CN103459559A - 用于加氢转化的装置和方法 - Google Patents
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Abstract
本发明提供一种借助于催化剂用具有高温和高压的氢气加氢转化烃给料的装置。该装置是具有用于改善的气液分配的格栅板分配器的反应器容器。该分配器包括格栅板和泡帽组件,多个上升管延伸通过格栅板。每个上升管具有在格栅板之上的上部分和在格栅板之下的下部分,下部分终止于用于进入氢气和烃给料的敞开底端,上部分具有终止于外壳帽的闭合顶部。每个上升管具有至少一个竖直狭槽和至少一个侧孔,所述侧孔充分地尺寸确定成使得在操作中,在格栅板之下的区域中的液位在竖直狭槽之上并且在侧孔开口之下。
Description
相关申请的交叉引用
本申请基于35USC119要求申请日为2011年6月7日的美国临时专利申请第61/494,320号的权益。本申请要求上述申请的优先权和权益,上述申请的公开通过引用被合并于本文中。
技术领域
本发明涉及用于加氢转化工艺的反应器中的分配器组件、包含分配器组件的反应器和用于加氢转化的方法。
背景技术
“重”烃给料流、特别是石油残渣、焦油砂、沥青、页岩油等通常包含有害污染物,例如硫、氮、金属和有机金属化合物。从烃给料流去除有害组分的加氢转化工艺(例如加氢处理)是催化地处理重烃给料以增加它们的商业价值的已知方法。另一加氢转化工艺是用于从化石燃料、尤其是煤炭制备液态烃的费托(FT)工艺,该工艺通过转化成合成气,接着在FT催化剂上转化成液态烃。
已成功地用于将煤炭或重烃给料转化成较轻产品的催化反应器系统是沸腾床反应器。示例性的沸腾床反应器在以下工艺中使用:氢煤工艺,如美国专利第4,400,263号中所述;用于残渣的加氢处理的氢油工艺,如美国专利第4,526,676号中所述;也用于残渣的加氢处理的LC精炼工艺,如美国专利第4,886,644号中所述。使用胶质或分子催化剂炼制重油给料的另一示例性沸腾床反应器系统在美国专利第7,449,103号中被描述。用于加氢转化中的其它类型的反应器系统包括内部循环浆料反应器或液体再循环反应器,如美国专利公报第2007/0140927A1和2009/0134064A1号中所述,和流化床反应器,如美国专利第4,220,518号中所述。
在上述的一些反应器系统中,格栅板(或分配器托盘)将反应器的底部分分成两个区域。在操作中,格栅板上的催化剂和焦炭结块可以导致需要停机的反应器壁温度的大幅变化并且减小运行时间。通过格栅板的气体和液体流动的改善均匀分配是优化反应器性能、最小化格栅板上的焦炭和催化剂的积累和延长工艺运行时间的重要因素。需要一种针对气体和液体流动的均匀分配具有改善的分配设计的反应器系统。
发明内容
在一个方面中,本发明涉及一种借助于催化剂用具有高温和高压的氢气加氢转化烃给料的反应器,反应器容器包含格栅板组件,所述格栅板组件包括:格栅板,所述格栅板将所述反应器分成两个区域,在所述格栅板之上的区域和在所述格栅板之下的区域;泡帽组件,所述泡帽组件包括延伸通过所述格栅板以将氢气和烃给料从在所述格栅板之下的区域输送到在所述格栅板之上的区域的多个上升管;每个上升管具有在所述格栅板之上的上部分和在所述格栅板之下的下部分,所述下部分终止于用于进入氢气和烃给料的敞开底端,所述上部分具有终止于外壳帽的闭合顶部;所述上升管的所述下部分具有从所述敞开底端延伸的至少一个竖直狭槽;并且所述上升管的所述下部分具有至少一个侧孔开口,所述侧孔开口的尺寸足够大并且定位成使得在操作中,在所述格栅板之下的区域中的液位在所述竖直狭槽之上并且在所述侧孔开口之下。
在一个实施例中,所述上升管是双管上升管,具有内管和外管,限定在内管和外管之间的环形开口作为用于进入氢气和烃给料的敞开底端,并且侧孔开口位于外管上。
附图说明
图1是使用改进的气液分配装置的实施例的反应器系统的正视图,该反应器系统使用外部沸腾泵。
图2A是泡帽组件的实施例的横截面图。
图2B是泡帽组件的第二实施例的横截面图。
图3是图1中的反应器容器的局部的分解透视图,示出具有泡帽上升管的格栅板的一个实施例。
图4是通过泡帽组件的流动分配的示意图。
图5是加氢转化系统的示意图,该加氢转化系统使用浆相反应器、具有内部沸腾泵的沸腾床反应器和热分离器,改进的气液分配装置用于任一或两个反应器中。
