CN105246574B - 陶瓷过滤元件以及用于制造陶瓷过滤元件的方法 - Google Patents
陶瓷过滤元件以及用于制造陶瓷过滤元件的方法 Download PDFInfo
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- CN105246574B CN105246574B CN201480028949.0A CN201480028949A CN105246574B CN 105246574 B CN105246574 B CN 105246574B CN 201480028949 A CN201480028949 A CN 201480028949A CN 105246574 B CN105246574 B CN 105246574B
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Abstract
本发明涉及陶瓷过滤元件(22),其用于在毛细抽吸干燥器中从含固体材料中去除液体。所述过滤元件包括由烧结的陶瓷微孔层(31)覆盖的陶瓷基体。烧结的微孔膜层设置有粗固体颗粒(71),粗固体颗粒的颗粒尺寸大于膜材料层(31)的孔尺寸,以形成纹理表面(50),所述纹理表面防止滤饼在预定的滤饼卸载之前从过滤元件的表面上滑落。
Description
技术领域
本发明总体上涉及陶瓷过滤元件。
背景技术
过滤是广泛使用的工序,通过该工序,浆料或固液混合物受迫穿过介质,固体保留在介质上而液相穿过介质。该工序在工业中通常是广为熟知的。过滤类型的示例包括深层过滤、压力和真空过滤、以及重力和离心过滤。
压力过滤器和真空过滤器均被用在选矿的脱水中。压力过滤器和真空过滤器之间的主要区别在于产生用于过滤的驱动力的方式。在压力过滤中,借助于(例如)隔膜、活塞、或外部装置(例如,供给泵)来在过滤腔中产生过压。结果,固体沉积在过滤介质上,而滤液流进滤液通道中。由于实现连续的滤饼卸载更加困难,因此压力过滤器经常以批量模式工作。
在真空过滤中,基于在滤液通道内产生的抽吸力形成滤饼。存在几种类型的真空过滤器,从带式过滤器到旋转式真空鼓状过滤器和旋转式真空盘状过滤器。
旋转式真空盘状过滤器用于过滤大规模的悬浮液,比如选矿的脱水。选矿的脱水除了生产具有低含水量的滤饼之外还要求大的容量。这种大的工序通常很耗费能量,因此需要用以降低单位能量消耗的装置。真空盘状过滤器可以包括多个过滤盘,所述多个过滤盘围绕中心管或轴同轴地串联布置。每个过滤盘可以由多个单独的过滤扇区(称为过滤板)形成,所述多个单独的过滤扇区围绕中心管或轴在径向平面中圆周地安装以形成过滤盘,并且当轴安装成旋转时,每个过滤板或扇区循序地置入浆料池中,并且进一步地,随着轴的继续旋转而升到池的外面。当过滤介质浸没到浆料池中时,在真空的影响下,滤饼形成在介质上。一旦过滤扇区或过滤板移到池的外面,孔在滤饼以预定的时间脱水时被清空,所述预定的时间主要受盘的旋转速度的限制。可以通过空气的反脉冲或通过刮擦来卸载滤饼,在此之后,再次启动循环。
在旋转式真空鼓状过滤器中,过滤元件(例如,过滤板)布置成形成大体连续的圆筒形壳体或包络面,即,过滤鼓。鼓旋转通过浆料池,并且真空将液体和固体抽吸到鼓表面上,液体部分被真空“抽吸”通过过滤介质到鼓的内部,并且滤液被泵走。固体粘附到鼓的外部并形成滤饼。随着鼓旋转,带有滤饼的过滤元件升到池的外面,滤饼被干燥并从鼓的表面上移除。
用于真空过滤器的最通常使用的过滤介质为聚合物过滤布和陶瓷膜过滤元件。鉴于使用布过滤介质需要重载真空泵(由于在滤饼的脱水期间通过布的真空度损失),而陶瓷过滤介质在其被湿润时不允许空气通过并且能够允许使用更小的真空泵,因此,产生了显著的节能效果。US7521012B2(EP1755870)公开了一种用于制造复合材料过滤板的方法。在完成大致平坦的过滤板10之后,可以采取额外的步骤以(例如)提供附加的功能和/或进一步地使过滤板能更适于随后附加地组装到更大的过滤装置中。这些步骤可以包括(例如):钻穿过过滤板的孔口;添加流量分配器和流动路径;去除毛边、铸口、和/或其它类似的不需要的残留模制废弃物;在表面施加疏水的或亲水的涂层;抛光表面或使表面粗糙;高压灭菌、蒸汽灭菌、或其它的化学消毒处理;以及封装。
