CN1149233C - 流化床中单体的聚合方法 - Google Patents
流化床中单体的聚合方法 Download PDFInfo
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Abstract
本发明涉及单独α-烯烃或另一种或多种其它α-烯烃于具有流化床与流化介质的气相反应器中进行聚合或共聚以便使进入反应器的流化介质含有气相和液相。
Description
技术领域
本发明涉及流化床反应器中烯烃的气相聚合方法。本发明通过明显地提高给定尺寸反应器的聚合物生产能力来实质性地降低能耗与成本。
背景技术
对流化床中聚合物生产方法的发现为生产多种多样聚合物提供了途径。采用气体流化床聚合方法与其它方法相比,能够实质性地减少对能量的需要,而最重要的是降低了实施这种方法以便生产聚合物所需的投资成本。
气体流化床聚合设备通常采用连续循环方式进行。在循环的一部分中,循环气流借助反应器中聚合反应产生的热量被加热。该热量借助反应器外部的冷却***在循环的另一部分中被移出。
一般地,在用于由α-烯烃单体生产聚合物的气体流化床方法中,含有一种或多种单体的气流连续地通过有催化剂存在的处于反应条件下的流化床。该气流离开流化床并且被循环回至反应器中。与此同时,聚合物产物离开反应器,加入新单体以便替代经过反应的单体。
重要的是移走反应热以便将反应器内气流的温度保持在聚合物与催化剂的降解温度以下。此外,重要的是防止附聚或形成无法作为产物移除的聚合物块。这可以通过将反应床内气流的温度控制在低于聚合反应期间形成的聚合物颗粒的熔点或粘结温度来实现。因此,可被理解的是流化床聚合过程中聚合物的生成量与由反应器内流化床中反应区撤走的热量有关。
传统上,通过冷却反应器外物流来从气体循环物流中脱除热量。流化床方法的要求之一是气体循环物流的速度应当足以将流化床保持在流化态。在传统的流化床反应器中,用于脱除聚合反应热的流体流量大于支撑流化床和使流化床中固体充分混合所需的流体量。然而,为了防止离开流化床的气流夹带过量固体,必须调节气体流速。此外,在其中聚合反应生成热基本上与聚合物生成速率成正比的稳态流化床聚合方法中,所产生的热量等于气流吸收的和为了保持床温恒定而由其它途径损失的热量。
人们曾经认为,同时还被称作循环物流温度的反应器外气流的温度不会被降至低于循环物流的露点的温度。循环物流的露点是气体循环物流中开始有冷凝液体形成的温度。人们相信,将液体导入流化床聚合反应过程中的气相循环物流之中会不可避免地导致循环物流管线、换热器、流化床以下部位或气体分布板出现堵塞现象。为了消除与气体循环物流中存在的液体相关的问题而在高于循环物流的露点的温度下进行操作的结果是在不增大反应器直径的条件下无法显著地提高工业反应器中的生产速率。
过去,人们担心循环物流中存在的过量液体会破坏流化过程达到使流化床倒塌的程度,导致固体聚合物颗粒烧结成为致使反应器停止操作的固体块。这一被广泛采纳的避免液体存在于循环物流中的观点见诸于U.S.P.No.3922322,4035560,4359561和5028670以及欧洲专利申请NO.0050477和0100879。
与此观点相反,正如Jenkins III等人在U.S.P.No.4543399和相关U.S.P.No.4588790中披露的那样,业已表明循环物流可被冷却至低于流化床聚合过程的露点的温度,导致循环物流中一部分冷凝。这两篇JenkinsIII专利的内容被结合在此以供参考。随后,所得到的含有被夹带的液体的物流在不发生上述据信由于液体被导入流化床聚合反应过程中而引起的附聚和/或堵塞现象这一条件下返回到反应器中。这种有意地将液体导入循环物流或反应器的方法在工业上被称作气相聚合方法的“冷凝式”操作。
上述授予Jenkins III等人的美国专利指出,当循环物流温度在“冷凝式”操作中被降至其露点以下时,与非冷凝生产方式相比,由于冷却能力得到提高而有可能增大聚合物产量。此外,Jenkins等人发现可以通过以“冷凝方式”在几乎不或完全不改变产物特性的条件下进行操作来明显地增大空时产率、在给定反应器体积中聚合物的产量。
“冷凝方式”中两相气/液循环物流混合物的液相在混合物的气相中保持被夹带或悬浮状态。为了产生这一两相混合物而将循环物流冷却的过程导致一种液/汽平衡。仅仅在加热或减压时方会出现液体汽化现象。由Jenkins III等人实现的空时产率的增加是循环物流的冷却能力增大的结果,而后者又是由于进入循环物流与流化床之间温差较大以及由于被夹带在循环物流中的冷凝液发生汽化造成的。
Jenkins等人介绍了为了在气相反应器中最优化空时产率而进行总体控制以及试图扩展稳定操作区域的困难程度与复杂性。
在其专利中,循环气被冷却并且被加至温度低于露点的反应器中以便使冷凝液在反应器内蒸发。在冷却传热介质的给定温度下,循环气的冷却能力可以得到进一步提高。所述的可供选择的方式之一是添加非聚合物料(异戊烷)以便提高露点。由于冷却程度越高,被脱除的热量就越多,所以有可能得到更高的空时产率。Jenkins等人建议循环气中冷凝液不得超过20%(重),以2-12%(重)为佳。所述的某些潜在的危害包括“泥浆”的形成,其结果是需要保持足够高的循环气速或避免液体在分布板上累积。Jenkins等人对非聚合或可聚合冷凝物料的上限以及如何利用冷凝方式最优化空时产率的问题保持缄默。
可以控制气体流化床反应器以便在最优化生产条件下给出所需的聚合物熔体指数和密度。一般情况下须十分谨慎地操作以免导致形成块或片或者在更坏的情况下导致形成可能坍塌的不稳定流化床或导致聚合物颗粒熔融在一起的条件出现。因此,不得不对流化床进行控制以便减少结块和成片并且防止床层坍塌或消除终止反应进行以及关闭反应器的必要。这就是工业规模反应器被设计成能够在得到证实的稳定操作区域中良好地运行以及反应器以仔细限定的方式被使用的原因。
如果人们希望发现新的改进操作条件的话,甚至在传统的安全操作限度内,控制都会进一步增大实施的难度和不确定性。
目前存在借助聚合物和催化剂确定的操作温度、共聚用单体/单体比值和氢/单体比值的目标值。反应器与冷却***被包容在压力容器中。在不会不合时宜地干扰流化过程的条件下通过测定下列参数来监控其含量:(1)顶部压力;(2)床层不同高度的压差;(3)床层的上流温度,(4)流化床温和床的下流温度以及(5)气体组成和(6)气体流速。这些测定值被用于控制催化剂的加入、单体分压和循环气的速度。在一定情况下,通过沉积堆积密度(非流态化)或流化堆积密度依据设备设计要求来限制聚合物的移出,必须予以关注的还有上述两种密度以及聚合物中飞灰的含量。该设备为封闭体系。操作期间,该方法中一种或多种测定值的变化导致其它结果发生变化。在设备的设计过程中,生产能力的最优化取决于总体设计中最为苛刻的因素。
对于导致结块或成片的原因尚无普遍接受的观点。很显然,聚合物颗粒熔融在一起可能是由于流化床中流化不充分导致的传热不充分造成的。不过,迄今为止尚未发现在单独的调节和测定结果与发生结块和成片之间存在明显的关联性。因此,为了处在给定设计的设备的已知安全操作区域中传统地利用全部测定值与控制。
大规模气相设备造价昂贵并且产量高。由于停工期间代价高,所以采用这种设备存在很大的危险性。因此,难以参照成本与安全性以实验方式探索设计与操作限度。
有必要提供一种为气体流化床聚合而确定稳定操作条件以便有助于设备最优化设计和在给定设备设计中确定所需方法条件的方法。同样有必要提供一种能够给出最大反应器生产率的气体流化床聚合方法。
发明内容
因此,本发明的目的是为气体流化床方法和设备设计确定稳定的操作区域,找到以低失误可能性同时以高反应器生产率进行安全操作的标准和/或避免由于反应器生产率而对整个设备的生产能力构成任何限制。
发明概述
首先,本发明提供了一种在具有流化床和包括气相的流化介质的气相反应器中聚合α-烯烃以生产聚合产物的方法,其中该流化介质包括饱和和不饱和烃的可冷凝流体且用于控制所述反应器的冷却能力,该方法包括在流化介质中使用以流化介质总重为基准计为18-50%(重)的进入反应器的液体,并保持堆积密度函数(Z)值
在等于或大于在本文的表A中的堆积密度函数的计算极限值,其中表A中的X和Y根据如下的等式计算:
其中Pbf为流化堆积密度,Pbs为沉积堆积密度,Pg为气体密度,Ps为固体(树脂)密度和其中dp为重均粒径,g为重力加速度(9.805米/秒2),Uo为气体空塔速度和u为气体粘度。
其次,本发明提供了一种提高气相聚合反应器的生产能力的连续方法,该反应器具有流化介质和流化床,所述方法包括使含有单体的气流在催化剂存在下通过反应区以便生产聚合产物,移出所述聚合产物,从所述反应区中撤出含有未反应单体的流化介质,使所述流化介质与烃和聚合单体混合成为液相和气相,该方法包括在流化介质中使用以流化介质总重为基准计为18-50%(重)的进入反应器的液体,并使流化介质回到所述反应器中,该方法包括:
a)将所述烃导入所述流化介质以便将流化介质的冷却能力提高至高于至少22cal/g(40Btu/lb);
b)将移出聚合物产物的速率提高至高于至少2441kg/hr-m2(500lb/hr-ft2);
c)保持堆积密度函数(Z)值
在大于或等于在本文的表A中的堆积密度函数的计算极限值,其中表A中的X和Y根据如下的等式计算:
其中Pbf为流化堆积密度,Pbs为沉积堆积密度,Pg为气体密度,Ps为固体(树脂)密度和其中dp为重均粒径,g为重力加速度(9.805米/秒2),Uo为气体空塔速度和u为气体粘度。
本发明涉及以明显地高于先前的生产速率在气相反应器中聚合α-烯烃的方法。本发明针对在具有流化床和流化介质的气相反应器中聚合α-烯烃的方法,而流化介质中液体含量大于18%(重)、优选大于20%(重),基于流化介质的总重量。
本发明还涉及在具有流化床和流化介质的气相反应器中聚合α-烯烃的方法,其中离开与进入反应器的流化介质的焓变大于22cal/g(40Btu/lb)、优选大于27.5cal/g(50Btu/lb)。
本发明还提供一种在气相反应器中以大于2441kg/hr-m2(500lb/hr-ft2)的生产速率聚合α-烯烃的方法。
本发明涉及一种通过确定适用于决定流化床稳定性的性质以及控制流化介质或循环物流的组成以便确定保持稳定操作条件的特性数值范围来决定气相流化床聚合反应器的稳定操作条件的方法。
本发明还涉及通过监测表示反应器开始呈现失常状况的条件和响应这种状况的出现而控制流化介质或循环物流组成以防产生这种状况来控制气相流化床聚合反应器的方法。监测堆积密度函数。该函数被保持在等于或优选高于某一数值,该值取决于温度,压力,颗粒变量如粒径、固体密度和沉积堆积密度以及气体变量如按照下文限定的组成和速度。
本发明还提供一种以冷凝方式操作的气体流化床聚合反应器的稳定操作条件的确定方法,其中包括观察与流化介质组成变化相关的反应器中流态化堆积密度的变化,在不超过使流态化堆积密度的减少成为不可逆现象的水平的条件下提高循环物流的冷却能力。通常情况下,堆积密度函数被减小至最小值或下文所限定的极限以下会导致流化床被破坏,所以应当避免发生。
在另一实施方案中,本发明提供一种用于聚合物聚合的气体流化床聚合方法,其中包括使含单体的气流于反应条件下通过一个存在有催化剂的流化床反应器以便产生聚合产物和含有未反应单体气体的物流,压缩并且冷却该物流,使该物流与进料组分混合并且使液相和气相返回该反应器,其改进之处包括冷却该物流以便使液相占返回物流总重的18%(重)以上、优选20%(重)以上,该物流组成导致堆积密度函数被保持在高于下文所述极限数值。
