CN101270169B - Method for controlling sheeting in gas phase reactors - Google Patents

Method for controlling sheeting in gas phase reactors Download PDF


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CN101270169B CN 200810091912 CN200810091912A CN101270169B CN 101270169 B CN101270169 B CN 101270169B CN 200810091912 CN200810091912 CN 200810091912 CN 200810091912 A CN200810091912 A CN 200810091912A CN 101270169 B CN101270169 B CN 101270169B
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continuity additive
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CN101270169A (en
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Embodiments of the present invention relate to measuring and controlling static in a gas phase reactor polymerization. In particular, embodiments relate to monitoring carryover static in an entrainment zone during gas phase polymerization to determine the onset of reactor discontinuity events such as chunking and sheeting. Embodiments also relate to monitoring carryover static to determine the need for effective additions of continuity additives that minimize reactor static activity and thereby preventing discontinuity events.


控制气相反应器中的结皮的方法 Control skinning gas phase reactor method

[0001] 本发明是申请日为2004年12月15日、申请号为200480039205. 5、发明名称为“控 [0001] The present invention is filing date of December 15, 2004, Application No. 200480039205.5, entitled "Control

制气相反应器中的结皮的方法”的中国专利申请的分案申请。 Divisional gas phase reactor system skinning Method "filed Chinese patent.

技术领域 FIELD

[0002] 本发明的实施方案涉及测量和控制气相聚合反应器中的静电的方法。 [0002] The embodiments of the present invention relates to a method for measuring and controlling a gas phase polymerization reactor of electrostatic. 尤其,本发明的实施方案涉及通常在采用金属茂催化剂的聚合中,监测在整个气相聚合反应器中的新部位的携带静电(carryoverstatic),以确定反应器中断事件例如结块和结皮的开始的方法。 In particular, embodiments of the present invention generally relates to polymerization using the metallocene catalyst, carrying an electrostatic monitoring (carryoverstatic) new parts throughout the gas phase polymerization reactor to determine reactor discontinuity events such as the start caking and crust Methods. 本发明的实施方案还涉及监测这些新部位的携带静电,以确定是否需要添加有效量的最大程度减小反应器静电活性和尤其携带静电的连续性添加剂(continuity additive), 从而防止或最大程度减少这种中断事件的方法。 Further embodiment of the invention relates to a new monitor these sites electrostatically charged, to determine whether adding an effective amount of a minimize reactor static activity, and in particular, static electricity carried continuity additive (continuity additive), in order to prevent or minimize this approach interrupt event.

[0003] 背景 [0003] BACKGROUND

[0004] 结皮和结块是已经困扰了工业气相聚烯烃生产反应器许多年的问题。 [0004] The caking and crust are gas industry has been plagued by problems in the production of polyolefin reactors for many years. 该问题的特征在于在反应器壁上形成固体团块聚合物。 It characterized the problem is to form solid masses of polymer on the reactor walls. 这些固体团块或聚合物(结皮)最终从壁上掉下并落入到反应段中,在那里它们干扰流化,堵塞产品排出口,并且通常迫使反应器停工以便清洗,这些事件中的任何一个可以被称为“中断事件”,其通常中断聚合反应器的连续操作。 These solid masses or polymer (skinning) eventually fall from the wall and fall into the reaction section, where they interfere with fluidization, blocked product discharge outlet and usually force a reactor shutdown for cleaning, these events any of which may be referred to as "interrupt event", which typically interrupt the continuous operation of a polymerization reactor. 术语“结皮,结块和/或结垢”虽然在本文中同义使用,但可以描述类似问题的不同表现,在每一种情况下,它们可导致反应器中断事件。 The term "crust, agglomeration and / or fouling" while used synonymously herein, may describe different manifestations of similar problems, in each case, which can lead to reactor discontinuity events.

[0005] 在气相反应器中发生至少两种不同形式的结皮。 [0005] at least two different forms of the crust occurs in the gas phase reactor. 该两种形式(或类型)的结皮被描述为壁结皮或拱顶结皮(dome sheets),取决于它们在反应器中形成的部位。 The two forms (or types) is described crust crust or crusts dome (dome sheets) for the wall, they form depends on the location in the reactor. 壁结皮在反应段的壁(一般垂直部分)上形成。 Crust wall formed in the wall (generally vertical portion) of the reaction section. 拱顶结皮在反应器中的更高位置,在拱顶的锥体部分上,或在反应器顶部的半球形头上形成(图1)。 Dome crust higher position in the reactor, on the conical section of the dome, or is formed (FIG. 1) at the head of the hemispherical top of the reactor.

[0006] 当用齐格勒_纳塔催化剂发生结皮的时候,它通常在反应器的下部形成,被称为壁结皮。 [0006] When the occurrence of the skinning _ with a Ziegler Natta catalyst, which usually is formed in a lower portion of the reactor, is referred to as wall skinning. 齐格勒-纳塔催化剂能够形成拱顶结皮,但很少发生。 Ziegler - Natta catalyst capable of forming a dome crust, but rarely occur. 但在金属茂催化剂的情况下,结皮可以在任何一种位置或这两种位置发生;也就是说,能够发生壁结皮和拱顶结皮。 In the case of metallocene catalysts, the crust can occur at any position or both position; that is, the walls and dome crust crust can occur.

[0007] 在金属茂催化剂体系的情况下,拱顶结皮是尤其麻烦的。 [0007] In the case of a metallocene catalyst system, the dome is particularly troublesome in the crust. 典型的金属茂化合物一般被描述为含有一个或多个能够键接于过渡金属原子的配体(通常是环戊二烯基衍生的配体或结构部分)与选自元素周期表的4、5或6族或镧系和锕系元素中的过渡金属结合。 Typical metallocene compounds are generally described as containing one or more ligands can be bonded to the transition metal atoms (usually a ligand or cyclopentadienyl moiety derived) and selected from Group 4, 5, or 6 or lanthanide and actinide transition metal binding.

[0008] 在金属茂催化剂的情况下难以控制结皮的一个特征是它们不可预测的静电倾向性。 [0008] In the case where the metallocene catalyst is difficult to control a skinning feature is their unpredictable static tendencies. 例如,EP 0811638A2描述了在长期的稳定行为之后能够出现突然不稳定的静电荷特性的金属茂催化剂。 For example, EP 0811638A2 describes Haute metallocene catalyst of electrostatic instability can appear suddenly after a long period of stable behavior.

[0009] 针对与使用金属茂催化剂有关的反应器中断问题,已经开发出了多种据说可获得改进的可操作性的技术。 [0009] for the reactor using a metallocene catalyst-related disruptions, it is said to have developed a variety of available technologies to improve operability. 例如,US专利No. 5,283,218讨论了用于制备具有减低的结垢倾向性和更好的可操作性的金属茂催化剂体系的各种担载工序或方法,该专利公开了金属茂催化剂的预聚合。 For example, US Patent No. 5,283,218 discusses various loading step or method for preparing a reduced tendency to fouling and better operability metallocene catalyst system, which discloses metallocenes of prepolymerized catalyst. US专利Nos. 5,332,706和5,473,028公开了用于通过“初期浸渍”形成催化剂的特定技术。 US Patent Nos. 5,332,706 and 5,473,028 disclose a particular technique for forming a catalyst by "initial impregnation." US专利Nos. 5,427,991和5,643,847公开了非配位阴离子活化剂与载体的化学结合。 US Patent Nos. 5,427,991 and 5,643,847 disclose chemically bound non-coordinating anion activator and a carrier. US专利No. 5,492,975公开了聚合物结合的金属茂催化剂体系。 US Patent No. 5,492,975 discloses a metallocene catalyst system to polymer bound. US专利No. 5,661,095公开了将金属茂催化剂担载于烯烃和不饱和硅烷的共聚物上的方法。 US Patent No. 5,661,095 discloses a process for metallocene catalysts supported on a copolymer of an olefin and an unsaturated silane. PCT公开W0 97/06186公开了在形成金属茂催化剂之后除去无机和有机杂质的方法。 PCT Publication W0 97/06186 discloses a method of removing inorganic and organic impurities after formation of the metallocene catalyst. TO 97/15602公开了容易担载的金属配合物。 TO 97/15602 discloses a supported metal complexes readily. W0 97/27224公开了在具有至少一个末端双键的不饱和有机化合物的存在下形成担载过渡金属化合物的方法。 W0 97/27224 discloses a method of forming a supported transition metal compound in the presence of at least one terminal double bond of the unsaturated organic compound.

[0010] 其他人已经论述了用于改进用金属茂催化剂和常规齐格勒-纳塔催化剂的反应器连续性的不同工艺变化。 [0010] Others have discussed for improving metallocene catalyst and a conventional Ziegler - different process variations reactor continuity Natta catalyst. 例如,wo 97/14721公开了通过将惰性烃加入到反应器中而抑制能够引起结皮的细粒的方法。 For example, wo 97/14721 discloses a method of fine particles can be suppressed due to skinning by adding an inert hydrocarbon to the reactor. US专利No. 5,627,243公开了用于流化床气相反应器的分配板。 US Patent No. 5,627,243 discloses a distributor plate for a fluidized bed gas phase reactor. W096/08520公开了避免将清除剂引入到反应器中的方法。 W096 / 08520 discloses avoid scavenger introduced into the reactor in the method. US专利No. 5,461,123公开了使用声波来减少结皮的方法。 US Patent No. 5,461,123 discloses a method of using sound waves to reduce skinning. US专利No. 5,066,736和EP-A10549252公开了将活性阻滞剂(activityretarder)引入到反应器中以减少附聚物的方法。 US Patent No. 5,066,736 and EP-A10549252 discloses an active blocker (activityretarder) is introduced into the reactor in a reducing agglomerates. US专利No. 5,610, 244 公开了将补充单体在床以上直接进给到反应器中以避免结垢并改进聚合物质量的方法。 US Patent No. 5,610, 244 discloses a method of the above make-up monomer directly into the bed to the reactor to avoid fouling and improve polymer quality. US 专利No. 5,126,414公开了采用低聚物去除系统用于减少分配板结垢和提供不合凝胶的聚合物的方法。 US Patent No. 5,126,414 discloses a method of using an oligomer removal system for reducing distributor plate fouling and providing undesirable gel polymer. 有多种其它已知的用于改进可操作性的方法,包括涂布聚合设备、控制聚合速率(尤其在起动时)、以及改装反应器设计和将各种试剂注入到反应器中。 There are various other methods known for improving operability including coating the polymerization equipment, controlling the polymerization rate (especially at start), and a modified reactor design and injecting various agents into the reactor.

[0011] 至于将各种试剂注入到反应器内,使用抗静电剂作为工艺“连续性添加剂”似乎很有前景并已成为许多出版物的主题。 [0011] As for injecting various agents into the reactor, the use of antistatic agents as process "continuity additives" seems promising and have been the subject of many publications. 例如,EP 0453116A1公开了将抗静电剂引入到反应器中以减少结皮和附聚物的量的方法。 For example, EP 0453116A1 discloses an antistatic agent is introduced into the reactor to a method of reducing the amount of crust and agglomerates. US专利No. 4,012,574公开了将具有全氟烃基的表面活性化合物加入到反应器中以减少结垢的方法。 US Patent No. 4,012,574 discloses a compound having a perfluoroalkyl surfactant was added to the reactor to reduce fouling of. W0 96/11961公开了作为担载催化剂体系的组分的用于减少气相、淤浆相或液相聚合方法中的结垢和结皮的抗静电剂。 W0 96/11961 discloses an antistatic agent as a component of a supported catalyst system for reducing the gas phase, slurry phase or liquid phase polymerization process fouling and skinning. US专利Nos. 5,034,480和5,034,481公开了常规齐格勒-纳塔钛催化剂与抗静电剂的反应产物,用于生产超高分子量乙烯聚合物。 . US Patent Nos 5,034,480 and 5,034,481 disclose conventional Ziegler - Natta titanium catalyst with the reaction product of an antistatic agent for the production of ultrahigh molecular weight ethylene polymer. 例如,W0 97/46599公开了可溶性金属茂催化剂在采用可溶性金属茂催化剂的气相方法中的应用,其中所述可溶性金属茂催化剂被进给到聚合反应器的贫区,用于生产有规立构聚合物。 For example, W0 97/46599 discloses the use of soluble metallocene catalysts in a gas phase method using a soluble metallocene catalyst, wherein the soluble metallocene catalyst depleted zone is fed to the polymerization reactor, for producing stereoregular polymer. W097/46599还公开,催化剂原料流可含有抗结垢剂或抗静电剂例如ATMER® 163(从ICI Specialty Chemicals, Baltimore, Md.商购)。 W097 / 46599 further discloses that the catalyst feedstream can contain an anti-fouling agent or antistatic agent such ATMER® 163 (from ICI Specialty Chemicals, Baltimore, Md. Commercially available).