在一些过滤应用(比如铁矿石应用)中,由于滤饼的重量和滤饼上的低压差,滤饼趋向于过早地从过滤板上分离。
发明内容
本发明的一个方面是为了减轻滤饼的过早分离的问题。根据独立权利要求的方法、过滤元件和装置实现本发明的各方面。本发明的实施例在从属权利要求中公开。
本发明的一个方面是一种用于制造过滤元件的方法,所述过滤元件用于将从在毛细抽吸干燥器中进行干燥的含固体材料中去除液体,所述过滤元件包含由陶瓷基体支撑的陶瓷微孔层,其中,所述方法包括:
提供陶瓷基体;
用陶瓷微孔材料层涂覆陶瓷基体;
将固体颗粒施加到膜材料层上,固体颗粒的颗粒尺寸大于膜材料层的孔尺寸;和
烧结包含有固体颗粒的陶瓷微孔膜材料。
在一个实施例中,所述涂覆包括将陶瓷基体浸到陶瓷浆料中,以形成微孔陶瓷膜。
在与前述任意实施例结合的实施例中,所述施加包括将固体颗粒喷涂到陶瓷微孔层上。
在与前述任意实施例结合的实施例中,所述固体颗粒包括氧化铝颗粒。
在与前述任意实施例结合的实施例中,所述方法包括:根据期望的摩擦效果,设定固体颗粒的大小和/或在陶瓷微孔膜上的期望的颗粒密度。
在与前述任意实施例结合的实施例中,颗粒尺寸介于10微米至800微米之间,优选介于40微米至300微米之间。
在与前述任意实施例结合的实施例中,在膜材料上的平均颗粒密度介于约50至250个颗粒/平方厘米之间。
本发明的另一方面是一种过滤元件,所述过滤元件用于从在毛细抽吸干燥器中进行干燥的含固体材料中去除液体,所述过滤元件包括由烧结的陶瓷微孔层覆盖的陶瓷基体,其中,所述烧结的微孔膜层包含粗固体颗粒,所述粗固体颗粒的颗粒尺寸大于膜材料层的孔尺寸。
本发明的又一方面是一种过滤装置,所述过滤装置包括一个或多个根据本发明的实施例的过滤元件。
附图说明
下面,参照附图,将通过示例性实施例更加详细地描述本发明,其中:
图1是示出了示例性盘状过滤装置的透视俯视图,本发明的实施例可以应用于其中;
图2是示例性扇形陶瓷过滤板的透视俯视图;
图3A、3B和3C示出了陶瓷过滤板的示例性结构,本发明的实施例可以应用于其中;
图4A、4B和4C示出了过滤循环的不同阶段;
图5A示出了设置有根据本发明的示例性实施例的粗纹理表面50的过滤板;
图5B是示出了实际陶瓷过滤板22的纹理表面50的放大部分的图片;
图5C是示出了纹理表面50的进一步放大的部分的另一幅图片;
图6A示出了根据一个实施例的示例性单体基体;
图6B示出了在图6A中显示的基体的横截面的俯视图;
图7A、7B和7C示出了浸渍涂敷工序的阶段;和
图7D示出了在膜浸渍涂敷之后将固体颗粒71喷涂在膜表面上的示例。
具体实施方式
本发明的原理能够应用于使任何工业过程(特别是矿物或采矿工业)中的流体材料干燥或脱水。在本文描述的实施例中,待过滤的材料指的是浆料,但是本发明的实施例不局限于这种类型的流体材料。浆料可以具有高固体浓度,例如,贱金属精矿(base metalconcentrates)、铁矿石、铬铁矿、铬铁合金、铜、金、钴、镍、锌、铅和黄铁矿。下面,示出了用于旋转式真空盘状过滤器的过滤板的示例性实施例,但是本发明的原理还能够应用于其它类型的真空过滤器(比如旋转式真空鼓状过滤器)的过滤介质。
图1是示出了示例性盘状过滤装置的透视俯视图,根据本发明的实施例的过滤板可以应用于其中。示例性盘状过滤装置10包括圆柱形鼓20,所述圆柱形鼓20通过轴承支撑在框架8上并且可以围绕鼓20的纵向轴线旋转,使得鼓的下部浸没在位于鼓20下方的浆料池9中。鼓驱动器12(比如电动马达、齿轮箱)设置用于转动鼓20。鼓20包括多个陶瓷过滤盘21,所述多个陶瓷过滤盘21围绕鼓20的中心轴线共轴地串联布置。例如,陶瓷过滤盘的数量可以介于2至20之间。每个盘21的直径可以很大,例如,介于1.5米至4米之间。可以应用本发明的实施例的市售盘状过滤器的示例包括由Outotec Oyj制造的型号CC-6、CC-15、CC-30、CC-45、CC-60、CC-96、CC-144的Outotec Larox CC过滤器。
