B01J2219/00254—Formation of unwanted polymer, such as "pop-corn"
本发明公开了一种方法,其包括在多反应器系统的至少一个连续管状环流反应器中,在稀释剂中、在存在聚合催化剂的情况下,将烯烃单体聚合,任选地将烯烃单体与烯烃共聚单体一起聚合,以产生包含固体粒状烯烃聚合物和稀释剂的淤浆,其中所述连续管状环流反应器总长的至少50%的平均内径为至少700mm。 The present invention discloses a method, which comprises at least one continuous tubular loop reactor in a multiple reactor system, in the diluent, in the presence of a polymerization catalyst, the polymerization of olefin monomers, optionally mono-olefins polymerized together with an olefin comonomer to produce a slurry comprising solid particulate olefin polymer and the diluent, wherein the continuous total length of the tubular loop reactor is at least 50% of the average inner diameter of at least 700mm.
 本申请是申请日为2007年5月18日,申请号为200780028638. 4 (国际申请号为PCT/GB2007/001862),发明名称为"用于聚合的环流型反应器"的专利申请的分案申请。  This application is filed May 18, 2007, Application No. 200780028638.4 (International Application No. PCT / GB2007 / 001862), entitled "loop-type reactor for polymerization" patent application the divisional application.
 本发明涉及在淤浆相环流反应器中、特别是在多反应器系统中的烯烃聚合。  The present invention relates to the slurry phase loop reactor, olefins, in particular in the multi-reactor polymerization system.
 烯烃的淤浆相聚合是众所周知的,其中烯烃单体和任选的烯烃共聚单体,在稀释剂中、在存在催化剂的情况下被聚合,其中固体聚合物产物在所述稀释剂中被悬浮和被转移。  The slurry phase polymerization of olefins is well known wherein an olefin monomer and optionally olefin comonomer, in a diluent, are polymerized in the presence of a catalyst, wherein the solid polymer product in the diluent and the suspension was transferred.
 本发明具体涉及在多反应器系统的至少一个环流反应器中的聚合,其中淤浆在反应器中通常通过泵或搅拌器而被循环。  The present invention particularly relates to a multi-reactor system in at least one loop reactor polymerization, in which the slurry typically is circulated by a pump or a stirrer in the reactor. 充满液体的环流反应器(liquid full loop reactor)在本领域中是尤其众所周知的,且在例如美国专利第3,152, 872号、第3, 242, 150 号和第4, 613, 484号中被描述。 Full loop reactor liquid (liquid full loop reactor) in the art and are particularly well known and, for example, U.S. Patent 3,152, 872, 3, 242, 150 and 4, 613, No. 484 are described .
 聚合反应通常在50_125°C的温度和在1-100绝对巴(bara)的压力下进行。  The temperature of the polymerization reaction is generally carried out 50_125 ° C and at a pressure of 1-100 bar absolute (Bara) in. 所用的催化剂可以是任何通常用于烯烃聚合的催化剂,例如氧化铬催化剂、Ziegler-Natta催化剂或金属茂型催化剂。 The catalyst used can be any catalyst typically used for olefin polymerization, for example chromium oxide catalysts, Ziegler-Natta catalysts or metallocene type catalysts. 包含聚合物和稀释剂(且在大多数情况下包含催化剂、烯烃单体和共聚单体)的产物淤浆,可被间歇地或连续地排出,任选地使用浓缩装置,例如水力旋流器或沉降柱(settling legs),来使得随聚合物一起被回收(withdrawn)的流体的数量最小化。 Comprising a polymer and a diluent (and including a catalyst, olefin monomer and comonomer in most cases) of the product slurry may be discharged intermittently or continuously, optionally using concentrating devices such as hydrocyclones or settling column (settling legs), such that the number to be recovered together with the polymer (Withdrawn) fluid is minimized.
 多反应器系统的所述至少一个环流反应器是连续管状结构,其包括至少两个(例如四个)垂直部分和至少两个(例如四个)水平部分。 The  Multiple reactor systems of the at least one loop reactor is a continuous tubular construction comprising at least two (e.g. four) vertical portion and at least two (e.g. four) of the horizontal portion. 通常利用与围绕至少部分管状环流反应器的套管中的冷却介质(优选水)的间接交换来除去聚合的热。 Typically using indirect exchange with a sleeve surrounding at least part of the tubular loop reactor in a cooling medium (preferably water) to remove the heat of polymerization. 多反应器系统的至少一个环流反应器的体积可变化,但通常在10至120m 3的范围,本发明的环流反应器即是这种普通的类型。 Multiple reactor system volume of at least one loop reactor can vary but is typically in the range of 10 to 120m 3, the loop reactor according to the present invention that is of this general type.
 最大的工业规模环流反应器工厂设备生产能力每年稳定地增长。  biggest industrial scale loop reactor plant production capacity and steady growth each year. 最近几十年不断增长的操作经验已使得能在反应环流中操作越来越高的淤浆和单体浓度。 Growing in recent decades has made operable experience increasingly high slurry and monomer concentrations in the reactor loop. 如EP432555和EP891990所阐述的,淤浆浓度的增加通常是由增加的循环速度来实现的,而循环速度的增加是由例如更高的反应器循环泵压头或多个循环泵来实现的。 , Increasing the concentration of the slurry as set forth in EP432555 and EP891990 usually caused by increased cycle speed is achieved, and the circulation velocity is increased, for example, higher reactor circulation pump head or multiple circulation pumps to achieve. 对于固定反应器体积来说, 固体载量的增加对于增加反应器停留时间是有利的,且对于降低下游稀释剂处理和再循环的要求也是有利的。 For a fixed reactor volume, increasing the solids loading is advantageous for increasing the reactor residence time, and to reduce downstream diluent treatment and recycling requirements are also advantageous. 但是,环流的增加的速度和压头(head)要求,导致随着淤浆浓度增加, 泵设计尺寸和复杂性,和能量消耗的增加。 However, the increased circulation speed and pressure head (head) required, resulting in increases as the slurry concentration, increasing pump design sizes and complexity, and energy consumption. 这暗示着资本成本和操作成本的增加。 This implies that the increase in capital costs and operating costs.
 以前,通常在反应环流中维持较高的循环速度,以确保整个反应器横截面上的良好的热分布、组成分布和粒子分布,特别是确保避免固体沉淀、稳定的流动特征或在管壁处的过高固体浓度,而不是减小循环速度以使聚合环流中的压降/功率最小化。  before the loop reactor is generally maintained at a higher circulation rate to ensure good heat distribution throughout the reactor cross section, particle distribution and composition distribution, in particular to ensure to avoid precipitation of solid, stable flow characteristics, or in high solids concentration at the pipe wall rather than reduced to the circulation rate of polymerization loop pressure drop / power is minimized.
 不充分的横截面分布可导致污垢增加、传热减少和聚合物产率和均一性减小。  insufficient cross-sectional profile can lead to increased fouling, reduced heat transfer and polymer productivity and homogeneity is reduced. 构建和投产新的商业设备非常昂贵,所以新设计试图避免或最小化对操作参数的改变,操作参数的改变被看作是增加新设备成功操作的风险。 Construction and commissioning of new business equipment is very expensive, so the new design attempts to avoid or minimize changes to the operating parameters, operating parameters change is seen as increasing the risk of successful operation of new equipment.
 根据本发明,其提供一种方法,该方法包括在多反应器系统的连续管状结构的至少一个环流反应器中,在稀释剂中、在存在聚合催化剂的情况下,将烯烃单体聚合,任选地将烯烃单体与烯烃共聚单体一起聚合,以产生包含固体粒状烯烃聚合物和稀释剂的淤浆, 其中反应器总长的至少50%的平均内径为至少700毫米,且反应器中的固体浓度为至少20 体积%,优选25体积%,任选地其中所述至少一个环流反应器的体积为至少10m 3,优选至少25m3。  According to the present invention there is provided a process which comprises at least one loop reactor of continuous tubular construction in a multi-reactor system, in the diluent, in the presence of a polymerization catalyst, the olefin monomer polymerizing an olefin monomer optionally with a comonomer polymerizable with an olefin to produce a slurry comprising solid particulate olefin polymer and the diluent wherein the average internal diameter of at least 50% of the total length of the reactor is at least 700 mm, and the reaction solids concentration in the reactor is at least 20% by volume, preferably 25% by volume, optionally, wherein said at least one loop reactor volume of at least 10m 3, preferably at least 25m3. 优选至少30wt%的,最优选多于40wt%的在多反应器系统中生成的聚合物,是在至少一个环流反应器中制造的,其中反应器总长的至少50%的平均内径为至少700毫米。 Produced in a multi-reactor system of the polymer is preferably at least 30wt%, most preferably more than 40wt%, and is produced in at least one loop reactor, wherein the mean diameter of at least 50% of the total length of the reactor is at least 700 mm .
 本发明的一个优点是,环流反应器的比能量消耗(specific energy consumption)(即,每产生单位重量的聚合物所消耗的能量)被减小,同时维持特定的反应器停留时间并防止产生不可接受的反应器污垢。  An advantage of the present invention is that the specific energy consumption of the loop reactor (specific energy consumption) (i.e., energy per unit weight of the polymer produced consumed) is reduced, while maintaining a specific reactor residence time and prevent unacceptable reactor fouling. 当想要设计和操作高固体载量的反应器时(之前被认为需要使用现在认为是过高的环流循环速度),本发明特别有优势。 When it is desired design and operation of a high solids loading of the reactor (before it is deemed necessary to use presently considered to be excessively high loop circulation rate), the present invention is particularly advantageous.
 本发明涉及在伸长的管状闭合环流反应区内连续聚合烯烃(优选阿尔法单烯烃) 的方法和仪器。  The present invention relates to an elongated tubular closed loop reaction zone for continuously polymerizing olefins (preferably alpha mono olefins) method and apparatus. 烯经被连续地加入到在经类稀释剂(hydrocarbon diluent)中的催化剂中并与催化剂接触。 Alkenyl by being continuously added to the catalyst by diluent (hydrocarbon diluent) and is in contact with the catalyst. 单体聚合以形成固体粒状聚合物的淤浆,所述固体粒状聚合物被悬浮在聚合介质或稀释剂中。 Polymerizing the monomer to form a slurry of solid particulate polymer, the solid particulate polymer suspended in the polymerisation medium or diluent.
