CN100337721C - 接触构造 - Google Patents
接触构造 Download PDFInfo
- Publication number
- CN100337721C CN100337721C CNB038135736A CN03813573A CN100337721C CN 100337721 C CN100337721 C CN 100337721C CN B038135736 A CNB038135736 A CN B038135736A CN 03813573 A CN03813573 A CN 03813573A CN 100337721 C CN100337721 C CN 100337721C
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- Prior art keywords
- disperser
- multifibres
- combination
- wire
- component
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Abstract
本发明公开了一种内部静态混合系统,例如与用选自惰性聚合物、催化聚合物、催化金属或其混合物的多丝材料编织在一起的金属丝网或金属网的分散器,及具有反应区的垂直反应器,而且分散器置于反应区中,特别用于使用酸催化剂进行烷烃的烷基化。金属丝网使系统的结构完整,同时提供反应器所需的敞开空间以使气体和液体移动通过系统。分散器可为置于框架内的片、束或捆。
Description
发明背景
发明领域
本发明涉及反应器内部安装的促进反应组分静态混合的反应接触构造。
相关信息
多数烷基化方法的通常目的是将异构烷烃(或芳烃)和轻烯烃与酸催化剂紧密接触,产生烷基化产物。在石油精制工业中,脂肪烃与烯烃的酸催化烷基化是众所周知的方法。烷基化是在强酸存在时烷烃,通常是异构烷烃与烯烃的反应,产生如辛烷值高于原料、沸程为汽油范围的烷烃。在石油精制中,该反应一般为C3-C5烯烃与异丁烷的反应。
在烷基化精制中,氢氟酸或硫酸催化剂在低温条件下被广泛使用。低温或冷酸方法有利,因为副反应最小。在传统方法中,反应在反应器中进行,其中烃反应物分散进酸连续相中。
虽然此方法非环境友好,操作起来又危险,但还没有其它更有效的方法,它仍然是世界上提高辛烷值的最主要的烷基化方法。因此,冷酸方法仍然是可选方法,人们提出各种改进和加强反应的建议,不期望的影响一定程度上得到减缓。
美国专利U.S.5,220,095公开,将粒状极性接触物质和氟化硫酸用于烷基化。
美国专利U.S.5,420,093和5,444,175寻求将粒状接触物质和无机或有机载体颗粒负载的硫酸结合。
接触液体/液体反应物的各种静态体系被提出,例如美国专利U.S.3,496,996;3,839,487;2,091,917和2,472,578。但是,最广泛使用的混合催化剂和反应物的方法是用各种片状、桨状和叶轮状装置剧烈搅拌,将组分混合在一起,例如美国专利U.S.3,759,318;4,075,258和5,785,933所公开。
本发明对烷基化相关技术,特别是石油精制烷烃烷基化提出重大改进,既为烷基化、异常烯烃原料提供了有效的方法,又为液体催化剂与流体反应物之间最大程度接触提供了设备,不采用机械搅拌,因此省去了轴封、减少了费用并改进了酸性产物的分离。
发明概述
简言之,本发明是一种内部静态搅拌系统,它包括将反应器与在反应器的反应区域放置的分散器结合,特别用于酸催化的烷基化反应。优选的分散器包括含有多丝组分的金属丝网,或者与多丝组分缠绕的金属网,所述多丝选自惰性聚合物、催化聚合物、催化金属、催化金属的组分或其混合物等。金属丝网既使系统结构具有整体性,又为通过系统的水汽和液体在反应器中移动提供了所需空间。分散器可由一起编织的金属丝和多丝成分的片、束或捆组成。系统也包括放在框架内的一起编织的金属丝和多丝。反应区可包括整个塔或其一部分。本分散器能使流体或流化物质在反应器中径向分散。
附图简述
图1为使用本静态内部混合物系统实现烷基化方法的设备示意图。
图2为在滴流床反应器反应区域结合本静态内部混合物系统的示意图。
图3为部分编织线和多丝物质的放大图(约200%)。
发明详述
优选地,分散器包括用于凝聚蒸发液体的常规液-液凝聚器。通常称之为“消雾器”或“去雾器”,但在本发明中,其基本作用是分散反应器里的流体物质以更好地接触。合适的分散器包括网如编织线和玻璃丝网。例如位于Texas,Alvin的Amistco Separation Products公司制造的90针管状一起编织的金属丝网和多丝玻璃丝网就可有效地利用,但应当理解,本设备也可有效地使用其他各种材料,如编织线和多丝特氟纶(Dupont TM)、钢丝棉、聚丙烯、PVDF、聚酯或其他各种编织材料。可使用各种机织而非编织的网筛作为包装。其他合适的分散器包括孔板和金属网、与玻璃丝或其它材料机织在一起的横向开口管道构造如与金属丝网或孔板机织一起的聚合物。可使用各种机织而非编织的网筛作为包装。
在本发明的一个方面,新式静态混合构造包括催化多丝组分。多丝催化材料可为聚合物如磺化乙烯基树脂(例如Amberlyst)和催化金属如Ni,Pt,Co,Mo,Ag。缠绕编织线或金属网的多丝有上百种或更多。催化金属细丝由于其高密度,一般具有较大的旦数。催化金属多丝与编织线的区别在于其优良的细丝,这大大有利于构造的催化功能。