每个过滤盘21可以由多个单独的扇形陶瓷过滤元件(称为过滤板)形成,所述扇形陶瓷过滤元件围绕鼓的中心轴线安装在径向平面阵列中,以形成大致连续和平坦的盘状表面。例如,过滤板的数量可以是12或15。图2是示例性扇形陶瓷过滤板的透视俯视图。过滤板22可以设置有安装部件,比如紧固毂26、27和28,紧固毂26、27和28用作将板22附接至鼓中的安装构件上的构件。图3A、3B和3C示出了可以应用本发明的实施例的陶瓷过滤板的示例性结构。微孔过滤板22可以包括第一抽吸结构31A、32A和相对的第二抽吸结构31B、32B。第一抽吸结构包括微孔膜31A和陶瓷基体32A,膜31A定位在陶瓷基体32A上。类似地,第二抽吸壁包括微孔膜31B和陶瓷基体32B。内部空间33限定在相对的第一抽吸结构31A、32A和第二抽吸结构31B、32B之间,形成夹层结构。过滤板22还可以设置有连接部件29,比如滤液管或滤液喷嘴,用于流体的汇聚。内部空间33提供一个或多个流体通道,所述一个或多个流体通道将(例如)通过管接头29与鼓20中的收集管流体连接。在收集管连接至真空泵时,过滤板22的内部空间33保持在负压处,即:在抽吸壁上保持压力差。膜31包含微孔,所述微孔与水接触时产生强烈的毛细作用。微孔膜31的孔尺寸优选介于0.2微米至5微米之间,并且孔尺寸将能够使得只有液体流经微孔层。内部空间33可以是敞开的空间,或者内部空间33可以填充有粒状核心材料,所述粒状核心材料起增强板的结构的作用。由于其孔尺寸很大和高体积分数的孔隙率,所述材料并不阻止进入中央内部空间33的液体的流动。内部空间33还可以包括支撑元件或分隔壁,以进一步增强板22的结构。板的边缘34可以通过涂漆或上釉或另外适当的密封方法进行密封,由此防止流经边缘。
在示例性实施例中,串联的盘的过滤板22布置在多排中,每一排形成盘21的一个扇区或区域。当过滤盘21的排旋转时,每个盘21的板22移进池9中并经过池9。因此,每个过滤板22在盘21的一转中经历四个不同的工序阶段或扇区。在滤饼形成阶段,局部真空被传递至过滤板22并且滤液在陶瓷板22浸没在浆料池9中时被抽吸通过过滤板22,并且在板22的表面上形成滤饼35。然后,中央内部空间33中的液体或滤液传递进收集管中,并进一步传递到鼓20的外面。板22在其离开池9之后进入滤饼干燥阶段(在图4B中示出)。在干燥阶段期间,还在过滤板22中保持局部真空或过压,以从滤饼35中抽吸更多的滤液并且将滤饼35保持在过滤板32的表面上。如果需要洗涤滤饼,则它在干燥阶段的起始时完成。在图4C示出的滤饼卸载阶段,滤饼35被陶瓷刮刀刮掉,使得在板22(在刮刀和板22之间的间隙)上留下薄滤饼。在卸载滤饼之后,在每一转的扇区清洗阶段(通常称为反洗或反冲阶段),利用过压将水或滤液沿着相反的方向泵过板22,以洗掉残留的滤饼并清洗过滤板的孔。
在一些过滤应用(比如铁矿石应用)中,由于滤饼的重量和滤饼上的低压差,滤饼倾向于过早从过滤板上分离。更具体地,铁矿石滤饼可以在实际预定的滤饼卸载之前的干燥阶段期间从过滤板22的表面上滑落。
根据本发明的一个方面,陶瓷过滤板的烧结的陶瓷微孔膜材料包含粗固体颗粒,以有效地增大过滤板和滤饼之间的接触面积,以增大滤饼和过滤板之间的摩擦力和粘附力,并因此防止滤饼在预定的滤饼卸载之前从过滤板的表面上滑落。固体颗粒提供了用于过滤板22的粗纹理表面50,如图5A、5B和5C所示。表面的外观像“砂纸”。纹理表面的摩擦力很高,并且其防止了滤饼从过滤板上掉落。图5B是示出了实际陶瓷过滤板22的纹理表面50的放大部分的图片。图5C是示出了纹理表面50的进一步放大的部分的另一幅图片。