 通常,在聚乙烯的淤浆聚合法中,反应器中的淤浆将包含粒状聚合物、烃类稀释齐ϋ、(共聚)单体、催化剂、链终止剂(例如氢)和其他反应器添加剂。  Generally, in the slurry polymerization of polyethylene, the slurry in the reactor will comprise the particulate polymer, the hydrocarbon is diluted Qi ϋ, (co) monomers, catalyst, chain terminating agent (e.g. hydrogen) and other The reactor additives. 特别地,淤浆将包含占淤浆总重量的20-75,优选30-70重量百分数的粒状聚合物和占淤浆总重量的80-25, 优选70-30重量百分数的悬浮介质,其中悬浮介质是在反应器中的所有流体成分(fluid components)的总和,且将包含稀释剂、烯烃单体和任何的添加剂;稀释剂可以是惰性稀释剂或者它可以是活性稀释剂(特别是液体烯烃单体);其中主要的稀释剂是惰性稀释剂,烯烃单体通常将占淤浆的2-20,优选4-10重量百分数。 In particular, the slurry will comprise from 20-75 total weight of the slurry, preferably 30 to 70 weight percent of the total weight of particulate polymer and 80-25 slurry, preferably 70-30 weight percent of the suspending medium, wherein the suspension it is the sum of all components of the fluid medium (fluid components) in the reactor and will comprise the diluent, olefin monomer and any additives; diluent may be an inert diluent or it can be a reactive diluent (especially a liquid olefin monomer); wherein the diluent is an inert diluent the main olefin monomer slurry will generally comprise 2-20, preferably 4-10 weight percent.
 以足以(i)保持聚合物悬浮在淤浆中和(ii)保持可接受的横截面浓度和固体加载梯度的流体速度,围绕相对平滑的、路径无尽的(path-endless)环流反应系统泵入淤浆。  sufficient to (i) keep the polymer suspension and (ii) maintaining the slurry in fluid velocity and acceptable cross-sectional concentration gradients of solids loading, about a relatively smooth, endless path (path-endless) loop reactor the slurry is pumped into the system.
 已发现,对于高固体载量,横截面淤浆浓度分布(由污垢、流动变化和/或传热所证实)可被维持在可接受的操作限度内,同时增加管状反应器的内径,使其大于通常被认为在操作上是可靠的内径(对于多反应器系统的至少一个反应器而言)。  It has been found, for high solids loadings, cross-sectional slurry concentration distributions (as evidenced by fouling, flow variations and / or heat transfer) can be maintained within acceptable operational limits, while increasing the diameter of the tubular reactor , is generally considered to be greater than the inner diameter of reliable operation (for at least one reactor of a multiple reactor system). 这与本领域技术人员根据常规方法条件所认为的情况(反应器的内径不大于600毫米且通常为约500毫米)相反。 This skilled in the art according to a conventional method where the condition that (diameter of the reactor is not greater than 600 millimeters and is typically about 500 mm) reversed.
 在至少一个环流反应器中的淤浆中的固体浓度优选至少为20体积%,更优选为至少25体积%,且最优选为至少30体积%,其中体积%是[(淤浆总体积-悬浮介质的体积V(淤浆总体积)]Χ1〇〇。以重量百分数形式测定的固体浓度(其与以体积百分数形式测定的固体浓度相等)将根据所产生的聚合物变化,但更特别地,将根据所用的稀释剂变化。当所产生的聚合物是聚乙烯且稀释剂是烷烃(例如异丁烷)时,优选地,固体浓度为大于游楽总重量的30重量%、特别优选大于40重量%,例如在40-60重量%的范围,优选45% -55 重量%。  In at least one loop reactor solids concentration in the slurry is preferably at least 20% by volume, more preferably at least 25% by volume, and most preferably at least 30 volume% where volume% is [(total slurry volume - the volume V (total volume of the slurry)] Χ1〇〇 solids concentration measured in percent by weight in the form (which is equal to the measured concentration of the solid volume percentage form) suspending medium will change according to the polymer produced but more in particular, according to changes in the diluent used. when the polymer produced is polyethylene and the diluent is an alkane (e.g., isobutane), preferably, the solid concentration is more than 30 wt% of the total weight of the tour yue, particularly preferably greater than 40% by weight, for example in the range of 40-60% by weight, preferably 45% -55% by weight.
 我们已发现,在其中至少一个反应器具有超过700毫米的内径的多反应器系统(即比在淤浆聚合中常规使用的反应器更大直径的反应器)中操作聚合过程没有任何重大问题,特别是没有任何关于在反应器壁上的污垢的问题。  We have found that at least one reactor having an inner diameter of more than 700 mm in a multiple reactor system (i.e., greater than the diameter of the reactor is conventionally used in slurry polymerization reactor) operated in the polymerization process without any major issues, especially without any problem on dirt walls of the reactor.
 优选大于50%的环流反应器的总长具有超过750mm的内径,例如超过850mm,且优选在700至800毫米之间。 Total length of  preferably greater than 50% of the loop reactor has an inner diameter of more than 750mm, for example more than 850mm, and preferably between 700-800 mm. 优选地,大于50 %,特别是大于70 %,例如大于85 %的反应器总长具有超过700毫米的内径,特别是超过750毫米,例如在700至800毫米之间。 Preferably, greater than 50%, in particular more than 70%, e.g. greater than 85% of the reactor total length with an internal diameter over 700 millimeters, in particular over 750 millimeters, for example between 700 to 800 mm.
 本发明的特殊的优点在于,可在相对低循环速度和相对高的反应器环流直径条件下使用高淤浆浓度。  The particular advantage of the present invention is that, using a high slurry concentration at relatively low circulation rate and relatively high reactor loop diameters conditions. 因此,反应器中的夫劳德(Froude)数优选被维持在30或以下,例如在24至0. 5的范围,更优选在20至1的范围,特别地是在15至2的范围,最优选的范围是10至3或9至2。 Thus, the Froude number in the reactor (The Froude) is preferably maintained at 30 or less, for example in the range from 24 to 0.5, more preferably in the range of 20 to 1, in particular in the range of 15 to 2, the most preferred range is 10-3 or 9-2. 夫劳德数是无因次参数,其指示淤浆中颗粒的悬浮倾向和沉淀倾向之间的平衡。 The Froude number is a dimensionless parameter indicative of the balance between the suspension and settling tendencies of particles in a slurry tendencies. 其提供了与流体相比,由颗粒向管壁的动量传递过程的相对测量。 Which provides a relative measurement compared with the fluid, the momentum transfer process to the pipe wall from particles. 较低数值的夫劳德数显示较强的颗粒-壁(相对于流体-壁)相互作用。 Froude number lower numerical display strong particles - a wall (relative to fluid - wall) interactions. 夫劳德数(Fr)被定义为v 2/ (g (s-1) D),其中v是淤浆的平均速度,g是万有引力常数,s是稀释剂中固体的比重,而D是管的内径。 Froude number (Fr) is defined as v 2 / (g (s-1) D), where v is the average velocity of the slurry, g is the gravitational constant, s is the specific gravity of the solid diluent and D is the pipe the inner diameter. 固体聚合物的比重(聚合物的密度与悬浮介质的密度的比率)是基于在被充分脱挥(devolatilised)之后并在即将进行任何挤压之前的脱气聚合物的退火密度,使用方法IS01183A测定。 The density in the specific gravity of the solid polymer (ratio of polymer density and the density of the suspending medium) and is based on the upcoming prior to any extrusion degassing of the polymer is sufficiently after devolatilization (devolatilised) using a measuring method IS01183A .
 已发现,可以每单位反应器长度和每单位聚合物质量特定的压降,和小于教导所要求的环流总压降来设计和操作反应器,特别是在高固体载量和大反应器直径时。  It has been found possible per unit reactor length and per mass of polymer specific pressure drop and less than the total circulation teachings required pressure drop design and operation of the reactor, especially at high solids loadings and large reactor diameter device. 甚至对于聚合物生产率为大于每小时25公吨,甚至大于每小时45公吨,本发明也允许小于1. 3绝对巴的总环流压降,特别是小于1绝对巴。 Even for polymer production rates of greater than 25 tonnes per hour, even more than 45 tonnes per hour, the present invention also allows the general circulation drop is less than 1.3 bar absolute, in particular less than 1 bar absolute. 可在环流中使用一个或不止一个泵,优选位于一个或多个水平部分上;这些可位于相同的水平部分或不同的部分上。 May be used in a loop of one or more than one pump, preferably located on one or more horizontal portions; or these different portions may be located at the same level section. 泵或多个泵可具有与所述泵或多个泵所在的反应器部分的内径相同的直径,或较大的或较小的直径,优选具有相同的直径。 Pump or pumps may have the same diameter of the reactor part and the pump or pumps where the diameter, or larger or smaller diameter, preferably have the same diameter. 优选使用单个泵,且本发明的特点在于,对于泵的数量和功率的要求没有常规方法那样麻烦(onerous)。 Preferably using a single pump, and the features of the present invention is that the requirements for number and power of the pump is not as troublesome a conventional method (onerous).
 反应器尺寸通常超过10m3,经常超过25m3,尤其是超过50m 3,例如75-200m3,优选在100-175m3 的范围。  The size of the reactor generally exceeds 10m3, often more than 25m3, in particular more than 50m 3, for example 75-200m3, is preferably in the range 100-175m3.
 将更高的内径的反应器用于本文以上所述的多反应器系统的至少一个环流反应器,使得建造出的反应器,例如体积大于80m 3的反应器,其反应器长度与直径的比率小于500,优选小于400,更优选小于250。  The at least one loop reactor higher internal diameter reactors for a multi-reactor system described herein above, the construction of the reactor, such as reactor volume greater than 80m 3, the reactor length to diameter ratio is less than 500, preferably less than 400, more preferably less than 250. 反应器长度与直径的比率的减小使得围绕反应环流的成分梯度最小化,并使得对于每种试剂,围绕反应器环流只使用单个引入点即可达到大于每小时(每个反应器)25公吨的生产率。 Reduction ratio of length to diameter of the reactor such that components around the reactor loop gradient minimized, and such that for each reagent around the reactor loop can only amounts to more than a single point of introduction per hour (per reactor) 25 mt productivity. 或者,对于反应物(例如烯烃)、催化剂或其他添加剂,可具有多个进入环流反应器的入口。 Alternatively, the reactants (e.g. olefins), catalyst, or other additives, may have a plurality of inlets into the loop reactor.
 当反应器系统被设计成操作不同催化剂类型(例如Ziegler-Natta、铬和/或金属茂)或操作其中在不同操作模式(regime)下不同反应器之间所需的活性或生产比率(production ratio)变化很大的催化剂系统时,通常使用具有相等体积的反应器,以最大的灵活性(flexibility)适应整个级别范围(grade range)。  When the reactor system is designed to be of different catalyst types (eg Ziegler-Natta, chromium and / or metallocene) operation or operating in different modes of operation (regime) required between the different reactors in which the activity or production ratio when (production ratio) of the catalyst system vary widely, typically using a reactor having a volume equal to the maximum flexibility (flexibility) fit the entire range of levels (grade range). 这样的外部强加的(externally imposed)反应器尺寸的存在约束了每个反应器可利用的操作窗口,因而约束了在每个反应器中的反应器活性、产物质量、产量和冷却的平衡能力。 The presence of such externally imposed (externally imposed) restricts the size of the reactor operating window available for each reactor, and thus constrain the reactor activity in each reactor, balance product quality, yield and cooled. 通常,优选这样反应器具有相同的平均内径,最优选地,反应器被建造成相同的尺寸。 Typically, such reactors preferably have the same average inner diameter, and most preferably, the reactor is constructed the same size.