[0012] US专利No. 5,410,002公开了使用常规齐格勒_纳塔钛/镁担载的催化剂体系,其中将选择的抗静电剂直接加入到反应器中以减少结垢。 [0012] US Patent No. 5,410,002 discloses the use of conventional Ziegler-Natta _ titanium / magnesium supported catalyst system where a selection of antistatic agents is added directly to the reactor to reduce fouling. 抗静电剂的量被描述为取决于聚合物或所形成的聚合物的颗粒分布,抗静电剂的一个例子是ATMER 163,但没有公开动态调节或优化抗静电剂的量的方法。 The amount of antistatic agent is described as depending on the polymer particles or a distribution of the formed polymer, one example of the antistatic agent is ATMER 163, but does not disclose a method of dynamically adjusting or optimizing the amount of antistatic agent.

[0013] US专利No. 4,978,722公开了用于制备丙烯-a -烯烃嵌段共聚物的方法,其中将选自芳族羧酸酯、亚磷酸酯(Pho sphorous ester)、不饱和二羧酸二酯、叔胺和酰胺中的一种化合物加入到聚合反应器的气相中,从而抑制低分子量聚合物的形成并防止聚合物附着于反应器壁上。 [0013] US Patent No. 4,978,722 discloses the preparation of a propylene -a - olefin block copolymer, wherein the aromatic carboxylic acid ester is selected from phosphites (Pho sphorous ester), unsaturated diesters of dicarboxylic acids, tertiary amines and an amide compound is added to the gas phase polymerization reactor, thereby suppressing the formation of low molecular weight polymers and to prevent the polymer adhering to the reactor walls. 但在US专利No. 4,978,722中没有提及测量静电活性,也没有提及优化为了防止附着而添加的化合物的量的方法。 Electrostatic activity measured no reference in US Patent No. 4,978,722, there is no mention of a method to optimize the amount of compound added to prevent the adhesion.

[0014] US专利No. 5,026,795公开了将抗静电剂与液体载体加入到气相聚合反应器的聚合区中。 [0014] US Patent No. 5,026,795 discloses an antistatic agent with a liquid carrier is added to the gas phase polymerization reactor in the polymerization zone. 优选地,将抗静电剂与稀释剂混合,并通过包含共聚单体的载体引入到反应器中。 Preferably, the antistatic agent is mixed with a diluent, and introduced into the reactor by a carrier comprising the comonomer. 所公开的优选抗静电剂是以STADIS® 450的商标由Octel Starreon出售并且含有聚砜、聚合多胺、磺酸和甲苯的混合物。 Preferred antistatic agents are disclosed in the trademark STADIS® 450 sold by Octel Starreon and which contains a polysulfone, a polymeric polyamine mixture, and toluene sulfonic acid. 据披露抗静电剂的量是非常重要的。 According to disclose the amount of antistatic agent is very important. 具体地说,必须有充足的抗静电剂来避免聚合物附着于反应器壁上,但不至于多得使催化剂中毒。 Specifically, the antistatic agent must be sufficient to prevent the polymer adhering to the reactor walls, but not so much to obtain poison the catalyst. US专利No. 5,026,795还公开,优选的抗静电剂的量是按重量计的所生产的聚合物的百万分之大约 Ppm disclosed in US Patent No. 5,026,795 is also preferred that the amount of the antistatic agent by weight of the polymer produced about

40. 2-5(ppmw);然而,没有公开根据可测定的反应器条件来优化抗静电剂的水平的方法。 40. 2-5 (ppmw); however, no disclosure can be determined according to the method of reactor conditions to optimize the level of antistatic agent.

[0015] 以上论述的EP 0811638A2公开了在聚合方法中在抗静电剂的存在下使用金属茂催化剂和活化助催化剂,还公开了ATMER 163的使用。 [0015] discussed above EP 0811638A2 discloses using a metallocene catalyst and an activating cocatalyst in the presence of an antistatic agent in the polymerization process, also discloses the use of ATMER 163. EP 0811638A2还公开了用于引入抗静电剂的各种方法,最优选将抗静电剂喷雾到反应器的流化床中。 EP 0811638A2 also discloses various methods for introducing an antistatic agent, most preferably the antistatic agent is sprayed into the fluidized bed reactor. 概括公开的另一种方法是添加抗静电剂与担载或液体催化剂料流,只要催化剂不受抗静电剂的严重影响或不被抗静电剂毒害。 Another method disclosed is to add an antistatic agent to summarize supported or liquid catalyst stream so long as the catalyst is not seriously affect the antistatic agent or an antistatic agent is not poisoned. EP 0811638A2给出了其中担载的催化剂在引入到反应器中之前在矿物油中制浆以及当使用非担载的催化剂时将抗静电剂直接引入到反应器中的实例。 EP 0811638A2 which gives supported catalyst slurried in mineral oil prior to introduction into the reactor, and when a non-supported catalyst antistatic agent is introduced directly into the reactor instance. 在流化床本身的分配板以上几英尺的位置测量静电。 Measuring static position a few feet above the distributor plate of the fluidized bed itself. 优选地,响应于例如静电的升高水平的变化,间歇地添加抗静电剂。 Preferably, in response to a change such as an electrostatic elevated level of antistatic agent is added intermittently.

[0016] 虽然已经开发了许多方法来控制金属茂催化剂的结皮问题并已经调查研究了连续性添加剂的使用,但该问题仍持续存在。 [0016] Although many methods have been developed to control skinning problems metallocene catalyst and has investigated the use of continuity additives, and the problem persists. 该问题持续存在的一个原因是连续性添加剂的使用会伴有催化剂效率和生产率的降低。 One reason the problem persists is that the use of continuity additive will be accompanied by reduction in productivity and efficiency of the catalyst. 在添加剂的注入就频率和/或量来说没有精确匹配以阻止反应器静电的瞬时情况(这能够预示不希望的“反应器中断事件”)的时候,发生了降低的催化剂效率和催化剂生产率。 In the additive injection on the frequency and / or amount is not an exact match to prevent transient conditions of the reactor static electricity (which can indicate undesirable "reactor discontinuity event") when the occurrence of the reduced catalyst efficiency and catalyst productivity.

[0017] 金属茂催化剂的结皮问题持续存在的另一个原因(和也许是该问题的根源)是缺乏对这种事件的预先警告(注:在以上第六段中的EP0811638A2)。 [0017] Another reason (and perhaps the source of the problem) skinning problems persist metallocene catalysts is the lack of advance warning of such events (Note: EP0811638A2 in paragraph 6 above). 用任何先前已知和/或使用的工艺仪器,包括迄今为止使用的常规静电探针,金属茂催化剂的大多数结皮事件在很少或无预先指示的情况下发生。 Any previously known and / or used process instruments, including the conventional static probes used so far, most of the crust metallocene catalysts event occurs in a case where little or no advance indication. (常规静电探针是如本文和US 4,855,370中所述,位于分配板顶部以上反应器直径的1/4到3/4的那些探针。)这种常规仪器缺乏预先获得可测定的指标的指示,它对查找和矫正使用金属茂催化的反应的结皮问题(和所导致的反应器中断)的努力提出了重要挑战。 (Conventional static probes as described herein and in the US 4,855,370, those probes are located above the top of the distribution plate of the reactor diameter 1/4 to 3/4.) This lack of a conventional instrument may be measured in advance to obtain indication of indicators, use it to find and correct the reaction of metallocene-catalyzed crust question (and the reactor caused by interruption) effort raises important challenges.

[0018] US 4,532,311是最先提供了对反应器结皮进行描述的文献之一。 [0018] US 4,532,311 is one of the first to provide a reactor crust literature been described. 该专利首先描述了使用齐格勒_纳塔催化剂的结皮是流化床带静电的结果的重要发现。 The first patent describes the use of important findings crust _ Ziegler Natta catalyst is a fluidized bed with the result of static electricity. (不确定它是否是描述该教导特点的好主意,除非它是明确的)。 (Not sure whether it is a description of the characteristics of this teaching good idea, unless it is clear). 后来的专利US 4,855,370将'311文件的静电探针与控制反应器中的静电水平的装置结合。 Later US patent electrostatic level 'static reactor probe and control means 311 file binding 4,855,370. 在US 4,855,370的情况下,控制静电的装置是将水加入到反应器中(以乙烯进料的I-IOppm的量)。 In the case of US 4,855,370, the apparatus is to control static water was added to the reactor (I-IOppm to the amount of the ethylene feed). 已证明该方法对于齐格勒_纳塔催化剂有效,但对于金属茂催化剂反应或反应器无效。 This method has proven effective for Ziegler _ Natta catalyst, a metallocene catalyst but the reaction or is not valid.

[0019] 许多年来,对金属茂催化剂结皮的原因的认识由于缺乏适合的检测仪器而受到阻碍。 [0019] For many years, the understanding of the reasons metallocene catalyst skinning because of the lack of suitable instrumentation hampered. 尤其,用于齐格勒-纳塔催化剂的静电探针(所谓的常规静电探针,如上所述位于反应器壁上)不能有效在金属茂催化的反应和采用这种反应的反应器中提供结皮或结块的警告或通知。 In particular, for a Ziegler - Natta catalyst electrostatic probes (so called conventional static probes, located on the reactor wall as described above) in the reaction is not effective to provide a metallocene catalyzed reactor and employed in such reactions skinning and agglomeration warning or notification. 用常规反应器静电探针,金属茂催化剂的壁结皮和拱顶结皮通常在没有预先(或同时)指示的情况下发生。 A conventional reactor static probe, the wall of the metallocene catalyst and the dome crust crust usually no previously (or simultaneously) is the instruction occurs. 这可以在图7中看出,图7表明在中试装置中,与显示了响应(即,零以上的静电)的其它静电探针部位相比,在使用金属茂催化剂的壁结皮事件之前,(常规)反应器静电探针基本上没有响应。 This can be seen in FIG. 7, FIG. 7 shows that in the pilot plant, as compared with the display response (i.e., static above zero) to other parts of the electrostatic probes, using a metallocene catalyst in a wall before the event crust , (conventional) reactor static probe substantially no response.

[0020] 因此,有利的是,有这样一种采用金属茂催化剂的聚合方法,该方法能够连续操作,具有提高的反应器可操作性(定义为一般不存在可能导致反应器中断事件发生的结皮或结块)。 [0020] Thus, advantageously, there is a method of polymerization using metallocene catalysts, the process can be operated continuously with enhanced reactor operability (defined as the general absence may result in reactor discontinuity events junction Paper or agglomeration). 还非常有利的是,有这样一种基于容易测定的反应器条件例如反应器系统各个位置的静电活性的具有更稳定的催化剂生产率和减低的结垢/结皮倾向性的连续操作的聚合方法,其需要由本发明的实施方案来解决。 Also it is very advantageous, there is a condition readily determined based on reactor fouling of the polymerization process having more stable continuous operation to reduce the catalyst productivity and / skinning e.g. electrostatic propensity of the active position of the respective reactor system, which need to be addressed by the embodiments of the present invention. [0021] 概述 [0021] Overview

[0022] 属于设想的我们的发明的实施方案之列的是在聚合期间监测静电产生以避免或最大程度减少反应器中断事件的方法,所述方法包括:采用至少一个再循环管道静电探针或至少一个环形盘探针中的一个或多个测定携带静电。 [0022] belonging to the column of contemplated embodiments of our invention is to monitor during the polymerization method for producing electrostatic to avoid or minimize reactor discontinuity events, the method comprising: using at least one recirculation line static probe, or at least one annular disk probe assay, one or more electrostatically charged.