具体实施方式
在一个实施例中,本发明涉及一种在用于加氢转化烃给料的高压反应器容器中使用的改进的气液分配装置,例如格栅板。该改进的气液分配装置可以用于在氢油工艺、LC精炼工艺、氢煤工艺、重油炼制工艺中使用的已知反应器。如本文中先前所述,这些反应器的使用在本领域中是公知的。本领域的技术人员将显而易见本文中所述的实施例可以具有在沸腾床反应器、浆料反应器、循环反应器或流化床反应器的范围之外的有用应用。它们可以单独地或组合地在适合于具有高温和高压的反应液体、液体-固体浆料、固体和气体的其它反应器类型(例如固定床反应器、聚合反应器和加氢反应器)中是有用的,从而用高压和高温(例如100至5000psi和300至1800°F)的氢处理烃给料。
在一个实施例中,反应器容器包含穿孔格栅板,该穿孔格栅板圆周地连接到反应器内壁。格栅板将反应器的底部分分成两个区域。该板可以用于支撑上部区域中的沸腾床、浆料床或固体催化剂颗粒的固定床。格栅板包含通过格栅板穿孔连接的多个泡帽上升管以便给料流流动通过,形成进入上部区域、例如催化剂床或浆料床的大量气泡。
取决于反应器容器的尺寸,多个上升管(短管)从每个格栅板孔向下延伸到格栅板的下侧之下例如大约8至24英寸。每个上升管带有在上升管的底部的至少一个竖直狭槽以帮助通过泡帽的双相流动。狭槽尺寸确定成使得如果油表面的升高高度将到达上升管的底部,则蒸气仍然可以经由狭槽进入上升管。在一个实施例中,狭槽尺寸确定成将液位保持在狭槽的中间高度附近。在一个实施例中,狭槽具有在1/8"到1"范围内的宽度,具有在2"到12"的范围内的竖直长度。在另一实施例中,竖直长度的范围为4到6"。在另一实施例中,狭槽具有在分配板之下的上升管的长度的1/8到1/2的范围内的竖直长度。
例如从环形分配器或喷洒器进给到反应器系统中的气体将在底部区域中脱离、积累在分配器托盘的下面并且形成气窝。在具有浆料催化剂给料的一个实施例中,浆料通过狭槽的底部敞开端部和下部分流动到上升管中。过量气体将向下推动液位并且通过狭槽的顶部分流动到上升管中。对于指定的气体速率,在狭槽的高度内建立稳态液位。通过分配器托盘的气体的流动分配对托盘组件的水平度敏感。即使对于完美水平的托盘,通过改变液位也将影响气流分配。
在反应器系统中,浆料通过在塔的底部的内部泵从下降管径向向外排出。该浆料流动的动量将朝着壁推动它并且导致接近壁区域的更高浆料水平。在例如如美国公报第2007/0140927A1和2009/0134064A1号(相关内容通过引用包括在本文中)中公开的使用浆料催化剂进行重油炼制的反应器系统的一个实施例中,反应器系统在起泡状况下操作并且气体速率可以不足够高以推动液位保持在狭槽的中间。在操作具有低气体速率的情况下,浆料水平将在壁区域中足够高以完全覆盖上升管上的狭槽并且仅仅留下在塔的中间的狭槽暴露于气窝。因此,仅仅在塔的中间的泡帽将具有气体流动通过,而接近壁的泡帽将主要具有浆料和很少量或没有气体流动通过它们。在具有更高液位的塔的一侧的泡帽上的狭槽可以完全浸没在液体中。因此,可能没有气体流动通过这些泡帽。在高温操作下,这将导致接近壁的泡帽中的焦炭形成,最终导致该区域中的堵塞和去流化。
在改进的反应器系统中,在分配器板之下的上升管部分具有用于气体流动到每个上升管中的至少一个侧孔。侧孔可以具有不同几何形状,例如圆形或椭圆形。在一个实施例中,侧孔在每个上升管的一侧。在第二实施例中,侧孔在每个上升管的两侧。在第三实施例中,多个侧孔围绕上升管的圆周等距离地间隔。在第四实施例中,沿着上升管的竖直长度的多个侧孔从顶部到底部成排,孔从所述孔的排的顶部到底部具有相同或不同的尺寸。
在一个实施例中,(最顶部)侧孔的(顶部)位于离分配板1到5"。在另一实施例中,(最顶部)侧孔的(顶部)位于离分配板至少2"。
侧孔是对于所有上升管具有相同尺寸的一个实施例。在另一实施例中,取决于分配板上的上升管的位置,侧孔具有不同尺寸。一个实施例中的侧孔尺寸足够大以确定成保持孔和(一个或多个)狭槽之间的浆料水平。在一个实施例中,孔具有在上升管开口的直径(上升管的直径)的1/16到1/2的范围内的直径。在另一实施例中,取决于操作中的设备的尺寸,侧孔具有开口的1/16"到1"的范围内的直径(或椭圆形开口的最短尺度)。在一个实施例中,侧孔的范围为开口的1/8到1/2"。