分散器包括至少50vol%~约97vol%的敞开空间。分散器被放置在反应器的反应区域。因此,举例而言,多丝组分和结构部件如编制线应占整个分散器的约3vol%~约50vol%,其余为敞开空间。
合适的分散器包括构造的催化蒸馏填料,其含有颗粒催化剂,或者构造的由催化活性金属组成的蒸馏填料,例如美国专利U.S.5,730,843所公开,在此引入其全部,它公开的构造有一个由两个基本垂直相隔的相同栅格构成的刚性框架,由多个基本水平的刚性部件和多个基本水平的金属丝网管子保持其刚性,管子安装在栅格上,在管子中形成多个流体通道,上述管子或为空或含有催化或非催化材料;构造的填料是催化惰性的,典型由各种倾角的波纹金属构造,金属丝网成波纹状或格子状,水平地一个个重叠放置,例如美国专利U.S.6,000,685所公开,在此引入其全部,它公开了包括多个成V形波纹、V形之间平坦的金属丝网板的接触构造,这些板的大小基本均匀,峰取向于同一方向基本对齐,它们被多个取向于并靠在V形件上的刚性部件分隔。
其它合适的分散器包括:(A)随意或倾卸装填的催化惰性的蒸馏填料,有较高的空隙率和较大的比表面积,例如Bert鞍(陶瓷)、Raschig环(陶瓷)、Raschig环(钢)、Pall环(金属)、Pall环(塑料如,聚丙烯)等,以及具催化活性的随意填料,它含有至少一种催化活性成分如Ag,Rh,Pd,Ni,Cr,Cu,Zn,Pt,Tu,Ru,Co,Ti,Au,Mo,V和Fe以及被浸渍的组分如金属螯合物、酸如磷酸,或者是键合的无机粉末催化活性材料;(B)催化惰性或活性的整料,其结构包括多种多样独立的垂直管道,可由各种材料构造,例如塑料、陶瓷或金属,其中管道典型成正方形;但是,其他几何形状也可采用,使用时可涂上催化材料。
本内部静态混合系统用于异构烷烃与烯烃或烯烃前驱体的烷基化工艺,其中包括接触含有酸催化剂的流体系统,异构烷烃和烯烃连续流动,优选向下流动,在上述异构烷烃与烯烃反应生成烷基化产物的温度和压力条件下与反应区域中本系统接触。优选地,流体系统包括液体,反应区域温度维持其沸点附近。烯烃前驱体是一种或多种叔烯烃的齐聚物,例如异丁烯的二聚物、三聚物等,或者是相当于齐聚物的物质。
叔烯烃与异构烷烃的齐聚反应基于构成齐聚物的叔烯烃的摩尔数而非齐聚物本身。烷基化产物相应于叔烯烃与异构烷烃的反应。
仅为说明之需,并非对此方法加以限制,可以相信,除了齐聚物与异构烷烃之间的期望反应,齐聚物还会裂解为烯烃组分,进而与异构烷烃以摩尔量反应:
1)二异丁烯+2异丁烷→2异辛烷(2,2,4-三甲基戊烷)
2)三异丁烯+3异丁烷→3异辛烷(2,2,4-三甲基戊烷)
传统观点是1)的产物为C12烷烃,2)的产物为C16烷烃;然而反应1)和2)的产物一样,与传统的冷酸烷基化反应产物不能分别:
3)2丁烯-2+2异丁烷→2异辛烷
4)3丁烯-2+3异丁烷→3异辛烷
虽然酸催化烷基化剧烈放热,需要基本致冷以维持反应温度在最佳范围,阻止副反应,但本发明中齐聚物与异构烷烃反应,以相同的产率生成烷基化物需要的致冷很少,使得产生相同量的有用产物所需的费用减少。
产生齐聚物的一个特殊方法是在催化蒸馏中进行,例如以前用于生产MTBE的装置很容易转用于生产齐聚物,只需改变反应器进料,因为两个反应使用的催化剂相同。
优选地,齐聚物包括C8-C16烯烃,由C3-C5烯烃制备而来。在优选的实施例中,齐聚物有8-16个碳原子,由C4-C5烯烃制备而来或为由C4-C5烯烃制备出的齐聚物。
烷烃烷基化最广泛的应用是制备C8汽油组分。该法的原料通常是包含于“冷酸”反应,通常为硫酸或HF的丁烯和叔丁烷。正丁烯(如丁烯-2)与正丁烷、异丁烷和叔丁烯一起是轻质石脑油的组分。由于其沸点接近,通过精馏来分离正丁烯和异丁烯比较困难。分离这些烯烃异构体或C5类似物的优选办法是将反应性较好的叔烯烃反应,形成较重的产物,再通过精馏就很容易将其与正构烯烃分离。
迄今为止,叔烯烃与低级醇如甲醇或乙醇反应形成醚,如甲基叔丁基醚(MTBE)、乙基叔丁基醚(ETBE)、叔戊基甲基醚(TAME),这些醚可用于提高汽油的辛烷值,但由于影响人体健康,正在被淘汰。
当处理石脑油时,叔烯烃的齐聚也是优选的反应,正构烯烃则容易通过精馏从重(高沸点)齐聚物(主要是二聚物和三聚物)中分离。齐聚物可用作汽油组分,但在期望或允许的汽油中烯烃的含量受到限制,因此经常需要对汽油中使用的烯烃进行加氢处理。用于调和汽油的最期望的组分是C8,例如异辛烷(2,2,4三甲基戊烷)。
齐聚物通过裂解可变回原来的叔烯烃,用于冷反应。但是发现,没必要裂解齐聚物,它可与烷烃一起作为冷酸反应的烯烃原料或与单烯烃一起作为共同原料。如上所述,单烯烃参与的反应总放热较少,需要较小的致冷,因此烷基化所需能耗较低,虽然有这些好处,但产生的产物都一样。
由于采用冷酸方法,齐聚产生的反应热不需要大量移走。事实上,当齐聚在催化精馏反应中进行时,反应热与馏出物一起移走,在这种反应中,馏出物是低沸点单烯烃和与齐聚物分离的烷烃。因此,即使齐聚放热,它也不会增加生产汽油的费用,因为这些热量可用于精馏,由于用齐聚物代替一些或全部传统的短链烯烃,烷基化装置的操作费用得到降低。
在烷基化方法的一个优选实施例中,包括正构和叔碳烯烃的轻石脑油在齐聚条件下与酸性树脂催化剂接触,优选地,其中一部分叔烯烃与自己反应形成齐聚物,与异构烷烃一起进入烷基化区域,在酸性烷基化催化剂存在下产生包括上述叔烯烃与上述异构烷烃的烷基化物的烷基化产物。