附图说明
本发明的上述目的、特征与优点在参照附图阅读下列详述内容之后可以更清楚和更充分地被理解,其中:
图1为用于本发明聚合物生产过程的改进的气体流化床聚合方法实施过程的反应器的优选实施方案。
图2为表1中异戊烷摩尔百分数和流化堆积密度的描点曲线。
图3为表2中异戊烷摩尔百分数与流化堆积密度的描点曲线。
发明详述
在下文中,相同的部分分别以相同的标号表示。附图不必标记刻度,某些部分被放大了,其目的在于更好地描述本发明的改进方法。
本发明并非仅限于任何特定类型的聚合或共聚反应,而是特别好地适用于涉及一种或多种单体聚合的聚合反应,例如烯烃单体乙烯、丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-辛烯和苯乙烯。其它单体可以包括极性乙烯单体、共轭与非共轭二烯、乙炔和醛单体。
用于该改进方法的催化剂可以包括配位阴离子催化剂、阳离子催化剂、游离基催化剂、阴离子催化剂并且包括过渡金属组分或含有与金属烷基或烷氧基组分或离子化合物组分反应的单或多环戊二烯基组分的金属茂组分。这些催化剂可以包括部分和充分活化的前体组合物,通过预聚或密封而被改性的催化剂以及被承载在载体上的催化剂。
虽然如上所述,本发明并非被局限于任何特定类型的聚合反应,但是下列有关该改进方法的操作过程的讨论内容针对于烯烃类单体的气相聚合例如聚乙烯,在这方面,本发明被证实是特别有利的。在对产品质量或特性不产生不利影响的条件下可以大幅度提高反应器的生产率。
为了达到具备更高的冷却能力进而达到具备更高的反应器生产率的目的,有必要提高循环物流的露点从而使有待从流化床脱除的热量得到更大幅度的增加。为此,术语“循环物流”与“流化介质”是可以互换的。循环物流的露点可以通过提高反应/循环体系的操作压力和/或以Jenkins等在US 4588 790和4543399中所述增大循环物流中可冷凝流体的百分比和降低循环物流中非冷凝气体的百分比来被提高。这种可冷凝流体对于催化剂,反应物和制得的聚合物产物呈惰性;它还可以包括共聚单体。可冷凝流体如图1所示可以在任何部位被导入反应/循环***。为此,可冷凝流体一词包括饱和或不饱和烃。适宜的惰性可冷凝流体的实例为选自C2-8饱和烃的易挥发液态烃。某些适宜的饱和烃为丙烷、正丁烷、异丁烷、正戊烷、异戊烷、新戊烷、正己烷、异己烷和其它饱和C6烃、正庚烷、正辛烷以及其它饱和C7-8烃或其混合物。优选的惰性可冷凝烃为C5-6饱和烃。可冷凝流体还可以包括可聚合可冷凝共聚单体如烯烃、α-烯烃、二烯烃、含有至少一个α-烯烃的二烯烃或其混合物,其中包括可被部分或全部地结合进入聚合物产物的某些上述单体。
在实施本发明过程中,循环物流中气体数量与循环物流的速度应该被保持在足以使混合物的液相悬浮在气相中直至循环物流进入流化床为止的水平上以便使液体不会积聚在分布板下面的反应器底盖上。循环物流的速度同样必须高得足以支持和混合反应器内的流化床。同时有必要快速分散与汽化进入流化床的液体。
在保持一个可行的流化床过程中,重要的是依据聚合物的组成与物理特性控制气体的组成,温度、压力和空塔速度。一种可行的流化床或稳定操作条件被定义为这样一种颗粒的流化床,这些颗粒以稳定状态于反应条件下和不会形成大量有可能破坏反应器或下游过程操作的附聚物(结块或成片)的条件下被悬浮并且被充分混合。
在一个优选实施方案中,在不使流态化过程中断的条件下,可以冷凝或使其处于液相的循环物流百分比为大于15%(重)、以大于20%(重)为佳,条件是不得超出借助流化床堆积密度测定结果确定的稳定操作区域的安全操作界限。
在聚合过程中,一小部分(典型地少于约10%)向上通过流化床的气流发生反应。未反应的气流即主要部分通入处在流化床上方可以是速度降低区的被称作干舷区的区域。在干舷区中,由于喷出表面的气泡而被喷射到床层上或被夹带在气流中的较大的固体聚合物颗粒落回到流化床中。在工业中被视作“细粒”的较小的固体聚合物颗粒由于其最终沉降速度低于干舷区中循环物流的速度而与循环物流一起被撤出。
过程的操作温度被调至低于制得的聚合物颗粒的粘结或熔融温度。重要的是保持该温度以免反应器被在高温时会迅速生长的聚合物结块堵塞。这些聚合物结块会变得太大以致无法作为产物从反应器中取出并且中止过程与反应器操作。此外,结块进入聚合物产物的下游处理过程会破坏,例如,传送***、干燥装置或挤出机。可以按照结合在此供参考的U.S.P.4876320处理反应器壁。
在本发明的优选实施方案中,循环物流的进入点优选地低于流化床的最低点以便在整个反应器中提供均匀流动的循环物流,其目的在于保持流化床处于悬浮状态并且确保向上通过流化床的循环物流均匀一致。在另一实施方案中,循环物流可被分成二股或多股独立物流,其中一股或多股可被直接导入流化床,条件是处于流化床下方或整个床层中的气体流速足以保持床层处于悬浮态。例如循环物流可被分为液体和气体物流,它们随后分别地被导入反应器中。
在本发明改进方法的实践过程中,处于分布板下方的反应器内的含有气相和液相混合物的循环物流可以通过在能够产生含有这两相的物流的条件下分别地注入液体和循环气体而形成。
本发明的优点并非局限于生产聚烯烃。因此,本发明可以与任何在气体流化床中发生的放热反应一道进行。与其它方法相比,以冷凝方式进行的方法的优点在于通常将温度由循环物流的露点附近直接升至流化床内的反应温度。对于给定的露点,该方法的优点是可以直接增大返回至反应器的循环物流中液体百分比,本发明允许在过程中使用高百分比液体。
尤其适用于借助本发明方法生产聚合物的在图1中通常用标号10表示的气体流化床反应器在附图中得到最佳描述。应该注意的是图1介绍的反应体系意味着仅供举例说明之用。本发明适用于任何传统的流化床反应体系。
现在介绍图1,反应器10包括反应区12和在此情况下同样为速度下降区域14的干舷区。反应区12的高度/直径比可以依据所需的生产能力与停留时间而变化。反应区12包括由生长聚合物颗粒组成、其中存在所形成的聚合物颗粒和少量催化剂的流化床。反应区12中的流化床被循环物流或通常由进料与循环流体组成的流化介质16支撑。循环物流通过处在反应器底部、有助于均匀流化和支撑反应区12中的流化床的分布板18进入反应器。为了保持反应区12的流化床处于悬浮态和可行状态,气体通过反应器的空塔速度通常超过流化所需的最低流速。
反应区12中的聚合物颗粒有助于防止定位“热点”的产生和以及在流化床中分布和捕集催化剂颗粒。开始时,于导入循环物流16之前在反应器10中加入聚合物颗粒作为基底。这些聚合物颗粒优选地与待生产的新聚合物颗粒相同,不过,如果不相同时,在循环开始后以及在催化剂开始流动和发生反应之后,它们便与新形成的第一批产物一起被撤出。该混合物通常与后面基本上新的产物分隔开来以便进行交替处置。用于本发明改进方法的催化剂通常与氧相互作用,因此,该催化剂优选地于一种气体覆盖下贮存在催化剂贮罐20之中,该气体对被贮存的催化剂呈惰性,例如但不限于氮或氩。
反应区12中的流化床的流化通过使循环物流16进入并且通过反应器10的高速度实现。典型地在操作过程中,循环物流16的流速约为进料被导入循环物流16的流速的10-50倍。循环物流16的这种高流速提供了在反应区12中使流化床以流化态悬浮与混合所需的空塔气速。
流化床的表现类似于剧烈沸腾的液体,由于气体在流化床中的渗滤与鼓泡而导致颗粒的密实体呈单一运动方式。随着循环物流16通过反应区12中的流化床而产生压降。该压降等于或略大于被反应区12的横截面分隔的反应区12中的流化床的重量,这样便使得压降取决于反应器的几何形状。
同样是关于图1,补充进料于点22(但并非仅限于该点)进入循环物流16。气体分析装置24由循环物流管线16接受气体样品并且监测通过其中的循环物流16的组成。该气体分析装置24同样被设计用于调节循环物流管线16与进料的组成以便将反应区12中循环物流16的组成保持在稳定状态。气体分析器24通常分析于干舷区14和换热器26之间、优选压缩机28与换热器26之间某一点由循环物流管线16取出的样品。
循环物流16向上通过反应区12,吸收聚合方法产生的热量。在反应区12中不发生反应的那部分循环物流16离开反应区12并且通过速度减小区14或干舷区,如上所述,在该区域中,大部分被夹带的聚合物落回到反应区12中的流化床中从而降低固体聚合物颗粒进入循环物流管线16的数量。一旦循环物流16于干舷区14上方被移出反应器,随后便在压缩机28中被压缩并且通过换热器26,在此聚合反应与空气压缩产生的热自循环物流16中被脱除,随后循环物流16返回反应器10中的反应区12中。该换热器26属于常规类型并且可以被放置在循环物流管线16中于直立或水平位置。在本发明可供选择替代的另一实施方案中,在循环物流管线16中可以包括一个以上换热区或压缩区。
参照图1进行说明,循环物流16在离开换热器26后便返回到反应器10的底部。优选地,流体流动折转板30位于气体分布板18下面。流体流动折转板30能够防止聚合物沉降进入固相并且能够保持流体与聚合物颗粒在分布板18之下于循环体物流16中呈夹带状态。优选的流体流动折转板类型呈环形盘状,例如,U.S.P.No.4933149中所述类型。采用环形盘能够提供中心向上流动和***周边流动。中心向上流动有助于夹带底盖上的液滴,而***周边流动有助于最大限度地减少聚合物颗粒在底盖上的积累量。分布板18分布循环物流16以免该物流以可能破坏反应区12中流化床的流化过程的中心向上流动物流或喷射物形式进入反应器12。
流化床温度的设定取决于颗粒粘结点,不过基本上取决于下列三个因素:(1)催化剂活性和催化剂的注入速率,用于控制聚合速率与伴随而来的热生成速率;(2)温度,压力与被导入反应器的循环和补充物流的组成以及(3)通过流化床的循环物流的体积。借助上述独立导入方式或与循环物流一起被导入床层的液体数量尤其能够影响温度,原因在于液体在反应器中蒸发并且促使流化床中的温度下降。一般地,采用催化剂的添加速率来控制聚合物的生产速度。
在优选实施方案中,反应区12中流化床的温度通过连续地移走反应热而保持恒定和稳态。当该方法中产生的热量与被移走的热量达到平衡时,反应区12到达稳态。这一稳态要求进入聚合过程的材料的总量通过被移除聚合物与其它材料的数量被平衡。其结果是,在该方法的任意给定点处的温度、压力和组成均不随时间变化。在反应区12中在大部分流化床层中不存在明显的温度梯度,然而,在高于气体分布板18的区域中在反应区域12的流化床底部存在温度梯度。该梯度源于在反应器10底部进入分布板18的循环物流16的温度与反应区12中流化床之间的温差。
为了使反应器10有效地操作,应当良好地分布循环物流16。如果生长或形成的聚合物与催化剂颗粒被允许沉降脱离流化床,则聚合物便会熔融。在一种极端情况下这会导致在整个反应器中形成固体物料。一个工业规模反应器在任意给定时间内含有数千磅或千克聚合物固体。脱除如此大量的聚合物固体物料会遇到许多困难,要求付出巨大的努力与长期停工。通过借助流化堆积密度测定结果来确定稳定操作条件可以实施改进的聚合方法,其中流化过程与反应器10中反应区12内流化床的支撑得到维持。
在优选实施方案中,对于给定等级的聚合物和/或催化剂组合物来说,流化堆积密度的变化被用于最优化过程条件和设备设计。流化堆积密度为向上通过反应器中心固定部分的压降测定值与该固定部分高度的比值。这是一个可以大于或小于固定反应器中任一点上局部堆积密度的平均值。应该理解,在本领域专业人员已知的条件下,大于或小于局部床层堆积密度的平均值可以测得。
