冷凝的金属氯化物

(49A)输送至初级蒸馏柱(LL),在初级蒸馏柱中,FeCl3从较轻 的AlCl3和TiCU中蒸馏出来。将FeCl3经柱的底部液流(52)移除, 且将AlCl3和TiCU作为馏出液(50)移除。将再沸器(OO)中的温度 保持在约640至约675。F,优选约660。F。根据所需蒸气比率,将 煮沸的氯化物(53A)返回至初级蒸馏柱中,且剩余物为FeCl3产 品(53B)。将在管线50中的馏出液液流通过其温度保持在约330 至约370。F之间,优选约350。F的冷凝器MM。然后冷凝物(51) 进入回流罐(NN)保存容器中,在这里,冷凝物根据回流速率通 过再循环一些至初级蒸馏柱(51B)和将剩余物(51A)进给至二级 分离系统(图5)而分开。将初级分离系统维持在比FeCb和/或 AlCl3在约140至约675。F之间任意温度下会凝华或冷冻的压力 更大的压力下。优选此压力高于大气压力至约80psig,更优选 在约20至约60psig之间,最优选在约35至约45psig之间。

在图5中,来自初级蒸馏柱的馏出液(51A)流至二级吸收器(PP),且通过要描述的塔顶馏出液冷却。当向上流动的气体与

向下流动的液体接触时,该气体冷却在280至330。F之间,优选 300。F(在吸收器PP的底部)。塔顶冷凝器(QQ)在210至220。F之 间、优选215。F的温度下保持在PP的顶部。将液流55冷却,且 将气体混合物中的一部分TiCU冷凝并返回至PP。将冷凝物在落 回至PP的液流56A和导入至TiCU分离系统的液流56B之间分 开。当冷凝物接触A1C13时,将入口液流(51A)冷却至约330至约 365。F之间,优选约355。F。第二吸收器的底部(重关4建部分)液 流(54A)包括冷凝的AlCb和一些气态TiCU和其它痕量金属氯化 物。将一些重的液流再循环(54B)返回至第二吸收器的入口 ,以 获得最佳吸收,将剩余物输送至第二蒸镏柱(RR)。

仍参考图5,在第二蒸馏柱中,将更重的且由此更高沸点的 AlCl3在底部液流(59)中去除,并将局部再沸器(UU)维持在约 390至约430。F,优选约410。F。根据所要求的柱蒸汽速率,将液 流60A煮沸返回至该蒸馏柱中。剩余的柱底物(60B)为纯化的 A1C13 。然后将这种A1C13的纯化的液流冷凝至固态A1C13并从管 线61收集并输送至铝池室。将馏出液流57通过其温度保持在约 280至330。F之间,优选约300。F的冷凝器SS。然后冷凝物(58) 进入回流罐(TT)保存容器中,在这里,冷凝物根据回流速率, 通过将 一 些(58A)再循环至第二蒸馏柱以及将剩余物(58B和 58C)分别进给至TiCU分离系统和初级吸收器而分开。液流47B 来自在初级分离系统中的副冷凝器(KK)(图4)。将第二阶段分离 系统维持在比AlCh在约280至约430。F之间的任意温度下会凝 华的压力更大的压力下。优选地,该压力维持在高于大气压至 约60psig,更优选约20psig至约40psig之间,最优选在约25psig 至约35psig之间。

参考图6,来自第二蒸馏柱(RR)的液流58B,其包含TiCU、痕量钒化合物和其它未冷凝的气体,其进入T i C14蒸馏柱(W W)。

该柱有助于将TiCU从未冷凝的气体、任何氯化氧钒(V0C13)和 任何四氯化钒(VCU)分离。该钒化合物由煤灰中痕量的氧化钒 在氯化器中与氯气反应并释放出氧气或水,而形成和累积。因 为TiCl4的沸点高于V0C13的沸点,所以它在柱底液流(62)中离 开柱WW, VOCl3随着未冷凝的气体作为馏出物(64)离开柱。该 馏出物进入冷凝器XX并将其冷凝和冷却至约155至约165。F之 间,优选约160。F。该冷凝物(65)进入回流罐I1,在其中将它才艮 据回流速率送回至柱(6 5 A)或输送(6 5 B)以进 一 步处理。底部液 流(62)进入再沸器YY,其中TiCU沸腾并加热到295至310。F,优 选300。F。蒸汽(63A)根据所要求的蒸汽速率返回至柱,以及将 该液体(63B)输送至冷却器ZZ,其中将温度降低至约275-290。F。 将主要为V C14的冷凝物(6 6 B)收集以进 一 步纯化。然后未冷凝的 气体(66A)进入副冷却器(subcooler)A 1,其中温度降低至0°F以 下。将所有TiCU冷凝并经管线67输送至钛生产装置。将未冷凝 的气体(70)与液流65B会合,以进一步处理。将冷却器ZZ通过 冷却水(液流6 8)冷却,以及将副冷却器A1通过连续的制冷循环 (液流69)冷却。优选地,将TiCU纯化系统维持在高于大气压至 40psig,更优选高于大气压至约20psig,以及更优选在大气压至 约17psig之间以优化才喿作。