[0023] 另一个实施方案包括以防止或逆转由至少一种烯烃的聚合反应所产生的聚合物的结皮的量将至少一种连续性添加剂引入到反应器系统中的方法,其中该聚合反应在反应器系统中进行,该反应器系统包括流化床反应器、夹带区、用于引入能够生产聚合物的催化剂体系的催化剂进给装置、用于与催化剂混合物独立地引入至少一种连续性添加剂的连续性添加剂进给装置、用于监测夹带区中的静电活性水平的装置,该方法包括:让至少一种烯烃与催化剂体系在流化床反应器中在聚合条件下接触;在聚合反应开始之前、期间或之后的任何时间将连续性添加剂引入到反应器系统中;监测夹带区中的静电活性水平;以及调节引入到反应器系统中的连续性添加剂的量,以便将夹带区中的静电活性水平保持在0或接近0。 [0023] Another embodiment comprises an amount of the crust to prevent or reverse the polymer of at least one olefin polymerization produced at least one continuity additive into a reactor system, wherein the polymerization in a reactor system, the reactor system comprises a fluidized bed reactors, entrainment zone, a catalyst is capable of producing a polymer catalyst system for introducing the feed means, for separately introducing the catalyst mixture and the at least one continuity additives continuity additive feed means, means for monitoring levels of electrostatic activity in the entrainment zone, the method comprising: at least one olefin with the catalyst let the system under polymerization conditions in the fluidized bed reactor; the polymerization reaction before the start, during or at any time after the continuity additive into the reactor system; monitoring levels of electrostatic activity in the entrainment zone; and adjusting the amount of continuity additive introduced into the reactor system in order to entrainment region electrostatic activity levels remained at or near zero. 在这种方法中,催化剂体系包括金属茂或常规过渡金属催化剂,该方法可以是气相方法,并且连续生产聚合物,单体包括乙烯或乙烯和一种或多种a-烯烃。 In this method, the catalyst system comprises a metallocene or a conventional transition metal catalyst, the process may be a gas phase process, and the continuous production of polymers, monomers comprising ethylene or ethylene and one or more a- olefins. 在该方法中,催化剂体系包括金属茂催化剂体系,其中用于测定夹带区中的静电活性水平的装置包括至少一个再循环管道静电探针、至少一个环形盘探针、至少一个分配板静电探针或至少一个反应器上部静电探针中的一个或多个。 In this method, the catalyst system comprises a metallocene catalyst system, wherein the means for determining the level of electrostatic activity in the entrainment zone comprises at least one recirculation duct static probe, at least one annular disk probe, at least one distribution plate static probe or at least one or a plurality of upper reactor static probes. 至少一种连续性添加剂包括一种或多种选自烷氧基化胺、羧酸盐、聚砜类、聚合多胺、磺酸类或它们的组合中的化合物。 The at least one continuity additive comprises one or more compounds selected from alkoxylated amines, carboxylic acid salts, polysulfones, polymeric polyamines, sulfonic acids or combinations thereof. 或者至少一种连续性添加剂包括乙氧基化硬脂基胺,或者至少一种连续性添加剂包括硬脂酸铝,或者至少一种连续性添加剂包括油酸铝。 Or at least one continuity additive comprises ethoxylated stearyl amine, or the at least one continuity additive comprises aluminum stearate, or the at least one continuity additive comprises aluminum oleate. 或者至少一种连续性添加剂包括如下组分的混合物:以混合物的5_15wt%的浓度存在的1-癸烯-聚砜,以混合物的5_15wt%的浓度存在的N-牛油-1, 3_ 二氨基丙烷和表氯醇的反应产物,以混合物的5_15wt%的浓度存在的十二烷基苯磺酸, 以及以混合物的60-88衬%的浓度存在的烃溶剂。 Or at least one continuity additive comprises a mixture of the following components: In the presence of 1-decene concentration of the mixture 5_15wt% - polysulfone at a concentration 5_15wt% mixture of N- tallow present -1 diamino 3_ propane and the reaction product of epichlorohydrin, at a concentration present in the mixture 5_15wt% of dodecylbenzene sulfonic acid, and a hydrocarbon solvent at a concentration of 60-88% mixture of substrate present. 至少一种连续性添加剂间歇地引入,和/ 或至少一种连续性添加剂作为在烃液体中的淤浆或作为在烃液体中的溶液引入。 The at least one continuity additive is introduced intermittently, introducing and / or at least one continuity additive in a hydrocarbon liquid slurry in a hydrocarbon liquid or as a solution. 至少一种连续性添加剂还可以存在于经由催化剂进料引入到反应器系统中的催化剂混合物中,以及该至少一种连续性添加剂在流化床反应器中的量保持在l_50ppm的浓度,以在流化床反应器中生产的聚合物的重量为基准计。 The at least one continuity additive may also be present in the catalyst is introduced into the catalyst via the feed mixture in the reactor system, and in an amount of at least one continuity additive in the fluidized bed reactor is maintained at a concentration l_50ppm to the produced in a fluidized bed reactor based on the weight weight of the polymer.

[0024] 另一个实施方案包括一种聚合方法,所述方法包括:让乙烯和一种或多种a _烯烃在一种或多种金属茂催化剂的存在下在气相反应器中聚合;通过监测装置监测气相反应器中的静电活性;响应于偏离零或大约零的测量所述静电活性的监测装置,将有效量的一种或多种连续性添加剂应用于聚合方法中,以使该静电活性返回到零或大约零。 [0024] Another embodiment includes a polymerization process, the method comprising: Let ethylene and one or more A _ olefin polymerization in a gas phase reactor in the presence of one or more metallocene catalysts; by monitoring means for monitoring electrostatic activity in the gas phase reactor; in response to deviate from zero or about zero measuring means monitoring the electrostatic activity, an effective amount of one or more continuity additives is applied to the polymerization process, so that the electrostatic activity return to zero or approximately zero.

[0025] 所设想的另一个实施方案是气相聚合方法,其中减低或消除在气相反应器的夹带区中产生的静电活性,所述方法包括:让乙烯和一种或多种a-烯烃在金属茂催化剂体系的存在下聚合;采用至少一个再循环管道静电探针、至少一个床上部静电探针、至少一个环形盘静电探针或至少一个分配板静电探针中的一个或多个测定夹带区静电活性,前提是如果通过由一个或多个探针测定的静电活性偏离零,那么以有效减小或消除偏离零的有效量将一种或多种连续性添加剂加入到气相反应器中。 [0025] Another embodiment contemplated is a gas phase polymerization process, wherein the reducing or eliminating static electricity generated in the active region of the entrainment gas phase reactor, said method comprising: Let ethylene and one or more a- olefins metal polymerized in the presence of metallocene catalyst system; using at least one recirculation duct static probe, at least a portion of the bed static probe, at least one annular disk static probe or at least one distributor plate static probe in a plurality of measuring entrainment zone or electrostatic activity, if the proviso that deviate from zero by electrostatic activity measured by one or more probes, then the effective amount is effective to reduce or eliminate the deviation from zero of one or more continuity additives is added to the gas phase reactor.

[0026] 所设想的另一个实施方案是气相聚合方法,所述方法包括:在金属茂催化剂体系的存在下将乙烯和一种或多种a-烯烃在气相反应器中聚合;监测反应器中的静电活性,该监测包括至少一个常规静电探针、至少一个再循环管道静电探针、至少一个床上部静电探针、至少一个环形盘静电探针、至少一个分配板静电探针或它们的组合中的一个或多个; 其中由至少一个再循环管道静电探针、至少一个床上部静电探针、至少一个环形盘静电探针或至少一个分配板静电探针中的至少一个测定的静电活性与由常规静电探针测定的静电活性相差在士0. 5纳安培/cm2以上。 [0026] Another embodiment contemplated is a gas phase polymerization process, the method comprising: ethylene and one or more a- olefins in a gas phase polymerization reactor in the presence of a metallocene catalyst system; monitoring the reactor electrostatic activity, the monitoring comprises at least one conventional static probe, at least one recirculation duct static probe, at least a portion of the bed static probe, at least one annular disk static probe, at least one distributor plate static probe, or combinations thereof one or more; wherein the at least one recirculation duct static probe, at least a portion of the bed static probe, at least one measurement of at least one annular disk static probe or at least one distributor plate static probe electrostatic activity electrostatic activity measured by a conventional static probes differ in / cm2 or more persons 0.5 nanoamperes.

[0027] 所设想的另一个实施方案是在采用金属茂催化剂、活化剂和载体的气相反应器中将乙烯和一种或多种a -烯烃共聚的方法,所述方法包括:在金属茂催化剂、活化剂和载体的存在下将乙烯和1-丁烯、1-己烯或1-辛烯中的一种或多种混合;通过至少一个再循环管道静电探针、至少一个床上部静电探针、至少一个环形盘静电探针或至少一个分配板静电探针中的一个或多个监测反应器内的携带静电;通过使用选自烷氧基化胺、羧酸盐、聚砜类、聚合多胺、磺酸类或它们的组合的一种或多种中的至少一种连续性添加剂将携带静电保持在零或大约零,该至少一种连续性添加剂以10-40ppm的量存在于反应器中,以由聚合所生产的聚合物的重量为基准计。 [0027] Another embodiment contemplated is use of a metallocene catalyst, a gas phase reactor activator and support of ethylene and one or more of a - olefin copolymer, the method comprising: a metallocene catalyst , the presence of an activator and a carrier of the one or more mixed ethylene and 1-butene, 1-hexene or 1-octene; and by at least one recirculation duct static probe, at least a portion of the bed static probe needle, at least one annular disk static probe or at least one of the one or more dispensing electrostatically charged in the reactor was monitored plate electrostatic probes; by using the selected alkoxylated amines, carboxylic acid salts, polysulfones, polymeric polyamines, sulfonic acids, or combinations thereof of one or more of the at least one continuity additive will carry an electrostatic remain at zero or about zero, the amount of the at least one continuity additive present in the reaction 10-40ppm vessel, the weight of the polymer produced by the polymerization is basis.

附图说明 [0028] 图 1示出了典型气相反应器的示意图,显示了中试规模反应器上的测量仪位置。 BRIEF DESCRIPTION [0028] FIG. 1 shows a schematic of a typical gas phase reactor, the meter displays the position on a pilot scale reactor. [0029] 图 2示出了常规反应器静电探针的一个例子。 [0029] FIG 2 illustrates an example of a conventional reactor static probe. [0030] 图 3示出了至少一个再循环管道静电探针的实例。 [0030] FIG. 3 shows an example of the at least one recirculation conduit electrostatic probe. [0031] 图 4示出了XCAT™ EZ100拱顶结皮事件。 [0031] FIG. 4 shows a crust XCAT ™ EZ100 dome event. [0032] 图 5示出了XCAT EZ100的四件拱顶结皮事件。 [0032] FIG. 5 shows four dome XCAT EZ100 crust of events. [0033] 图 6示出了XCAT EZ100的分配板静电。 [0033] FIG. 6 shows the distribution plate electrostatic XCAT EZ100. [0034] 图 7示出了XCAT™ HP100的壁结皮事件。 [0034] FIG. 7 shows a wall XCAT ™ HP100 skinning event. [0035] 图 8示出了XCAT HP100的壁结皮事件的夹带静电。 [0035] FIG. 8 shows entrainment static XCAT HP100 wall skinning event. [0036] 图 9示出了XCAT HP100的表皮温度和添加剂流量。 [0036] FIG. 9 shows skin temperature and additive flow XCAT HP100. [0037] 图 10示出了XCAT HP 100的静电分布和添加剂流量。 [0037] FIG. 10 shows a distribution of electrostatic XCAT HP 100 and additive flow. [0038] 图 11示出了具有XCAT HP100的Octastat 3000®的表皮温度分布。 [0038] FIG. 11 shows a skin temperature of Octastat 3000® having XCAT HP100 distribution. [0039] 图 12示出了使用具有XCAT HP 100的Octastat 3000®的静电分布。 [0039] FIG. 12 shows a XCAT HP Octastat 100 having an electrostatic distribution of 3000®. [0040] 描述 [0041] 我们令人惊奇地发现,通过改变聚合反应器中实际测定的静电活性的位置(实际 [0040] Description [0041] We surprisingly found that, by changing the position of the electrostatic activity in the polymerization reactor actually measured (actual

测定单位面积的电流),我们能够检测和因此预防反应器中断事件例如结皮或结块的开始, 尤其对于用金属茂催化剂的聚合而言。 Measuring current per unit area), we can detect and therefore prevention of reactor discontinuity events such as skinning and agglomeration begins, especially for polymerization catalyst in terms of metallocene. 另外,我们能够稳定或消除反应器中断事件,这里定义为结皮、结块或结垢。 In addition, we were able to stabilize or eliminate reactor interrupt events, defined here as the crust, agglomeration or fouling. 尤其,我们已经发现对于气相聚合,大量的静电由在夹带的催化剂颗粒和/或夹带的树脂颗粒(如通常所理解的,所谓夹带的颗粒,我们是指不包含在反应器的密相区中并因此是在流化床的外部的那些颗粒)与壁和反应器再循环系统中的其它金属组分的摩擦接触所导致。 In particular, we have found that for gas phase polymerization, a large amount of static electricity from the catalyst particles entrained resin particles / or entrained (as is commonly understood, the so-called entrained particles we mean not contained in the dense phase zone of the reactor and it is thus external those particles) and the walls of the fluidized bed reactor and then the other metal components in frictional contact circulation system caused. 我们将该静电称为“携带静电”。 We refer to this electrostatic called "carry static electricity." 现在,在本发明的实施方案中通过发现和测定携带静电,解决了已知对金属茂催化剂而言的持久性问题(其中已知结皮和结块不能由常规反应器静电探针所预测)。 Now, in the embodiments of the present invention by discovering and measuring electrostatic carrying solve the problem of the known persistence for metallocene catalysts (where known skinning and agglomeration can not be predicted from the conventional reactor static probes) . 能够在本文所述的位置对该携带静电进行监测,并且使用常规手段或技术来加以控制,这进而减少、防止或消除了结皮、结块或结垢。 Described herein can be performed in a position to carry the said electrostatic monitored and be controlled using conventional means or techniques, which in turn reduce, prevent or eliminate skin settled, caking or fouling. [0042] 固体颗粒的摩擦带电(或摩擦生电)在文献中是公知的。 [0042] triboelectrically charged solid particles (or triboelectrification) are well known in the literature. 一般,在两种不同材料密切接触时,能够产生静电。 Generally, when two different materials in intimate contact, static electricity can be generated. 不同材料可以是两种不同金属(导体),两种不同绝缘体(典型例子是羊毛与琥珀棒),或者导体和绝缘体。 Different materials can be two different metals (conductors), two different insulators (a typical example wool amber rod), or a conductor and an insulator. 在气相聚合反应器的情况下,静电由聚乙烯树脂和催化剂颗粒(两种绝缘体)与反应器壁的碳钢(导体)的摩擦接触获得。 In the case of gas phase polymerization reactor, static electricity is obtained from a polyethylene resin and catalyst particles (of both insulators) frictional contact carbon steel (conductor) and the reactor wall.