申请人发现,随着流过床层的气流中可冷凝组分浓度增大,可以达到一个标记点,如果浓度继续增大,超过该点就会出现该方法操作失败的危险。该点的特征在于随着气体中可冷凝流体浓度的增大,流化堆积密度会不可逆地减小。进入反应器的循环物流中液体含量可以是并非直接相关。流化堆积密度的下降通常不伴随有最终产物颗粒的沉积堆积密度发生相应的变化。因此,通过流化堆积密度下降反映出的流化行为的变化显然不涉及聚合物颗粒特性的任何永久性改变。
流化堆积密度出现下降时刻的气体中可冷凝流体浓度值大小取决于被生产的聚合物类型与其它方法条件。随着对于给定类型聚合物与其它方法条件来说气体中可冷凝流体浓度增大,它们可以通过监测流化堆积密度而得到确定。
除了气体中可冷凝流体浓度以外流化堆积密度(FBD)还取决于其它变量,例如包括气流通过反应器的空塔速度以及颗粒特征如粒径、密度和沉积堆积密度(SBD)、气体密度、粘度、温度和压力。因此,在测定由于气体中可冷凝流体浓度变化导致的流化堆积密度变化的试验中,应该避免使其它条件发生显著改变。因此,监测这些其它能够影响床层不稳定性的变量,进而由这些变量确定流化堆积密度属于本发明范围。为此,监测或保持流化堆积密度包括监测或保持上述那些能够影响流化堆积密度或被用于确定流化堆积密度的变量。
在不失控的条件下可以有节制地降低流化堆积密度,进一步改变气体组成或其它同样会提高露点温度的变量会使流化堆积密度不可逆地降低,使反应器床层中出现“热点”,形成熔融附聚物并且最终使反应器停止操作。
与流化堆积密度降低直接相关的其它实际结果包括固定体积反应器卸料***的聚合物排放能力下降和在聚合物生产速度恒定时聚合物/催化剂反应器停留时间被缩短。对于给定催化剂而言,后者会降低催化剂的生产率并且增大产物聚合物中催化剂残渣的含量。在优选实施方案中,对于给定的目标反应器生产速率与相关的冷却需要,期望最大限度地降低气体中可冷凝流体浓度。
利用这类流化堆积密度变化形式,可以确立稳定的操作条件。一旦找到适宜的组合物,该组合物便可被用于通过将该组合物冷却至更深程度而使循环物流(在不遇到床层不稳定的条件下)具备更高的冷却能力。对于特定等级的聚合物而言,可以适宜的量加入可冷凝的非聚合材料以便得到高反应器生产率,与此同时,通过处在如此确定的稳定操作区内使流化床保持良好的条件。可以在一个过程中实现高反应器生产率,或者,就设备设计而言,大生产能力的设备可被设计成具有较小的反应器直径或者现存的反应器可在不改变反应器尺寸的条件下被改进以便提高其生产能力。
业已发现,在反应器生产率较高时,若处于被可接受流化堆积密度变化限定的界限内,在避免出现由于流化床坍塌而产生大量结块或成片的条件下冷凝液含量典型地高于约15%、18%、20%、22%、25%、27%、30%或甚至35%是可被允许的。基于循环物流或流化介质的总量的冷凝液含量范围为15-50%(重),以大于约20-50%(重)为佳,甚至以20-约40%(重)为更佳,以约25-约40%(重)为最佳。
优选地,通过利用于分布板之上一部分不易被扰动的流化床上测定的压差观察流化堆积密度。而常规情况下,在床层下部流化堆积密度的改变可被视作分布板上床层坍塌的表征,远离分布板测得的上部流化堆积密度被用作稳定参考,现在出人意料地发现上部流化堆积密度的改变与物流组成的变化相关并且可被用于发现与限定稳定操作区。
本文中,堆积密度函数Z被限定为:
其中Pbf为流化堆积密度,Pbs为沉积堆积密度,Pg为气体密度,Ps为固体(树脂)密度。堆积密度函数(Z)可以由工艺与产物测定值计算产生。
在一个实施方案中,堆积密度函数(Z)被定义为:
其中Pbf为流化堆积密度,Pbs为沉积堆积密度,Pg为气体密度,Ps为固体(树脂)密度。
在本发明中,通过将堆积密度函数(Z)保持在高于下表A与B中所示基于X与Y计算值的最低数或极限值来避免流化受到破坏。
在本发明中,X与Y如下式限定:
其中dp为重均粒径,g为重力加速度(9.805米/秒2),Uo为气体空塔速度,u为气体粘度。
在本发明中,堆积密度函数的计算极限基于如利用上述公式计算的X与Y函数值。该计算极限为采用X与Y的计算值由表A和/或B确定的数值。
表A为堆积密度函数范围X与Y的计算极限值。表B为堆积密度函数优选范围X与Y的计算极限值。
当表A和/或B仅代表X和Y的选择点数值时,本领域专业人员会认为,通常有必要内推数值X与Y以便得到相应的Z值极限。
在优选实施方案中,堆积密度函数(Z)被保持在大于或等于、更优选地大于利用数值X和Y的表A和/或B提供的数值。
在另一实施方案中,堆积密度函数(Z)被保持在比由表A和B确定的堆积密度函数值的极限大于1%,更优选地大于2%,甚至更优选地大于4%并且最优选地大于5%的水平上。
在另一实施方案中,堆积密度函数(Z)值范围约为0.2-0.7,优选为约0.3-0.6,以大于约0.4-0.6为更佳。
粒径(dp)范围为100-3000μm,以约500-2500μm为佳,以约500-2000μm为更佳,以500-1500μm为最佳。
气体粘度(μ)范围为约0.01-约0.02cp(厘泊),以0.01-0.18cp为佳,以0.011-约0.015cp为最佳。
沉积堆积密度(SBD)或(Pbs)范围为约10-35lb/ft3)(160.2-561kg/m3),优选约12-35lb/ft3)(193-561kg/m3),更优选约14-32lb/ft3(224.3-513kg/m3),以约15-30lb/ft3(240.3-481kg/m3)为最佳。
气体密度(Pg)范围为约0.5-4.8lb/ft3(8-77kg/m3),优选约1-4lb/ft3(16-64.1kg/m3),更优选约1.1-4lb/ft3(17.6-64.1kg/m3),以约1.2-3.6lb/ft3(19.3-57.9kg/m3)为最佳。
固态树脂密度(Ps)范围为0.86-约0.97g/ml,优选0.87-约0.97g/ml,更优选0.875-约0.970g/ml,以0.88-约0.97g/ml为最佳。反应器温度在60-120℃,优选60-115℃,以70-110℃为最佳。
反应器压力为100-1000psig(689.5-6895kPag),优选约150-600psig(1034-4137kPag),更优选200-约500psig(1379-3448kPag),以250-400psig(1724-2758kPag)为最佳。
表A
极限堆积密度函数
Y | 2.0 | 2.5 | 3.0 | 3.5 | 4.0 | 4.5 | 5.0 | 5.5 | 6.0 | 6.5 | 7.0 | 7.5 | 8.0 |
X | |||||||||||||
0.3 | 0.411 | ||||||||||||
0.4 | 0.403 | ||||||||||||
0.5 | 0.393 | ||||||||||||
0.6 | 0.381 | ||||||||||||
0.7 | 0.367 | 0.460 | |||||||||||
0.8 | 0.351 | 0.450 | |||||||||||
0.9 | 0.332 | 0.437 | |||||||||||
1.0 | 0.311 | 0.422 | 0.522 | ||||||||||
1.1 | 0.289 | 0.404 | 0.510 | ||||||||||
1.2 | 0.265 | 0.384 | 0.496 | ||||||||||
1.3 | 0.239 | 0.361 | 0.480 | ||||||||||
1.4 | 0.214 | 0.336 | 0.460 | 0.561 | |||||||||
1.5 | 0.188 | 0.309 | 0.438 | 0.546 | |||||||||
1.6 | 0.281 | 0.413 | 0.529 | ||||||||||
1.7 | 0.252 | 0.386 | 0.508 | 0.598 | |||||||||
1.8 | 0.223 | 0.355 | 0.484 | 0.582 | |||||||||
1.9 | 0.324 | 0.457 | 0.563 | ||||||||||
2.0 | 0.291 | 0.427 | 0.541 | 0.620 | |||||||||
2.1 | 0.258 | 0.394 | 0.516 | 0.602 | |||||||||
2.2 | 0.226 | 0.360 | 0.487 | 0.581 | |||||||||
2.3 | 0.324 | 0.455 | 0.557 | 0.633 | |||||||||
2.4 | 0.288 | 0.421 | 0.529 | 0.614 | |||||||||
2.5 | 0.252 | 0.384 | 0.497 | 0.590 | |||||||||
2.6 | 0.346 | 0.462 | 0.563 | 0.635 | |||||||||
2.7 | 0.307 | 0.425 | 0.533 | 0.614 | |||||||||
2.8 | 0.270 | 0.385 | 0.499 | 0.588 | |||||||||
2.9 | 0.339 | 0.461 | 0.559 | 0.628 | |||||||||
3.0 | 0.299 | 0.422 | 0.526 | 0.605 | |||||||||
3.1 | 0.261 | 0.381 | 0.490 | 0.577 | 0.641 | ||||||||
3.2 | 0.339 | 0.451 | 0.546 | 0.619 | |||||||||
3.3 | 0.298 | 0.410 | 0.511 | 0.593 | |||||||||
3.4 | 0.259 | 0.368 | 0.473 | 0.564 | 0.631 | ||||||||
3.5 | 0.325 | 0.433 | 0.531 | 0.608 | |||||||||
3.6 | 0.284 | 0.391 | 0.494 | 0.580 | 0.643 | ||||||||
3.7 | 0.245 | 0.348 | 0.455 | 0.549 | 0.621 | ||||||||
3.8 | 0.306 | 0.413 | 0.514 | 0.595 | 0.653 | ||||||||
3.9 | 0.266 | 0.371 | 0.476 | 0.566 | 0.633 | ||||||||
4.0 | 0.328 | 0.435 | 0.532 | 0.609 | |||||||||
4.1 | 0.287 | 0.393 | 0.496 | 0.581 | |||||||||
4.2 | 0.247 | 0.350 | 0.456 | 0.550 | |||||||||
4.3 | 0.308 | 0.415 | 0.515 | ||||||||||
4.4 | 0.267 | 0.372 | 0.477 | ||||||||||
4.5 | 0.329 | 0.436 | |||||||||||
4.6 | 0.288 | 0.394 |