考虑包括但不限于上升管直径、粒度和密度、流动特性、流体性质、气体和液体和/或浆料通量等的因素,可以使用压力平衡模型、数据表设计工具和本领域中已知的计算机流体动态模型包、例如FLUENT确定侧孔的尺寸。具有(一个或多个)狭槽和(一个或多个)侧孔的改进的上升管设计允许关于气体速率的灵活操作,气流分配与变化的液位无关,允许到达分配器托盘的具有公差的均匀气体分配不水平。当操作以比设计规范更高的气体速率运行时,可以预料气窝将降低液位以允许额外气体流动通过上升管上的狭槽,同时仍然保持横越该部分的气体流动。
在防止催化剂回流到反应器(增压室)的底部分的沸腾床的一个实施例中,在格栅板之上的上升管部分具有止回阀部分以限制内部的流体流动。在一个实施例中,止回阀包括具有球和阀座的球止回阀。在改进的反应器系统的另一实施例中,允许流体在上升管中无阻塞地流动,即,在上升管中没有诸如止回阀或钢球的可动部件。代替止回阀,在一个实施例中泡帽上升管带有收缩部,例如文丘里或喉管喷嘴,该收缩部在具有限制开口的泡帽上升管中增强混合。考虑诸如流体性质和操作条件的因素,该收缩部可以尺寸确定成避免来自高剪切双相流动的泡沫形成。
参考图1,该图示出具有改进的气液分配剖面的反应器容器。反应器容器10装配有用于进给重油和含氢气体的入口管道12。出口管道24设计成通过管线24a抽出蒸气和液体。进入管道15用于新催化剂给料16,并且离开管道17用于抽出用过的催化剂14。重油给料通过管线11引入,而含氢气体通过管线13引入。两个给料可以经由在反应器的底部的管线12组合并且引入。给料穿过包含泡帽19的分配器板18,分配器板将流体从可以是增压室的下室40分配到床22中。液体和气体的混合物向上流动,并且催化剂颗粒由此通过由可以在反应器10的内部或外部的再循环泵20输送的气体流动和液体流动迫使变为沸腾运动。由该再循环泵输送的向上液体流动足以导致床22中的催化剂颗粒的质团膨胀,因此允许通过反应器10的如方向箭头21所示的气体和液体流动。
由于由泵提供的向上定向流动和由重力提供的向下力,催化剂床颗粒到达行程或沸腾的向上水平,而较轻液体和气体继续向上移动超过该水平。催化剂或催化剂-液体界面的上部水平显示为23,并且催化反应区域从横向分配器板18延伸到水平23。在稳定状态,很少的催化剂颗粒升高到催化剂-液体界面23之上。在界面23之上的体积29充满液体并且夹带气体或蒸气。气体和蒸气在再循环帽30中与液体分离,并且具有显著减小的气体和蒸气含量的液体再循环通过下降管25。气体、蒸气和液体产品一起通过管道24被抽出。在一个实施例中,多个竖直定向管道27和28提供反应区域和再循环帽30之间的流体连通。夹带气体的流体向上移动通过管道27和28,并且当离开这些管道的上端时,流体的一部分反向并且向下流动到并且通过再循环管道25到达再循环泵20,由此再循环通过反应器10的下部分。
图2B示出用于改进的气体浆料分配的泡帽组件的一个实施例的竖直截面。该实施例中的泡帽组件属于双管上升管类型,即,具有限定用于进入氢气和烃给料的环形开口的外管102和内管103,用内管的顶部105支撑钟帽104。帽外壳为具有锥形壁的钟形。钟帽的底部边缘107可以开槽或形成锯齿以具有锯齿形三角。外管103的底部边缘终止于110,与格栅空间之下的蒸气空间连通。内部管102的底部边缘111浸没在格栅板之下的液体之下。多个间隔器112位于内管和外管之间。在外管103上有至少一个侧孔(开口)108以便气体流动。在一个实施例(未显示)中,外管102包括至少一个竖直狭槽,该竖直狭槽从管的敞开底部分向上延伸以允许向上流动通过内管和外管之间的环形开口的气体通过。
参考图2B,该图示出泡帽组件的第二实施例的竖直截面。该实施例中的帽外壳在形状上为管状。上升管56包括提供下室40和催化剂床22之间的流体连通的流体出口60。泡帽19通过诸如焊接、垫圈、螺栓和螺母或它们的组合的紧固装置以这样的方式紧固到上升管56,使得泡帽19的下边缘19b位于分配器板18之上。上升管56包括定位成允许板18之下的气体进入上升管56中的至少一个狭槽58。在狭槽58之上和上升管56内有至少一个侧孔(开口)50以便气体流动。
图3是用于改善的气体浆料分配的图1和2B的格栅板18和泡帽组件的实施例的分解透视图。