[0043] 摩擦带电的基本驱动力是两种材料对电子的亲和力的不同。 [0043] The basic driving force of the friction materials charged are two different electron affinities. 具有较高亲和力的材料获得电子并带负电荷,另一种材料释放电子并带正电荷。 A material having a higher affinity gains electrons and negatively charged, another material liberate electrons and positively charged. 在固体颗粒与聚合反应器的壁、 管道或其它金属部件碰撞时,传递的电荷量取决于金属和颗粒的电性能、接触程度、表面粗糙度和其它因素。 When the solid particles collide with the walls, piping or other metal parts of a polymerization reactor, the amount of charge transferred depends on the electrical properties of the metal and the particles, the degree of contact, the surface roughness, and other factors. 气动输送领域中的研究已经表明,固体颗粒的摩擦生电对于输送气体的速度也是敏感的。 Study art pneumatic conveying have indicated that triboelectrification of solid particles is also sensitive to the speed of the conveying gas.

[0044] 所产生的电荷的量也对可能存在于与固体颗粒接触的反应器壁或其它金属部件的表面上的任何污染物敏感。 [0044] The amount of charge generated is also sensitive to any contamination that may exist on the surface of the reactor walls in contact with the solid particles or other metal member. 带电荷高度取决于可能存在于反应器内表面的任何树脂涂层的特性。 Height charged depending on the characteristics of any resin coating layer may be present in the surface of the reactor. 一般,当壁(理想地)涂有高电阻的聚乙烯时,减少了静电产生。 Generally, when the walls (desirably) coated with polyethylene of high electrical resistance, static electricity is reduced.

[0045] 已知的是,聚合反应器系统中的静电活性能够与聚合物结皮的形成和/或反应器的聚合物结垢以及所导致的聚合物生产的降低或中断(间断事件)相关。 [0045] It is known that electrostatic activity to reduce the polymer scale formation in a polymerization reactor system capable of skinning the polymer and / or reactor, and the resulting polymer production or interruption (discontinuity event) . 对这种静电活性的检测和讨论通常局限于反应器的流化床部分,即床的致密部分,通常在分配板以上直至分配板以上距离为反应器直径的大约3/4,或分配板以上反应器直径的1/4到3/4。 About 3/4, or the distribution plate and the fluidized bed section detects the electrostatic discussion of such activity is usually restricted to the reactor, i.e., the dense portion of the bed, generally above the distributor plate over a distance until the distribution plate of the reactor diameter above reactor diameter 1/4 to 3/4. 然而, 对于气相反应中的金属茂催化剂来说,常规的先前已知的静电探针常常不能有效预测反应器中断事件。 However, for metallocene catalysts in gas phase reactions, conventional previously known static probes often can not effectively predict reactor discontinuity event. 在金属茂催化的反应中,常规静电探针常常显示了很小或无静电活性(即使在结皮事件过程中)。 In the metallocene catalyzed reaction the conventional static probes frequently show little or no electrostatic activity (even in the event skinning process). 具体地说,虽然在反应器的夹带区中一个或多个静电探针显示了静电活性(我们现在知道它是反应器中断事件的预示),但常规静电探针常常显示了很小或无静电活性。 Specifically, although one or more electrostatic probe showed electrostatic activity in the entrainment zone of the reactor (we now know it is a reactor discontinuity event indicates), but conventional static probes often show little or no static active. 也已知这些问题在聚合物生产工艺过程中随时间而改变。 These problems are also known to change over time in the polymer production process. 在本发明的实施方案中,先前没有用于检测静电荷的监测静电电荷(通过电流/单位面积测定)和在反应器的夹带区中这样做的能力,使得可以动态调节所使用的连续性添加剂的量。 In an embodiment of the present invention, not previously used to detect static charge monitoring electrostatic charge (by current / unit area measured) and entrainment zone of the reactor capacity to do so in such continuity additive can be dynamically adjusted used amount. 也就是说,根据如由一个或多个非常规夹带区静电探针检测的反应器系统中的静电活性的水平调节连续性添加剂的量。 That is, the level of electrostatic activity in the reactor system, such as by one or more electrostatic probe for detecting the entrainment zone unconventional amount of continuity additive is adjusted. 术语静电活性、带静电和静电在这里可以互换使用。 The terms electrostatic activity, electrostatic charging, and static electricity may be used interchangeably herein. 当论述夹带区中的静电活性时,还用“携带静电”来表示。 When the discussion of electrostatic activity in the entrainment zone, also represented by "carrying static electricity."

[0046] 夹带区被定义为反应器系统的密相区以上或以下的任何区域。 [0046] The entrainment zone is defined as any region above the dense phase zone of the reactor system or less. 具有鼓泡床的流化容器包括两个区,一个致密鼓泡相,其具有将它与贫相或分散相隔开的上表面。 Bubbling fluidized bed comprising a vessel having two zones, a dense bubbling phase with an upper surface of which it is spaced apart from a lean or dispersed phase. 在致密床的(上)表面和排出气流(到再循环系统)之间的容器部分被称为“稀相区”。 In (a) a dense bed portion between the container surface and the exhaust gas stream (to the recycle system) is called "freeboard zone." 因此,夹带区包括稀相区,循环(再循环)气体系统(包括管道和压缩机/冷却器)和反应器的底部到分配板的顶部。 Therefore, the entrainment zone comprises a bottom freeboard zone, cycle (recycle) gas system (including piping and compressor / coolers) and the reactor to the top of the distribution plate. 在夹带区的任何地方测定的静电活性在这里被称为“携带静电”,照此,与通过流化床中的一个或多个常规静电探针测定的静电活性有差别。 Electrostatic activity in the entrainment zone at any place of measurement referred to herein as "electrostatically charged", as such, a difference with the electrostatic activity measured by a conventional fluidized bed or a plurality of electrostatic probes.

[0047] 我们已经令人惊奇地发现,在夹带区中在携带颗粒上的在“零或大约零”水平(如以上定义)以上的测定静电活性(携带静电)与结皮、结块或它们在聚合物反应系统中的开始相关,是与一个或多个“常规”静电探针测定的静电活性相比相关性更高的结皮或中断事件的指示。 [0047] We have surprisingly found that, in the region carrying the entrained in the "zero or about zero" level of particles (as defined above) than electrostatic activity measured (carrying electrostatic) with crust, agglomeration, or at the beginning of the relevant polymer in the reaction system, an electrostatic activity measured by one or more "normal" electrostatic probe as compared to the correlation indicative skinning or more interrupt events. 另外,已经发现监测夹带区中的携带颗粒的静电活性提供了反应器参数,由此可以动态调节连续性添加剂的量并获得最佳水平,以减少或消除中断事件。 Further, it has been found that particles carrying an electrostatic activity in the entrainment zone monitored reactor parameters is provided, whereby the amount of continuity additive can be dynamically adjusted and an optimum level obtained to reduce or eliminate the discontinuity event.

[0048] 如果夹带区中的静电活性水平的数量级在反应过程中增高,那么可以如进一步描述的那样相应调节反应器系统中的连续性添加剂的量。 [0048] If the number of levels of electrostatic activity in the entrainment zone increases in stages during the reaction, it can be adjusted accordingly as the amount of reactor system of continuity additives as further described.

[0049] 静电探针[0050] 在这里被描述为在夹带区中的静电探针包括下列的一个或多个:至少一个再循环管道静电探针;至少一个环形盘探针;至少一个分配板静电探针;或至少一个反应器上部静电探针,后者是在该一个或多个常规探针的分配板以上1/4到3/4反应器直径高度之外或以上。 [0049] The electrostatic probe [0050] In the electrostatic probes described herein in the entrainment zone comprise one or more of the following: at least one recirculation duct static probe; at least one annular disk probe; at least one distribution plate electrostatic probe; or at least one upper reactor static probe, which is above the distribution plate of the one or more conventional probes than 1/4 to 3/4 reactor diameter height or more. 这些探针可以单独或与来自以上提及的每一组中的一个或多个其它探针一起来测定夹带静电。 Such probes may be used alone or with a group from each of the above-mentioned one or more other measured entrainment static probes together. 图1示出了在本发明的实施方案中使用所述仪器的一些主要部位。 Figure 1 illustrates some of the major parts of the apparatus used in an embodiment of the present invention. 这些仪器包括如本文所述的在流化床中的一个或多个常规静电检测器(“常规反应器静电探针”)。 These instruments include a fluidized bed of one or more conventional electrostatic detectors as described herein ( "conventional reactor static probe").

[0051] 图2示出了常规反应器静电探针的一个实例。 [0051] FIG 2 illustrates an example of a conventional reactor static probe. 该一个或多个探针测定作为颗粒冲击结果(通过催化剂和/或树脂)的从探针顶端流过的电流。 The one or more probes as measurement result of particle impact (by the catalyst and / or resin) flows from the tip of the probe current. 来自探针顶端的测定电流(每单位面积)提供了总体上在反应器壁上发生的电荷传递的估计值。 Measured from the tip of the probe current (per unit area) provides an estimate of the value of the charge transfer generally occurs in the reactor wall. 探针顶端有效地代表了已经装备了仪器用于测定电荷流动的反应器壁的部分。 Effectively represent the probe tip has been equipped with some of the instruments for measuring the reactor wall charges flowing. 这些检测器的探针顶端以及本文所述的所有其它探针可以由任何导体制成,包括碳钢,铁,不锈钢,钛,钼,镍,Monel®合金,铜,铝,或者它们可以是双金属(其中一种金属形成了芯,另一种金属形成了表皮或表层)。 All other probes and probe distal herein these detector may be made of any conductor, including carbon steel, iron, stainless steel, titanium, molybdenum, nickel, Monel® alloys, copper, aluminum, or they may be bis metal (wherein the core is formed of a metal, another metal forming a surface layer or skin). 在US6,008, 662中提供了常规静电探针的进一步说明。 In US6,008, 662 are provided to further illustrate a conventional static probe.

[0052] 用常规反应器探针测定的典型电流水平是士0. 1-10,或士0. 1-8,或士0. 1_6,或士0. 1-4,或士0. 1-2纳安培/cm2。 [0052] Typical current levels measured with the conventional reactor probes is 0. 1-10 persons, or persons 0. 1-8 0. 1_6 or persons, or 0. 1-4 persons, or persons 0. 1- 2 nanoamperes / cm2. 与本文所述的所有电流测量值一样,这些值通常也是在本文所述的时间段内的平均值,还有,它们可以代表均方根值(RMS),在该情况下,它们全部是正值。 As with all current measurements described herein, these values ​​are generally an average value of the time period described herein, as well, they may represent root mean square value (the RMS), in which case, all of them are positive value. 然而,最通常的是,在采用金属茂催化剂的反应器中,常规反应器探针在结皮事件的开始或中期记录零或大约零。 However, most typically, in a reactor using metallocene catalysts, the conventional reactor probes skinning or interim recording start event zero or about zero. 所谓零或大约零,我们是指常规静电反应器探针以及夹带区中的探针的值彡士0.5,或彡士0.3,或彡士0. 1,或彡士0. 05,或彡士0. 03,或彡士0.01, 或彡士0. 001或0纳安培/cm2。 The so-called zero or about zero, we mean the value of a conventional reactor static probe and the entrainment zone probes San 0.5 persons, or persons San 0.3, 0.1 or San persons, or persons San 0.05, or San disabilities 0.03, 0.01, or San persons, or persons San 0 nanoamperes or .001 / cm2. 例如,-0. 4的测量值是“小于” “士0. 5”,+0. 4的测量值同样如此。 For example, measurements -0. 4 is "less than" "Disabled 0.5", measured value + 0.4 of the same.