表B
极限堆积密度的优选范围
Y | 4.00 | 4.25 | 4.50 | 4.75 | 5.00 | 5.25 | 5.50 | 5.75 | 6.00 | 6.25 | 6.50 | 6.75 | 7.00 |
X | |||||||||||||
2.00 | 0.541 | 0.584 | |||||||||||
2.05 | 0.529 | 0.574 | |||||||||||
2.10 | 0.516 | 0.562 | |||||||||||
2.15 | 0.502 | 0.550 | 0.592 | ||||||||||
2.20 | 0.487 | 0.537 | 0.581 | ||||||||||
2.25 | 0.472 | 0.524 | 0.569 | ||||||||||
2.30 | 0.455 | 0.509 | 0.557 | 0.598 | |||||||||
2.35 | 0.438 | 0.493 | 0.543 | 0.587 | |||||||||
2.40 | 0.420 | 0.477 | 0.529 | 0.574 | |||||||||
2.45 | 0.402 | 0.460 | 0.513 | 0.561 | 0.602 | ||||||||
2.50 | 0.384 | 0.442 | 0.497 | 0.547 | 0.590 | ||||||||
2.55 | 0.424 | 0.480 | 0.532 | 0.577 | |||||||||
2.60 | 0.405 | 0.462 | 0.515 | 0.563 | 0.605 | ||||||||
2.65 | 0.386 | 0.444 | 0.499 | 0.548 | 0.592 | ||||||||
2.70 | 0.425 | 0.481 | 0.533 | 0.579 | |||||||||
2.75 | 0.405 | 0.463 | 0.516 | 0.564 | 0.601 | ||||||||
2.80 | 0.385 | 0.444 | 0.499 | 0.549 | 0.588 | ||||||||
2.85 | 0.424 | 0.480 | 0.533 | 0.574 | 0.609 | ||||||||
2.90 | 0.404 | 0.461 | 0.515 | 0.559 | 0.597 | ||||||||
2.95 | 0.384 | 0.442 | 0.497 | 0.543 | 0.583 | ||||||||
3.00 | 0.422 | 0.478 | 0.526 | 0.568 | 0.605 | ||||||||
3.05 | 0.401 | 0.459 | 0.509 | 0.553 | 0.591 | ||||||||
3.10 | 0.381 | 0.439 | 0.490 | 0.536 | 0.577 | 0.612 | |||||||
3.15 | 0.418 | 0.471 | 0.519 | 0.562 | 0.599 | ||||||||
3.20 | 0.398 | 0.451 | 0.501 | 0.546 | 0.585 | ||||||||
3.25 | 0.377 | 0.431 | 0.482 | 0.529 | 0.571 | 0.607 | |||||||
3.30 | 0.410 | 0.462 | 0.511 | 0.555 | 0.593 | ||||||||
3.35 | 0.389 | 0.442 | 0.493 | 0.539 | 0.579 | 0.613 | |||||||
3.40 | 0.422 | 0.473 | 0.521 | 0.564 | 0.601 | ||||||||
3.45 | 0.401 | 0.453 | 0.503 | 0.548 | 0.587 | ||||||||
3.50 | 0.379 | 0.433 | 0.484 | 0.531 | 0.572 | 0.608 | |||||||
3.55 | 0.412 | 0.464 | 0.513 | 0.556 | 0.594 | ||||||||
3.60 | 0.391 | 0.444 | 0.494 | 0.540 | 0.580 | ||||||||
3.65 | 0.423 | 0.475 | 0.522 | 0.565 | |||||||||
3.70 | 0.402 | 0.455 | 0.504 | 0.549 | |||||||||
3.75 | 0.381 | 0.434 | 0.485 | 0.532 | |||||||||
3.80 | 0.413 | 0.465 | 0.514 | ||||||||||
3.85 | 0.392 | 0.445 | 0.495 | ||||||||||
3.90 | 0.424 | 0.476 | |||||||||||
3.95 | 0.403 | 0.456 | |||||||||||
4.00 | 0.382 | 0.435 |
有利地,将循环物流冷却并且使其通过反应器,其通过速度导致其冷却能力足以使以每小时每平方英尺反应器横截面积中聚合物磅数表示的反应器生产率超过500lb/hr-ft2(2441kg/hr-m2)、尤其是600lb/hr-ft2(2929kg/hr-m2),循环物流自反应器进口条件下至反应出口条件下焓变至少为40Btu/lb(22cal/g)、优选为50Btu/lb(27cal/g)。优选地,将物流的液体与气体组分加入处在反应器分布板下面的混合物中。该反应器的生产率等于空时产率乘以流化床高度。
在本发明的优选实施方案中,被导入反应器10的液体蒸发以便提高聚合过程中反应器的冷却能力。床层中液体含量高有利于形成无法借助床层中存在的机械力破碎的附聚物,从而潜在地导致非流态化、床层坍塌与反应器停止操作。此外,液体的存在会影响局部床层温度并且降低该方法制备具备均匀特性的聚合物的能力,原因在于这种情况要求整个床层具有基本上恒定的温度。为此,在给定条件下被导入流化床的液体量不应该明显地超出流化床下部的蒸发量,在流化床下部,与通过分布板进入的循环物流相关的机械力足以破碎通过液体一颗粒相互作用形成的附聚体。
本发明人发现,对于流化床中产物颗粒的给定组成和物理特征以及其它给定的或相关的反应器与循环条件而言,通过限定与流过床层的气体的组成相关的边界条件,可以将可行的流化床保持在高冷却水平。
在不希望被任何理论局限的同时,申请人认为所观察到的流化堆积密度的降低可以反映出密实颗粒相的膨胀与流化床中鼓泡行为的变化。
图1中,如果需要其种类依据所用催化剂决定的催化剂活化剂通常由换热器26顺流地被加入。该催化剂活化剂可以由分散器32被导入循环物流16之中。然而,本发明的改进方法并非限于催化剂活化剂或任何其它所需组分如催化剂促进剂的注入位置。
来自催化剂储罐的催化剂可被间歇地或连续地以优选速率于高于气体分布板18的点34处注入流化床反应区12中。在上述优选实施方案中,催化剂在能够与聚合物颗粒于流化床12中完成最佳混合的点被注入。由于某些催化剂非常活泼,所以,注入反应器10的位置优选高于而不是低于气体分布板18。在低于气体分布板18的区域中注入催化剂会导致产物在该区域中聚合,最终使气体分布板18被堵塞。此外,将催化剂导入气体分布板18上方有助于将催化剂均匀分布在流化床12之中,因而有利于防止由于局部催化剂浓度增大而形成“热点”。优选地,将其注入反应区12中流化床的下部以便提供均匀分布并且最大限度地减少进入其中进行聚合反应会导致堵塞的循环管线和换热器的催化剂载带量。
可以将许多催化剂注入技术用于本发明的改进方法,例如其中披露的内容被列入本文供参考的U.S.3779712。优选采用易于在反应器条件下挥发的惰性气体如氮或惰性液体。以便将催化剂带入流化床反应区12之中。循环物流16中催化剂注入速率与单体浓度决定了流化床反应区12中聚合物生产速率。可以通过简单地调节催化剂注入速率来控制聚合物生产速率。
在利用本发明改进方法的反应器10的优选操作方式中,反应区12中流化床的高度通过以与聚合物产物的形成相一致的速率撤出一部分聚合物产物来保持。为了监测反应区12中流化床条件的变化,设置检测反应器10中与循环物流16中温度或压力变化的仪器是适用的。另外,这些仪器可以手动或自动调节催化剂的注入速率和/或循环物流的温度。
在反应器10的操作过程中,产物通过排料***36离开反应器。在排出聚合物产物之后,优选地分离出其中流体。这些流体在点38处作为气体和/或在点40处作为冷凝液返回到循环物流管线16中。该聚合物产物于点42处进入下游加工过程。聚合物产物的排放过程不限于图1所示方法,图1描述了一种特定的排料方法。举例来说,可以采用诸如Jenkins等的U.S.454399和4588790之类所述的其它排料***。
按照本发明,提供了一种通过将循环物流冷却至低于其露点并且将所产生的循环物流送回反应器来提高利用放热聚合反应的流化床反应器的聚合物生产率的方法。含有大于15,优选大于20%(重)液体的循环物流可被循环至反应器中以便将流化床保持在所需温度。
在本发明方法中,循环物流或流化介质的冷却能力可以通过被夹带在循环物流中的冷凝液的蒸发以及由于进入循环物流与流化床之间温差较大而得到明显增强。
在一个实施方案中,本发明方法生产的聚合物产物的密度范围约为0.90-0.939g/ml。
在优选实施方案中,制得的聚合物、均聚物或共聚物选自MI为0.01-5.0、优选0.5-5.0、密度为0.900-0.930的薄膜级树脂;或MI为0.10-150.0、优选4.0-150.0、密度为0.920-0.939的模塑级树脂;或MI为0.01-70.0、优选2.0-70.0、密度为0.940-0.970的高密度树脂;所有密度单位均为g/cm3,按照ASTM-1238条件E测定的熔体指数为g/10分钟。
依据目标树脂采用不同循环条件,得到先前未曾设想到的反应器生产率水平。
首先,可以制得例如薄膜级树脂,其中循环物流的丁烯/乙烯摩尔比为0.001-0.60、优选0.30-0.50或4-甲基-1-戊烯/乙烯的摩尔比为0.001-0.50、优选为0.08-0.33或己烯/乙烯摩尔为0.001-0.30、优选为0.05-0.20;或1-辛烯/乙烯摩尔比为0.001-0.10,优选为0.02-0.07;氢/乙烯摩尔比为0.00-0.4,优选为0.1-0.3;异戊烷含量为3-20%(摩尔)或异己烷含量为1.5-10%(摩尔),其中循环物流的冷却能力至少为40Btu/lb、优选至少为50Btu/lb,冷凝物料的重量百分数至少为15,以大于20为佳。
其次,该方法可被用于生产模塑级树脂,其中循环物流中1-丁烯/乙烯摩尔比为0.001-0.60、优选为0.10-0.50,4-甲基-1-戊烯/乙烯摩尔比为0.001-0.50,优选为0.08-0.20,或己烯/乙烯摩尔比为0.001-0.30,优选为0.05-0.12,或者1-辛烯/乙烯摩尔比为0.001-0.10、优选为0.02-0.04;氢/乙烯摩尔比为0.00-1.6,优选为0.3-1.4;异戊烷含量为3-30%(摩尔)或异己烷含量为1.5-15%(摩尔),其中循环物流的冷却能力至少为40Btu/lb、优选为至少50Btu/lb,冷凝物料的重量百分数至少为15,以大于20为佳。