仍参考图6,对于电解还原法,将来自储罐Bl的TiCU使用 泵Cl泵送通过热交换器Dl,经管线71A到电解池中。将TiCU 溶解在通过管线72输送的熔融盐电解质中,并在阴极电解为熔 融钛。将在阳极产生的氯通过真空从电解池中去除,并经管线 42再循环返回至氯化器(见图3)。将熔融的钛经管线74A从电解 池中收集,并凝固为4定或板坯。这种方法可以连续地运行以使 效率最大化。该工艺称为吉纳塔法(Ginatta)法。仍参考图6,用于使用还原剂例如碱金属或碱土金属还原

TiCU的第二连续工艺在流化床反应器(E1)中进行。将还原剂经 管线7 7投入到立式反应器内,并使用经7 5输送的惰性气体流化, 使用来自管线76的添加的惰性气体补充,然后与TiCU反应,以 生产经液流7 9离开的钛粉末和石威金属氯化物或石威土金属氯化 物。在将TiCU蒸汽引入到反应器中并且反应热将温度升至碱金 属氯化物或碱土金属氯化物的熔点之前,可预热该床。为了防 止还原剂熔化,温度控制系统是适当的,例如包括蒸汽或冷却 剂夹套。 一旦流化和反应,排出物(79)在包含具有可选过滤器 的旋风分离器的单元F1中分离,并经管线80进给至分离容器 H2。也可将熔融的钛从反应器经液流78去除直接进入H2中。此 容器使经管线7 4 C的熔融钛从液流碱金属氯化物或碱土金属氯 化物和任何未反应的还原剂分离,该液流碱金属氯化物或碱土 金属氯化物和任何未反应的还原剂经管线81去除。然后,如果 需要,可输送钛用于进一步纯化。随后在其本身的电解池中分 离氯气,然后再循环返回至氯化器。将在此池中产生的氯返回 至氯化器。美国专利6,995,703公开了相似的方法,通过参考以 其整体在此引入。

从氯化钛中获得钛的另 一 种方法是通过熔融镁或钠的化学 还原。镁法,称为克劳尔法(Krollprocess)在不锈钢蒸馏罐中进 行。在将液态TiCl4緩慢进料之前,加热过量的镁。镁变为氯化 4美和TiCU变为Ti的反应作为间歇法在几天内进行。当反应进行 时,MgCl2周期性地从蒸馏罐中去除。反应完成之后,将Ti作为 "海绵,,或多孔金属去除。然后将海绵在真空电弧炉中熔融并冷 却几次以去除全部杂质。MgCh盐经过电解池生产熔融镁和氯 气。将镁送回至钛反应器,以及将氯气输送至氯化器。这种间 歇化学还原法也可使用金属钠进行。作为亨特(Hunter)法,这是已知的,并且与克劳尔法相似,只是由钠取代镁。克劳尔和亨 特法全部在间歇系统中进行,并包括从反应容器中提取海绵钛。

用于生产氯化铝(AlCb)的通用方法是铝土矿(含八1203的矿 石)和纯铝的氯化。AlCl3池已经成功地运4亍,^f旦是^皮认为是不 经济的,这是因为生产A1C13的高成本。此种电解法消耗比通常 使用的Hall-Heroult法一半还少的电能。Hall-Heroult法使用大约 6.35-7.25kwh/lb在3.0-4.0伏特下生产的铝。日产100吨Al的铝冶 炼厂使用1270-1450MWhr。 AlCl3电解法使用大约2.88kwh/lb在 1.8伏特下生产的铝。电解生产每天100吨Al将^f吏用576MWhr。

用于通过电解AlCh生产铝的工艺可如下进行:

参考图5,无水的AlCl3从其分离工艺经管线61输送至电解 池室VV1。由导管将固体分配至各单独的池给料罐。使各个罐 的出口通到洗涤系统以防止过压。洗涤器风机维持各个给料罐 轻度的真空,并且如果需要,当启动该电解池时,还用于洗涤 氯气。这些罐位于电解池上方以使得重力给料。将AlCb使用旋 转阀进给到电解池中,该旋转阀还将给料罐与在进料管线中的 任何气体隔离。AlCl3向下流动,并通过添加以克服在电解池中 的熔融盐电解质的静压的无水氯气对A1C13加压。氯气将A1C13 分配到熔融盐电解质中以快速溶解。

仍参考图5, A1C13电解池VV1由具有由保温砖或氮化含氧 硅制的完全耐火内衬的碳钢壳体构建,其可耐氯气和盐气氛。 每一个池使用高温保温材料隔热,以使热量损失最小化和保持 电解池的温度。在电解池内具有下部贮槽,以收集在阴极生产 的熔融铝。在电解池的上部区域存在熔融盐浴贮存器,其可以 连续补充AlCl3。电解池盖包括三个口, 一个用于将AlCh经管 线61进给至电解池贮存器中, 一个用于经管线42A排出生产的 氯气,第三条管线61A用于向下延伸进入下部铝金属贮槽中底部的汲取管(diptube)。使用汲取管从电解池中去除熔融铝。还 可能的是:使熔融铝从下部贮槽底部流入倾析槽中,以从任何 夹带的电解质分离铝。然后将铝进给至储罐,并将电解质泵送 或加压进给回电解池中。在贮存器之下是上端阳极、几个双极 电极,和下端阴极,全部由石墨构建。以叠置的方式配置电极。 每一个内电极空间由一个电极的上表面(其起到阳极表面的作 用)相对于另 一个电极的下表面(其起到阴极表面的作用)而限 定。电流、阳极表面积,和电压合并到称作k因数方程的方程中。 k因数越低,电解池越接近100%的效率运行。阳极-阴极距离越 小,电解池效率越高。电解质浴充满电解池所有未占用的空间, 当该电解质浴通过电极之间并与电流接触时,铝金属在阴极形 成和氯气在阳极形成。在阳极产生的氯气具有浮力,它的移动 用于进行浴循环,同时铝通过移动的浴从阴极表面沖走并从外 部流动浴中沉降出来。电流经汇流排(buss bar)流向电解池和流 至电解池之间以及电解池内从阴极到阳极通过电解质。电流密 度范围5-15安培/英寸2阳极表面积。

熔融盐电解质必须包括至少50%氯化钠(NaCl)和40%氯化 锂(LiCl)。剩余物必须包括至少5%A1C13和每个小于1 %的氯化钾 (KC1)、氯化镁(MgCl2)和氯化钙(CaCl2)。这种电解质浴能够维 持在约1220至约1316。F之间的温度下。

以下实施例说明本发明,并不解释为限制本发明的范围。 根据此处的本公开、图和权利要求书,实施例的变化和等同物 对于本领域熟练技术人员是显而易见的。

实施例

将已知量的煤矿废料磨碎成粗粉,并放置在温度受控的电 炉中。然后,将温度升到1550至1650。F之间,并保持直到材料 达到该温度。在图7中,在高温下保持几个小时后,将煤矿废料随同原煤(先前磨碎成粗粉)一起进给到氯化器中。同时,来自 氯钢瓶经管线l的氯气和来自氮钢瓶经管线5b的氮气喷射至氯 化器中。氮气的目的是帮助床流化。当氯气与经煅烧的煤矿废 料中的氧化物反应时,氧释放并燃烧原煤(碳)还原剂。在不锈

钢氯化器中的温度升至1850。F,以及气体、液体和流化的未反 应的固体流出顶部(液流la)。将一小部分反应器排出物再循环 (lb)到氯化器的底部,以得到最佳的反应。反应器排出物(la) 经过仿效固体去除操作的筛网和用于控制系统压力的节流阀。 当启动系统时,节流阀设置为50%打开。由于该阀打开,系统 的压力降低且在反应器排出物中的气体开始膨胀和冷却,这降 低了FeCl3冷凝器的冷却负担。