[0053] 如本文的其它地方所指出的,常规静电探针可以记录零或大约零的静电或电流(如本文定义的),而夹带区的至少一个部位的至少一个其它静电探针可以记录高于由常规静电探针测定的静电活性或电流(在金属茂催化剂的情况下,常规静电探针最有可能是零或大约零)。 [0053] As noted elsewhere herein, the conventional static probe may record zero or approximately zero static or current (as defined herein), while at least a portion of at least one additional entrainment zone static probes can record high electrostatic activity measured by a conventional current or electrostatic probe (in the case of metallocene catalysts, the conventional static probes is most likely to be zero or approximately zero). 在该情况下,如果在由常规静电探针测定的电流和由一个或多个其它(非常规)静电探针测定的电流之间的差彡士0.1,或彡士0.3,或彡士0.5纳安培/cm2或更高, 要采取行动来减少或消除在一个或多个夹带区探针的检测中的静电荷。 In this case, if the difference between the current measured by the conventional static probe and the current generated by one or more other (non-conventional) electrostatic probe for the determination of the persons San 0.1, 0.3 or San persons, or persons San 0.5 is satisfied amperes / cm2 or higher, to take action to reduce or eliminate the electrostatic charge detection in one or more of the entrainment zone probes. 这种行动可以是添加至少一种连续性添加剂(或至少一种连续性添加剂在反应器中的存在量的净增加),或减小催化剂进料速率,或减小气体通过速度,或它们的组合。 Such action may be addition of at least one continuity additive (or a net increase of at least one continuity additive in the reactor in an amount of), or decreasing the feed rate of the catalyst, or by reducing the gas velocity, or a combination. 这些行动构成了保持携带静电和反应器静电在零或大约零、减小或消除携带静电和反应器静电的手段。 These actions constitute the reactor to maintain and carry an electrostatic electrostatic at zero or approximately zero, reducing or eliminating the means to carry static electricity and electrostatic reactor.

[0054] 再循环管道静电探针 [0054] Electrostatic recirculation duct probe

[0055] 至少一个再循环管道静电探针可以位于再循环管道的任何部位,即从反应器顶部的再循环管道的进口到反应器底部的再循环管道的出口。 Any portion of [0055] the at least one recirculation duct static probe may be located in the recirculation line, i.e. from the inlet of the recirculation line to the top of the reactor recirculation outlet conduit reactor's bottom. 这包括从反应器顶部的再循环管道进口到冷却器或压缩机(它们可以在空间上彼此互换),在冷却器和压缩机之间,在冷却器或压缩机之后,在冷却器或压缩机和反应器底部的再循环管道出口之间。 This comprises an inlet from the top of the reactor recirculation line to the cooler or compressor (which may be interchanged spatially with one another), between the cooler and compressor, after the cooler or compressor, or compressed in a cooler recirculation conduit and the bottom of the machine between the outlet of the reactor. 对于至少一个再循环管道静电探针,我们设想了在一个或多个部位的1、2、3、4、5、6、7、8、9、10或更多个的这些再循环管道静电探针。 For at least one recirculation duct static probe, we assume these recirculation pipes electrostatic probe or a plurality of locations of 1,2,3,4,5,6,7,8,9,10 or more in needle.

[0056] 图3示出了至少一个再循环管道静电探针的实施方案。 [0056] FIG. 3 illustrates at least one embodiment of the recirculation line static probe. 在该实施方案中的探针顶端可以是碳钢棒(或如本文所述的其它材料),且其可以大约延伸到再循环管道的中心。 In this embodiment, the probe tip may be a carbon steel rod (or other materials as described herein) and may extend approximately to the center of the recirculation conduit. 此外,至少一个再循环管道探针可以与再循环管道壁成任何角度或与再循环管道壁垂直。 Further, at least one recirculation duct probe may be at any angle or perpendicular to the wall with the recirculation duct and the recirculation duct wall. 此外,至少一个再循环管道探针可以延伸至再循环管道内0. 1-0.90,或0.2-0.80, 或0. 3-0. 7D,或0. 4-0. 6D,或0. 5D,其中D是再循环管道的内径。 Further, at least one recirculation duct probe may extend into the recirculation line 0.5 1-0.90, or 0.2-0.80, or 0. 3-0. 7D, or 0. 4-0. 6D, or 0. 5D, where D is the inner diameter of the recirculating conduit. 当再循环气体和夹带的固体颗粒(树脂和/或催化剂/载体颗粒)流过探针时,一些固体颗粒撞击该棒并转移电荷。 When the recycle gas and entrained solid particles (resin and / or catalyst / support particles) flow through the probe, some of the solid particles strike the rod and transfer charge. 来自至少一个再循环管道静电探针的电流可以是士0-50纳安培/cm2,或士0.01-25, 或士0. 01-20,或士0. 1-15,或士0. 1-10,或士0. 1-7. 5,或士0. 1-5. 0,或士0. 1-2. 5,或士0. 1-1. 5,或士0. 1-1. 0 纳安培/cm2。 Current from the at least one recirculation duct static probe may be persons 0-50 nanoamperes / cm2, or 0.01 to 25 persons, or persons 01-20 0., 0. 1-15 or persons, or persons 0. 1- 10, or 0. 1-7 persons. 5, or persons 0. 1-5. 0, 0.5, or 1-2 persons. 5, or 0. 1-1 persons. 5, or 0. 1-1 persons. 0 nanoamperes / cm2.

[0057] 环形盘静电探针 [0057] The annular disk static probe

[0058] 至少一个环形盘静电探针可以位于环形盘上的任何位置,或与环形盘水平,所述环形盘为气体和/或液体和/或夹带的固体颗粒的料流(在相对高的速度下)流动通过环形开口提供了入口。 [0058] at least one annular disk static probe may be located anywhere on the annular disc or annular disc level, the annular disc is a gas and / or liquid and / or entrained stream of solid particles (at a relatively high the speed) through the annular inlet opening is provided. 探针的顶端可以突出到环形开口内达0. 1-0.90,或0.2-0.80,或0. 3-0. 7D,或0. 4-0. 6D,或0. 5D的距离,其中D是环形盘的内径。 The probe tip may protrude into the annular opening of 0.5 1-0.90, or 0.2-0.80, or 0. 3-0. 7D, or 0. 4-0. 6D, or from 0. 5D, wherein D is the inner diameter of the annular discs. 我们设想了1、2、3、4、5、 6、7、8、9、10或更多个的这些环形盘静电探针。 We envision a 1,2,3,4,5, 6,7,8,9,10 or more of these annular disk static probe. 探针顶端必须通过绝缘材料来安装,以便防止在探针顶端和环形的金属表面(和反应器壁)之间的电接触。 Probe tip must be mounted by insulating material so as to prevent electrical contact between the probe tip and the annular surface of the metal (and the reactor walls). 来自至少一个环形盘静电探针的电流可以是士0-50纳安培/cm2,或士0.01-25,或士0.01-20,或士0. 1_15,或 At least one annular disk static probe current may be from 0-50 persons nanoamperes / cm2, or 0.01 to 25 persons, or 0.01 to 20 persons, or persons 0. 1_15, or

士0. 1-10,或士0. 1-7. 5,或士0. 1-5. 0,或士0. 1-2. 5,或士0. 1-1. 5,或士0. 1-1. 0 纳安培 0. 1-10 persons, or persons 0. 1-7. 5, or persons 0. 1-5. 0, 0.5, or 1-2 persons. 5, or 0. 1-1 persons. 5, or persons 0 1-1. 0 nanoamperes

/ 2 /cm ο / 2 / cm ο

[0059] 床上部静电探针 [0059] bed static probe portion

[0060] 至少一个床上部静电探针在反应器中的位置可以高于常规静电探针的上限(等于反应器直径的3/4倍的在分配板以上的距离),或通常等于反应器直径的0. 8、或0. 9或1.0倍的距离及以上的距离,直至反应器的垂直壁接触反应器的锥体部分的位置。 [0060] at least a portion of the bed static probe position in the reactor may be higher than the upper limit of a conventional static probe (equal to 3/4 times the reactor diameter distance above the distributor plate), or generally equal to the diameter of the reactor of 0.8, or 1.0, or 0.9 times the distance from and above, until the position of the cone portion of the vertical contact reactor wall of the reactor. 我们设想了1、2、3、4、5、6、7、8、9、10或更多个的床上部静电探针。 We envision 1,2,3,4,5,6,7,8,9,10 or more of the bed of the electrostatic probe. 来自至少一个床上部静电探针的电流可以是士0-50 纳安培/cm2,或士0. 01-25,或士0. 01-20,或士0. 1-15,或士0. 1-10,或士0. 1-7. 5,或士0. 1-5. 0,或士0. 1-2. 5,或士0. 1-1. 5,或士0. 1-1. 0 纳安培/cm2。 Current from the at least a portion of the bed static probe may be persons 0-50 nanoamperes / cm2, or 0. 01-25 persons, or persons 01-20 0., 0. 1-15 or persons, or persons 0.1 -10, or 0. 1-7 persons. 5, or persons 0. 1-5. 0, 0.5, or 1-2 persons. 5, or 0. 1-1 persons. 5, or 0. 1-1 persons 0 nanoamperes / cm2.

[0061] 分配板静电探针 [0061] The distributor plate static probe

[0062] 至少一个分配板静电探针,还称之为分配板帽,代表测量携带静电的另一种方式。 [0062] at least one distributor plate static probe, also called a distribution plate cap, represents the measured electrostatic another way of carrying. 至少一个分配板探针包括置于分配板中的一个或多个孔以上的金属帽。 At least one distributor plate probe comprises more than one distribution plate disposed in a plurality of holes or metal cap. 这些帽与分配板绝缘,并且通过电缆连接于电流计。 The insulation cap and the distribution plate, and connected to a current meter by a cable. 至少一个探针测定由于催化剂和/或树脂细粒对所述一个或多个金属帽的冲击所导致的电流转移。 Measuring at least one probe current transfer since the catalyst and / or resin fine particles to impact one or more of the resulting metal cap. 分配板静电探针(帽)可以由碳钢或如上所述的其它导体制成,以模拟在分配板上的所有其它(没有装配仪器)帽上所发生的电荷转移。 Distributor plate static probes (caps) may be made of carbon steel or other conductors as described above, to simulate the charge in all the other distribution plate (not equipped with the instrument) the transfer cap occurring. 理想地,这些分配板探针(帽)由与分配板和帽相同的材料制成。 Ideally, these distributor plate probes (caps) and the distribution plate is made of the same material as the cap. 2002年12月26日提交白勺、2004$ 7 @ 8 H Measurement and Detection in a GasPhase Polyethylene Reactor,,的US公开20040132931提供了可用于测定携带静电的分配板静电探针的附加细节。 December 26, 2002 filed white spoon, 2004 $ 7 @ 8 H Measurement and Detection in a GasPhase Polyethylene Reactor ,, the US public 20,040,132,931 provides additional details it can be used to assign static probe assay plates carry the static electricity. 我们设想了1、2、3、4、5、6、7、8、9、10或更多个的这些分配板静电探针。 We envision 1,2,3,4,5,6,7,8,9,10 or more of these distribution plate electrostatic probe. 至少一个分配板探针所测定的电流可以是士0-50纳安培/cm2,或士0. 01-25,或士0. 01-20, 或士0. 1-15,或士0. 1-10,或士0. 1-7. 5,或士0. 1-5. 0,或士0. 1-2. 5,或士0. 1-1. 5,或士0. 1-1. 0 纳安培/cm2。 At least one current distributor plate probe may be measured Disabled 0-50 nanoamperes / cm2, or 0. 01-25 persons, or persons 01-20 0., 0. 1-15 or persons, or persons 0.1 -10, or 0. 1-7 persons. 5, or persons 0. 1-5. 0, 0.5, or 1-2 persons. 5, or 0. 1-1 persons. 5, or 0. 1-1 persons 0 nanoamperes / cm2.