 在本发明的另一实施方式中,优选地,环流反应器具有水平部分和垂直部分,且垂直部分占反应器总长的至少50%,优选至少60%,更优选至少70%。  In another embodiment of the present invention, preferably, a loop reactor having a horizontal portion and a vertical portion, and the vertical part represents at least 50% of the total length of the reactor, preferably at least 60%, more preferably at least 70%.
 还优选的是,聚合物粉末颗粒的密度跨度(density span)(被定义为排出反应器的粒度大于D90的聚合物颗粒的平均密度与粒度小于D10的物质的平均密度之间密度差(g/cm3)的绝对值)为小于0. 005,优选小于0. 003,更优选小于0. 0026,最优选小于0. 0023。  It is also preferred that the density of the polymer powder particles span (density span) (defined as the particle size exiting the reactor and the average density is greater than the D90 particle size of the polymer particles is less than the difference in density between the average density of the substance D10 absolute value (g / cm3)) is less than 0.005, preferably less than 0.003, more preferably less than 0.0026 and most preferably less than 0.0023.
 因此,本发明的另一独立方面提供在存在聚合催化剂的情况下,控制淤浆相(共) 聚合过程的方法,特征在于所述方法包括将聚合物粉末颗粒的密度跨度维持在〇. 005以下,优选0. 003以下,更优选0. 0026以下,最优选0. 0023以下。  Accordingly, further independent aspects of the present invention provides in the presence of a polymerization catalyst, the control slurry phase (co) polymerization process, characterized in that the method comprises the density of the polymer powder particles is maintained in square span 005 or less, preferably 0.003 or less, more preferably 0.0026 or less, most preferably 0.0023 or less.
 D95 :95%重量的被收集颗粒低于此值。  D95: 95% by weight of the particles being collected below this value.
 优选的实施方式还维持这样的粒度分布,其使得(D90_D10)/D50小于2,优选小于1. 5,更优选小于L 2。  The preferred embodiment also maintains a particle size distribution such that (D90_D10) / D50 is less than 2, preferably less than 1.5, more preferably less than L 2. 还优选的是,D95小于2000 μ m,优选小于1500 μ m,更优选小于100(^111,最优选小于355以111,其中095、090、050和010是这样被定义的:其使得95¥七%、 9(^%、5(^%或1(^%的聚合物颗粒分别具有小于095、090、050和010的直径。平均粒度D50优选在100至1500微米之间,最优选在150至1000微米之间。 It is also preferred that, a D95 of less than 2000 μ m, preferably less than 1500 μ m, more preferably less than 100 (111 ^, and most preferably less than 355 to 111, 095,090,050 and 010 which are so defined: 95 which makes ¥ seven percent, 9 (% ^, 5 (1%, or ^ (^% polymer particles each having a diameter of less than 095,090,050 and 010. the average particle size D50 of preferably between 100 and 1500 microns, most preferably 150 to 1000 microns.
 特别优选的实施方式具有的粒度分布为D95小于355 μ m,且(D90-D10) /D50小于1. 2,其中D95、D90、D50和D10如上所述。  A particularly preferred embodiment has a particle size distribution D95 of less than 355 μ m, and (D90-D10) / D50 is less than 1.2, where D95, D90, D50, and D10 as described above.
 本发明的另一独立方面提供一种方法,其包括在连续管状结构的环流反应器中, 在稀释剂中、在存在聚合催化剂的情况下,将烯烃单体聚合,任选地将烯烃单体与烯烃共聚单体一起聚合,以产生包含固体粒状烯烃聚合物和稀释剂的淤浆,其中反应器总长的至少50%的平均内径至少为650毫米,反应器中的固体浓度至少为15体积%且粒度分布使得(D90-D10)/D50 小于2。  Another independent aspect of the present invention provides a method in a loop reactor comprising a continuous tubular structure, in the diluent, in the presence of a polymerization catalyst, the polymerization of olefin monomers, optionally olefin monomer is polymerized together with an olefin comonomer to produce a slurry comprising solid particulate olefin polymer and the diluent wherein the average internal diameter of at least 50% of the total length of the reactor is at least 650 millimeters the solids concentration in the reactor is at least 15% by volume and a particle size distribution such that (D90-D10) / D50 is less than 2.
 本发明的又一独立方面提供一种在聚合反应器中聚合烯烃的方法,特征在于从反应器中回收的聚合物粉末的粒度分布使得D95小于1500 μ m且(D90-D10)/D50小于1. 5。  A further independent aspect of the present invention provides a process for polymerizing olefins in the polymerization reactor, characterized in that the particle size of the recovered polymer from the reactor so that the distribution of the powder is less than 1500 μ m, and D95 (D90-D10) / D50 less than 1.5.
 根据本发明的另一优选实施方式,已发现所述的控制,即将密度跨度维持在特定值以下,对于金属茂催化剂非常关键。  According to another preferred embodiment of the present invention, it has been found according to the control, i.e. the density SPAN is maintained at a certain value or less, it is critical for the metallocene catalysts.
 本发明的另一益处在于提高了与启动(start-ups)和等级转变(grade transitions)有关的速度和安全性。  Another advantage of the present invention to improve the speed and safety associated with start (start-ups) and grade transitions (grade transitions). 当改变等级时,氢和单体的组成和产物性质可连续地改变,聚合物中单体的吸收数量又将被变化的产物性质(主要是密度)和气体成分改变。 When changing grades, the composition of monomers and hydrogen and the product properties may be changing continuously, the number of absorbent polymer in turn changes the product properties (mainly density) and gas composition changes.
 根据本发明的跨度的控制使得提高了启动和转变的速度,并使得宽泛规格的(wide-specification)物质的生产最小化。  According to such that the span of control of the invention improves the speed and start transitions, and such that the broad specification (wide-specification) produced substance is minimized.
 特别是已发现,高容量反应器的、特别是大直径环流反应器的稳定操作,可通过严格控制反应器内或从反应器回收的粉末的密度跨度来优化。  in particular has been found that a stable operation, in particular a large diameter loop reactor a high capacity of the reactor, or may be optimized from the density SPAN of the reactor powder recovered in the reactor by the strictly controlled.
 使用许多催化剂系统,密度跨度可随粒度和/或粒度分布而显著改变。  Many catalyst systems used, the density may vary with the particle size span and / or significantly change the particle size distribution. 粉末的平均粒度的主要决定因素是在反应器中的停留时间和催化剂产率。 The main determinant of the average particle size of the powder is the residence time and catalyst productivity in the reactor. 粉末的粒度分布可受许多因素影响,包括加入到反应器中的催化剂的类型和粒度分布、初始的和平均的催化剂活性、 催化剂载体的坚固性(robustness)和在反应条件下粉末对碎片(fragment)的敏感性。 Powder particle size distribution can be influenced by many factors, comprising adding to the type and particle size of the reactor catalyst distribution sturdiness initial and average catalyst activity, the catalyst support (robustness is) and the powder debris under the reaction conditions (the fragment ) sensitivity. 固体分离装置(例如水力旋流器)可被用于从反应器中回收的淤浆,以辅助控制反应器中粉末的平均粒度和粒度分布。 Solids separation means (e.g. hydrocyclones) can be used in slurry recovered from the reactor, the reactor is controlled to assist the powder average particle size and particle size distribution. 浓缩装置的回收位点的位置和浓缩装置系统(优选至少一个水力旋流器再循环环流)的设计和操作条件,也使得反应器内的粒度和粒度分布被控制。 Position and concentrating device system (preferably at least one hydrocyclone recycle loop) concentration recovery site apparatus design and operating conditions, but also makes the size and particle size distribution within the reactor is controlled.
 或者,选择已被发现提供想要的粒度分布的特定催化剂。  Alternatively, selecting a specific catalyst has been found to provide the desired particle size distribution. 提供想要的粒度分布的催化剂系统的优点在于,它们可以高产率被使用:通常产率(以每g催化剂聚合物的克数测定)越高,所形成的单个聚合物颗粒越大。 The advantage of the catalyst systems provide a desired particle size distribution that they can be used in a high yield: generally yield (measured in grams of polymer per g of catalyst), the larger the individual polymer particles formed. 所以,本发明允许使用产率为至少5000g聚烯烃/g催化剂,且通常为至少l〇〇〇〇g聚烯烃/g催化剂,最优选为大于15000g聚烯烃/g催化剂的催化剂系统。 Therefore, the present invention allows the use yield of at least 5000g polyolefin / g of catalyst, and is usually at least l〇〇〇〇g polyolefin / g catalyst, most preferably greater than 15000g polyolefin / g of catalyst catalyst system.
 使用任何上述催化剂制造的具有受控粒度分布的预聚物也可被引入到聚合反应器中。  Using any of the aforementioned catalyst for the production of prepolymers having a controlled particle size distribution may also be introduced into the polymerization reactor. 聚合可通过任何适合的方法进行,例如,利用分批法、半连续法或连续法,在液态烃类稀释剂中或在气相中的聚合。 The polymerization may be carried out by any suitable method, e.g., by using a batch, semi-continuous or continuous process, or polymerized in a liquid hydrocarbon diluent in the gas phase. 向预聚物的转化通常通过将催化剂与一种或多种阿尔法烯烃接触而进行,阿尔法烯烃的量使得每克预聚物含有〇. 002至10毫摩尔的过渡金属。 Typically the conversion is carried out by contacting the prepolymer catalyst with one or more alpha olefins, such that the amount of alpha olefins per gram of prepolymer contains square. 002-10 millimoles of transition metal. 预聚物粒度可通过筛分、水力旋流器或精细或大颗粒的淘析分离,或其他已知技术来控制。 The prepolymer particle size can be obtained by elutriation sieving, hydrocyclone or large particles or fine separation, or other known techniques to control.