图4是基于具有4英尺直径塔的大型冷流单元中的实验示出通过图2a的泡帽组件的流动分配的示意图,其中使用水/空气/砂模拟商业反应器系统中的油/氢/催化剂。如图中所示,气流的均匀分配通过上升管上的侧孔上的压降(“DP”)控制实现。在实验中,以0-12%的固体浓度操作冷流单元,固体是具有6微米的平均粒度的细硅砂。格栅板具有帽外径为3"的总共72个泡帽。在一个实验中,如现有技术中所教导的,不锈钢球安装在泡帽中以防止生成有害振动的催化剂浆料的回流,高速浆料和气体混合物流动通过支撑球的喉管。在第二实验中,去除球并且重新确定喉管的尺寸。
图5示出包含改进的格栅板设计的示例性沸腾床加氢处理反应器系统400。沸腾床加氢处理系统400包括浆相加氢裂化反应器402、热分离器404以及布置在浆相加氢裂化反应器402和热分离器404之间的沸腾床反应器430。重油给料406初始被混合并且用催化剂组分408进行调节。来自混合器410的经调节的给料由泵412加压、通过预热器413并且与氢气414一起通过位于浆相反应器402的底部处或附近的端口418连续地或周期性地进给到浆相反应器402中。在浆相反应器402的底部的搅拌器420有助于更均匀地分散给料406内的氢414,示意性地显示为气泡422。
作为搅拌器420的替代或附加,浆相反应器402可以包括再循环通道、再循环泵和改进的分配格栅板(未显示)以促进反应剂、催化剂和热的更均匀分散。给料406内的胶质或分子催化剂示意性地显示为催化剂颗粒424。将领会气泡422和催化剂颗粒424显示为过大尺寸使得可以在图中看到它们。实际上,它们很可能是裸眼不可见的。
在浆相反应器402内有氢和胶质或分子催化剂的情况下催化地炼制重油给料406以形成炼制给料426,该炼制给料与残余氢一起从浆相反应器402通过位于浆相反应器402的顶部或附近的输出口428连续地被抽出。炼制给料426可选地由泵432加压并且与补充氢414一起通过位于沸腾床反应器430的底部处或附近的输入口436引入沸腾床反应器430。炼制给料426也包含氢和浆料催化剂或分子(胶质)催化剂,示意性地显示为沸腾床反应器430内的催化剂颗粒424'在反应器430的上部分中的424"。具有改进的分配器格栅板470的沸腾床反应器430也包括在沸腾床反应器430的顶部处或附近的输出口438,另外的加氢处理的给料440通过该输出口被抽出。
在一个实施例中,在分配器格栅板470之上的膨胀的催化剂区域442还包括多孔载体催化剂444。在另一实施例中,仅仅用浆料催化剂或分子催化剂执行加氢转化。无催化剂区域448位于分配器格栅板470之下。上部无载体催化剂区域450位于膨胀催化剂区域442之上。浆料催化剂或分子催化剂424分散在包括膨胀催化剂区域442和无载体催化剂区域448、450、452的沸腾床反应器430内的给料中,由此可用于促进构成常规沸腾床反应器中的无催化剂区域的区域内的炼制反应。沸腾床反应器430内的给料借助于与沸腾泵454连通的再循环通道452从上部无载体催化剂区域450连续地再循环到下部无载体催化剂区域448。漏斗状再循环帽456在再循环通道452的顶部,通过该再循环帽从上部无载体催化剂区域450抽出给料。再循环的给料与新炼制的给料426和补充氢气434混合。
在使用载体催化剂的一个实施例中,新载体催化剂444通过催化剂输入管458引入沸腾床反应器430中,并且用过的载体催化剂444通过催化剂抽出管460被抽出。从沸腾床反应器430抽出的加氢处理的给料440被引入热分离器404中,其中挥发部分405从热分离器404的顶部被抽出,并且包含催化剂颗粒424"的非挥发部分407从热分离器404的底部被抽出。
为了本说明书和附带的权利要求的目的,除非另外指出,表达数量、百分比或比例的所有数字和在说明书和权利要求中使用的其它数值应当被理解为在所有情况下由术语“大约”修饰。应当注意,当在本说明书和附带的权利要求中使用时,单数形式“一”和“所述”包括多个指代物,除非清楚地和明确地限制到一个指代物。“包括”、“包含”或“具有”、“含有”、“涉及”及其变型的使用表示涵盖其后列出的所有项及其等效物以及附加项。
本发明可以以其它具体形式体现而不脱离它的精神和实质特性。所述实施例应当在所有方面被认为仅仅是示例性的而不是限制性的。所以本发明的范围由附带的权利要求而不是前面的描述限定。在权利要求的含义和等效范围内的所有变化应当属于它们的范围内。
Claims (21)