[0063] 在夹带区的任何部位上的这些静电探针的任何一个可以用作决定反应器中断事件的开始或存在的静电探针,或在每一个位置上的一个或多个(再循环管道、环形盘、床上部和/或分配板静电探针)可以与在另一部位上的一个或多个联合使用,起这种决定性作用。 [0063] The static probes in any portion of any entrained zone may be used as a decision to start or interrupt the reactor static probe in the presence of an event, or one or more (recycle conduit at a position on each , an annular disk, the bed and / or distributor plate static probes) may be used in combination with one or more of the other sites, which play a decisive role. 所述静电探针还可以单独发挥作用,即如果在一个位置上的一个探针开始记录到静电活性,那么可以采取行动(如在以下所指出的)通过添加连续性添加剂来减小或消除电荷, 或者在一种或多种连续性添加剂已经存在于反应器中的情况下(例如,由于与催化剂一起进给),那么可以通常通过除了催化剂进料以外的另一进料来添加另外的连续性添加剂。 The electrostatic probe alone may also play a role, that is, if one probe in a position to start recording the electrostatic activity, then action can be taken (as indicated below) by addition of continuity additive to reduce or eliminate the charge or, in the case where one or more continuity additives are already present in the reactor (e.g., due to a feed with the catalyst), it may generally be added through another feed than the catalyst feed addition further continuous additives.

[0064] 用于监测反应器系统中的静电活性的方式通过如本领域已知或如本文所述的静电探针来提供。 Embodiment [0064] for monitoring electrostatic activity in the reactor system known in the art such as electrostatic or probe as described herein is provided by. 这种静电探针包括金属探针顶端,一个或多个信号线,电连接线(feed-through),和测量仪器。 Such static probes include a metallic probe tip, one or more signal lines, electrical connection lines (feed-through), and measuring instruments. 探针顶端可以包括圆柱形棒,但可以是任何横断面形状例如正方形、长方形、三角形或椭圆形。 Probe tip may comprise a cylindrical rod, but can be any cross sectional shape such as square, rectangular, triangular or oval. 至于材料,探针顶端可以是如这里所述的任何导体。 As for the material, the probe tip may be any conductor as described herein. 至于信号线,可以使用任何常规绝缘线。 As for the signal line, any conventional insulated wire may be used. 至于电连接线,可以使用任何适合的连接线,只要它提供了与地面(和反应器壁)的必要电绝缘,并且提供了所需的压力密封来防止高压反应器气体从反应器中漏出。 As for electrical connecting lines, using any suitable connecting lines, as long as it provides the necessary electrically insulated from the ground (and the reactor walls), and provides the required pressure seal to prevent leakage of high pressure reactor gases from the reactor. 适合的电连接线可以从Conax Buffa Io Corp.和其它供应商那里购买到。 Suitable electrical connections can be purchased from Conax Buffa Io Corp. and other suppliers to.

[0065] 至于监测静电探针的读数,可以使用能够测量从探针顶端到地面的电流的任何仪器或设备。 [0065] As for the electrostatic probe monitoring readings, may be used in any instrument or device capable of measuring the current from the probe tip to the ground. 适合的仪器包括安培计、皮可安培计(高灵敏度安培计)、万用表或静电计。 Suitable instruments include an ammeter, a picoammeter (a high sensitivity ammeter), a multimeter, or electrometer. 还可以间接地通过测量由通过串联电阻器的电流所产生的电压来监测测定电流。 It may also be monitored indirectly by measuring the voltage generated by the current through the series resistor measuring the current. 在该情况下的电流通过欧姆定律I = V/R由测定的电压来测定,其中I是电流(安培),V是测定电压(伏特)和R是电阻(欧姆)。 In this case, the current through Ohm's law I = V / R is determined from the measured voltage, where I is the current (amperes), V is the measured voltage (volts) and R is the resistance (ohms). 如在US 6,008,662中所指出的,串联电阻器的值可以是1 欧姆到4X1011欧姆,基本上不影响所获得的电流读数的值。 As pointed out in US 6,008,662, a series resistor may be from 1 ohm to a value 4X1011 Ohm, does not substantially affect the value of the current readings obtained.

[0066] 处理电流水平的方法 [0066] The method of process current level

[0067] 本领域的那些技术人员会认识到,可以有许多处理来自静电探针的电流信号的方法。 [0067] Those skilled in the art will recognize that there are many method for processing a signal from the current static probe. 这些方法包括简单加权平均,用平均10毫秒到10小时,或10秒到10小时,或30秒到5小时,或1分钟到1小时,或1分钟到1/2小时,或1分钟到10分钟的时间。 These methods include simple weighted averaging, with an average of 10 milliseconds to 10 hours, 10 hours, or 10 seconds, or 30 seconds to 5 hours, or 1 minute to 1 hour, or 1 minute to 1/2 hour, or 1 minute to 10 time minutes. 另外或作为替代方案,可对所述信号进行处理,以提供基本电流信号的均方根(RMS)导数,基本电流信号的标准偏差,基本电流信号的绝对值,或基本电流信号的绝对值的平均(采用上述平均时间)。 Additionally or alternatively, it may process the signals, the absolute value of the basic current signal to provide a root mean square (RMS) derivative, the standard deviation of the basic current signal, an absolute value of the basic current signal, or the basic current signal The average (time average of the above).

[0068] 连续性添加剂 [0068] The continuity additive

[0069] 当以上刚讨论过的一个或多个静电探针开始记录到高于或低于零的静电活性(分别定义为高于或低于“零或大约零”)时,应该采取措施降低该水平或使静电活性水平返回到零或大约零,我们已经指出这会防止、减小或消除反应器中断事件。 [0069] When the one or more static probes discussed immediately above begin to record the electrostatic activity above or below zero, (defined as above or below the "zero or about zero"), the measures should be taken to reduce the level of electrostatic activity level or to return to zero or about zero, we have already pointed out that this would prevent, reduce or eliminate reactor discontinuity event. 所考虑的措施包括添加一种或多种连续性添加剂。 Measures contemplated include addition of one or more continuity additives. 这种添加可具有提高连续性添加剂在反应器中的水平的效果(如果已经存在一定水平的话)。 This addition may have the effect of increasing the level of continuity additive in the reactor (if it already exists a certain level). 存在于反应器中的一种或多种连续性添加剂的总量一般不超过250或200,或150,或125或100或90或80,或70,或60,或50,或40,或30,或20或10ppm(所要生产的聚合物的重量百万分率)和/或连续性添加剂的量是基于所要生产的聚合物的重量的0,或大于1,或3,或5,或7,或10,或12,或14,或15,或17或20ppm(通常按单位时间的磅数或千克数来表示)。 Present in the reactor in one or more of the total amount of continuity additives is generally no more than 250 or 200, or 150, or 125 or 100 or 90 or 80, or 70, or 60, or 50, or 40, or 30 or 10 ppm (by weight of the polymer to be produced per million), and / or the amount of continuity additives is 20 or 0 based on the weight of the polymer to be produced, or greater than 1, or 3, or 5, or 7 , or 10, or 12, or 14, or 15, or 17 or 20ppm (generally represented by the number of pounds or kilograms per unit time). 任何这些下限可与任何上限组合。 Any of these lower limits can be combined with any upper limit. 这些连续性添加剂的量考虑了一种、两种、三种、四种或更多种连续性添加剂,一种或两种或多种连续性添加剂在反应器中的总量将被认为是所有以上公开的来自于任何来源的添加剂。 These amounts contemplates a continuity additive, the total amount of two, three, four or more continuity additives, one or two or more continuity additives in the reactor will be considered in all the above disclosed additive from any source. 连续性添加剂可以通过专用的给料管道直接加入到反应器中,和/或加入到任何适当的原料流中,包括乙烯原料流,共聚单体原料流,催化剂进料管道,或再循环管道。 It can be added through a dedicated continuity additive feed pipe directly to the reactor, and / or to the feed stream in any suitable, including ethylene feed stream, the comonomer feed stream, the catalyst feed conduit, or recirculation line. 如果使用一种以上的连续性添加剂,每一种可以作为单独的原料流加入到反应器中,或者作为单独原料流或混合物的任何组合加入到反应器中。 If more than one continuity additive, each of which may be added as a separate feed stream into the reactor, or as a separate feed stream, or any combination of mixture added to the reactor. 将连续性添加剂加入到反应器中的方式不是重要的,只要添加剂在流化床内充分分散,以及它们的进料速率(或浓度)以提供如上文所述的最低携带静电水平的方式调节。 The continuity additive added to the reactor in such a manner is not critical, as long as the additive is well dispersed within the fluidized bed, and their feed rates (or concentrations) to provide a level above the lowest carrying an electrostatic manner hereinbefore described adjustment.

[0070] 我们设想,以上所述的连续性添加剂的总量可包括来自任何来源的连续性添加齐U,例如随催化剂加入的连续性添加剂,在专用的连续性添加剂管道中加入的连续性添加齐U,在任何再循环物料中含有的连续性添加剂,或它们的组合。 [0070] We envisage, above the total amount of continuity additive may comprise from any source continuity added together U, for example with the addition of the continuity additive catalyst is added in a dedicated continuity additive added continuity conduit Qi U, continuity additive contained in any recycle material, or in a combination thereof. 在一个实施方案中,一部分的连续性添加剂作为预防措施在可测到任何静电活性之前加入到反应器中,在这种情况下,当一个或多个静电探针记录了高于“零或大约零”水平的静电活性时,增加连续性添加剂以使记录到静电活性的该一个或多个探针返回到零或大约零。 In one embodiment, a portion of the continuity additive can be measured as a preventive measure in any electrostatic activity added to the reactor before, in this case, when one or more of the above records an electrostatic probe "or approximately zero when electrostatic activity in the zero "level, so that the continuity additive to increase one or more probes to the electrostatic recording activity return to zero or about zero.

[0071] 也在本发明的实施方案的范围内的是,在催化剂混合物中引入至少一种连续性添加剂,再将该催化剂混合物(含有至少一种连续性添加剂)注入到反应器系统中;另外或作为替代方案,经由专用连续性添加剂进料管道、与催化剂混合物独立地将至少一种连续性添加剂引入到反应器系统中,使得将足够浓度的该至少一种连续性添加剂引入到反应器中以防止或消除反应器中断事件。 Within the scope of the embodiments [0071] Also according to the present invention are, introducing at least one continuity additive in the catalyst mixture, the catalyst mixture (containing at least one continuity additive) injected into the reactor system; Further or alternatively, via a dedicated continuity additive feed line, the catalyst mixture is independently at least one continuity additive introduced into the reactor system, such that a sufficient concentration of the at least one continuity additive is introduced into the reactor in order to prevent or eliminate a reactor discontinuity event. 可以采用这些给料方案的任何一种或这两种。 Any of these feed schemes or both may be employed. 在催化剂/连续性添加剂混合物中的连续性添加剂和经由单独的连续性添加剂进料管道添加的连续性添加剂可以是相同或不同的。 And continuity additives continuity additive in the catalyst / continuity additive mixture was added via the separate continuity additive feed line may be the same or different.

[0072] 进给到反应器系统的最佳连续性添加剂进料速率的确定由如本文所规定的零或大约零的携带静电值来加以证明。 [0072] fed to determine the optimal continuity additive feed rate to the reactor system by carrying the electrostatic value of zero or about zero as defined herein to be proved. 例如在稳定反应器中的携带静电读数后,如果添加附加(即更高)量的连续性添加剂,以及如果反应器的夹带区中的一个或多个静电探针显示了静电读数的增高,那么这是已经超过最佳连续性添加剂水平的定性指示。 After stabilization, for example, reactors carrying electrostatic readings, if adding additional (i.e. higher) the amount of continuity additive, and if one of the entrainment zone of the reactor or more static probes show increased static readings, then this is a qualitative indication of continuity additives has been exceeded the optimum level. 在该情况下,应该降低连续性添加剂的水平,直到再次达到静电活性的稳定(如由一个或多个静电探针的相对稳定的静电活性读数所指示的),或者将静电活性降低至大约零或恢复到零。 In this case, the level of continuity additive should be lowered until it reaches a stable static activity (as indicated by one or more of the relatively stable electrostatic activity readings from the static probe) again, or to reduce static activity to approximately zero or return to zero. 因此,动态调节连续性添加剂的量以达到最佳浓度范围是所希望的,并且在本发明的实施方案的范围内。 Thus, dynamically adjusting the amount of continuity additive to reach the optimum concentration range is desirable and are within the scope of the embodiments of the present invention. 所谓最佳浓度在这里是指有效量。 The so-called optimum concentration herein refers to an amount effective. 因此,有效量的至少一种连续性添加剂是减小或消除如由一个或多个静电探针所测定的静电荷或静电荷获得稳定的量。 Thus, an effective amount of at least one continuity additive is reduced or eliminated, such as by one or more electrostatic probes or measuring electrostatic charge amount of stable electrostatic charge. 因此,如本文所指出的,如果添加太多的连续性添加剂,静电荷将重新出现;这种连续性添加剂的量被认为在有效量范围之外。 Thus, as noted herein, if you add too much continuity additive, the electrostatic charge will reappear; the amount of such continuity additives are considered outside the range of an effective amount.