此外,该方法可被用于生产高密度级树脂,其中循环物流中1-丁烯/乙烯摩尔比为0.001-0.30、优选为0.001-0.15,4-甲基-1-戊烯/乙烯摩尔比为0.001-0.25,优选为0.001-0.120,或己烯/乙烯摩尔比为0.001-0.15,优选为0.001-0.07,或者1-辛烯/乙烯摩尔比为0.001-0.05、优选为0.001-0.02;氢/乙烯摩尔比为0.00-1.5,优选为0.3-1.0;异戊烷含量为10-40%(摩尔)或异己烷含量为5-20%(摩尔),其中循环物流的冷却能力至少为60Btu/lb、优选为大于73Btu/lb,最优选地大于至少约75Btu/lb,冷凝物料的重量百分数至少为12,以大于20为佳。
具体实施方式
为了更好地理解本发明,其具有代表性的优点与局限性,提供与在本发明实践中进行的实际试验相关的下列实施例。
实施例1
操作流化气相反应器以便制备含有乙烯和丁烯的共聚物。所用的催化剂为由四氢呋喃、被氯化二乙基铝还原的氯化镁和氯化钛(氯化二乙基铝与四氢呋喃的摩尔比为0.50)以及被浸渍于经过三乙基铝处理的二氧化硅之上的三正己基铝(三正己基铝与四氢呋喃的摩尔比为0.30)形成的配合物。活化剂为三乙基铝(TEAL)。
表1与图2中的数据表明反应器的参数在异戊烷含量逐渐增大以便实现为了获得更高的反应器生产能力而附加的冷却步骤期间的变化情况。该实施例表明过量异戊烷导致流化床中发生变化并且最终由于形成迫使反应器停车的热点与附聚物而导致床层坍塌。随着异戊烷浓度的增大,流化堆积密度降低,这表明床层流化状态发生变化,这还会导致床高增大。降低催化剂导入速率以便减小床高。此外,异戊烷浓度被减小以便使流化床发生逆向变化。然而,此时,尽管床高恢复正常,但是伴随着床层中形成的热点与附聚而产生的坍塌现象却是不可逆转的,这样反应器便停止操作。
此外,由表1的数据可以看出,只要将堆积密度函数(Z)值保持在高于计算极限(基于X与Y的函数与表A和B的数值)的水平便可以稳定地操作该反应器。一旦该堆积密度函数(Z)值低于计算极限值,反应器的运行便不稳定并且被迫停车。
再者,在第二试验中,表2与图3表明正如表1所预计的那样随着异戊烷浓度的逐渐增大,流化堆积密度减小。然而,此时流化堆积密度的逐渐增大是由于异戊烷浓度的降低造成的。因此,此时床层中流化状态的变化是可以恢复和可逆转的。
表2中的数据表明将堆积密度函数(Z)值保持在等于或大于计算极限值(由X与Y函数和表A与B的数值确定),床层流化状态的变化保持稳定状态。
表1和2中所示的堆积密度函数清楚地表明了出现由于过量使用可冷凝流体而导致床层流化状态发生不可逆变化的位置。该位置被定义为堆积密度函数(Z)低于堆积密度函数计算极限值的位置。
实施例2
下列实施例以与实施例1基本上相同的方式采用同类催化剂和活化剂进行,以便生产不同密度和熔体指数范围的均聚物和乙烯/丁烯共聚物。
这些试验表明在将堆积密度函数(Z)保持在高于上述堆积密度函数的计算极限值的同时,在冷凝液含量超出20%(重)的条件下实现更高反应器生产能力的优点。
由于下游的处理方法,例如产物排放***、挤出机等的作用,不得不调整某些反应器操作条件以免超出整个设备的生产能力。因此,表3所示的实施例无法充分展示本发明的全部优点。
例如,在表3的试验1中,气体空塔速度被保持在约1.69英尺/秒(0.52m/秒),这样,被反映出的空时产率远远低于实际情况。若速度被保持在约2.4英尺/秒(0.74m/秒),预计的空时产率超过15.3lb/hr/ft3(244.8kg/hr-m3)是可以实现的。表3的试验2和3表明在高空塔气速和冷凝物料重量百分比高于20%的情况下操作反应器的效果。空时产率约为14.3-13.0lb/hr-ft3(228.8和208kg/hr-m3),这表明生产速率得到明显提高。Jenkins等人并未介绍或提及如此高的空时产率或生产速率。与试验1类似,表3的试验4表明在冷凝液含量为21.8%(重)时空塔气速为1.74ft/sec(0.53m/秒)。若试验4的速度被增至3.0ft/sec(0.92m/秒),则可实现的空时产率会由7.7增至13.3lb/hr-ft3(123.2-212.8kg/hr-m3)。若试验5中的速度被增至3.0ft/sec(0.92m/秒),则能达到的空时产率会由9.8增至17.0lb/hr-ft3(156.8-272kg/hr-m3)。对于所有试验1-5来说,流化堆积密度函数(Z)保持在高于上述堆积密度函数的极限值。
实施例3
采用本领域公知的用于设计目标条件的热力学方程通过由实际操作信息外推来制备实施例3,表4所示的数据。表4中的数据表明在去除辅助反应器设备的限制条件的情况下本发明的优点。
在试验1中,空塔气速由1.69ft/sec增至2.40ft/sec(0.52m/秒-0.74m/秒),这导致空时产率由初始的10.8lb/hr-ft3(172.8kg/hr-m3)增至15.3lb/hr-ft3(244.8kg/hr-m3)。在另一步骤中,循环进料由46.2℃被冷却至40.6℃。该冷却步骤将循环冷凝物料含量增至34.4%(重)并且将空时产率进一步提高至18.1lb/hr-ft3(289.6kg/hr-m3)。在最后步骤中,通过提高可冷凝的惰性异戊烷的浓度从而提高其冷却能力来改变气体组成。通过这种方式,循环冷凝物料含量进一步增至44.2%(重),空时产率达到23.3lb/hr-ft3(372.8kg/hr-m3)。总之,这些步骤使反应器***的生产能力提高了116%。
在试验2中,循环进料温度由42.1℃被冷却至37.8℃。该冷却步骤将循环冷凝物料由25.4%(重)增至27.1%(重)并且将空时产率由14.3增至15.6lb/hr-ft3(228.8-249.6kg/hr-m3)。在其它步骤中,C6烃的浓度由7%(摩尔)增至10%(摩尔)。这一冷却能力的改进使得空时产率增至17.8lb/hr-ft3(284.8kg/hr-m3)。作为表示这种改进值的最终步骤,循环进料温度再次被降至29.4℃。这一附加的冷却步骤使得空时产率随着循环物流中冷凝物含量达到38.6%(重)而达到19.8lb/hr-ft3(316.8kg/hr-m3)。总之,这些步骤使得反应器体系的生产能力提高39%。
尽管参照具体实施方案描述了本发明,但是本领域专业人员应该理解本发明包括不必在其中描述的变化形式。例如,使用其活性得到增强的催化剂以便提高生产速率或通过使用制冷机装置降低循环物流的温度属于本发明范围。为此,应该仅仅依据权利要求书来确定本发明的真实保护范围。
表1
时间(小时) | 1 | 7 | 10 | 13 | 15 | 17 | 18 |
树脂熔体指数(dg/10min) | 1.01 | 1.04 | 1.03 | 1.12 | 1.09 | 1.11 | 1.11 |
树脂密度(g/cc) | 0.9176 | 0.9183 | 0.9190 | 0.9190 | 0.9183 | 0.9193 | 0.9193 |
循环物流组成 | |||||||
乙烯 | 47.4 | 46.0 | 44.7 | 44.1 | 44.0 | 45.9 | 46.3 |
1-丁烯 | 19.0 | 18.1 | 17.3 | 17.0 | 16.9 | 18.5 | 19.5 |
1-己烯 | |||||||
氢 | 9.5 | 9.4 | 9.3 | 9.3 | 8.9 | 8.7 | 8.9 |
异戊烷 | 8.0 | 10.8 | 13.7 | 15.1 | 15.4 | 14.3 | 13.2 |
C6饱和烃 | |||||||
氮 | 14.3 | 13.9 | 13.3 | 12.8 | 13.2 | 11.2 | 10.7 |
乙烷 | 1.8 | 1.8 | 1.7 | 1.7 | 1.6 | 1.4 | 1.4 |
甲烷 | |||||||
C8饱和烃 | |||||||
循环气体露点(°F) | 142.9 | 153.5 | 163.8 | 168.3 | 170.1 | 168.8 | 165.0 |
循环气体露点(℃) | 61.6 | 67.5 | 73.2 | 75.7 | 76.7 | 76.0 | 73.9 |
反应器入口温度(°F) | 126.2 | 135.6 | 143.5 | 144.0 | 149.0 | 150.2 | 146.3 |
反应器入口温度(℃) | 52.3 | 57.6 | 61.9 | 62.2 | 65.0 | 65.7 | 63.5 |
循环气中的液体(WT%) | 11.4 | 12.1 | 14.3 | 17.4 | 14.5 | 11.6 | 12.3 |
反应器温度(°F) | 182.4 | 182.1 | 182.7 | 182.8 | 183.1 | 184.8 | 185.2 |
反应器温度(℃) | 83.6 | 83.4 | 83.7 | 83.8 | 83.9 | 84.9 | 85.1 |
反应器压力(psig) | 311.9 | 311.5 | 314.2 | 313.4 | 314.7 | 313.5 | 312.6 |
反应器压力(Kpag) | 2150.5 | 2147.7 | 2166.3 | 2160.8 | 2169.8 | 2161.5 | 2155.3 |
反应器空塔气速(ft/sec) | 2.29 | 2.30 | 2.16 | 2.10 | 1.92 | 2.00 | 2.11 |
反应器空塔气速(m/sec) | 0.70 | 0.70 | 0.66 | 0.64 | 0.59 | 0.61 | 0.64 |
反应器床高(ft) | 43.4 | 43.3 | 43.5 | 49.3 | 51.3 | 45.8 | 45.4 |
反应器床高(m) | 13.2 | 13.2 | 13.3 | 15.0 | 15.6 | 14.0 | 13.8 |
树脂沉降堆积密度(lb/ft3) | 30.1 | 30.2 | 30.2 | 30.2 | 30.0 | 29.9 | 29.9 |
树脂沉降堆积密度(kg/m3) | 482.2 | 483.8 | 483.8 | 483.8 | 480.6 | 479.0 | 479.0 |
反应器床流化堆积密度(lb/ft3) | 18.9 | 19.6 | 18.1 | 17.8 | 17.2 | 16.4 | 15.8 |
反应器床流化堆积密度(kg/m3) | 302.8 | 314.0 | 290.0 | 285.2 | 275.5 | 262.7 | 253.1 |
空时产率(lb/hr-ft3) | 9.6 | 9.5 | 9.3 | 8.5 | 6.6 | 7.1 | 7.3 |
空时产率(kg/m3) | 153.0 | 151.8 | 149.3 | 136.0 | 106.0 | 113.8 | 117.2 |
生产速率(klb/hr) | 68.5 | 67.8 | 67.0 | 69.2 | 56.1 | 53.8 | 54.9 |
生产速率(Tons/hr) | 31.1 | 30.7 | 30.4 | 31.4 | 25.4 | 24.4 | 24.9 |
反应器生产能力(lb/hr-ft2) | 415 | 411 | 406 | 419 | 340 | 326 | 332 |