 在这些和其他包含多反应器系统(其中一个反应器是环流反应器)的本发明的实施方式中,环流反应器可具有一个或多个如本文以上所述的环流反应器的特点。  In these and other embodiments of the present invention comprises a multiple reactor system (in which the reactor is a loop reactor), a loop reactor may have one or more features as described herein above loop reactor . 多反应器系统的第二个或任何后续的反应器可以是另一个环流反应器或任何用于烯烃聚合的反应器,例如流化床反应器。 Multiple reactor systems second or any subsequent reactor may be another loop reactor or any reactor for the polymerization of olefins, such as fluidized bed reactors. 但是,优选地,多反应器系统的第二个或任何后续的反应器是另一个环流反应器,其可具有或不具有一个或多个如本文以上所述的环流反应器的特点。 However, preferably, the multi-reactor system a second or any subsequent reactor is a loop reactor to another, which may or may not have one or more loop reactors as described herein above recited features. 例如, 本发明的环流反应器其长度的至少50%可具有大于700毫米的内径,同时第二个或任何后续的环流反应器可具有大于500毫米,例如大于600毫米,优选大于700毫米的内径。 For example, the loop reactor according to the present invention is at least 50% of its length may have an inner diameter greater than 700 mm, while the second or any subsequent loop reactor may be greater than 500 mm, such as greater than 600 mm, preferably larger than an inner diameter of 700 mm .
 多反应器系统可被用来制造单峰(monomodal)聚合物或多峰(multimodal)聚合物,优选多峰聚合物。  The multiple reactor system can be used to make monomodal (monomodal) or multimodal polymer (Multimodal) polymers, preferably multimodal polymers. 优选地,本发明的方法包括制造多峰乙烯聚合物,特别是双峰乙烯聚合物,其中低分子量(LMW)聚合物在一个反应器中被制造,而高分子量(HMW)聚合物在另一个反应器中被制造,聚合物可以任何顺序被制造,且第二种聚合物在存在第一种聚合物的情况下被制造。 Preferably, the manufacturing method of the invention comprises a multimodal ethylene polymers, in particular bimodal ethylene polymer, wherein the low molecular weight (LMW) polymer is made in a reactor, and the high molecular weight (HMW) polymer other reactor is manufactured, the polymer can be manufactured in any order, and the second polymer is made in the presence of the first polymer. 其中一个反应器或两个反应器沿其长度的至少50%具有至少700mm的内径。 Wherein one reactor or two reactors having a diameter of at least 700mm along at least 50% of its length.
 占多峰乙烯聚合物总重量的70至30wt %的第二种聚乙烯部分,所述第二种聚乙烯部分包含乙烯单元和任选地至多5摩尔%的至少一种含有3至12个碳原子的其他阿尔法烯烃,且熔体流动指数MI 2小于10g/10分钟。  70 to 30wt% of the total weight of the multimodal ethylene polymer, the second portion of the polyethylene, the second polyethylene fraction comprising units of ethylene and optionally up to 5 mol% of at least one containing 3 to other alpha olefins of 12 carbon atoms, and a melt flow index MI 2 of less than 10g / 10 min.
 占多峰乙烯聚合物总重量的70至30wt%的第二种聚乙烯部分,所述第二种聚乙烯部分包含乙烯单元和0. 1至20摩尔%的含有3至12个碳原子的阿尔法烯烃,且熔体流动指数MI2小于10g/10分钟。 The second part of the polyethylene  70 to 30wt% of the total weight of the multimodal ethylene polymer, the second polyethylene fraction comprising units of ethylene and 0.1 to 20 mole% containing 3 to 12 carbons alpha olefins atoms, and a melt flow index MI2 of less than 10g / 10 min.
 本发明中使用的环流反应器即是在其中制造上述第一种或第二种聚烯烃部分的反应器。  The loop reactor used in the present invention, i.e., in which the production of the first or second polyolefin reactor portion.
 虽然可在不止两个反应器中制造,但最优选地,聚合物是在连续的两个串接的反应器中制造的双峰聚合物。  Although more than two can be produced in the reactor, but most preferably, the polymer is in a continuous series of two reactors in a bimodal polymer produced. 一个或两个反应器沿其长度的至少50%可具有至少700mm的内径。 One or two reactors in at least 50% of its length may have an inner diameter of at least 700mm. 在第一个反应器中制造的第一种聚合物可以是低分子量(LMW)聚合物,而在第二个反应器中制造的第二种聚合物可以是高分子量(HMW)聚合物。 A first polymer produced in the first reactor may be a low molecular weight (LMW) polymer and the second polymer is produced in the second reactor may be a high molecular weight (HMW) polymer. 在一个实施方式中,3〇-7〇Wt% 且更优选40-60wt%的低分子量(LMW)聚合物是在第一个反应器中制造的,而70-30wt% 且更优选60-40wt%的高分子量(HMW)聚合物是在第二个反应器中制造的。 In one embodiment, the 3〇-7〇Wt% and more preferably 40-60 wt% of a low molecular weight (LMW) polymer is produced in a first reactor, and 70-30wt% and more preferably 60-40wt % high molecular weight (HMW) polymer is made in the second reactor. HMW聚合物和LMW聚合物的比率的最优选范围是45-55wt%比55-45wt%。 The most preferred range of the ratio of HMW polymer and LMW polymers is 45-55wt% over 55-45wt%.
 在另一实施方式中,HMW聚合物是在第一个反应器中制造的,而LMW聚合物是在第二个反应器中制造的,优选如以上所述的相同比率。  In another embodiment, the HMW polymer is made in the first reactor, while the LMW polymer is made in the second reactor, preferably the same ratio as above. 以下的要求只适用于此实施方式。 The following requirements apply to this embodiment only. 在这种情况下,第一种(HMW)反应器优选具有大于l〇〇kg/m 3/h、更优选大于150kg/m3/h,且最优选大于250kg/m3/h的时空产率(被定义为每单位体积反应器的聚合物生产(kg/h))。 In this case, the first (HMW) reactor is preferably greater than l〇〇kg / m 3 / h, more preferably greater than 150kg / m3 / h, and most preferably greater than 250kg / m3 / h of the space time yield ( It is defined as the volume of the reactor per unit polymer production (kg / h)). 在这种情况下还优选的是,第一个(HMW)反应器中的时空产率与第二个(LMW)反应器中的时空产率的比率大于1,更优选大于1. 2,最优选大于1. 5。 In this case, further preferably, the ratio of the first space-time yield of the reactor (HMW) and second (LMW) reactor space time yield greater than 1, more preferably greater than 1.2, most preferably greater than 1.5. 这可通过将第一个(HMW)反应器的体积设计成不大于第二个(LMW)反应器体积的90%,优选在30-70%,且更优选约40-60% 来实现。 This may be accomplished by a volume of the first (HMW) reactor is designed to not more than 90%, the second (LMW) reactor volume, preferably 30-70%, more preferably about 40-60% is achieved. 在上述情况下,优选地,第一个反应器的长度与直径(L/D)比大于350,更有选在500至3000之间,最优选大于750。 In the above case, preferably, the first reactor length to diameter (L / D) ratio greater than 350, more selected from between 500 to 3,000, most preferably greater than 750. 或者或并且,第一个反应器的L/D与第二个反应器的L/ D的比率也优选大于1. 5,最优选大于2。 Alternatively or in addition, the ratio L / D L / D of the second reactor and the first reactor is also preferably greater than 1.5, most preferably greater than 2.
 在本发明的HMW-LMW实施方式中,当反应器的体积差别不大于10%时,优选地,通过将第一个反应器的温度维持在60°C至80°C之间,优选不高于75°C,来平衡反应器之间的活性和各自的冷却能力。  In the HMW-LMW embodiment of the invention, when the difference in the volume of the reactor is no greater than 10%, preferably, by the first reactor was maintained at a temperature of between 60 ° C to 80 ° C, preferably not more than 75 ° C, to balance the activity and the ability of each of the cooling between the reactors. 还优选的是,第一个反应器中的固体浓度与第二个反应器中的固体浓度的比率被维持在小于1. 〇,优选在〇. 6至0. 8之间,因为这也帮助将两个反应器之间的活性平衡维持在想要的范围。 It is also preferred that the ratio of solids concentration in the solids concentration in the first reactor and the second reactor is maintained at less than 1 billion, preferably square. Between 6 to 0.8, as this also helps the balance of activity between the two reactors in the desired range. 通常,在最后的反应器中的固体浓度至少为35wt%,最优选在45wt%至60wt%之间,而在HMW反应器中的固体浓度在20wt%至50wt%之间,更优选在25wt%至35wt%之间。 Typically, the solids concentration in the final reactor is at least 35wt%, most preferably between 45wt% to 60wt%, and the solids concentration in the HMW reactor is between 20wt% to 50wt%, more preferably 25wt% to between 35wt%. 在这些情况下,优选使用沉降区和/或水力旋流器浓缩从第一个反应器转移至第二个反应器的固体,以浓缩固体浓度。 In these cases, preferably using a settling zone and / or hydrocyclone concentrated transferred from the first reactor to the second reactor solids, and concentrated to a solid concentration. 最优选将无共聚单体的稀释剂流体在水力旋流器的上游引入,以使得被转移至下游反应器的共聚单体最小化,从而使LMW反应器中的密度潜能(density potential)最大化。 Most preferably the diluent fluid is free comonomers upstream of the hydrocyclone is introduced, so that the comonomer transferred to the downstream reactor to be minimized, so that the density of the LMW reactor potential (density potential) maximization . 固体浓度基于聚合物在粒状聚合物游楽总重量中的重量。 Based on the weight of polymer solids concentration in the total weight of the particulate polymer yue travel.
 如果HMW聚合物是在LMW聚合物反应器的上游的反应器中产生的,则优选HMW反应器的平均内径与LMW反应器的平均内径的比率在0. 8至1. 4之间,通常小、于1,优选小于1.2,最优选小于1.4。  If the HMW polymer is produced in a reactor upstream of LMW polymer in the reactor, the average ratio of the average inner diameter of the inner diameter of the HMW and LMW reactor is preferably reactor between 0.8 to 1.4 usually less, than 1, preferably less than 1.2, most preferably less than 1.4. 在此构造中,优选地,LMW反应器总长的至少50%为至少700mm, 而HMW反应器的平均内径小于700毫米,优选小于600毫米。 In this configuration, preferably at least 50%, of the total length of the LMW reactor is at least 700mm, and the average inner diameter of HMW reactor is less than 700 mm, preferably less than 600 mm.
 如果LMW聚合物是在HMW聚合物反应器的上游的反应器中产生的,则优选HMW反应器的平均内径与HMW反应器的平均内径的比率在〇. 6至1. 4之间,通常在0. 8至1. 2之间,最优选在〇. 9至1. 1之间。  If the LMW polymer is produced in a reactor upstream of the HMW polymer in the reactor, the ratio of the average inner diameter and an average inner diameter of the HMW reactor is preferably in the HMW reactor is square. Between 6 to 1.4 between 9 to 1.1, typically between 0.8 to 1.2, most preferably square. 优选地,反应器具有相同的平均内径,最优选地,两个反应器被建造成相同的尺寸。 Preferably, the reactor has the same average inner diameter, and most preferably, two reactors are built to the same dimensions.