[0073] 适用于本发明的连续性添加剂包括一种或多种选自烷氧基化胺、羧酸盐、聚砜类、 聚合多胺和磺酸类中的化合物。 [0073] adapted to include one or more compounds selected from alkoxylated amines, carboxylic acid salts, polysulfones, polymeric polyamines and sulfonic classes of continuity additive in the present invention.

[0074] 连续性添加剂可以包括乙氧基化硬脂基胺。 [0074] The continuity additive may comprise ethoxylated stearyl amine. 可从ICI及其分支机构商购的乙氧基化硬脂基胺以商标ATMER 163供应,可从Witco ChemicalCompany商购的另一种乙氧基化硬脂基胺以商标AS 990供应。 Can be supplied from ICI and its affiliates 990 commercially available ethoxylated stearyl amine supplied under the trademark ATMER 163 commercially available from Witco ChemicalCompany another ethoxylated stearylamine the trademark AS.

[0075] 其它适合的连续性添加剂包括硬脂酸铝和油酸铝。 [0075] Other suitable continuity additives include aluminum stearate and aluminum oleate. 还有一些其它适合的连续性添加剂以商标0CTASTAT和STADIS (这些被认为是相同或类似的化学物质)在市场上供应和/或在US专利No. 5,026, 795中描述并可从Octel Starreon购得。 Still other suitable continuity additives and 0CTASTAT trademark STADIS (these are considered the same or similar chemical substance) supply and / or 795 described in US Pat. No. 5,026 on the market and available from Octel Starreon purchased.

[0076] 在另一个实施方案中,连续性添加剂可以是上述2种或更多种连续性添加剂的混合物。 [0076] In another embodiment, the continuity additive may be a mixture of two or more of the above-described continuity additives. 这种混合物可以包括:烷氧基化胺和羧酸盐;或烷氧基化胺和聚砜类;或烷氧基化胺和聚合多胺;或烷氧基化胺和磺酸类;或羧酸盐和聚砜类;或羧酸盐和聚合多胺;或羧酸盐和磺酸类;或聚砜类和聚合多胺;或聚砜类和磺酸类;或聚合多胺和磺酸类。 Such mixtures may include: alkoxylated amines and carboxylic acid salts; or alkoxylated amines and polysulfones; or alkoxylated amines and polymeric polyamines; or alkoxylated amines and sulfonic acids; or carboxylates and polysulfones; or carboxylates and polymeric polyamines; and sulfonic acids or carboxylate; or polysulfones and polymeric polyamines; or polysulfones and sulfonic acids; sulfonic or polymeric polyamine, and acids. 另外,我们考虑了烷氧基化胺、羧酸盐和聚砜类;或烷氧基化胺、聚合多胺和磺酸类;或羧酸盐、聚砜和聚合多胺;或羧酸盐、磺酸类和聚砜类;烷氧基化胺、羧酸盐和聚合多胺;烷氧基胺、羧酸盐和磺酸盐;烷氧基胺、聚砜类和磺酸类;烷氧基胺、聚合多胺和聚砜类;聚砜类、聚合多胺和磺酸类;羧酸盐、聚合多胺和磺酸类。 Further, we consider the alkoxylated amines, carboxylic acid salts and polysulfones; or alkoxylated amines, polymeric polyamines and sulfonic acids; or salts of carboxylic acids, polysulfones and polymeric polyamines; carboxylates or , sulfonic acids and polysulfones; alkoxylated amines, carboxylic acid salts and polymeric polyamines; alkoxy amines, carboxylates and sulfonates; alkoxy amines, polysulfones and sulfonic acids; alkyl alkoxy amines, polymeric polyamines and polysulfones; polysulfones, polymeric polyamines and sulfonic acids; carboxylates, polymeric polyamines and sulfonic acids. 四种或更多种的这些连续性添加剂的组合也被考虑。 The combination of these four or more continuity additives are also contemplated thereof. 这些组合物可以以10 : 90-90 : 10,或25 : 75-75 : 25,或40 : 60-60 : 40,或50 : 50的比率合并,或者在三种连续性添加剂的情况下,以10 : 10 : 80-80 : 10 : 10 或10 : 80 : 10的比率合并。 These compositions may be 10: 90-90: 10, or 25: 75-75: 25, or 40: 60-60: 40, or a 50: 50 ratio of the combined, or the case where three kinds of the continuity additive, combined ratio of 10: 10: 10: 80-80: 10: 10 or 10: 80 这些连续性添加剂的绝对量如上所述。 The absolute amount of these continuity additives as described above.

[0077] 用于本发明的实施方案的另外的连续性添加剂包括如下组分的混合物:以混合物的5-15wt%的浓度存在的1-癸烯-聚砜,以混合物的5-15wt%的浓度存在的N-牛油-1, 3_ 二氨基丙烷和表氯醇的反应产物,以混合物的5-15wt%的浓度存在的十二烷基苯磺酸, 以及以混合物的60-88wt %的浓度存在的烃溶剂,该混合物可以商标0CTASTAT3000 (还可以作为STADIS 450 获得)或0CTASTAT 200 (还可以作为STADIS 425)从Octel Starreon 及其分支机构商购,它们各自可以具有与以上刚讨论过的那些不同的百分率组成。 [0077] Further embodiments of the continuity additives used in the present invention comprises a mixture of the following composition: a concentration of 5-15wt% of a mixture of 1-decene is present - polysulfone to 5-15wt% of a mixture of present in a concentration of N- tallow-1, the reaction product 3_ diaminopropane and epichlorohydrin, at a concentration of 5-15wt% of a mixture of dodecylbenzene sulfonic acid present, as well as mixtures of 60-88wt% present at a concentration of hydrocarbon solvent, the mixture may mark 0CTASTAT3000 (also obtained as STADIS 450) or 0CTASTAT 200 (also as STADIS 425) from Octel Starreon and its affiliates commercially available, each of which may have just those discussed above different percentage composition.

[0078] 如果采用连续性添加剂的组合物,存在于反应器中的全部量如上所述。 [0078] If continuity additive composition is present in the whole amount in the reactor as described above.

[0079] 催化剂 [0079] Catalyst

[0080] 包括常规过渡金属催化剂和金属茂催化剂或它们的组合的所有聚合催化剂适合在本发明的方法的实施方案中使用。 [0080] Conventional transition metal catalysts include metallocene catalysts, and combinations thereof, or all of the polymerization catalysts suitable for use in embodiments of the method of the present invention. 还可以考虑诸如AlCl3、钴、铁、钯、铬/氧化铬或“菲利普”催化剂之类的催化剂。 It can also be considered a catalyst such as AlCl3, cobalt, iron, palladium, chromium / chromium oxide or "Phillips" catalyst or the like. 以下是可用于本发明的各种聚合催化剂的非限制性论述。 The following are non-limiting discussion of the present invention can be used in various polymerization catalysts.

[0081] 一般定义 [0081] General definitions

[0082] 如本文所使用的短语“催化剂体系”包括至少一种“催化剂组分”和至少一种“活化剂”,或者至少一种助催化剂。 [0082] As used herein, the phrase "catalyst system" includes at least one "catalyst component" and at least one "activator", or at least one cocatalyst. 催化剂体系还可以包括其它组分,例如载体,并且不限于单独或结合的催化剂组分和/或活化剂。 The catalyst system may also include other components, such as carriers and is not limited to the catalyst component alone or in combination and / or activators. 催化剂体系可以包括任何如本文所述的任意组合的许多催化剂组分,以及任何如本文所述的任意组合的活化剂。 The catalyst system may include any of a number of catalyst components in any combination as described herein, as well as any combination of any of the herein activators.

[0083] 本文所使用的短语“催化剂化合物”包括一旦被适当活化,能够催化烯烃的聚合或低聚的任何化合物,该催化剂化合物包括至少一个3-12族原子,以及任选的键接于其上的 [0083] As used herein, the phrase "catalyst compound" includes Once suitably activated, the polymerization can be any compound or olefin oligomerization catalyst, the catalyst compound comprising at least one Group 3 to 12 atoms, and optionally bonded thereto Up

至少一个离去基团。 At least one leaving group.

[0084] 本文所使用的短语“离去基团”是指能够用活化剂从催化剂组分上夺取,因此形成具有烯烃聚合或低聚活性的物质的键接于催化剂组分的金属中心的一个或多个化学结构部分。 [0084] The phrase "leaving group" as used herein refers to a component capable of abstracting from the catalyst with an activating agent, thereby forming a metal center with an olefin polymerization or oligomerization active substance bonded to the catalyst component or more chemical moieties. 在以下进一步对活化剂进行描述。 Activators are described further below.

[0085] 关于元素的周期表“族”,采用如在CRC HANDBOOK OF CHEMISTRYAND PHYSICS (David R. Lide ed.,CRC Press 81st ed. 2000)中的周期表的“新”编号方案。 [0085] with respect to the elements of the periodic table, "family", such as the use of "new" numbering scheme (2000 David R. Lide ed., CRC Press 81st ed.) Of the periodic table in the CRC HANDBOOK OF CHEMISTRYAND PHYSICS.

[0086] 本文所使用的“烃基”包括缺少一个氢的包括碳和氢的脂族、环状、烯属、炔属和芳族基团(即烃基)。 [0086] As used herein, "hydrocarbyl" includes the lack of a hydrogen, aliphatic, cyclic, olefinic, acetylenic and aromatic radicals (i.e., hydrocarbon group) include carbon and hydrogen. “亚烃基”缺少两个氢。 "Alkylene" is missing two hydrogen.

[0087] 本文所使用的短语“杂原子”包括能够键接于碳的除了碳和氢以外的任何原子。 [0087] As used herein, the phrase "heteroatom" includes any atom can be bonded to a carbon other than carbon and hydrogen. “含杂原子的基团”是含有杂原子并且可以含有一个或多个相同或不同杂原子的烃基。 "Heteroatom-containing group" is a heteroatom and may contain one or more identical or different hetero atoms plurality of hydrocarbon. 在一个实施方案中,含杂原子的基团是含有1-3个选自硼、铝、硅、锗、氮、磷、氧和硫中的原子的烃基。 In one embodiment, a heteroatom-containing group is a hydrocarbon group of 1 to 3 atoms selected from boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen and sulfur contained. 含杂原子的基团的非限制性实例包括亚胺类、胺类、氧化物、膦类、醚类、酮类、oxoazolines杂环、噁唑啉类和硫醚类基团。 Non-limiting examples of heteroatom-containing groups include imines, amines, oxides, phosphines, ethers, ketones, oxoazolines heterocyclyl, oxazolines, and thioethers group.

[0088] 如本文所使用的“杂环”是指具有包含1-3个选自硼、铝、硅、锗、氮、磷、氧和硫中的原子的碳骨架的环体系,除非杂原子(非碳原子)被说明。 [0088] The "heterocyclic" as used herein refers to groups having 1 to 3 comprising selected from boron, carbon backbone atoms of aluminum, silicon, germanium, nitrogen, phosphorus, oxygen and sulfur in a ring system, unless the heteroatom (non-carbon atom) is described.

[0089] 本文所使用的“烷基羧酸根”、“芳基羧酸根”和“烷芳基羧酸根”分别是在任何位置具有羧基的烷基、芳基和烷芳基。 [0089] As used herein, "alkyl carboxylate", "aryl carboxylate" and "alkaryl carboxylates" are an alkyl group having a carboxyl group in any position, aralkyl and alkaryl groups. 实例包括C6H5CH2C(O)O-, CH3C(O)O-等。 Examples include C6H5CH2C (O) O-, CH3C (O) O- and the like.

[0090] 本文所使用的术语“取代”是指在该术语之后的基团具有代替任何位置的一个或多个氢的至少一个结构部分,该结构部分选自诸如卤素基(尤其Cl,F,Br),羟基,羰基,羧基,胺基,膦基,烷氧基,苯基,萘基,C1-Cltl烷基,C2-Cltl链烯基以及它们的组合之类的基团。 [0090] As used herein, the term "substituted" means having at least one moiety in place of one or more hydrogens in any position of the group following the term moiety is selected from the group such as halo (especially Cl, F, br), a hydroxyl group, a carbonyl group, a carboxyl group, amine, phosphino, alkoxy, phenyl, naphthyl, C1-Cltl alkyl, C2-Cltl alkenyl groups, and combinations thereof and the like. 取代的烷基和芳基的实例包括但不限于酰基,烷基氨基,烷氧基,芳氧基,烷硫基,二烷基氨基,烷氧基羰基,芳氧基羰基,氨基甲酰基,烷基氨基甲酰基和二烷基氨基甲酰基,酰氧基, 酰基氨基,芳基氨基,以及它们的组合。 Examples of substituted alkyl and aryl groups include, but are not limited to, acyl, alkylamino, alkoxy, aryloxy, alkylthio, dialkylamino, alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, alkylcarbamoyl and carbamoyl, acyloxy, acylamino, arylamino, dialkylamino, and combinations thereof.