通过节流阀之后,液流2进入FeCl3冷凝器的底部,并通过 流经内蛇管的水冷却。流过蛇管的水控制冷凝器的温度,该温 度维持在大约400。F。在该温度下,在气体流中的FeCl3冷凝并 落到冷凝器的底部。将 一 小部分冷凝器流出物再循环(3b)返回 至入口,这有助于冷却。然后大多数流出物(3a)进入AlCl3冷凝 器,其中温度降低至约350。F,这依赖于系统的压力。这通过正 冷凝的热AlCl3蒸气与冷氮气/AlCl3固体和液体接触而实现。将 固态A1C13装填至给料斗并用氮气吹入冷凝器。氮气管线具有节 流阀,这可帮助保持系统压力平衡。当氮气/AlCl3混合物进入 冷凝器时, 一些固体熔融,这依赖于系统的压力。固态/液态混 合物冷却和冷凝气态AlCl3, AlCh落到冷凝器的底部。冷凝器 具有旋风分离器形状,气体以切线方向进入,这有助于任意携 带的固体的分离。 一小部分AlCh冷凝器排出物经液流4b再循环 至其入口 。气体流(4a)的剩余物然后输送至其完全按照FeCl3冷 凝器设计的TiCl4冷凝器的底部。TiCU流使用流动自来水冷凝并 在容器的底部收集。使用氢氧化钠溶液洗涤剩余气体以形成漂白剂。

实验结果如下: 分离:

在FeCb冷凝器中Fe浓度-88。/。作为Fe 在FeCl3冷凝器中Na浓度-10%作为Na 在FeCl3冷凝器中Al浓度-2.4%作为Al 在AlCl3冷凝器中Al浓度-99.4。/。作为Al 在AlCl3冷凝器中Fe浓度-0.37。/o作为Fe 在AlCl3冷凝器中Na浓度-0.06。/。作为Na 在TiCU冷凝器中发现钛,但不能确定量。 基于起始的1 lb煤矿废料的产率,该废料包含30重量%氧 化铝、3重量%氧化铁、1.5重量%氧化钛:

在产品容器中检测到0.035 lbs的FeCl3,其为85.4%的产

在产品容器中检测到0.48 lbs的A1C13,其为92.5%的产率 TiCU的产率不能确定。

产率不计算可能已经反应但没有冷凝的任何氯化物。

尽管本发明已对于其某些形式进行了非常详细地描述,但 其它形式也是可行的,在阅读说明书和研究图时,所示形式的

而且,此处形式的各种特征可以各种方式组合,以提供本发明 另外的形式。此外,出于描述清楚的目的,已使用某些术语, 但不限定本发明。因此,任何所附的权利要求应不限于此处包 含的优选形式的描述,且应包括全部改变、变体和等同物,如 图落在本发明的真正主旨和范围之内。

现已全部描述了本发明,对于本领域普通的技术人员应了 解本发明的方法能够带有宽的和等同范围的条件、配方和其它参数实现而不脱离本发明或其任何实施方案的范围。

据此,此处引用的所有专利和公布通过参考以其整体全部 引入。任何公布的引用是由于其在提交日期之前的公开,并不 应解释为一种许可,该许可为此公布是现有技术或本发明并未

被授权由于在先发明而先于此公布。

专利公开号:CN101448741A 专利状态/类型:申请 专利申请号:CN 200780018739 专利公开日:2009年6月3日 专利申请日:2007年3月22日 发明者:乔治·威廉姆·马图司威奇, 杰森·迈克尔·菲力普斯, 理查德·I·柴菲茨, 科里·克拉格·莫顿 申请人:基斯顿金属回收有限公司
被以下专利引用
引用专利 申请日期公开日 申请人专利名
CN103274479A *2013年6月4日2013年9月4日滨州坤宝化工有限责任公司一种用于三氯化铁生产的熔化氯化炉及生产工艺
CN103288141A *2013年6月4日2013年9月11日滨州坤宝化工有限责任公司一种用于生产三氯化铁的熔化氯化炉及其生产工艺
CN103288141B *2013年6月4日2015年5月20日滨州坤宝化工有限责任公司一种用于生产三氯化铁的熔化氯化炉及其生产工艺
* 由审查员引用
分类
国际分类号C01G1/06
合作分类C22B5/00, C01F7/56, C25C3/06, C01G49/10, C01G1/06, C01G23/022, B01J2219/00006, C01B9/02
欧洲专利分类号C25C3/06, C01G49/10, C01B9/02, C01G23/02B, C01G1/06
法律事件
日期代码事件说明
2009年6月3日C06Publication
2009年7月29日C10Entry into substantive examination
2015年11月25日C12Rejection of a patent application after its publication
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