 总体地参考本发明,当多反应器系统包括两个环流反应器时,优选地,在至少一个环流反应器中的夫劳德数不大于30,且在那个反应器中的夫劳德数与在另一个环流反应器中的夫劳德数的比率在〇. 1至10、优选〇. 2至5的范围。  Referring generally to the present invention, when the multi-reactor system comprising two loop reactors, preferably the, the Froude number in at least one loop reactor is no greater than 30, and in that Fulao reactor de ratio of Froude number and another loop reactor in the square. range of 1 to 10, preferably square. 2 to 5.
 在本发明的另一实施方式中,含有聚合物的淤浆被从第二个反应器中回收并被转移至闪蒸罐中,所述闪蒸罐在一定压力P和温度下操作,使得至少50摩尔%的淤浆的液体成分作为蒸气被从闪蒸罐回收。  In another embodiment of the invention, the polymer containing slurry is recovered from the second reactor and transferred to a flash tank, the flash tank operating at a pressure P and temperature , such that at least 50 mole% of the slurry liquid component is recovered as a vapor from the flash tank. 优选地,上述方法使得至少98摩尔%、更优选98. 5摩尔%、 最优选98. 5摩尔%的从闪蒸罐中回收的蒸气在没有压缩的情况下被冷凝。 Preferably, the above method such that at least 98 mol%, more preferably 98.5 mol%, 98.5 mol% and most preferably recovered from the flash tank vapor is condensed without compression. 还优选地,至少80摩尔%、优选90摩尔%、最优选95摩尔%的淤浆的液体成分作为蒸气被从闪蒸罐回收。 Also preferably, at least 80 mol%, preferably 90 mol%, the liquid component 95 mol%, most preferably the slurry is recovered as a vapor from the flash tank.
 在环流或多个环流中使用的压力优选足以保持反应系统"充满液体",即基本没有气相。  used in a loop or more preferably a pressure sufficient to maintain the circulation of the reaction system 'liquid full', i.e. substantially no gas phase. 通常使用的压力在1-100绝对巴,优选在30至50绝对巴之间。 Pressure of usually 1-100 bara, preferably between 30 to 50 absolute bar. 在乙烯聚合中,乙烯分压通常在0. 1至5MPa的范围,优选为0. 2至2MPa,最具体地是0. 4至1. 5MPa。 In ethylene polymerization the ethylene partial pressure generally in the range of 0.1 to 5MPa, preferably 0.2 to 2MPa, most particularly 0.4 to 1. 5MPa. 所选择的温度使得基本上所有产生的聚合物基本上(i)是非粘性的和非结块的固体颗粒形式和(ii)在稀释剂中是不溶的。 Temperature selected such that substantially all of the polymer produced is essentially (i) non-tacky and non-agglomerated solid particulate form and (ii) is insoluble in the diluent. 聚合温度取决于所选择的烃类稀释剂和所产生的聚合物。 The polymerization temperature depends on the hydrocarbon diluent chosen and the polymer produced. 在乙烯聚合中,温度通常低于130°C,通常在50至125°C之间,优选在75至115°C之间。 In ethylene polymerisation the temperature is generally below 130 ° C, typically between 50 and 125 ° C, preferably between 75 and 115 ° C. 例如,在乙烯聚合中,在异丁烷稀释剂中,环流中使用的压力优选在30-50绝对巴的范围,乙烯分压优选在0. 2-2MPa的范围,且聚合温度在75-115°C的范围。 For example, in the polymerization of ethylene in isobutane diluent, the pressure used in circulation preferably in the range 30-50 bara, the ethylene partial pressure is preferably in the range of 0. 2-2MPa, and the polymerization temperature is 75-115 range ° C of. 本发明方法的时空产率(每单位环流反应器体积的聚合物生产率)在0. 1-0. 4、优选为0. 2-0. 35吨(ton) /小时/m3的范围。 Space-time yield of the process of the present invention (per unit volume of the loop reactor polymer production rate) at 0. 1-0. 4, preferably 0. 2-0. 35 tons (TON) / hr / m3 of the range. 当有两个或更多环流时,在不同环流中,反应条件可能相同或不同。 When there are two or more circulation loop at different reaction conditions may be the same or different.
 本发明的方法适用于制备含有烯烃(优选乙烯)聚合物的组合物,所述烯烃聚合物可包括一种或多种烯烃均聚物和/或一种或多种共聚物。  The method of the present invention is suitable for preparing compositions containing olefin (preferably ethylene) polymers, the olefin polymer may comprise one or more olefin homopolymers and / or one or more copolymers. 它特别适合于乙烯聚合物或丙烯聚合物的制造。 It is particularly suitable for producing ethylene polymers or propylene polymer. 乙烯共聚物通常包含的阿尔法-烯烃含量是可变的,其可达到12%重量, 优选为〇. 5至6%重量,例如约1 %重量。 Ethylene copolymers typically comprise an alpha - olefin content is variable, which can reach 12% by weight, preferably 5-6% by weight square, for example, from about 1% by weight.
 通常用于这样的反应中的阿尔法单烯烃单体是一种或多种每分子具有至多8个碳原子且在比4位更接近双键处没有分支的1-烯烃。  alpha monoolefin monomers commonly used in such reactions are one or more per molecule and having up to 8 carbon atoms and 1-alkenes in the nearer the double bond than the 4 without branches. 典型的例子包括乙烯、丙烯、丁烯-1、 戊烯-1、己烯-1和辛烯-1,以及混合物(例如乙烯和丁烯-1或乙烯和己烯-1)。 Typical examples include ethylene, propylene, butene-1, pentene-1, hexene-1 and octene-1 and mixtures (e.g., ethylene and butene-1 or ethylene and hexene-1). 丁烯-1、 戊烯-1和己烯-1是特别优选的用于乙烯共聚合的共聚单体。 Butene-1, pentene-1 and hexene-1 are particularly preferred comonomers for ethylene copolymerization.
 通常用于这样的反应中的稀释剂包括每分子具有2至12个、优选3至8个碳原子的烃,例如线性烷烃(例如丙烷、正丁烷、正己烷和正庚烷)或支链烷烃(例如异丁烷、异戊烷、异辛烷和2,2_二甲基丙烷),或环烷(例如环戊烷和环己烷)或它们的混合物。  commonly used in such reactions include diluents having per molecule 2 to 12, preferably from 3 to 8 carbon atoms, hydrocarbons such as linear alkanes (e.g. propane, n-butane, n-hexane and n-heptane), or branched paraffins (such as isobutane, isopentane, isooctane and 2,2_-dimethylpropane) or cycloalkyl (such as cyclopentane and cyclohexane) or mixtures thereof. 在乙烯聚合的情况下,在使至少50% (优选至少70%)的所形成的聚合物不溶于稀释剂的温度下,稀释剂通常对于催化剂、助催化剂和所产生的聚合物(例如液体脂族烃、脂环烃和芳烃)是惰性的。 In the case of ethylene polymerization, at least 50% (preferably at least 70%) of the polymer formed is insoluble in the diluent temperature, the catalyst is usually a diluent, cocatalyst and polymer produced (such as liquid aliphatic aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons) inert. 异丁烷是特别优选的用于乙烯聚合的稀释剂。 Isobutane is particularly preferred diluents for the polymerization of ethylene.
 操作条件也可以是使得单体(例如乙烯、丙烯)用作稀释剂,就像在所谓的本体聚合法中那样。  The operating conditions can also be such that the monomers (e.g. ethylene, propylene) act as diluents, as in so-called polymerization method as the body. 已发现,能够独立于稀释剂的分子量以及稀释剂是否为惰性的或活性的、液态的或超临界的,使用淤浆浓度极限(体积百分数)。 It has been found, independently of the molecular weight of the diluent and whether the diluent is inert or reactive, liquid or supercritical, using a slurry concentration limit (volume percent). 丙烯单体是丙烯聚合的特别优选的稀释剂。 Propylene monomer is particularly preferred propylene polymerization diluent.
 分子量调节的方法在本领域是已知的。  The method of adjusting the molecular weight are known in the art. 当使用Ziegler-Natta型催化剂、金属茂型催化剂和三齿新近(tridentate late)过渡金属型催化剂时,优选使用氢,较高的氢压力导致产生较低的平均分子量。 When using Ziegler-Natta type catalysts, metallocene-type catalysts and tridentate recently (tridentate late) transition metal type catalysts, hydrogen is preferably used, a higher hydrogen pressure resulting in a lower average molecular weight. 当使用铬型催化剂时,优选使用聚合温度来调节分子量。 When using chromium type catalysts, polymerization temperature is preferably used to regulate molecular weight.  在商业性工厂中,粒状聚合物以稀释剂不受污染的方式与稀释剂分离,以允许利用最低限度(如果有的话)的纯化,将稀释剂再循环至聚合区。  The particulate polymer with a diluent separated from the diluent in a manner contamination commercial plant, to allow the use of a minimum (if any) purification, the diluent is recycled to the polymerization zone. 将本发明方法生产的粒状聚合物与稀释剂分离通常可通过本领域任何已知的方法进行,例如该方法可包括:(i)使用不连续立式沉降柱,使得经过其开口的淤浆流提供聚合物颗粒可从稀释剂沉降至一定程度的区域,或者(ii)通过单个或多个回收口的连续产物回收,回收口的位置可以是在环流反应器上的任何地方,但优选邻近环流的水平部分的下游末端。 The method of the present invention for producing particulate polymer is separated from the diluent typically can be by any method known in the art, for example, the method may include: (i) the use of discontinuous vertical settling legs such that the opening through which the slurry flows providing polymer particles can settle to some extent from the diluent region, or (ii) recovering the product by a single or multiple continuous recovery port, the recovery port location may be anywhere on the loop reactor but is preferably adjacent the circulation the downstream end of the horizontal portion. 任何连续的回收口通常具有2-25、优选4-15、特别是5-lOcm范围的内径。 Any continuous recovery port generally has 2-25, preferably 4-15, in particular an inner diameter of 5-lOcm range. 本发明可操作大规模聚合反应器,且稀释剂回收方面的要求低。 The present invention is operable to scale the polymerization reactor, and the low recovery of diluent required. 以淤浆中的高固体浓度操作大直径反应器使得从聚合环流中回收的主要稀释剂的量最小化。 A slurry of high solids concentration operation of large diameter reactors such that the amount of the principal diluent withdrawn from the polymerisation loop is minimized. 对回收的聚合物淤浆使用浓缩装置,优选水力旋流器(单个的,或在多个水力旋流器的情况下,并列的或串接的),可进一步以能量有效的方式促进稀释剂的回收,因为避免了显著的减压和回收的稀释剂的汽化。 The recovered polymer slurry was concentrated using means, preferably hydrocyclones (single or in the case where a plurality of hydrocyclones, in parallel or in series), further facilitate energy efficient manner diluent recovery of the vaporized diluent is avoided because of the significant pressure and recovered.