齐聚在酸性阳离子树脂催化剂存在下可在部分液相中进行,要么为纯反应,要么为催化蒸馏反应,后者既有气相也有液相,反应与蒸馏共存。优选地,原料为C4-C5、C4或C5的轻石脑油馏分。叔烯烃包括异丁烯、异戊烯,比正构烯烃异构体更具反应性,首先被齐聚。主要的齐聚物产物为二聚物和三聚物。异构烷烃优选包括异丁烯、异戊烯或其混合物。
当采用直通反应器时,例如美国专利U.S.4,313,016;4,540,839;5,003,124和6,335,473所公开,包括齐聚物、正构烯烃和异构烷烃的全部流出物作为原料进入酸性烷基化反应。在烷基化反应条件下正构烷烃是惰性的。在烷基化反应条件下,异构烷烃与正构烯烃反应形成烷基化产物,也与个别烯烃的齐聚物反应形成烷基化产物。本结果暗示,齐聚物发生了分解或者以某种方式使其烯烃可与异构烷烃反应。因此,将产生反应:
1)异丁烯低聚物+异丁烷→异辛烷;
2)异丁烯低聚物+异戊烷→支链C9烷烃;
3)异戊烯低聚物+异丁烷→支链C9烷烃;
4)异戊烯低聚物+异戊烷→支链C10烷烃;
其中,可预见,反应1)将产生至少或大部分C12烷烃,反应2)将产生至少或大部分C13烷烃,反应3)将产生至少或大部分C14烷烃,反应4)将产生至少或大部分C15烷烃。
当齐聚采用如美国专利U.S.4,242,530或4,375,576公开的催化蒸馏反应时,齐聚物通过蒸馏与反应产物中低沸点正构烯烃和烷烃分离。馏分、正构烯烃和烷烃(塔顶)以及齐聚物(塔底)一起或者单独作为烷基化原料,或者单独至少与作为烷基化原料的齐聚物一起使用。
本发明提供改进的接触设备以及使用硫酸作为催化剂产生和分离烷基化产物的方法。对其他的酸或酸混合物也可采用同样的或相同的设备。
方法优选地采用滴流床反应器,内部装有接触物或填料(可为惰性或催化性),硫酸、烃溶剂和反应物的共存多相混合物在系统沸点温度下通过其中。系统包括烃相和酸/烃乳液相。填料中存在大量硫酸。反应在滴流的烃相与分散在填料中的硫酸之间发生。烯烃连续地溶入酸相,烷基化产物被连续地萃取进入烃相。调整压力和烃组成可控制沸点温度。反应器优选在气相连续的情况下运转,但也可在液体连续的情况下操作。反应器顶部压力优选高于底部压力。
调节流速和蒸馏程度可控制反应器的压力降。优选采用多个烯烃进料口。由于存在酸相累积,填料类型也影响压力降。精馏前产物混合物是优选循环溶剂。酸乳化液很快与烃液分离,通常在塔底分离器中只有很短的停留时间就被循环。由于实质上产物很快从酸相(乳化液)中萃取出来,因此可以加入传统的硫酸烷基化方法使用的反应和/或乳化促进剂,而不像通常那样考虑是否破坏乳化液。对应于酸连续,可将该方法描述为烃连续。
烷基化的烃原料以连续相进入反应区域,它含有足以形成烷基化产物的有效量烯烃和异构烷烃原料。在总反应原料中烯烃与异构烷烃之摩尔比为约1∶1.5~约1∶30,优选为1∶5~约1∶15。也可使用更低的烯烃与异构烷烃摩尔比。
烯烃组分优选含有2-16个碳原子,异构烷烃组分优选含有4-12个碳原子。合适异构烷烃的代表包括异丁烷、异戊烷、3-甲基己烷、2-甲基己烷、2,3-二甲基丁烷和2,4-二甲基己烷。
合适烯烃的代表包括丁烯-2、异丁烯、丁烯-1、丙烯、戊烯、乙烯、己烯、辛烯和庚烯,仅指出这几个,如上所述,也可为这些烯烃的齐聚物。
在流体方法时,在较低的温度下,系统使用氢氟酸或硫酸催化剂。例如硫酸烷基化反应对低温特别敏感,同时低温有利于减少烯烃聚合副反应。石油精制技术中,产生有用轻质链烯烃的同时产生大量的高辛烷值产物,相对于聚合,这更有利于烷基化。在这些液体酸催化的烷基化方法中,通过连续加入新酸以及连续撤出用过的酸,维持酸强度优选为88~94%(重量)。也可使用其它酸如固体磷酸,把它作为填料里面或上面催化剂的载体。
优选地,该法应当在反应器顶部添加相对量的体积比为约0.01∶1~约2∶1的酸和烃原料,更优选的体积比为约0.05∶1~约0.5∶1。在最优选的具体实施方式中,酸与烃的比例为约0.1∶1~约0.3∶1。
而且,在酸扩散进反应区域的同时保持反应器的温度为约0~约200,更优选为约35~约130。同样,反应器的压力为约0.5atm~约50atm,更优选地为约0.5atm~约20atm。更优选地,反应器温度为约40~约110,反应器压力为约0.5atm~约5atm。
一般地,该法使用的特殊的操作条件一定程度上取决于进行的特殊的烷基化反应。工艺条件如温度、压力和空速以及反应物的摩尔比将影响最终烷基化产物的性质,可根据本领域普通技术人员所熟知的参数进行调节。
在沸点下操作本反应体系的优势是蒸发的存在有助于反应热消散,使进料的温度与离开反应器的物料温度接近,如同等温反应。
一旦烷基化反应进行完毕,反应混合物就进入合适的分离容器,含有烷基化产物和未反应的反应物的烃与酸分离。烃相的典型密度为约0.6g/cc~约0.8g/cc,酸的密度一般为约0.9g/cc~2.0g/cc,因此两相很容易用传统的重力法分离。合适的重力分离器包括重力沉降槽。通过密度差别分离的水力旋流器也适用。
一种烷基化具体实施方式示于图1中,它是本方法设备和流程的简化示意图。术语如阀、再沸器、泵等被略去。
反应器含有一个分散器网40。进入反应器的原料包括通过管线12进料的烯烃如正丁烯和通过管线14及管线52进料的异构烷烃(如异丁烷)。优选地,一部分烯烃通过管线16a、16b和16c沿反应器进入。液体酸催化剂如硫酸通过管线56进料,补充酸通过管线38提供。烃反应物通过管线58进入优选为一般圆柱体的反应器,再经过合适的分散装置(未绘出)进入分散器网40如编织在一起的线和玻璃丝网。