1.一种用于在使用催化剂的情况下用高温和高压的氢气对烃给料进行加氢转化的反应器中的格栅板组件,包括:
格栅板,所述格栅板将所述反应器分成两个区域:在所述格栅板之上的区域和在所述格栅板之下的区域;
泡帽组件,所述泡帽组件包括延伸通过所述格栅板以将氢气和烃给料从在所述格栅板之下的区域输送到在所述格栅板之上的区域的多个上升管;
每个上升管具有在所述格栅板之上的上部分和在所述格栅板之下的下部分,所述下部分终止于用于进入氢气和烃给料的敞开底端,所述上部分具有终止于外壳帽的闭合顶部;
所述上升管的所述下部分具有从所述敞开底端延伸的至少一个竖直狭槽;
所述上升管的所述下部分具有至少一个侧孔开口,所述侧孔开口形成足够的尺寸并且被定位成使得在操作中,在所述格栅板之下的区域中的液位在所述竖直狭槽之上并且在所述侧孔开口之下。
2.根据权利要求1所述的格栅板组件,其中所述侧孔开口的尺寸确定成具有在所述上升管的敞开底端的直径的1/16到1/2的范围内的最短尺寸。
3.根据权利要求2所述的格栅板组件,其中所述侧孔开口具有在1/8到1/2"的范围内的最短尺寸。
4.根据权利要求1所述的格栅板组件,其中所述侧孔开口位于分配板之下至少1"处。
5.根据权利要求3所述的格栅板组件,其中所述侧孔开口位于所述分配板之下至少1"到5"处。
6.根据权利要求1所述的格栅板组件,其中每个上升管具有竖直狭槽,所述竖直狭槽从所述敞开底端延伸并且具有在所述下部分的长度的1/8到1/2的范围内的长度。
7.根据权利要求1所述的格栅板组件,其中所述上部分具有用于所述上升管中的气体液体混合的收缩部。
8.根据权利要求6所述的格栅板组件,其还包括位于所述上升管的上部分中的收缩部之上的止回阀。
9.根据权利要求5所述的格栅板组件,其中所述止回阀包括钢球和阀座。
10.根据权利要求1所述的格栅板组件,其中具有收缩部的所述上部分不具有允许流体在所述收缩部和外壳帽之间无阻塞地移动的可移动部件。
11.根据权利要求1所述的格栅板组件,其中外壳帽在形状上为管状。
12.根据权利要求1所述的格栅板组件,其中所述外壳帽为钟形。
13.根据权利要求1所述的格栅板组件,其中所述上升管具有相同或不同尺寸的多个侧孔。
14.根据权利要求1所述的格栅板组件,其中所述上升管具有沿着所述上升管的竖直长度间隔的多个侧孔。
15.根据权利要求1所述的格栅板组件,其中所述上升管具有围绕所述上升管周向等距地间隔的多个侧孔。
16.根据权利要求1所述的格栅板组件,其中所述上升管包括内管和外管,限定在所述内管和所述外管之间的环形开口作为用于进入氢气和烃给料的敞开底端。
17.根据权利要求1所述的格栅板组件,所述格栅板组件用在沸腾床反应器中。
18.根据权利要求1所述的格栅板组件,所述格栅板组件用在流化床反应器中。
19.根据权利要求1所述的格栅板组件,所述格栅板组件用于固定床反应器中。
20.根据权利要求1所述的格栅板组件,所述格栅板组件用于浆料床反应器中。
21.根据权利要求1所述的格栅板组件,其中所述多个上升管均具有至少一个侧孔开口,至少两个上升管具有不同尺寸的侧孔开口。
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US13/162,742 | 2011-06-17 | ||
PCT/US2012/040132 WO2012170272A2 (en) | 2011-06-07 | 2012-05-31 | Apparatus and method for hydroconversion |
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CN (1) | CN103459559A (zh) |
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MX (1) | MX2013009813A (zh) |
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PT (1) | PT2718406T (zh) |
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CN105542843A (zh) * | 2014-10-28 | 2016-05-04 | 中国石油化工股份有限公司 | 一种沸腾床渣油加氢方法 |