 已发现,通过控制反应器环流中粉末的平均粒度和/或粒度分布,可优化反应器环流中的淤浆浓度。  It has been found, the average particle size of the powder circulation and / or by controlling the particle size distribution of the reactor, the slurry concentration may be optimized in a loop reactor. 粉末的平均粒度的主要决定因素是在反应器中的停留时间。 The main determinant of the average particle size of the powder is the residence time in the reactor. 粉末的粒度分布可受许多因素影响,包括加入至反应器中的催化剂的粒度分布、初始的和平均的催化剂活性、催化剂载体的坚固性和在反应条件下粉末对碎片的敏感性。 Powder particle size distribution may be influenced by many factors, including the catalyst was added to the reactor in a particle size distribution, initial firmness and average catalyst activity, the catalyst support and susceptibility of the powder to fragment under reaction conditions. 固体分离装置(例如水力旋流器)可被用于从反应器环流中回收的淤浆,以进一步辅助控制反应器中粉末的平均粒度和粒度分布。 Solids separation means (e.g. hydrocyclones) can be used in slurry recovered from the reactor loop in order to further assist control reactor powder has an average particle size and particle size distribution. 浓缩装置的回收位点的位置和浓缩装置系统(优选至少一个水力旋流器再循环环流)的设计和操作条件,也使得反应器内的粒度和粒度分布被控制。 Position and concentrating device system (preferably at least one hydrocyclone recycle loop) concentration recovery site apparatus design and operating conditions, but also makes the size and particle size distribution within the reactor is controlled. 平均粒度优选在100至1500微米之间,最优选在250至1000微米之间。 The average particle size is preferably between 100 and 1500 microns, most preferably between 250 and 1000 microns.
 当多反应器系统的最后的反应器是环流反应器时,在引入至主闪蒸器之前,所回收的(且优选被浓缩的)聚合物淤浆被减压,且任选地被加热。  When the last reactor of a multiple reactor system is a loop reactor when, prior to introduction to the main flasher, recovered (and preferably concentrated) is reduced polymer slurry, and optionally substituted with heating. 流体优选在减压后被加热。 It is preferably heated after depressurisation the fluid.  在主闪蒸器中回收的稀释剂和任何单体蒸气通常被冷凝(优选没有再次压缩)且被再用于聚合过程中。  recovered in the primary flash vessel diluent and any monomer vapors are typically condensed (preferably without recompression) and is re-used in the polymerization process. 主闪蒸器的压力优选被控制,以使得在任何再次压缩之前,用可容易获得的冷却介质(例如,冷却水)来冷凝基本上所有的闪蒸蒸气,通常在所述主闪蒸器中的这样的压力将是4-25绝对巴,例如10-20绝对巴,优选15-17绝对巴。 Flasher primary pressure is preferably controlled such that prior to any recompression, using readily available cooling medium (e.g. cooling water) of essentially all of the flash vapor is condensed, typically in the primary flash vessel so the absolute pressure is 4-25 bar, e.g. 10-20 bar abs, preferably 15-17 bar abs. 从主闪蒸器中回收的固体优选被转到次级闪蒸器中,以除去残留的挥发物。 Solids recovered from the primary flash vessel is preferably transferred in the secondary flash vessel to remove residual volatiles. 或者,淤浆可被转到具有比上述主闪蒸器更低压力的闪蒸器中,因而需要再次压缩以冷凝回收的稀释剂。 Alternatively, the slurry may be transferred to a lower pressure than the main flasher flasher, and thus need to be compressed again to condense the recovered diluent. 优选使用高压闪蒸器。 Using a high pressure flash vessel is preferred.
 本发明的方法可被用来生产比重在890至930kg/m3 (低密度)、930至940kg/m3 (中等密度)或940至970kg/m3 (高密度)范围内的树脂。  The method of the present invention may be used in 890 to 930kg / m3 (low density) 930 to 940kg / m3 (medium density) or to 970kg / m3 within the resin (high-density) specific gravity range of production, 940.
 本发明的方法与所有的烯烃聚合催化剂系统有关,特别是选自Ziegler型催化剂(特别是来自钛、锆或钒的催化剂)、热活化二氧化硅或无机物负载的氧化铬催化剂和金属茂型催化剂的系统(金属茂是过渡金属元素(特别是钛或锆)的环戊二烯基衍生物)。  The method of the present invention with all the relevant olefin polymerization catalyst system, in particular from Ziegler-type catalysts (especially a catalyst from titanium, zirconium or vanadium), thermally activated chromium oxide catalyst and a silica or inorganic supported metallocene-type catalyst systems (metallocene transition metal element (in particular titanium or zirconium) cyclopentadienyl derivatives).
 Ziegler型催化剂的非限制性例子是,通过将镁化合物与过渡金属化合物和卤代化合物混合而获得的包含选自元素周期表的IIIB族、IVB族、VB族或VIB族的过渡金属、镁和卤素的化合物。  Non-limiting examples of Ziegler-type catalyst is a transition metal selected from groups comprising a group IIIB by mixing a magnesium compound with a transition metal compound and a halogenated compound is obtained, IVB group, VB or Group VIB of , magnesium and a halogen compound. 卤素可任选地形成镁化合物的组成部分或形成过渡金属化合物的组成部分。 Halogen can optionally form an integral part of the magnesium compound or form part of a transition metal compound.
 金属茂型催化剂可以是由茂氧烧(alumoxane)或由例如专利申请EP-500,944_A1 (Mitsui Toatsu Chemicals)中描述的电离剂活化的金属茂。  The metallocene-type metallocene catalyst may be burned by the oxygen (an alumoxane) or for example, patent application EP-500,944_A1 (Mitsui Toatsu Chemicals) activated metallocene ionizer described.
 其余通常由来源于用于制备它们的产物的元素组成,例如碳、氢和氧。  The remaining elements are usually used in the preparation thereof derived from a composition of a product, such as carbon, hydrogen and oxygen. 过渡金属和卤素优选为钛和氯。 The transition metal and the halogen preferably titanium and chlorine.
 聚合反应,特别是Ziegler催化的聚合反应,通常是在存在助催化剂的情况下进行的。  Polymerization reactions, particularly Ziegler catalysed polymerization reaction is usually carried out in the presence of a cocatalyst. 可能使用本领域已知的任何助催化剂,特别是包含至少一个铝-碳化学键的化合物, 例如任选地卤代的有机铝化合物(其可包含氧或来自元素周期表的I族的元素)和铝氧烧(aluminoxanes)。 Known in the art may use any cocatalyst, in particular comprising at least one aluminum - carbon chemical bond of the compound, such as optionally halogenated organoaluminium compounds (which can comprise oxygen or an element from group I of the periodic table) and burning aluminoxane (aluminoxanes). 特别的例子可能是以下的有机错化合物:二烧基错,例如二乙基错;二链烯基铝,例如三异丙烯基铝;铝单醇盐和铝二醇盐,例如二乙基铝乙醇盐;一卤代的和二齒代的烧基错,例如氣化-乙基错;烧基错一氧化物和烧基错-氧化物,例如-丁基错氧化物;和含锂的有机铝化合物,例如LiAl (C2H5) 4。 Specific examples may be a compound of the following organic error: error Second Sintering group, such as diethyl fault; two alkenyl aluminum such as tri triisopropenylaluminium; mono aluminum alkoxides and aluminum dialkoxide, diethylaluminum e.g. ethoxide; halogenated and a bidentate group substituted burning fault, e.g. gasification - ethyl fault; fault burning yl oxides and a burn-yl wrong - oxides, e.g. - butyl wrong oxide; and lithium-containing organoaluminum compounds such as LiAl (C2H5) 4. 有机铝化合物,特别是那些未被卤化的,是非常适合的。 Organic aluminum compounds, especially those who are not halogenated, are well suited. 三乙基铝和三异丁基铝是特别有利的。 Triethylaluminum and triisobutylaluminum are particularly advantageous.
 基于铬的催化剂优选包括具有含二氧化钛的载体的负载的氧化铬催化剂,所述含二氧化钛的载体例如是复合的二氧化硅和二氧化钛载体。  The chromium-based catalyst preferably comprises a supported chromium oxide catalyst containing titania carrier, the carrier containing titania, for example a composite silica and titania support. 特别优选的基于铬的催化剂可包含占含铬催化剂重量的0. 5至5wt %的铬,优选约lwt %的铬,例如0. 9wt %的铬。 A particularly preferred chromium-based catalyst may comprise 0.5 to 5wt% chromium by weight accounted chromium-containing catalyst, preferably about lwt% chromium, for example, 0. 9wt% chromium. 载体包含占含铬催化剂重量的至少2wt %的钛,优选约2至3wt %的钛,更优选约2. 3wt %的钛。 Vector comprising comprises at least 2wt% by weight of titanium chromium-containing catalyst, preferably about 2 to 3wt% titanium, more preferably from about 2. 3wt% titanium. 基于铬的催化剂可具有200至700m2/g的比表面积,优选为400至550m2/g,和大于2cc/g的体积孔隙度,优选为2至3cc/g。 Chromium-based catalyst may have a 200 to 700m2 / g specific surface area, preferably 400 to 550m2 / g, and a volume porosity of greater than 2cc / g, preferably from 2 to 3cc / g.
 由二氧化硅负载的铬催化剂通常要在空气中、在升高的活化温度下经受初始活化步骤。  a silica-supported chromium catalysts typically in air, is subjected to an initial activation step at an elevated activation temperature. 活化温度优选在500至850°C的范围,更优选为600至750°C。 The activation temperature preferably in the range from 500 to 850 ° C, more preferably 600 to 750 ° C.
 反应器系统可包括一个或多个串接或并列连接的环流反应器,优选为串接的。  The reactor system may comprise one or more loop reactors connected in series or connected in parallel, preferably in series.