当烷基化进行时,烃反应物和非反应性的烃(如正丁烷)与酸催化剂紧密接触。反应为放热。体系组分呈混合气/液相滴流通过反应器,并通过管线18出来,进入倾析槽30,在此过程中,调节压力以及反应物的量,以维持体系组分处于沸点温度但部分为液相。在倾析槽中,体系组分分离为包含催化剂的酸相46,含有烷基化物、未反应烯烃和未反应异构烷烃以及非反应性烃的烃相42,含有一些各组分的气相44,以及通过管线50从体系中除去以进一步做适当处理的更轻的烃组分。
大部分酸相通过管线24和56循环进入反应器。补充酸通过管线38加入,累积的用过的酸通过管线48排出。
烃液相通过管线22排出,其中一部分通过管线28循环回到反应器顶部。其余的烃相通过管线26进入蒸馏塔20,进行精馏。如果原料中有的话,正丁烷通过管线36排出,烷基化产物通过管线34排出。塔顶32主要为未反应的异构烷烃,它通过管线52循环回到反应器10顶部。
图2为反应器110内部分散器(段140a-k)布置方式的简化示意说明。各分散器段(如140a、140f、140g)均横过反应器宽(优选装满整个宽度),其全部或部分长度小于多片分散器形式的反应器所有长度。硫酸通过管线158进入反应器,烯烃与异构烷烃的混合液流(或是如上所述的多种原料)通过管线116进入。包括烷基化物、未反应的烯烃、未反应的异构烷烃和用过的酸(从反应器出来的全部物质)通过管线118排出反应器,再进行如前所述的处理。
优选的分散器200示于图3中,包括与多丝材料210编织在一起的线205。
异构烷烃与烯烃的烷基化实验装置
在下面的实施例中,实验室反应器高15英尺,直径为1.5英寸。其中装填各种量和类型的填料。根据所用填料的容量,硫酸的总量大约为1L。缓冲罐大约为3L,所有酸和液体烃从其底部出来,用一个泵循环两相混合物。原料进入反应器顶部,与循环混合物一起流下。反应热以及环境温度产生气体,促进流过填料的液体剧烈搅动和混合。大部分气体在反应器出口冷凝。未冷凝的气体和液体烃通过酸去雾塔,经过背压调节器,进入脱异丁烷塔。用质量流量计测量进料流速,用Doppler流量计测量循环速率。对脱异丁烷塔出来的液体产物进行称重。但是,出口流速估计为进料的质量流量与称出的液体产物重量之差。用GC分析所有烃产物。
操作
在下面的实施例中,烃和酸在烃的沸点温度下在实验装置中向下循环。压力和温度的显示用电子仪器。采用异丁烷/烷基化物快速计算法,用反应器出口温度和压力计算循环烃中异丁烷的量。
用背压调节器维持压力,产物液体和气体都经过它进入脱异丁烷塔。少量N2主要用于阻止酸倒流回进料管线。但是,N2太多会稀释气相中反应性的异构烷烃,从而引起产品质量下降。
实验中使用的循环泵既循环酸乳化层,又循环液体烃层。分别用泵轮流循环这两相。
用三通阀,通过一根测量管,将全部循环随时分馏以维持总酸量。收集的物料很快分为两层。酸层和烃层的体积百分比结合Dopper流量计,可估算出两相的循环体积比。
通过控制循环比率和装置周围的热平衡,维持DP(在顶部或反应器入口的较高压力)为0~3psi。不同的填料通常需要不同的气体和液体流速,以达到相同的DP。大多数时候,室温的上升以及反应热可产生足够的气体(大部分为异丁烷)量。
由于致冷的约束,原料中要补充大约1-3lbs/hr的液态异丁烷,以使冷却完全。这部分过量的C4较少,对异丁烷/烯烃比影响不大,因为烃的循环比例一般为100-200磅/小时的量级。正是循环烃流速控制着异丁烷与其它组分的比例。
实施例中C4烷基化的典型操作条件
烯烃原料 C4′
烯烃进料量lbs/hr 0.25-0.50
产生的烷基化物lbs/hr 0.50-1.2
Rxn出口温度 50-60
Rxn出口压力Psi 6-16
DP Psi 0.5-3.0
循环比率:
酸相L/min 0.3-1
烃相L/min 1-3
异丁烷在烃循环中含量wt.% 75-45
硫酸在用过的酸中含量wt.% 83-89
水在用过的酸中含量wt.% 2-4
新鲜酸加入量lbs/gal烷基化物 0.3-0.5
填料类型 1或2-见下面的说明
填料高ft 10-15
填料密度lbs/ft3 5-14
注:
1.填料类型1为与每针400旦多丝玻璃丝编织在一起的0.011英寸的304ss金属丝。
2.填料类型2为与每针800旦多丝聚丙烯纱线编织在一起的0.011英寸的合金20金属丝。
实施例1
用精制C4烯烃作为实验室装置的原料:其中含38%异丁烯(iB)
低含量iB 总烯烃
甲烷 0.02 0.00
乙烷 0.00 0.00
乙烯 0.00 0.00
丙烷 0.77 0.41
丙烯 0.14 0.16
丙炔 0.02 0.00
丙二烯 0.01 0.02
异丁烷 23.91 47.50
异丁烯 0.90 15.90
1-丁烯 20.02 10.49
1,3-丁二烯 0.02 0.19
正丁烷 22.63 10.79
反-2-丁烯 18.05 7.93
2,2-二甲基丙烷 0.09 0.00
1-丁炔 0.00 0.01
m-环丙烷 0.03 0.03
顺-2-丁烯 12.09 5.43
1,2-丁二烯 0.00 0.01
3M-1-1丁烯 0.26 0.04
异丙烷 0.98 0.02
1-戊烯 0.06 0.82
2M-1-丁烯 0.01 0.01
n-戊烷 0.01 0.03
反-2-戊烯 0.00 0.08
顺-2-戊烯 0.00 0.00