在一个实施例中,固体颗粒包括氧化铝(Al2O3)颗粒。但是,还能够使用除了氧化铝之外的其它类型的颗粒。选择材料的标准可以是:颗粒在焙烧期间不应该熔融或改变膜的化学性质或以别的方式干扰制造过程。
固体颗粒的尺寸对增大滤饼和过滤板之间的摩擦力和粘附力具有影响。固体颗粒的颗粒尺寸大于膜材料层的孔尺寸。颗粒尺寸可以为孔尺寸的至少两倍,优选地,大于孔尺寸的十倍。颗粒的大小可以根据使用过滤板的应用进行选择。在特定的应用中,使用的颗粒尺寸可以介于40微米至300微米之间。在一些应用中,膜上摩擦力的非常小的增大可以足以避免滤饼的掉落问题。对于这种类型的应用来说,颗粒尺寸可以是10微米至100微米。在大的铁矿石颗粒介于0.5毫米至1.5毫米之间并且滤饼具有很高质量的应用中,膜的摩擦力必须显著地增大,并且可能有必要使用介于0.2毫米至0.8毫米之间的颗粒进行砂砾喷涂。
施加在膜上的颗粒数量(即,每单位面积上的颗粒密度)也影响摩擦力。优选地,颗粒的数量不应该太大,以便不影响膜的水力特性。在固体颗粒之间存在间隔和敞开的空间,所述间隔和敞开的空间暴露出微孔膜并允许膜的正常功能。正常的膜表面(即,所述空间)覆盖大部分膜表面(例如,70%-95%)。在示例性实施例中,平均颗粒密度可以介于约50至250个颗粒/每平方厘米(cm2)之间。应当理解,局部的颗粒密度可以在过滤板的表面上变化。例如,计量的最小密度可以是158个颗粒/cm2,最大密度为226个颗粒/cm2,以及平均密度为182个颗粒/cm2。在图5B和图5C中示出了具有该颗粒密度的纹理表面50的外观。可以根据使用过滤板的应用来选择适当的颗粒密度。颗粒尺寸和颗粒密度相互关联,因此其中一个的选择可以影响另一个的选择。
本发明的另一方面是用于制造过滤元件(比如过滤板22)的方法,所述过滤元件用于从将在毛细抽吸干燥器(比如旋转式真空盘状过滤器10)中干燥的含固体材料中去除液体。过滤元件或过滤板22可以包括由陶瓷基体32支撑的陶瓷微孔膜层31,例如,如在上文参照图2、3A、3B和3C所讨论的。
在一个实施例中,当制造陶瓷过滤元件时,首先由至少一个陶瓷基体32形成内层。可以利用任何适当的制造技术制造陶瓷基体。基体可以由呈粉末状的陶瓷材料制成,比如氧化铝和二氧化钛。陶瓷材料可以与结合介质和液体混合,使得形成的陶瓷混合物和用于期望的凹部区域或滤液通道的核心材料能够装入模具中。然后,模具中的材料被压制成生坯。在压制之后,生坯可以在高温下(例如,在介于800-1600摄氏度之间的温度下)烧结。因此,可以在单个模具中形成一体式陶瓷基体(所谓的单体板)。形成凹部区域或滤液通道的核心材料可以包括(例如)允许滤液流动的粒状核心材料。作为另一示例,形成凹部区域的核心材料可以在烧结期间通过陶瓷混合物的孔结构被烧尽。因此,基体包括呈核心材料形状的敞开的凹部区域或敞开的滤液通道。图6A示出了根据示例性实施例的单体基体32,其可以通过如上所述的模压制造。图6B示出了露出了滤液通道或凹部区域33的单体基体的横截面俯视图。
在一个实施例中,过滤板22的基体可以由半板制造并粘合在一起。每个半板可以通过(例如)模压制造。
在一个实施例中,陶瓷微孔膜层31可以通过浸渍涂敷工序制造在陶瓷基体32上,在图7A、7B和7C中示出了浸渍涂敷工序的示例。在浸渍涂敷工序中,基体32优选以恒定的速度浸没在膜材料浆料的悬浮液70中(图7A)。当基体32已经停留在膜材料浆料70内一段时间后,基体32优选以恒定的速度从基体浆料70中拉起。在拉起基体时,微孔膜材料31的薄层将其沉积在基体32上。在拉起期间,多余的膜材料浆料将从表面上排掉71。悬浮流体从微孔膜材料31上蒸发72,形成薄层(图7C)。膜层31的厚度可以是(例如)约1毫米。
在另一示例性实施例中,陶瓷微孔膜层31可以通过喷涂形成在陶瓷基体32上。
针对这一点,过滤板22的制造可以类似于传统过滤板的制造。通常来说,当膜层31在浸渍涂敷或喷涂或其它涂覆方法后已经干燥之后,涂覆有膜31的基体32将在高温下(例如,在介于1150-1550摄氏度之间的温度下)焙烧和烧结,形成最终的过滤板。