 如果是串接反应器,则反应器串的第一个反应器除稀释剂和单体外,还被供应催化剂和助催化剂,且每个后续的反应器至少被供应单体(特别是乙烯)和来源于反应器串的在前反应器的淤浆,此混合物包含催化剂、助催化剂和在反应器串的在前反应器中产生的聚合物的混合物。 The first reactor  If the reactor is connected in series, the series except the reactor diluent and monomers, is also supplied the catalyst and cocatalyst, and each subsequent reactor is supplied with at least the monomers (especially ethylene) and slurry from the preceding reactor in the series reactor, the mixture comprises a mixture of catalyst, cocatalyst and polymer produced in the first reactor in the reactor train. 任选地,可能向第二个反应器和/或,如果合适,至少一个其后的反应器供应未使用过的催化剂和/或助催化剂。 Optionally, it is possible to the second reactor and / or, if appropriate, at least one subsequent reactor is supplied unused catalyst and / or cocatalyst. 但是,优选只将催化剂和助催化剂引入至第一个反应器中。 Preferably, however, only the catalyst and cocatalyst introduced into the first reactor.
 如果至少两个反应器串接,具有最高熔体指数的聚合物和具有最低熔体指数的聚合物可在反应器串中的两个相邻的或不相邻的反应器中产生。  If at least two reactors connected in series, and polymers having a melt index having the highest lowest melt index can be produced in two adjacent or non-adjacent reactors in the reactor in the string . 氢(i)在制造高分子量成分的反应器中被保持在低(或零)浓度,例如包括0-0.1体积%的氢百分数,和(ii)在制造低分子量成分的反应器中被保持在非常高的浓度,例如0. 5-2. 4体积%的氢百分数。 Hydrogen (i) is kept at a low (or zero) concentration in the reactor for producing the high molecular weight component includes, for example 0-0.1% by volume percent hydrogen, and (ii) is maintained at a low molecular weight component in the production reactor very high concentrations, for example 0. 5-2. 4% hydrogen by volume percent. 反应器可被同等地操作,以在连续的反应器中产生基本上相同的聚合物熔体指数。 The reactor can equally be operated to produce essentially the same polymer melt index in successive reactors.
 如前所述,本发明的一个优点在于,横截面淤浆浓度分布在高反应器直径,甚至高固体载量时,可被维持在可接受的操作限度内。  As described above, an advantage of the present invention is that the cross-sectional slurry concentration distributions in the high reactor diameter, even at high solids loading can be maintained within acceptable operational limits. 实际的横截面淤浆浓度分布不可被直接测量,但可测量其他参数作为淤浆均一性的标示。 The actual cross-sectional slurry concentration distributions can not be measured directly, but may measure other parameters as indicated homogeneity of the slurry.
 排出反应器的液体的体积=[加入的质量总和-生成的PE质量]/液体密度。  The volume of liquid exiting the reactor = [sum of the added mass - mass of PE produced] / liquid density.
 PE密度是对干燥和脱气粉末测定的。  PE density powder is dried and degassed assay.
 液体密度是基于任何合适的模型(model)(利用组分、温度和压力)而计算的。  Any suitable liquid density model (Model) (using the composition, temperature and pressure) is calculated based on.
 环流反应器中的循环泵的功率要求不仅受流体的压力影响,而且受淤浆浓度梯度影响。  The loop reactor circulation pump power requirements not only by the influence of pressure fluid, and the slurry concentration gradient by impact. 它对浓度梯度特别敏感,因为它位于环流反应器的弯曲处,在这里最可能有流体隔离(segregation),这导致被泵送的淤浆的密度的改变。 Particularly sensitive to the concentration gradient, since it is located at the bend of the loop reactor, where most likely to fluid isolation (segregation), which results in a change in the density of the slurry to be pumped. 当具有很少的污垢和良好的循环时, 观察到功率需量(power demand)随时间变化而相对恒定。 When the dirt and with few good cycle observed power demand (power demand) is relatively constant over time. 图1显示对于实施例1的聚合反应,在一个小时的时间内,泵的功率和电流要求的图表(以相对值而非绝对值绘制)。 Figure 1 shows a graph for the (relative values rather than absolute values plotted) polymerization reaction of Example 1, in an hour, the pump power and current requirements. 此处显示出的变化大于对于纯溶剂所预期的变化,但对于含聚合物的淤浆来说是小的,显示出发生很小的或没有发生淤浆隔离。 Herein exhibit changes larger than expected for a pure solvent changes, but for the small polymer-containing slurry is, the slurry exhibits little isolated occurrence or non-occurrence.
 反应器中不同位点的温度也受淤浆浓度梯度的影响。  The temperature in the reactor at different sites also affected by the concentration gradient of the slurry. 在反应器中不同位点测定的温度间的绝对差别可能归因于热电偶的刻度的差异,因此为了确定温度的"真正"差异,测定了温度转变期间的变化。 The absolute difference between the temperatures measured at different sites in the reactor may be due to differences in scale of the thermocouple, so in order to determine the "true" difference in temperature, measured temperature changes during the transition. 在不均一的淤浆中,这种温度转变的趋势会改变。 In a variation of the slurry, and this trend will change the temperature transition. 图2显示实施例1的聚合反应的这样的转变。 Figure 2 shows this shift polymerization reaction of Example 1. 图2显示出,在实施例1中,温度转变趋势在整个反应器中是不变的,显示出良好的均一性。 Figure 2 shows, in Example 1, the temperature change in the trend is constant throughout the reactor, and showed good uniformity.
1. 一种在存在聚合催化剂的情况下控制淤浆相聚合或共聚合过程的方法,所述方法包括维持聚合物粉末颗粒的密度SPAN小于0. 005,聚合物粉末颗粒的D95小于1000 μ m,聚合物颗粒的粒度分布使得(D90-D10)/D50小于1. 5,其中所述密度SPAN被定义为排出反应器的、粒度大于D90的聚合物颗粒的平均密度与粒度小于D10的物质的平均密度之间以g/cm 3 为单位的密度差的绝对值,010、050、090和095分别是这样的直径:10%、50%、90%和95% 重量被收集的颗粒的直径小于此直径,所述方法在至少一个环流反应器中进行,所述环流反应器中的固体浓度为至少20体积%,夫劳德数被维持在30或30以下。 A method of controlling a slurry catalyst in the presence of a polymerization phase polymerization or copolymerization process, the method comprising maintaining a density SPAN of the polymer powder particles is less than 0. 005, D95 of the polymer powder particles is less than 1000 μ m , a particle size distribution such that the polymer particles (D90-D10) / D50 is less than 1.5, wherein the density SPAN is defined as the discharge of the reactor, the mean particle size greater than the material density and particle size of the polymer particles smaller than D90 D10 of between the average density g / cm 3 density differences in units of absolute value, 010,050,090 and 095, respectively, is such that the diameter: 10%, 50%, 90% and 95% of the diameter of the weight of the collected particles is less than this diameter, the method proceeds in at least one loop reactor, said loop reactor solids concentration is at least 20% by volume, the Froude number is maintained at 30 or less.
2. 权利要求1的方法,其中所述密度SPAN小于0. 003。 The method of claim 1, wherein the density SPAN of less than 0.003.
3. 权利要求1的方法,其中所述密度SPAN小于0. 0026。 The method of claim 1, wherein the density SPAN of less than 0.0026.
4. 权利要求1的方法,其中所述密度SPAN小于0. 0023。 The method of claim 1, wherein the density SPAN of less than 0.0023.
5. 权利要求1的方法,其中聚合物颗粒的粒度分布使得(D90-D10)/D50小于1. 2。 The method of claim 1, wherein the particle size distribution of the polymer particles is such that (D90-D10) / D50 is less than 1.2.
6. 权利要求1的方法,其中D95小于355 μ m。 6. The method of claim 1, wherein the D95 is less than 355 μ m.
7. 权利要求1-6中任一项的方法,其中在多反应器系统的至少一个连续管状环流反应器中,在稀释剂中、在存在聚合催化剂的情况下,将烯烃单体聚合,任选地将烯烃单体与烯烃共聚单体一起聚合,以产生包含固体粒状烯烃聚合物和稀释剂的淤浆,其中所述连续管状环流反应器总长的至少50%的平均内径为至少700mm。 The method claimed in any one of claim 1, wherein at least one continuous tubular loop reactor in a multiple reactor system, in the diluent, in the presence of a polymerization catalyst, polymerizing olefin monomers, any Alternatively olefin monomer is polymerized together with an olefin comonomer to produce a slurry comprising solid particulate olefin polymer and the diluent, wherein the continuous total length of the tubular loop reactor is at least 50% of the average inner diameter of at least 700mm.
8. 权利要求7的方法,其中在所述连续管状环流反应器中的固体浓度为至少20体积%。 The method of claim 7, wherein the solids concentration in the continuous tubular loop reactor is at least 20% by volume.
9. 权利要求7的方法,其中在所述连续管状环流反应器中的固体浓度为至少25体积%。 9. The method of claim 7, wherein the solids concentration in the continuous tubular loop reactor is at least 25% by volume.
10. 权利要求7的方法,其中在所述连续管状环流反应器中的固体浓度为至少30体积%。 10. The method of claim 7, wherein the solids concentration in the continuous tubular loop reactor is at least 30% by volume.
11. 权利要求7的方法,其中所述连续管状环流反应器总长的至少50%的平均内径为至少750_。 11. The method of claim 7, wherein the mean diameter of at least 50% of the total length of the continuous tubular loop reactor is at least 750_.
12. 权利要求7的方法,其中所述连续管状环流反应器的大于70%的总长具有至少700mm的内径。 12. The method of claim 7, wherein greater than 70% of the total length of said continuous tubular loop reactor having a diameter of at least 700mm.
13. 权利要求7的方法,其中所述连续管状环流反应器的大于70%的总长具有至少750mm的内径。 13. The method of claim 7, wherein greater than 70% of the total length of said continuous tubular loop reactor having a diameter of at least 750mm.
14. 权利要求7的方法,其中在所述多反应器系统中的至少一个反应器中,夫劳德数被维持在30或30以下。 14. The method of claim 7, wherein the multi-reactor system in at least one reactor, the Froude number is maintained at 30 or less.
15. 权利要求7的方法,其中在所述多反应器系统中的至少一个反应器中,夫劳德数被维持在1至20之间。 15. The method of claim 7, wherein the multi-reactor system in at least one reactor, the Froude number is maintained between 1-20.
16. 权利要求7的方法,其中在所述多反应器系统中的至少一个反应器中,夫劳德数被维持在2至15之间。 16. The method of claim 7, wherein the multi-reactor system in at least one reactor, the Froude number is maintained between 2-15.
17. 权利要求7的方法,其中在反应器的环流中的总压降小于1. 3巴,且聚合物生产率大于每小时25公吨。 17. The method of claim 7, wherein the total pressure drop in the loop reactor is less than 1.3 bar, and a polymer production rate greater than 25 metric tons per hour.
18. 权利要求17的方法,其中在反应器的环流中的总压降小于1巴。 18. The method of claim 17, wherein the total pressure drop in the loop reactor is less than 1 bar.
19. 权利要求17的方法,其中聚合物生产率大于每小时45公吨。 19. The method of claim 17, wherein the polymer production rate greater than 45 tonnes per hour.