反应器生产能力(kg/hr-m2) | 2026 | 2006 | 1982 | 2045 | 1660 | 1591 | 1621 |
循环物流的焓变(Btu/lb) | 42 | 40 | 40 | 42 | 37 | 34 | 33 |
循环物流的焓变(cal/g) | 23 | 22 | 22 | 23 | 21 | 19 | 18 |
气体密度lb/ft3 | 1.82 | 1.89 | 1.98 | 2.01 | 2.03 | 2.03 | 2.00 |
气体密度kg/m3 | 29.1 | 30.2 | 31.7 | 32.2 | 32.6 | 32.5 | 32.1 |
气体粘度(cp) | 0.012 | 0.012 | 0.012 | 0.012 | 0.012 | 0.012 | 0.012 |
粒径(英寸) | 0.030 | 0.030 | 0.030 | 0.030 | 0.030 | 0.030 | 0.030 |
粒径(μm) | 762 | 762 | 762 | 762 | 762 | 762 | 762 |
X函数 | 3.11 | 3.13 | 3.12 | 3.12 | 3.09 | 3.10 | 3.12 |
Y函数 | 5.61 | 5.63 | 5.65 | 5.66 | 5.66 | 5.66 | 5.65 |
密度函数(Z) | 0.59 | 0.61 | 0.55 | 0.54 | 0.52 | 0.50 | 0.48 |
表A和B*的极限 | 0.51 | 0.50 | 0.51 | 0.51 | 0.52 | 0.52 | 0.51 |
*基于X与Y函数值;表A与B被用于确定极限
表2
时间(小时) | 1 | 3 | 5 | 7 | 9 | 11 | 14 | 16 | 18 |
树脂熔体指数(dg/10min) | 0.92 | 0.99 | 1.08 | 1.02 | 1.05 | 1.09 | 1.11 | 1.05 | 0.98 |
树脂密度(g/cc) | 0.9187 | 0.9184 | 0.9183 | 0.9181 | 0.9178 | 0.9177 | 0.9186 | 0.9184 | 0.9183 |
循环物流组成 | |||||||||
乙烯 | 52.6 | 53.2 | 52.6 | 52.0 | 52.1 | 51.6 | 52.9 | 52.8 | 52.8 |
1-丁烯 | 20.0 | 19.8 | 19.7 | 20.4 | 19.7 | 19.8 | 19.1 | 20.1 | 20.1 |
1-己烯 | |||||||||
氢 | 9.7 | 10.2 | 10.3 | 9.9 | 9.9 | 9.9 | 10.4 | 10.0 | 9.6 |
异戊烷 | 9.9 | 9.5 | 10.7 | 11.2 | 12.2 | 12.8 | 11.5 | 10.4 | 9.6 |
C6饱和烃 | |||||||||
氮 | 8.7 | 8.0 | 7.3 | 6.7 | 6.3 | 6.0 | 6.5 | 7.3 | 8.1 |
乙烷 | 1.2 | 1.2 | 1.1 | 1.1 | 1.1 | 1.1 | 1.2 | 1.2 | 1.3 |
甲烷 | |||||||||
C8炮和烃 | |||||||||
循环气体露点(°F) | 154.1 | 152.5 | 156.9 | 160.0 | 161.9 | 165.0 | 159.4 | 155.9 | 153.3 |
循环气体露点(℃) | 67.8 | 66.9 | 69.4 | 71.1 | 72.2 | 73.9 | 70.8 | 68.8 | 67.4 |
反应器入口温度(°F) | 124.2 | 118.3 | 119.7 | 125.3 | 127.3 | 133.2 | 128.0 | 126.2 | 123.0 |
反应器入口温度(℃) | 51.2 | 47.9 | 48.7 | 51.8 | 52.9 | 56.2 | 53.3 | 52.3 | 50.6 |
循环气中的液体(WT%) | 22.2 | 24.9 | 27.4 | 26.4 | 27.0 | 24.3 | 23.2 | 22.1 | 22.2 |
反应器温度(°F) | 184.6 | 185.2 | 184.1 | 183.4 | 183.5 | 183.3 | 182.8 | 181.9 | 181.8 |
反应器温度(℃) | 84.8 | 85.1 | 84.5 | 84.1 | 84.2 | 84.0 | 83.8 | 83.3 | 83.2 |
反应器压力(psig) | 314.7 | 315.2 | 315.2 | 315.1 | 315.3 | 314.8 | 312.9 | 312.9 | 313.4 |
反应器压力(Kpag) | 2170.0 | 2173.3 | 2173.3 | 2172.5 | 2174.2 | 2170.7 | 2157.6 | 2157.7 | 2160.6 |
反应器空塔气速(ft/sec) | 1.73 | 1.74 | 1.75 | 1.76 | 1.77 | 1.76 | 1.75 | 1.74 | 1.74 |
反应器空塔气速(m/sec) | 0.53 | 0.53 | 0.53 | 0.54 | 0.54 | 0.54 | 0.53 | 0.53 | 0.53 |
反应器床高(ft) | 44.7 | 45.0 | 44.6 | 44.9 | 46.0 | 47.0 | 45.5 | 45.6 | 45.2 |
反应器床高(m) | 13.6 | 13.7 | 13.6 | 13.7 | 14.0 | 14.3 | 13.9 | 13.9 | 13.8 |
树脂沉降堆积密度(lb/ft3) | 29.9 | 29.9 | 29.7 | 28.8 | 29.0 | 29.1 | 29.3 | 29.4 | 29.4 |
树脂沉降堆积密度(kg/m3) | 479.0 | 479.0 | 475.8 | 461.4 | 464.6 | 465.4 | 468.6 | 471.3 | 471.8 |
反应器床流化堆积密度(lb/ft3) | 20.2 | 20.7 | 19.6 | 19.3 | 18.2 | 17.1 | 18.5 | 19.2 | 20.0 |
反应器床流化堆积密度(kg/m3) | 323.9 | 330.9 | 314.4 | 309.9 | 291.1 | 274.3 | 296.2 | 308.1 | 321.1 |
空时产率(lb/hr-ft3) | 9.7 | 10.3 | 11.1 | 11.1 | 11.1 | 9.9 | 9.3 | 9.1 | 9.2 |
空时产率(kg/m3) | 154.9 | 165.1 | 178.1 | 178.0 | 177.0 | 158.4 | 149.1 | 144.9 | 147.3 |
生产速率(klb/hr) | 71.3 | 76.6 | 82.2 | 82.3 | 84.0 | 76.8 | 69.9 | 68.0 | 68.5 |
产速率(Tons/hr) | 32.3 | 34.7 | 37.3 | 37.3 | 38.1 | 34.8 | 31.7 | 30.8 | 31.1 |
反应器生产能力(lb/hr-ft2) | 432 | 464 | 498 | 498 | 509 | 465 | 423 | 412 | 415 |
反应器生产能力(kg/hr-m2) | 2109 | 2265 | 2431 | 2431 | 2485 | 2270 | 2065 | 2011 | 2026 |
循环物流的焓变(Btu/lb) | 54 | 59 | 61 | 60 | 61 | 55 | 52 | 51 | 52 |
循环物流的焓变(cal/g) | 30 | 33 | 34 | 33 | 34 | 31 | 29 | 28 | 29 |
气体密度lb/ft3 | 1.91 | 1.89 | 1.93 | 1.97 | 1.99 | 2.01 | 1.93 | 1.93 | 1.91 |
气体密度kg/m3 | 30.6 | 30.2 | 30.9 | 31.6 | 31.9 | 32.3 | 31.0 | 30.9 | 30.6 |
气体粘度(cp) | 0.012 | 0.012 | 0.012 | 0.012 | 0.011 | 0.011 | 0.012 | 0.012 | 0.012 |
粒径(英寸) | 0.029 | 0.029 | 0.030 | 0.030 | 0.031 | 0.031 | 0.031 | 0.031 | 0.031 |
粒径(μm) | 737 | 737 | 749 | 762 | 775 | 787 | 787 | 787 | 787 |
X函数 | 3.00 | 2.99 | 3.01 | 3.03 | 3.08 | 3.10 | 3.03 | 3.03 | 3.03 |
Y函数 | 5.59 | 5.58 | 5.61 | 5.63 | 5.73 | 5.76 | 5.67 | 5.67 | 5.67 |
密度函数(Z) | 0.63 | 0.65 | 0.62 | 0.62 | 0.58 | 0.54 | 0.59 | 0.61 | 0.64 |
表A和B*的极限 | 0.54 | 0.54 | 0.54 | 0.54 | 0.54 | 0.54 | 0.55 | 0.55 | 0.55 |
*基于X与Y函数值;表A与B被用于确定极限
表3
试验 | 1 | 2 | 3 | 4 | 5 |
树脂熔体指数(dg/10min) | 0.86 | 6.74 | 7.89 | 22.22 | 1.91 |
树脂密度(g/cc) | 0.9177 | 0.9532 | 0.9664 | 0.9240 | 0.9186 |
循环物流组成 | |||||
乙烯 | 53.1 | 40.5 | 49.7 | 34.1 | 44.0 |
1-丁烯 | 20.2 | 14.9 | 18.2 | ||
1-己烯 | 0.6 | ||||
氢 | 8.9 | 17.7 | 26.5 | 25.0 | 11.9 |
异戊烷 | 9.7 | 3.7 | 0.7 | 14.1 | 9.6 |
C6饱和烃 | 7.0 | 10.2 | |||
氮 | 8.7 | 19.2 | 8.8 | 9.4 | 14.9 |
乙烷 | 1.7 | 9.4 | 4.0 | 2.5 | 3.3 |
甲烷 | 1.1 | 0.3 | |||
C8饱和烃 | 0.4 | 0.5 | |||
循环气体露点(°F) | 154.0 | 172.6 | 181.6 | 162.1 | 148.5 |
循环气体露点(℃) | 67.8 | 78.1 | 83.1 | 72.3 | 64.7 |
反应器入口温度(°F) | 115.2 | 107.8 | 117.7 | 135.0 | 114.2 |
反应器入口温度(℃) | 46.2 | 42.1 | 47.6 | 57.2 | 45.7 |
循环气中的液体(WT%) | 28.6 | 25.4 | 27.6 | 21.8 | 24.4 |