然而,在本发明的示例性实施例中,在浸渍涂敷或喷涂或其它涂覆方法之后以及在焙烧或烧结之前将固体颗粒施加在膜材料层31上。提供了纹理表面50的固体颗粒可以在膜浸渍涂敷之后立即通过喷涂(利用适当的喷涂工具72,例如,压缩空气喷涂枪)将固体颗粒71施加在膜表面31上(例如,砂砾喷涂工序),如图7D所示。膜31可能已经被稍微干燥,但是其在喷涂之前优选为仍然湿润的,因为喷涂的颗粒撞击并容易粘在湿润的膜表面31上。过滤板22在喷涂期间可以优选位于直立位置中。可以从距膜表面31恒定的距离处实施喷涂。喷雾71优选以恒定的速度沿着膜表面31移动,使得单位面积上撞击膜表面31的颗粒数量保持在期望的范围内。对于盘状过滤板来说,在过滤板22的两侧均实施颗粒喷涂。当膜层31在颗粒喷涂之后已经被干燥时,涂覆有膜31和固体颗粒的基体32将在高温下(例如,在介于1150-1550摄氏度之间的温度下)焙烧和烧结,形成最终的过滤板。在干燥和焙烧期间,喷涂的颗粒很好地固定并烧结在膜表面31上,以产生粗纹理50。
应当理解,在本文中使用时,术语“烧结”还指的是其它的在窑中加热到高温以实现第二粘结相(即,富硅相)的熔融。
尽管上文已经示出了用于旋转式真空盘状过滤器的过滤板的示例性实施例,但是本发明的原理也能够应用于其它类型的真空过滤器(比如旋转式真空鼓状过滤器)的过滤介质。
在其它实施例中,可以利用除喷涂之外的一些其它方法施加固体颗粒,比如颗粒摊涂、将颗粒添加到用于制造微孔膜31的膜浆料中,等。在通过将粗固体颗粒添加到膜浆料中来施加粗固体颗粒的情况下,颗粒将遍布膜的整个厚度。然而,在生产中喷涂方法更容易控制,使得颗粒密度处于期望的范围内,并且颗粒施加不会像用于使表面粗糙的其它研磨方法(比如喷砂)可能做出的那样改变膜的特性或局部地破坏膜。
通过阅读本申请,显而易见的是,本领域的技术人员能够以各种方式实施本发明构思。本发明及其实施例不局限于上文描述的示例,而是可以在权利要求的精神和范围内进行改变。
Claims (19)
1.一种用于制造过滤元件的方法,所述过滤元件用于从在毛细抽吸干燥器中进行干燥的含固体材料中去除液体,所述过滤元件包含由陶瓷基体支撑的陶瓷微孔膜层,其中,所述方法包括:
提供陶瓷基体;
用陶瓷微孔膜材料层涂覆陶瓷基体;
将固体颗粒施加到膜材料层上,固体颗粒的颗粒尺寸大于膜材料层的孔尺寸;和
烧结包含有固体颗粒的陶瓷微孔膜材料。
2.根据权利要求1所述的方法,其中,所述涂覆包括将陶瓷基体浸入陶瓷浆料中,以形成陶瓷微孔膜材料层。
3.根据权利要求1所述的方法,其中,所述施加包括将固体颗粒喷涂到陶瓷微孔层上。
4.根据权利要求2所述的方法,其中,所述施加包括将固体颗粒喷涂到陶瓷微孔层上。
5.根据权利要求1所述的方法,其中,根据期望的摩擦效果设定所述固体颗粒的颗粒尺寸和/或在膜材料上的期望的颗粒密度。
6.根据权利要求2所述的方法,其中,根据期望的摩擦效果设定所述固体颗粒的颗粒尺寸和/或在膜材料上的期望的颗粒密度。
7.根据权利要求3所述的方法,其中,根据期望的摩擦效果设定所述固体颗粒的颗粒尺寸和/或在膜材料上的期望的颗粒密度。
8.根据权利要求1所述的方法,其中,所述颗粒尺寸介于10微米至800微米之间。
9.根据权利要求1所述的方法,其中,所述颗粒尺寸介于40微米至300微米之间。
10.根据权利要求1所述的方法,其中,在膜材料上的平均颗粒密度介于50至250个颗粒/平方厘米之间。
11.根据权利要求2所述的方法,其中,在膜材料上的平均颗粒密度介于50至250个颗粒/平方厘米之间。
12.根据权利要求8所述的方法,其中,在膜材料上的平均颗粒密度介于50至250个颗粒/平方厘米之间。
13.根据权利要求1所述的方法,其中,所述固体颗粒包括氧化铝颗粒。