CN109261085A (zh) * | 2018-11-16 | 2019-01-25 | 重庆华峰化工有限公司 | 己二胺合成系统 |
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CN106732190A (zh) * | 2015-11-25 | 2017-05-31 | 中石化洛阳工程有限公司 | 一种气液分配器 |
CN106076207B (zh) * | 2016-08-19 | 2019-04-26 | 兰州兰石集团有限公司 | 抽吸溢流型气液分配器 |
CN109985574B (zh) * | 2017-12-29 | 2021-08-31 | 中国石油化工股份有限公司 | 顶部设置减冲盘的加氢反应器 |
CN109012512B (zh) * | 2018-09-14 | 2020-10-13 | 中国科学院过程工程研究所 | 一种内构件及包括该内构件的流化床反应器 |
FI128456B (en) * | 2018-11-21 | 2020-05-29 | Neste Oyj | Riser pipe for a reactor in a hydrocarbon treatment plant and method for maintaining said reactor |
IT202000009880A1 (it) * | 2020-05-05 | 2021-11-05 | Luigi Patron | Reattori upflow di idrotrattamento ad alta superficie di contatto idrogeno-liquido idrocarburico a migliorata capacità di idrogenazione |
KR102441667B1 (ko) * | 2020-06-19 | 2022-09-08 | 성균관대학교산학협력단 | 석유의 개질 방법 및 슬러리 기포탑 반응기 |
CN112569874B (zh) * | 2020-11-20 | 2022-05-20 | 上海竣铭化工工程设计有限公司 | 一种用于沸腾床反应器的气液分配器及其装配方法 |
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CA2829148A1 (en) | 2012-12-13 |
US20140147352A1 (en) | 2014-05-29 |
KR20140045496A (ko) | 2014-04-16 |
WO2012170272A3 (en) | 2013-01-31 |
PT2718406T (pt) | 2020-07-23 |
US9314759B2 (en) | 2016-04-19 |
EA025812B1 (ru) | 2017-01-30 |
MX2013009813A (es) | 2013-10-07 |
WO2012170272A2 (en) | 2012-12-13 |
BR112013020529A2 (pt) | 2016-10-25 |
JP2014520185A (ja) | 2014-08-21 |
US20120315202A1 (en) | 2012-12-13 |
ES2806943T3 (es) | 2021-02-19 |
KR101937431B1 (ko) | 2019-01-14 |
EP2718406A2 (en) | 2014-04-16 |
EP2718406B1 (en) | 2020-04-22 |
EA201391441A1 (ru) | 2014-03-31 |
EP2718406A4 (en) | 2015-01-21 |
JP6110847B2 (ja) | 2017-04-05 |
CA2829148C (en) | 2021-04-27 |
PL2718406T3 (pl) | 2020-11-02 |
SG194505A1 (en) | 2013-12-30 |
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