反-3-戊二烯 0.00 0.08
顺-1,3-戊二烯 0.00 0.00
未知 0.01 0.08
100.00 100.00
使用相似低含量异丁烯的C4原料时,炼厂生产的烷基化物与实验室装置结果对比
厂A 厂B 实验1 实验2
iC5 6.27 2.70 2.51 2.78
2,3-dmb 4.05 2.84 2.80 3.02
C6 1.63 1.19 1.00 1.15
2,2,3-tmb 0.20 0.17 0.18 0.19
C7 7.17 5.55 4.35 4.35
TM C8 53.88 61.76 66.84 66.93
DM C8 12.27 12.47 12.69 12.44
TM C9 5.04 4.22 2.89 2.74
DM C9 0.57 1.01 0.29 0.18
TM C10 1.14 0.91 0.70 0.64
UNK C10 0.51 0.54 0.29 0.29
TM C11 0.99 0.77 0.69 0.71
UNK C11 1.09 0.02 0.00 0.00
C12 4.37 1.71 4.72 4.60
C13 0.00 1.58 0.00 0.00
C14 0.03 1.57 0.05 0.00
C15 0.00 0.13 0.00 0.00
HV′S 0.05 0.04 0.00 0.00
UNK 0.74 0.83 0.00 0.00
sum 100.00 100.00 100.00 100.00
Av MW 113.4 116.0 114.9 114.6
溴价 <1 <1 <1 <1
总硫ppm <10 <10 <10 <10
总TM% 61.05 67.66 71.12 71.01
TM C8/DM C8比 4.39 4.95 5.27 5.38
TM C9/DM C9比 8.85 4.19 10.08 15.57
典型的尾气分析结果:
wt.%
氢气 0.000
氧气 0.124
氮气 3.877
甲烷 0.019
一氧化碳 0.000
二氧化碳 0.000
乙烷 0.000
乙烯 0.000
乙炔 0.000
丙烷 1.066
丙烯 0.000
丙二烯 0.000
异丁烷 81.233
异丁烯 0.021
1-丁烯 0.000
1,3-丁二烯 0.031
正丁烷 3.398
反-2-丁烯 0.000
m-环丙烷 0.000
顺-2-丁烯 0.000
异戊烷 0.968
1-戊烯 0.000
正戊烷 0.000
C5+ 0.391
实施例2
异丁烯(iB)对烷基化质量的影响
实验1
100% iB 38% iB low iB
iC5 3.66 3.97 2.78
2,3-dmb 3.60 3.56 3.02
C6 1.42 0.52 1.15
2,2,3-tmb 0.40 0.23 0.19
C7 5.27 5.08 4.35
TM C8 50.79 56.95 66.93
DM C8 11.77 12.64 12.44
TM C9 6.07 4.22 2.74
DM C9 0.58 0.45 0.18
TM C10 2.06 1.33 0.64
UNK C10 1.14 0.67 0.29
TM C11 2.54 1.28 0.71
UNK C11 1.00 0.00 0.00
C12 8.30 8.99 4.60
C13 0.07 0.00 0.00
C14 0.28 0.14 0.00
C15 0.12 0.00 0.00
HV’S 0.38 0.00 0.00
UNK 0.54 0.00 0.00
sum 100.00 100.00 100.00
Av MW 119.1 117.3 114.9
溴价 -1 <1 <1
总硫ppm <10 <10 <10
总TM% 61.46 63.77 71.12
TM C8/DM C8比 4.31 4.51 5.27
TM C9/DM C9比 10.51 9.34 10.08
实施例3
丙烯+iC4烷基化
取样点产物 产品
丙烷 0.01
异丁烷 9.25
正丁烷 0.32
异戊烷 0.97
正戊烷 0.00
2,3-dm丁烷 2.07
2M-戊烷 0.30
3M-戊烷 0.14
n-己烷 0.00
2,4-dm戊烷 15.59
2,2,3-tm丁烷 0.04
3,3-dm戊烷 0.01
环己烷 0.00
2M-己烷 0.34
2,3-dm戊烷 48.97
1,1-dm环戊烷 0.00
3M-己烷 0.35
2,2,4-tm戊烷 3.42
n-庚烷 0.00
2,5-dm己烷 0.37
2,4-dm己烷 0.56
2,3,4-tm戊烷 1.52
2,3,3-tm戊烷 1.21
2,3-dm己烷 0.64
2,2,5-tm己烷 0.68
2,3,4-tm己烷 0.13
2,2-dm庚烷 0.01
2,4-dm庚烷 0.03
2,6-dm庚烷 0.03
2,2,4-tm-庚烷 1.83
3,3,5-tm-庚烷 1.70
2,3,6-tm-庚烷 1.16
2,3,5-tm-庚烷 0.16
tm-庚烷 1.00
2,2,6-三甲基辛烷 2.32
C8s 0.20
C9s 0.20
C10s 0.98
C11s 1.62
C12s 1.73
C13s 0.09
C14s 0.05
C15s 0.01
未知物 0.01
重组分 0.00
100.00
实施例4
异丁烯+戊烯1的烷基化产物
Wt%
C5 5.03
2,3-dmb 0.74