20. 权利要求7的方法,其中在所述多反应器系统中产生的全部聚合物的至少30wt% 是在所述连续管状环流反应器中制造的。 20. The method of claim 7, wherein at least 30wt% of the total polymer produced in which the multi-reactor system is produced in the continuous tubular loop reactor.
21. 权利要求1的方法,其包括制造多峰乙烯聚合物,其中低分子量聚合物在一个反应器中被制造,而高分子量聚合物在另一个反应器中被制造,聚合物以任一顺序被制造且第二种聚合物在存在第一种聚合物的情况下被制造。 21. The method of claim 1, comprising producing the multimodal ethylene polymer, wherein the low molecular weight polymer is made in a reactor, and the high molecular weight polymer is made in another reactor, polymer is either order It is manufactured and a second polymer is made in the presence of the first polymer.
22. 权利要求21的方法,其中: 多峰乙烯聚合物的密度大于940kg/m3且熔体流动指数MI5为0. 05至50g/10分钟,所述乙烯聚合物包含: 占乙烯聚合物总重量30至70wt%的、密度至少为950kg/m3且熔体流动指数MI2至少为10g/10分钟的第一种聚乙烯部分,和占多峰乙烯聚合物总重量70至30wt%的第二种聚乙烯部分,所述第二种聚乙烯部分包含乙烯单元和任选的至多5摩尔%的含有3至12个碳原子的至少一种其他阿尔法烯烃, 且熔体流动指数MI2小于10g/10分钟;或者多峰乙烯聚合物的密度在900至930kg/m3之间且熔体流动指数MI2为0. 1至20g/10 分钟,所述乙烯聚合物包含: 占乙烯聚合物总重量30至70wt%的、密度小于950kg/m3且熔体流动指数MI2至少为10g/10分钟的第一种聚乙烯部分,和占所述多峰乙烯聚合物总重量70至30wt %的第二种聚乙烯部分,所述第二种聚乙烯部分包含乙烯单元和〇. 1至20摩尔 22. The method of claim 21, wherein: the density of the multimodal ethylene polymer is greater than 940kg / m3 and a melt flow index MI5 of 0.05 to 50g / 10 minutes, and the ethylene polymer comprises: an ethylene polymer based on the total weight of the 30 to 70wt% of the density of at least 950kg / m3 and a melt flow index MI2 of at least a first polyethylene fraction 10g / 10 min, and accounts for the total weight of the multimodal ethylene polymer is 70 to 30wt% of a second polyethylene ethylene moiety, said second polyethylene fraction comprising units of ethylene and optionally up to 5 mol% of at least one other alpha olefin containing from 3 to 12 carbon atoms, and a melt flow index MI2 of less than 10g / 10 min; or density multimodal ethylene polymer is between 900 to 930kg / m3 and a melt flow index MI2 of 0.1 to 20g / 10 minutes, and the ethylene polymer comprises: accounting for 30 to 70wt% of the total weight of the ethylene polymer , a density of less than 950kg / m3 and a melt flow index MI2 of at least a first polyethylene fraction 10g / 10 min, and accounts for the total weight of the multimodal ethylene polymer of the second polyethylene fraction of 70 to 30wt%, of the said second polyethylene fraction comprising units of ethylene and a square. 1 to 20 mol 的含有3至12个碳原子的阿尔法烯烃,且熔体流动指数MI2小于10g/10分钟。 Alpha olefins containing from 3 to 12 carbon atoms, and a melt flow index MI2 of less than 10g / 10 min.
BE1007653A3 (en) * 1993-10-26 1995-09-05 Fina Research Polyethylene production process with broad molecular weight distribution.


text:
NGC 4411A (другие обозначения — NGC 4411-1, ZWG 70.74, IC 3339, VCC 905, UGC 7537, KCPG 336A, MCG 2-32-48, PGC 40695) — галактика в созвездии Дева.

Этот объект не входит в число перечисленных в оригинальной редакции «Нового общего каталога» и был добавлен позднее.

Примечания

4411
Дева (созвездие)

redpajama_set_name: RedPajamaWikipedia


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text:
The Indian Political Intelligence Office (IPIO) was an intelligence organisation initially established in England in 1909 in response to the dissemination of anarchist and revolutionary elements of Indian nationalism to different countries in Europe after the liquidation of India House (where it was based between 1905 and 1910) in London in 1909. It formally came to be called the Indian Political Intelligence (IPI) from 1921.

By the time World War I broke out the IPIO, headed by John Wallinger, had been established in mainland Europe. In scale, this office was larger than those operated by the British War Office, approaching the size of the European intelligence network of the Secret Service Bureau. This network already had agents in Switzerland against possible German intrigues. After the outbreak of the war, Wallinger, under the cover of an officer of the British General Headquarters, proceeded to France where he operated out of Paris, working with the French Political Police, the Sûreté.<ref>: "With the outbreak of the First World War the Indian intelligence network set up by Superintendent Wallinger ... within the general structure of British intelligence in Europe ... In scale it was not much smaller than the European intelligence operations of the Secret Service Bureau, let alone those of the War Office. Moreover, John Wallinger already controlled agents operating in Switzerland, which was to become an important centre of German intrigue ... [he] had cultivated friendly relations with the Paris political police, the Sūreté.

Notes

References
International Institute for Asian Studies: Indian Political Intelligence Files Released for Research
.

Indian intelligence agencies
Hindu–German Conspiracy
Revolutionary movement for Indian independence
World War I espionage
Government of British India


As Jessica mentioned on Friday, that afternoon we loaded up the trailer and Jeep and headed to Omaha, NE. For what? A track day of course! At about 5 1/2 hours drive time, this was the furthest we have traveled to do a track day.
We also took the dogs, which always makes a trip more work, but also more enjoyable. We've been really lucky, Clive and Matilda are really good sports when it comes to traveling. Even with the added noise of pulling the car on a trailer and alongside noisy semis didn't seem to upset them too much. They were in a constant cycle of naps and begging for road snacks.
This was my first time to Mid America Motorplex and I can say now that I really enjoyed the track. After the massive floods in the area in 2011, I wasn't sure quite what conditions would be like, but for the most part the track was still in very good shape and enjoyable to drive on.
This particular event was put on by the guys at Find The Line. I got a chance to talk with Find The Line owner Damian Dela Huerta a good bit about the track and how to drive it. Damian has a race car of his own and was a great resource to have, and I definitely took the opportunity to pick his brain about how to find the good racing lines at Mid America Motorplex.
Mid America Motorplex is a 2.23 mile circuit (about double the size of Gateway!) and as you can see has a lot of really great turns. There is a little bit of something for everyone at Mid America. You have two straights that are good for well over 100mph, you have a couple late apex turns, and you have two sets of slower speed technical transitions that allow the lower horsepower cars to gain some time on the more powerful cars if you get those turns right.
Some of my favorite things about the track would be turn 3 to 4 where in my car I can exit turn 3 in 3rd gear and hit 4th and have the pedal to the floor all the way through turn 4 before braking for turn 5.
Turn 5 to 6 is a sweeper that since the track sweeps outward you can carry a lot of early exit speed because you will not have to worry about going off track there. Turn 7 comes up very very fast!
Turn 7-8 was perhaps the most tricky for me to get right. As you can see you can do a "double apex" on the turn where you hit the turn apex on 7 and then hit the turn apex on 8. OR you can give up turn 7 apex and track out to the left and then late apex turn 8.
9-10-11 and 12-13-14 turns were such a joy to drive and really reminded me of my Autocross days in that if you got these smooth and efficient you could make up so much time on someone who was not very good at those transitions.
Here are some videos of my laps. Sorry about the terribly shaky camera. I tried to dampen the camera mount the best I could but the exhaust note/vibration is just too much for it. I will be ordering a new mount soon that will eliminate this problem for next time.
5-18-2013 Mid America Motorplex Open Lapping HPDE from Kohler Created on Vimeo.
5-18-2013 Mid America Motorplex Open Lapping HPDE – Session 2 from Kohler Created on Vimeo.
5-18-2013 Mid America Motorplex – Open Lapping HPDE – Session 3 from Kohler Created on Vimeo.
Here is a slideshow of the pictures of the day! Unfortunately due to how large the track is, it is quite hard to get good on-track photos so we do not have any of those.
Since there were only around 20 cars there we were able to get over an hour and a half of track time! That is about the most track time I have had at any event. The kind of focus and concentration that is required to keep getting faster and faster on the track and the heat inside the car I was quite tired by the end of the day.
Packing up is always bittersweet because while you are quite tired and typically feeling pretty accomplished with your day, you know that what comes next is the wait for the next track day.


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The preferred airport for Hotel Polatdemir is Istanbul (IST).


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text:
Eva Carneiro's constructive dismissal case against Chelsea to have first hearing
• Date for former Chelsea team doctor's full hearing likely to be June
• Separate legal action continues against José Mourinho
Tue 5 Jan 2016 11.38 EST Last modified on Mon 27 Nov 2017 06.47 EST
Eva Carneiro ran into problems with José Mourinho on the opening day of the season. Photograph: BPI/REX Shutterstock
Eva Carneiro's case for constructive dismissal against Chelsea will have its first tribunal hearing on Wednesday.
The preliminary hearing will take place at the London South Employment Tribunal in Croydon and is expected to be in private before an employment judge.
The hearing will fix the timetable for the case and deal with witness statements and disclosure of documents – including texts and emails – by each side, as well as any legal procedural disputes that exist between the two parties.
A date for a full hearing could be fixed for some time in June but there may be another preliminary hearing arranged before that takes place. The parties may also agree to a settlement before the case is heard.
Chelsea filed their defence last month. The former Chelsea team doctor also has a separate personal legal action against the club's former manager José Mourinho, who left in December, for alleged victimisation and discrimination.
The 42-year-old doctor was dropped from first-team duties after Mourinho criticised her and the first-team physio Jon Fearn for going on to the pitch to treat Eden Hazard on the opening day of the season.
The action meant Chelsea were temporarily down to nine men against Swansea and Mourinho called Carneiro and Fearn "impulsive and naive". Carneiro did not appear on the bench again for first-team duties and later parted company with the club.
Mourinho was cleared of using discriminatory language towards her following an investigation by the Football Association. Afterwards, Carneiro and the FA's independent board member Dame Heather Rabbatts criticised the governing body for not interviewing the doctor as part of its investigation.
Carneiro has also had backing from Fifa's medical chairman Michel D'Hooghe, who contacted the doctor to offer his support and that of the world governing body. He has backed Carneiro's insistence she was simply doing her job.

redpajama_set_name: RedPajamaCommonCrawl