14.一种过滤元件,所述过滤元件用于从在毛细抽吸干燥器中进行干燥的含固体材料中去除液体,所述过滤元件包括由烧结的陶瓷微孔层覆盖的陶瓷基体,其中,烧结的陶瓷微孔膜层包含粗固体颗粒,所述粗固体颗粒的颗粒尺寸大于膜材料层的孔尺寸。
15.根据权利要求14所述的过滤元件,其中,所述固体颗粒包括氧化铝颗粒。
16.根据权利要求14所述的过滤元件,其中,所述颗粒尺寸介于10微米至800微米之间。
17.根据权利要求14所述的过滤元件,其中,在膜材料上的平均颗粒密度介于50至250个颗粒/平方厘米之间。
18.根据权利要求16所述的过滤元件,其中,在膜材料上的平均颗粒密度介于50至250个颗粒/平方厘米之间,并且颗粒尺寸介于40微米至300微米之间。
19.一种过滤装置,所述过滤装置包括一个或多个过滤元件,每个过滤元件还包括由烧结的陶瓷微孔层覆盖的陶瓷基体,其中,烧结的微孔膜层包含粗固体颗粒,所述粗固体颗粒的颗粒尺寸大于膜材料层的孔尺寸。
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FI20155796A (fi) * | 2015-11-03 | 2017-05-04 | Outotec Finland Oy | Menetelmä ja suodatinelementti |
US10729994B2 (en) * | 2015-12-03 | 2020-08-04 | Veolia Water Solutions & Technologies Support | Rotary disc filter |
WO2018031884A1 (en) | 2016-08-12 | 2018-02-15 | Evoqua Water Technologies Llc | Disc filter pre-screen dual media disc filter |
US11000791B2 (en) * | 2019-03-06 | 2021-05-11 | Veolia Water Solutions & Technologies Support | Rotary disc filter having backwash guides |
CA3132555A1 (en) | 2019-03-08 | 2020-09-17 | Steve C. Benesi | Filter apparatus, filter disc sectors, filter elements and uses |
CN110433545A (zh) * | 2019-08-29 | 2019-11-12 | 飞潮(上海)环境技术有限公司 | 一种过滤叶片 |
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WO2014188071A1 (en) | 2014-11-27 |
CN105246574A (zh) | 2016-01-13 |
EA030985B1 (ru) | 2018-10-31 |
BR112015028985A2 (pt) | 2017-07-25 |
SE539805C2 (en) | 2017-12-05 |
UA113691C2 (xx) | 2017-02-27 |
BR112015028985B1 (pt) | 2022-03-22 |
CA2912091C (en) | 2018-04-24 |
EA201591980A1 (ru) | 2016-08-31 |
AU2014270290B2 (en) | 2016-09-01 |
US20140346104A1 (en) | 2014-11-27 |
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SE1551549A1 (sv) | 2015-11-27 |
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