C6 0.35
DM C7 1.14
C7 0.17
TM C8 22.26
DM C8 3.70
TM C9 52.40
DM C9 6.72
TM C10 1.51
UNK C10 0.56
TM C11 0.16
UNK C11 0.38
C12 3.68
C13 0.33
C14 0.11
C15 0.08
HV′S 0.03
UNK 0.63
100.00
Av MW 123.2
预期MW 128
烯烃料#/hr 0.25
烷基化产物#/hr 0.47
实施例5
烯烃中含38%iB的C4原料的齐聚产物
(该产物又可作为实验室烷基化装置的烯烃原料)
异丁烷 48.8
异丁烯+1-丁烯 1.6
正丁烯 11.2
反-2-丁烯 14.3
顺-2-丁烯 6.5
异戊烯 1.0
反-2-戊烯 0.1
未知物 1.5
2,4,4-tm-1-戊烯 4.7
2,4,4-tm-2-戊烯 1.3
其它C8 3.4
C12组 4.4
C16组 1.2
100.0
用烯烃中iB=38%的C4为原料时,齐聚对烷基化产物的影响
前 后
iC5 3.97 2.39
2,3-dmb 3.56 2.87
C6 0.52 1.17
2,2,3-tmb 0.23 0.20
C7 5.08 4.95
TM C8 56.95 58.34
DM C8 12.64 12.80
TM C9 4.22 4.15
DM C9 0.45 0.35
TM C10 1.33 1.29
UNK C10 0.67 0.57
TM C11 1.28 1.41
UNK C11 0.00 0.00
C12 8.99 9.41
C13 0.00 0.00
C14 0.14 0.11
C15 0.00 0.00
HV′S 0.00 0.00
UNK 0.00 0.00
sum 100.00 100.00
Av MW 117.3 118.3
溴价 <1 <1
总硫ppm <10 <10
总TM% 63.77 65.19
TM C8/DM C8 4.51 4.56
TM C9/DM C9 9.34 11.75
操作条件:
烯烃进料lbs/hr .25 .25
烷基化产物lbs/hr .53 .53
Rxn出口温度 52.0 52.2
Rxn出口压力Psi 12.2 11.8
DP Psi ~1 ~1
循环比率:
酸相L/min 1.0 1.0
烃相L/min 2.6 2.6
iC4在烃循环中含量% 69 67
填料类型 2 2
填料高ft 15 15
填料密度lbs/ft3 7 7
实施例6
正丁烯+正丁烷或iB+iC4的齐聚物的烷基化产物质量
iB DIB TIB+
IC5 3.66 3.97 3.41
2,3-dmb 3.60 3.70 3.18
C6 1.42 1.36 1.53
2,2,3-tmb 0.40 0.38 0.27
C7 5.27 4.96 6.39
TM C8 50.79 47.93 38.35
DM C8 11.77 8.92 12.91
TM C9 6.07 6.60 10.31
DM C9 0.58 0.81 1.10
TM C10 2.06 3.09 3.29
UNK C10 1.14 1.18 1.35
TM C11 2.54 2.53 2.72
UNK C11 1.00 1.79 0.00
C12 8.30 10.51 14.97
C13 0.07 0.31 0.07
C14 0.28 1.47 0.14
C15 0.12 0.29 0.00
HV′S 0.38 0.19 0.00
UNK 0.54 0.01 0.00
Sum 100.00 100.00 100.00
Av MW 119.1 122.1 122.9
溴价 ~1 ~1 ~1
总硫ppm <10 <10 <10
总TM% 61.46 60.15 54.67
TM C8/DM C8 4.31 5.37 2.97
TM C9/DM C9 10.51 8.15 9.37
操作条件:
烯烃料 iB DIB TIB+
烯烃进料lbs/hr 0.25 0.40 0.25
烷基化产物lbs/hr 0.49 0.78 0.48
Rxn出口温度 52 51.6 51.7
Rxn出口压力Psi 13 13.5 5.7
DP Psi 2.5 1.1 ~1
循环比率:
酸相L/min 0.8 0.5 1.0
烃相L/min 1.8 1.4 3.0
iC4在烃循环中含量% 73 76 45
填料类型 1 1 2
填料高ft 10 10 15
填料密度lbs/ft3 6 6 7
实施例7
期望的和实际的烷基化产物MW值以及各种烯烃料中iC4所占摩尔数(例如理论上,1mol C6烯烃应当与1mol iC4反应生成C10烷基化物;MW=142),结果显示,解聚作用产生更多、更低MW值的烯烃,同时iC4增加。
每mol烯烃料中 产物的
iC4摩尔数 平均MW值
烯烃 预期 实际 预期 实际
己烯-1 1.0 1.2 142 129
辛烯-1 1.0 1.4 170 135
二异丁烯 1.0 1.8 170 122
三异丁烯+ 1.0 2.6 226 123
实施例8
异丁烷+戊烯-1烷基化产物
Wt%
IC5 5.03
2,3-dmb 0.74
C6 0.35
DM C7 1.14
C7 0.17
TM C8 22.26
DM C8 3.70
TM C9 52.40
DM C9 6.72
TM C10 1.51
UNK C10 0.56