反应器温度(°F) | 183.3 | 208.4 | 209.3 | 178.0 | 183.7 |
反应器温度(℃) | 84.1 | 98.0 | 98.5 | 81.1 | 84.3 |
反应器压力(psig) | 315.7 | 300.2 | 299.8 | 314.7 | 314.3 |
反应器压力(Kpag) | 2176.7 | 2069.7 | 2066.8 | 2169.8 | 2167.2 |
反应器空塔气速(ft/sec) | 1.69 | 2.76 | 2.36 | 1.74 | 1.73 |
反应器空塔气速(m/sec) | 0.52 | 0.84 | 0.72 | 0.53 | 0.53 |
反应器床高(ft) | 47.2 | 43.0 | 42.0 | 44.3 | 45.6 |
反应器床高(m) | 14.4 | 13.1 | 12.8 | 13.5 | 13.9 |
树脂沉降堆积密度(lb/ft3) | 28.3 | 23.2 | 29.0 | 24.5 | 29.3 |
树脂沉降堆积密度(kg/m3) | 453.4 | 371.0 | 464.0 | 392.5 | 468.6 |
反应器床流化堆积密度(lb/ft3) | 19.6 | 16.7 | 21.7 | 15.7 | 19.1 |
反应器床流化堆积密度(kg/m3) | 314.0 | 267.9 | 347.4 | 251.5 | 305.7 |
空时产率(lb/hr-ft3) | 10.8 | 14.3 | 13.0 | 7.7 | 9.8 |
空时产率(kg/m3) | 172.8 | 228.8 | 208.0 | 123.2 | 157.2 |
生产速率(klb/hr) | 83.7 | 101.2 | 90.2 | 56.6 | 73.7 |
生产速率(Tons/hr) | 38.0 | 45.9 | 40.9 | 25.7 | 33.4 |
反应器生产能力(lb/hr-ft2) | 507 | 613 | 546 | 343 | 446 |
反应器生产能力(kg/hr-m2) | 2475 | 2992 | 2665 | 1674 | 2177 |
循环物流的焓变(Btu/lb) | 65 | 67 | 75 | 49 | 60 |
循环物流的焓变(cal/g) | 36 | 37 | 42 | 27 | 33 |
气体密度lb/ft3 | 1.93 | 1.38 | 1.29 | 1.69 | 1.81 |
气体密度kg/m3 | 31.0 | 22.2 | 20.6 | 27.1 | 29.0 |
气体粘度(cp) | 0.012 | 0.013 | 0.013 | 0.012 | 0.012 |
粒径(英寸) | 0.030 | 0.027 | 0.022 | 0.026 | 0.029 |
粒径(μm) | 749 | 686 | 558 | 660 | 737 |
X函数 | 3.00 | 2.99 | 2.80 | 2.90 | 2.97 |
Y函数 | 5.59 | 5.18 | 4.97 | 5.31 | 5.55 |
密度函数(Z) | 0.65 | 0.68 | 0.72 | 0.59 | 0.61 |
表A和B*的极限 | 0.54 | 0.47 | 0.49 | 0.53 | 0.54 |
*基于X与Y函数值;表A与B被用于确定极限
表4
试验1 | 试验2 | |||||||
1 | 2 | 3 | 4 | 1 | 2 | 3 | 4 | |
树脂熔体指数 | 0.86 | 6.74 | ||||||
树脂密度 | 0.9177 | 0.9532 | ||||||
循环物流组成 | ||||||||
乙烯 | 53.1 | 53.1 | 53.1 | 53.1 | 40.5 | 40.5 | 40.5 | 40.5 |
1-丁烯 | 20.2 | 20.2 | 20.2 | 20.2 | ||||
1-己烯 | 0.6 | 0.6 | 0.6 | 0.6 | ||||
氢 | 8.9 | 8.9 | 8.9 | 8.9 | 17.7 | 17.7 | 17.7 | 17.7 |
异戊烷 | 9.7 | 9.7 | 9.7 | 13.0 | 3.7 | 3.7 | 3.7 | 3.7 |
C6饱和烃 | 7.0 | 7.0 | 10.0 | 10.0 | ||||
氮 | 8.7 | 8.7 | 8.7 | 5.9 | 19.2 | 19.2 | 17.2 | 17.2 |
乙烷 | 1.7 | 1.7 | 1.7 | 1.2 | 9.4 | 9.4 | 8.5 | 8.5 |
甲烷 | 1.1 | 1.1 | 1.0 | 1.0 | ||||
C8饱和烃 | 0.4 | 0.4 | 0.4 | 0.4 | ||||
循环气体露点(°F) | 154.0 | 154.0 | 154.0 | 167.9 | 172.6 | 172.6 | 188.3 | 188.3 |
循环气体露点(℃) | 67.8 | 67.8 | 67.8 | 75.5 | 78.1 | 78.1 | 86.8 | 86.8 |
反应器入口温度(°F) | 115.2 | 115.2 | 105.0 | 105.0 | 107.8 | 100.0 | 100.0 | 85.0 |
反应器入口温度(℃) | 46.2 | 46.2 | 40.6 | 40.6 | 42.1 | 37.8 | 37.8 | 29.4 |
循环气中的液体(WT%) | 28.6 | 28.6 | 34.4 | 44.2 | 25.4 | 27.1 | 35.9 | 38.6 |
反应器温度(°F) | 183.3 | 183.3 | 183.3 | 183.3 | 208.4 | 208.4 | 208.4 | 208.4 |
反应器温度(℃) | 84.1 | 84.1 | 84.1 | 84.1 | 98.0 | 98.0 | 98.0 | 98.0 |
反应器压力(psig) | 315.7 | 315.7 | 315.7 | 315.7 | 300.2 | 300.2 | 300.2 | 300.2 |
反应器压力(Kpag) | 2176.7 | 2176.7 | 2176.7 | 2176.7 | 2069.7 | 2069.7 | 2069.7 | 2069.7 |
反应器空塔气速(u/sec) | 1.69 | 2.40 | 2.40 | 2.40 | 2.76 | 2.76 | 2.76 | 2.76 |
反应器空塔气速(m/sec) | 0.52 | 0.73 | 0.73 | 0.73 | 0.84 | 0.84 | 0.84 | 0.84 |
反应器床高(ft) | 47.2 | 47.2 | 47.2 | 47.2 | 43.0 | 43.0 | 43.0 | 43.0 |
反应器床高(m) | 14.4 | 14.4 | 14.4 | 14.4 | 13.1 | 13.1 | 13.1 | 13.1 |
空时产率(lb/hr-ft3) | 10.8 | 15.3 | 18.1 | 23.3 | 14.3 | 15.6 | 17.8 | 19.8 |
空时产率(kg/hr-m3) | 172.8 | 245.4 | 290.3 | 372.2 | 228.8 | 249.9 | 284.4 | 317.6 |
生产速率(klb/hr) | 83.7 | 118.9 | 140.6 | 180.3 | 101.2 | 110.5 | 125.8 | 140.5 |
生产速率(Tons/hr) | 38.0 | 53.9 | 63.8 | 81.7 | 45.9 | 50.1 | 57.0 | 63.7 |
反应器生产能力(lb/hr-ft3) | 507 | 720 | 851 | 1092 | 613 | 669 | 762 | 851 |
反应器生产能力(kg/hr-m3) | 2475 | 3515 | 4154 | 5331 | 2992 | 3266 | 3720 | 4154 |
循环物流焓变(Btu/lb) | 67 | 67 | 77 | 95 | 69 | 76 | 81 | 90 |
循环物流焓变(cal/G) | 37 | 37 | 43 | 53 | 38 | 42 | 45 | 50 |
树脂沉降堆积密度(lb/ft3) | 28.3 | 28.3 | 28.3 | 28.3 | 23.2 | 23.2 | 23.2 | 23.2 |
树脂沉降堆积密度(kg/m3) | 453.4 | 453.4 | 453.4 | 453.4 | 371.0 | 371.0 | 371.0 | 371.0 |
气体密度(lb/ft3) | 1.93 | 1.93 | 1.93 | 2.05 | 1.38 | 1.38 | 1.48 | 1.48 |
气体密度(kg/m3) | 31.0 | 31.0 | 31.0 | 32.8 | 22.2 | 22.2 | 23.7 | 23.7 |
气体粘度(cp) | 0.012 | 0.012 | 0.012 | 0.011 | 0.013 | 0.013 | 0.013 | 0.013 |
粒径(英寸) | 0.030 | 0.030 | 0.030 | 0.030 | 0.027 | 0.027 | 0.027 | 0.027 |
粒径(μm) | 749 | 749 | 749 | 749 | 686 | 686 | 686 | 686 |
X函数 | 3.00 | 3.15 | 3.15 | 3.21 | 2.99 | 2.99 | 3.02 | 3.02 |
Y函数 | 5.59 | 5.59 | 5.59 | 5.69 | 5.18 | 5.18 | 5.21 | 5.21 |
表A和B*的极限 | 0.54 | 0.49 | 0.49 | 0.49 | 0.47 | 0.47 | 0.46 | 0.46 |
*基于X与Y函数值;表A与B被用于确定极限
Claims (10)
1、一种在具有流化床和包括气相的流化介质的气相反应器中聚合α-烯烃以生产聚合产物的方法,其中该流化介质包括饱和和不饱和烃的可冷凝流体且用于控制所述反应器的冷却能力,该方法包括在流化介质中使用以流化介质总重为基准计为18-50重量%的进入反应器的液体,并保持堆积密度函数(Z)值
在等于或大于在本文的表A中的堆积密度函数的计算极限值,其中表A中的X和Y根据如下的等式计算:
其中Pbf为流化堆积密度,Pbs为沉积堆积密度,Pg为气体密度,Ps为固体密度和其中dp为重均粒径,g为重力加速度,Uo为气体空塔速度和u为气体粘度。
2、一种提高气相聚合反应器的生产能力的连续方法,该反应器具有流化介质和流化床,所述方法包括使含有单体的气流在催化剂存在下通过反应区以便生产聚合产物,移出所述聚合产物,从所述反应区中撤出含有未反应单体的流化介质,使所述流化介质与烃和聚合单体混合成为液相与气相,该方法包括在流化介质中使用以流化介质总重为基准计为18-50重量%的进入反应器的液体,并使流化介质回到所述反应器中,该方法包括:
a)将所述烃导入所述流化介质以便将流化介质的冷却能力提高至至少22cal/g(40Btu/lb);