TM C11 0.16
UNK C11 0.38
C12 3.68
C13 0.33
C14 0.11
C15 0.08
HV′S 0.03
UNK 0.63
100.00
Av MW 123.2
预期MW 128
烯烃料#/hr 0.25
烷基化产物#/hr 0.47
Claims (21)
1.一种进行催化反应的垂直反应器的结合体,包括垂直反应器和位于所述垂直反应器中的分散器,其中所述分散器被布置成多个垂直排列的横向垫子,位于上述垂直反应器内或横跨该反应器,所述分散器包括至少50vol%的敞开空间,并包括与多丝组分编织在一起的金属丝网或与多丝成分缠绕的金属网,所述多丝组分选自惰性聚合物、催化聚合物、催化金属或其混合物。
2.如权利要求1所述结合体,其中所述敞开空间高达97vol%。
3.如权利要求1所述结合体,其中分散器包括金属丝网和聚合物网一起编织的网。
4.如权利要求1所述结合体,其中分散器包括一起编织的金属丝网和玻璃丝。
5.如权利要求1所述结合体,其中分散器包括一起编织的金属丝和多丝组分形成的网,多丝组分包括特氟纶、钢丝棉、聚丙烯、PVDF、聚酯或其组合物。
6.如权利要求1所述结合体,其中分散器包括一起编织的金属丝和多丝组分或其结合的片、束或捆。
7.如权利要求1所述结合体,其中分散器包括磺化乙烯基树脂、Ni、Pt、Co、Mo、Ag或其混合物的多丝催化材料。
8.如权利要求1所述的结合体,其中分散器包括一种结构,该结构有一个由两个基本垂直间隔的相同栅格构成的刚性框架,由多个基本水平的刚性部件和多个基本水平的金属丝网管保持其刚性,管子安装在栅格上以在管子中形成多个流体通道,上述管子是空的或含有催化或非催化材料。
9.如权利要求1所述的结合体,其中分散器包括一种结构,该结构包括多个成V形波纹的金属丝网片,波纹的V形之间具有平台,上述多个片的大小基本均匀,峰取向于同一方向基本对齐,所述片被多个通常取向于并靠在所述V形件上的刚性部件分隔。
10.一种进行催化反应的垂直反应器的结合体,包括垂直反应器和位于所述垂直反应器中的分散器,所述分散器包括至少50vol%的敞开空间,并包括与多丝组分编织在一起的金属丝网或与多丝成分缠绕的金属网,所述多丝组分选自惰性聚合物、催化聚合物、催化金属或其混合物,其中所述金属丝网使系统的结构完整,反应器所需的敞开空间使气体和液体移动通过其中。
11.一种以并流向下方式进行催化反应的结合体,包括垂直反应器、位于所述垂直反应器的分散器,所述分散器包括一起编织的金属丝和多丝成分的片、束或捆或其组合,包括至少一种部分液态的反应物、催化剂和维持上述部分液态反应物在沸点的反应条件。
12.如权利要求11所述结合体,其中分散器包括与多丝组分编织在一起的金属丝网或与多丝成分缠绕的金属网,所述多丝组分选自惰性聚合物、催化聚合物、催化金属或其混合物。
13.如权利要求11所述结合体,其中分散器包括金属丝网和聚合物网一起编织的网。
14.如权利要求11所述结合体,其中分散器包括一起编织的金属丝网和玻璃丝。
15.如权利要求11所述结合体,其中分散器包括一起编织的金属丝和多丝组分形成的网,多丝组分包括特氟纶、钢丝棉、聚丙烯、PVDF、聚酯或其组合物。
16.如权利要求11所述结合体,其中分散器包括磺化乙烯基树脂、Ni、Pt、Co、Mo、Ag或其混合物的多丝催化材料。
17.如权利要求11所述结合体,其中至少存在两相。
18.一种分散器,包括与多丝催化聚合物编织在一起的金属丝网或金属网。
19.如权利要求18所述分散器,其中分散器单独地包括磺化乙烯基树脂的多丝催化材料,或具有选自Ni、Pt、Co、Mo、Ag和其混合物的金属。
20.如权利要求18所述分散器,其中分散器包括至少50vol%的敞开空间。
21.如权利要求18所述分散器,其中分散器包括高达97vol%的敞开空间。
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US10/219,653 | 2002-08-15 | ||
US10/219,653 US20040052703A1 (en) | 2001-08-21 | 2002-08-15 | Contact structures |
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EP (1) | EP1534406B1 (zh) |
JP (1) | JP4700964B2 (zh) |
KR (1) | KR100970802B1 (zh) |
CN (1) | CN100337721C (zh) |
AR (1) | AR040707A1 (zh) |
AT (1) | ATE516067T1 (zh) |
AU (1) | AU2003256743B2 (zh) |
BR (1) | BR0313181B1 (zh) |
CA (1) | CA2493811C (zh) |
EG (1) | EG23477A (zh) |
MX (1) | MXPA05001555A (zh) |
RO (1) | RO123325B1 (zh) |
RU (1) | RU2318590C2 (zh) |
TW (1) | TWI288660B (zh) |
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US6858770B2 (en) * | 2001-08-21 | 2005-02-22 | Catalytic Distillation Technologies | Paraffin alkylation |
US20080063593A1 (en) * | 2006-09-08 | 2008-03-13 | Catalytic Distillation Technologies | Low temperature process for regenerating spent sulfuric acid |
CN101574632B (zh) * | 2008-05-09 | 2011-07-13 | 北京化工大学 | 一种鱼肝油乳液的制备方法 |
US8235361B2 (en) * | 2009-02-09 | 2012-08-07 | Tribute Creations, Llc | Structured packing for a reactor |
DE102010016595B4 (de) * | 2010-04-22 | 2012-05-31 | Zeppelin Reimelt Gmbh | Mischer |
US9551282B2 (en) * | 2014-10-17 | 2017-01-24 | General Electric Company | Media pads with mist elimination features |
US10967352B1 (en) | 2017-04-07 | 2021-04-06 | Triad National Security, Llc | Microfluidic liquid-liquid contactor |
CN108786376A (zh) * | 2017-04-28 | 2018-11-13 | 中国石化工程建设有限公司 | 一种回收挥发性有机物的方法和系统 |
US11033873B2 (en) | 2017-08-31 | 2021-06-15 | Refining Technology Solutions, Llc | Conversion of a hydrogen fluoride alkylation unit to a sulfuric acid alkylation unit and apparatus utilized therein |
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- 2003-07-24 KR KR1020057002104A patent/KR100970802B1/ko active IP Right Grant
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- 2003-07-24 RU RU2005107001/04A patent/RU2318590C2/ru active
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US20060245990A1 (en) | 2006-11-02 |
EG23477A (en) | 2005-11-19 |
CA2493811C (en) | 2010-07-06 |
CA2493811A1 (en) | 2004-02-26 |
ZA200500098B (en) | 2005-11-30 |
MXPA05001555A (es) | 2005-04-19 |
AU2003256743A1 (en) | 2004-03-03 |
WO2004016342A2 (en) | 2004-02-26 |
RU2318590C2 (ru) | 2008-03-10 |
BR0313181B1 (pt) | 2012-09-04 |
EP1534406A2 (en) | 2005-06-01 |
RO123325B1 (ro) | 2011-08-30 |
RU2005107001A (ru) | 2005-08-10 |
US20040052703A1 (en) | 2004-03-18 |
CN1658947A (zh) | 2005-08-24 |
AU2003256743B2 (en) | 2008-06-26 |
JP4700964B2 (ja) | 2011-06-15 |
EP1534406A4 (en) | 2007-02-28 |
ATE516067T1 (de) | 2011-07-15 |
WO2004016342A3 (en) | 2005-02-24 |
JP2006500199A (ja) | 2006-01-05 |
KR100970802B1 (ko) | 2010-07-16 |
EP1534406B1 (en) | 2011-07-13 |
US7850929B2 (en) | 2010-12-14 |
TWI288660B (en) | 2007-10-21 |
BR0313181A (pt) | 2005-07-26 |
AR040707A1 (es) | 2005-04-13 |
TW200407195A (en) | 2004-05-16 |
KR20050037570A (ko) | 2005-04-22 |
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