b)将移出聚合物产物的速率提高至至少2441kg/hr-m2(500lb/hr-ft2);
c)保持堆积密度函数(Z)值
在大于或等于在本文的表A中的堆积密度函数的计算极限值,其中表A中的X和Y根据如下的等式计算:
其中Pbf为流化堆积密度,Pbs为沉积堆积密度,Pg为气体密度,Ps为固体密度和其中dp为重均粒径,g为重力加速度,Uo为气体空塔速度和u为气体粘度。
3.按照权利要求2的方法,其中液体含量以流化介质总重为基准计20-40重量%。
4.按照权利要求1或2的方法,其中计算极限取值范围为0.2-0.7。
5.按照权利要求1或2的方法,其中堆积密度函数(Z)比堆积密度函数的计算极限高2%以上。
6.按照权利要求1或2的方法,其中所述流化介质包括:
i)摩尔比为0.001-0.60的1-丁烯与乙烯或摩尔比为0.001-0.50的4-甲基-1-戊烯与乙烯或摩尔比为0.001-0.30的1-己烯与乙烯或摩尔比为0.001-0.10的1-辛烯与乙烯;
ii)占流化介质1.5-20摩尔%的可冷凝流体,或
i)摩尔比为0.001-0.60的1-丁烯与乙烯或摩尔比为0.001-0.50的4-甲基-1-戊烯与乙烯或摩尔比为0.001-0.30的1-己烯与乙烯或摩尔比为0.001-0.10的1-辛烯与乙烯;
ii)占流化介质1.5-30摩尔%的可冷凝流体,或
i)摩尔比为0.001-0.30的1-丁烯与乙烯或摩尔比为0.001-0.25的4-甲基-1-戊烯与乙烯或摩尔比为0.001-0.15的1-己烯与乙烯或摩尔比为0.001-0.05的1-辛烯与乙烯;
ii)占流化介质5-40摩尔%的可冷凝流体。
7.按照权利要求1或2的方法,其中,气相独立地以分离于液相的方式进入反应器。
8.按照权利要求1或2的方法,其中,液相于分布板下方进入反应器。
9.按照权利要求2的方法,其中流化堆积密度与沉积堆积密度的比值小于0.59。
10.按照权利要求1或2的方法,其中堆积密度函数(Z)大于或等于(0.59-Pg/Pbs)/(1-Pg/Ps),其中Pbf为流化堆积密度,Pbs为沉积堆积密度,Pg为气体密度,Ps为固体密度。
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DE1720292B2 (de) * | 1967-08-10 | 1975-05-22 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von Propylenpolymerisaten |
JPS5634709A (en) * | 1979-08-31 | 1981-04-07 | Mitsui Petrochem Ind Ltd | Gas phase polymerization or copolymerization of olefin |
JPS56166207A (en) * | 1980-05-27 | 1981-12-21 | Mitsui Petrochem Ind Ltd | Gas-phase polymerization of olefin |
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JPS57155204A (en) * | 1981-02-19 | 1982-09-25 | Chisso Corp | Vapor-phase polymerization of olefin and equipment therefor |
DE3123115A1 (de) * | 1981-06-11 | 1982-12-30 | Basf Ag, 6700 Ludwigshafen | Verfahren zum herstellen von homopolymerisaten oder copolymerisaten des propylens |
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DE3442659A1 (de) * | 1984-11-23 | 1986-05-28 | Basf Ag, 6700 Ludwigshafen | Verfahren zur kontinuierlichen messung des fuellungsgrades von wirbelschichtapparaten |
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AU682821B2 (en) * | 1993-04-26 | 1997-10-23 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
-
1994
- 1994-10-03 US US08/317,153 patent/US5436304A/en not_active Expired - Lifetime
-
1995
- 1995-09-26 PT PT95933939T patent/PT784637E/pt unknown
- 1995-09-26 EP EP95933939A patent/EP0784637B2/en not_active Expired - Lifetime
- 1995-09-26 WO PCT/US1995/012241 patent/WO1996010590A1/en active IP Right Grant
- 1995-09-26 JP JP51194496A patent/JP3356434B2/ja not_active Expired - Lifetime
- 1995-09-26 DE DE69512928T patent/DE69512928T3/de not_active Expired - Lifetime
- 1995-09-26 CN CNB951949047A patent/CN1149233C/zh not_active Expired - Lifetime
- 1995-09-26 CA CA002196590A patent/CA2196590C/en not_active Expired - Fee Related
- 1995-09-26 DK DK95933939T patent/DK0784637T3/da active
- 1995-09-26 AT AT95933939T patent/ATE185821T1/de not_active IP Right Cessation
- 1995-09-26 CZ CZ1997998A patent/CZ292982B6/cs not_active IP Right Cessation
- 1995-09-26 KR KR1019970700993A patent/KR100375154B1/ko not_active IP Right Cessation
- 1995-09-26 PL PL95319376A patent/PL184510B1/pl not_active IP Right Cessation
- 1995-09-26 BR BR9509223A patent/BR9509223A/pt not_active IP Right Cessation
- 1995-09-26 AU AU36411/95A patent/AU697428B2/en not_active Ceased
- 1995-09-26 ES ES95933939T patent/ES2140709T3/es not_active Expired - Lifetime
- 1995-09-26 RU RU97107336A patent/RU2139888C1/ru not_active IP Right Cessation
- 1995-09-28 MY MYPI95002892A patent/MY112736A/en unknown
- 1995-10-09 SA SA95160299A patent/SA95160299B1/ar unknown
-
1997
- 1997-03-19 NO NO19971275A patent/NO310878B1/no unknown
-
2000
- 2000-01-12 GR GR20000400032T patent/GR3032334T3/el unknown
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Publication number | Publication date |
---|---|
JP3356434B2 (ja) | 2002-12-16 |
US5436304A (en) | 1995-07-25 |
WO1996010590A1 (en) | 1996-04-11 |
RU2139888C1 (ru) | 1999-10-20 |
MX9702418A (es) | 1997-10-31 |
NO971275D0 (no) | 1997-03-19 |
KR100375154B1 (ko) | 2003-05-22 |
NO310878B1 (no) | 2001-09-10 |
PL184510B1 (pl) | 2002-11-29 |
CA2196590C (en) | 2002-11-05 |
CZ292982B6 (cs) | 2004-01-14 |
BR9509223A (pt) | 1998-01-27 |
AU3641195A (en) | 1996-04-26 |
ATE185821T1 (de) | 1999-11-15 |
EP0784637B2 (en) | 2008-03-19 |
AU697428B2 (en) | 1998-10-08 |
ES2140709T3 (es) | 2000-03-01 |
MY112736A (en) | 2001-08-30 |
CN1181090A (zh) | 1998-05-06 |
EP0784637B1 (en) | 1999-10-20 |
PL319376A1 (en) | 1997-08-04 |
SA95160299B1 (ar) | 2006-08-22 |
PT784637E (pt) | 2000-04-28 |
JPH10506936A (ja) | 1998-07-07 |
DE69512928T3 (de) | 2009-03-26 |
EP0784637A1 (en) | 1997-07-23 |
GR3032334T3 (en) | 2000-04-27 |
NO971275L (no) | 1997-03-19 |
DE69512928T2 (de) | 2000-06-15 |
CA2196590A1 (en) | 1996-04-11 |
CZ99897A3 (cs) | 1998-10-14 |
DE69512928D1 (de) | 1999-11-25 |
DK0784637T3 (da) | 2000-04-25 |
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