[0091] 除非另有规定,本发明的任何实施方案在这里不限于如以下在各个描述和实施例中所定义的金属原子“M”的氧化态。 [0091] Unless otherwise specified, any of the embodiments of the invention herein is not limited to metal atoms in the following description of various embodiments and defined in "M" oxidation state.

[0092] 金属茂催化剂组分 [0092] The metallocene catalyst component

[0093] 可用于本发明的实施方案的催化剂体系包括如本文所述的至少一种金属茂催化剂组分。 The catalyst system [0093] may be used in embodiments of the present invention include, for example at least one metallocene catalyst component as described herein. 例如,金属茂催化剂化合物在1&2METALL0CENE-BASED P0LY0LEFINS (John Scheirs & W. Kaminsky eds. , John Wiley & Sons, Ltd. 2000) ;GG Hlatky,181 C00RDINATI0NCHEM. REV. 243-296(1999)以及特别是用于合成聚乙烯的金属茂催化剂化合物在1 METALLOCENE-BASED P0LY0LEFINS 261-377(2000)中被总体描述。 For example, the metallocene catalyst compound 1 & 2METALL0CENE-BASED P0LY0LEFINS (John Scheirs & W. Kaminsky eds, John Wiley & Sons, Ltd. 2000.);.. GG Hlatky, 181 C00RDINATI0NCHEM REV 243-296 (1999) and in particular for the metallocene catalyst compounds are generally described in the synthesis of polyethylene in (2000) in 1 mETALLOCENE-BASED P0LY0LEFINS 261-377. 如在本文中所述的金属茂催化剂化合物包括具有键接于至少一个3-12族金属原子的一个或多个Cp配体(环戊二烯基和与环戊二烯基同构(isolobal)的配体)以及键接于该至少一个金属原子的一个或多个离去基团的“半夹心”和“全夹心”化合物。 As described herein, the metallocene catalyst comprises a compound having bonded to at least one or more of a Group 3 to 12 metal atom Cp ligands (cyclopentadienyl and cyclopentadienyl isomorphic (the isolobal) ligands) and bonded to at least one of the "half sandwich" and "full sandwich" compounds having one or more metal atom leaving group. 下文中,这些化合物被称为“金属茂”或“金属茂催化剂组分”。 Hereinafter, these compounds are referred to as "metallocenes" or "metallocene catalyst components." 在一个实施方案中,金属茂催化剂组分担载于载体材料上,并且可以与或不与另一催化剂组分一起担载。 In one embodiment, the metallocene catalyst component supported on a carrier material, and may not be supported with or in conjunction with another catalyst component.

[0094] Cp配体是一个或多个环或环体系,它的至少一部分包括π键接的体系,如环二烯基配体和杂环类似物。 [0094] Cp ligands are one or more rings or ring system, which comprises at least a portion of the π-bonded systems, such as cycloalkadienyl ligands and heterocyclic analogues. 该环或环体系通常包括选自13-16族原子中的原子,或者组成Cp 配体的原子选自碳,氮,氧,硅,硫,磷,锗,硼和铝以及它们的组合,其中碳占环原子的至少50%。 The ring or ring system generally comprising atoms selected from Groups 13 to 16 atoms, or constituent atoms selected from carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum and combinations Cp-ligands thereof, wherein at least 50% carbon ring atoms. 或者,Cp配体选自取代和未取代的环戊二烯基配体和与环戊二烯基同构的配体,它们的非限制性实例包括环戊二烯基,茚基,芴基和其它结构。 Alternatively, Cp ligand is selected from substituted and unsubstituted cyclopentadienyl ligand and a cyclopentadienyl ligand homogeneous, non-limiting examples thereof include cyclopentadienyl, indenyl, fluorenyl group and other structures. 这些配体的进一步非限制性实例包括环戊二烯基,环戊并菲基,茚基,苯并茚基,芴基,八氢芴基,环辛四烯基,环戊并环十二碳烯,菲啶基,3,4-苯并芴基,9-苯基芴基,8-Η-环戊并苊基(acenaphthylenyl),7H- 二苯并芴基,茚并[1,2-9]蒽烯,噻吩并茚基,噻吩并芴基,它们的氢化变型(例如4,5,6,7_四氢茚基,或“H4Ind”),它们的取代变型,以及它们的杂环变型。 Further non-limiting examples of these ligands include cyclopentadienyl, cyclopentyl and phenanthryl, indenyl, benzoindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentyl and cyclododecyl carbene, phenanthridine, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-Η- cyclopenta acenaphthyl (acenaphthylenyl), 7H- dibenzofluorenyl, indeno [1,2 -9] anthrene, thieno indenyl, fluorenyl and thienyl, hydrogenated versions thereof (e.g. 4,5,6,7_ tetrahydroindenyl, or "H4Ind"), substituted versions thereof, and their hetero ring modifications.

[0095] 含15族原子的催化剂组分 [0095] Group 15-containing catalyst component of

[0096] 本发明的一个方面包括单独或与金属茂或其它烯烃聚合催化剂组分一起使用所谓的“含15族原子”的催化剂组分作为理想的催化剂组分。 One aspect of the [0096] present invention include, alone or with a metallocene or other olefin polymerization catalyst component used with the catalyst component a so-called "Group 15 atom-containing" catalyst components as desired. 通常,这里提到的“含15族原子的催化剂组分”包括3-12族金属配合物,其中金属是2-8配位的,该一个或多个配位结构部分包括至少两个15族原子,和至多4个15族原子。 Generally, "Group 15-containing catalyst component of" referred to herein include Group 3-12 metal complexes, where the metal is coordinated to 2-8, the one or more ligand moiety comprises at least two Group 15 atoms, and up to four group 15 atoms. 在一个实施方案中,含15族原子的催化剂组分是4族金属和1-4个配体的配合物,使得4族金属是至少2配位的,该一个或多个配位结构部分包括至少两个氮。 In one embodiment, the Group 15-containing catalyst component is a Group 4 metal complex of ligands and 1-4, such that the Group 4 metal is at least 2 bits with the one or more ligands comprising a moiety at least two nitrogens. 代表性含15族原子的化合物例如公开在WO 99/01460 ;EP A10893454 ;EP A10894005 ;US 5,318,935 ;US 5,889,128,US6, 333,389B2 和US 6,271,325B1 中。 Representative Group 15-containing compounds, for example, disclosed in WO 99/01460; EP A10893454; EP A10894005; US 5,318,935; US 5,889,128, US6, 333,389B2, and in US 6,271,325B1.

[0097] 在一个实施方案中,可用于本发明的实施方案的含15族原子的催化剂组分包括具有任意程度的烯烃聚合活性的4族亚氨基-苯酚配合物,4族双(氨基)配合物,和4族吡啶基-氨基配合物。 The catalyst component [0097] In one embodiment, can be used in embodiments of the present invention containing a Group 15 atoms include any olefin having a degree of polymerization activity Group 4 imino - phenol complexes, Group 4 bis (amino) complexes thereof, and group 4 pyridyl - amino complexes.

[0098] 活化剂 [0098] Activator

[0099] 本文所使用的术语“活化剂”被定义为担载或非担载的任何化合物或化合物的组合,它们例如能够通过由催化剂组分产生阳离子物质而活化单中心催化剂化合物(例如金属茂,含15族原子的催化剂)。 [0099] As used herein, the term "activator" is defined as any compound or combination of compounds of supported or unsupported, which can be, for example, a single-site catalyst compound activated by creating a cationic species from the catalyst component (e.g., metallocene , group 15-containing catalysts). 通常,这涉及从催化剂组分的金属中心那里夺取至少一个离去基团(以上通式/结构式中的X基团)。 Typically, this involves from the metal center of the catalyst component wrest at least one leaving group (the above formula / X group in the structural formula). 本发明的实施方案的催化剂组分因此使用此类活化剂活化,用于烯烃聚合。 Catalyst component of the present invention is therefore the use of such activators activated for olefin polymerization. 这些活化剂的实例包括路易斯酸如环状或低聚的聚(氧化烃基铝)和所谓的非配位活化剂(“NCA”)(或者,“电离活化剂”或“化学计量活化剂(stoichiometricactivator)”),或能够将中性金属茂催化剂组分转化为具有烯烃聚合活性的金属茂阳离子的任何其它化合物。 Examples of such activators include Lewis acids such as cyclic or oligomeric poly (hydrocarbylaluminum oxide) and so called non-coordinating activators ( "NCA") (or, "ionizing activators" or "stoichiometric activators (stoichiometricactivator ) "), or can be a neutral metallocene catalyst component is converted to any other compound of the olefin polymerization activity with metallocene cation.

[0100] 在本发明范围内的是,使用路易斯酸如铝氧烷(例如“ΜΑΟ”),改性铝氧烷(例如“ΤΙΒΑ0”),和烷基铝化合物作为活化剂,和/或使用电离活化剂(中性或离子)例如四(五氟苯基)硼三(正丁基)铵和/或三全氟苯基硼准金属前体,以活化本文所述的金属茂。 [0100] within the scope of the present invention, the use of Lewis acids such as alumoxane (e.g., "ΜΑΟ"), modified alumoxane (e.g., "ΤΙΒΑ0"), and alkylaluminum compounds as activators, and / or ionizing activators (neutral or ionic) such as tetrakis (pentafluorophenyl) boron, tri (n-butyl) ammonium before and / or trisperfluorophenyl boron metalloid precursor, to activate the metallocenes described herein. MAO和其它铝基活化剂在本领域中是公知的。 MAO and other aluminum-based activators are well known in the art of. 电离活化剂在本领域中是公知的, 例如由Eugene You-Xian Chen 禾口Tobin J. Marks,在Cocatalystsfor Metal-Catalyzed Olefin Polymerization :Activators,Activation Processes,and Struc ture-Activity RelationshipslOO (4) CHEMICAL REVIEWS 1391-1434(2000)中进行过描述。 Ionizing activators in the present art is well known, for example Eugene You-Xian Chen Wo port Tobin J. Marks, in Cocatalystsfor Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Struc ture-Activity RelationshipslOO (4) CHEMICAL REVIEWS 1391 -1434 been described (2000). 如GregoryG. Hlatky,在Heterogeneous Single-Site Catalysts for OlefinPolymeriza tion 100(4) CHEMICAL REVIEWS 1347-1374(2000)中所述的,所述活化剂可以与载体缔合或结合,这要么与催化剂组分(例如金属茂)一起,要么与催化剂组分分开进行。 The GregoryG. Hlatky, in Heterogeneous Single-Site Catalysts for OlefinPolymeriza tion 100 (4) CHEMICAL REVIEWS 1347-1374 in the (2000) according to the activator may be associated or combined with a carrier, which catalyst component is either ( e.g. metallocene) together, or separately from the catalyst component.

[0101] 齐格勒-纳塔催化剂组分 [0101] Ziegler - Natta catalyst component

[0102] 催化剂组合物包括属于(或包括)非金属茂化合物的催化剂组分。 [0102] The catalyst composition include those belonging to (or includes) a non-metallocene compound catalyst component. 在一个实施方案中,该催化剂组分包括齐格勒-纳塔催化剂化合物,例如在ZIEGLER CATALYSTS 363-386 (G. Fink, R. Mulhaupt 禾口HH Brintzinger, eds. , Springer-Verlag 1995);或EP 103120 ;EP 102503 ;EP 0231102 ;EP 0703246 ;RE 33,683 ;US 4, 302, 565 ;US5, 518, 973 ; US 5,525,678 ;US 5,288,933 ;US 5,290,745 ;US 5,093,415 和US 6,562,905 中公开的化合物。 In one embodiment, the catalyst component comprises a Ziegler - Natta catalyst compounds, for example, in ZIEGLER CATALYSTS 363-386 (G. Fink, R. Mulhaupt Wo port HH Brintzinger, eds, Springer-Verlag 1995.); Or EP 103120; EP 102503; EP 0231102; EP 0703246; RE 33,683; US 4, 302, 565; US5, 518, 973; US 5,525,678; US 5,288,933; US 5,290,745; US 5,093,415 and the compounds disclosed in US 6,562,905. 此类催化剂的实例包括那些包含如下组分的催化剂:4、5或6族过渡金属氧化物、醇盐和卤化物,或者钛、锆或钒的氧化物、醇盐和卤化物;任选与镁化合物、内和/或外电子给体(醇,醚,硅氧烷等),烷基铝或烷基硼和烷基卤化物,和无机氧化物载体结合。 Examples of such catalysts include those catalysts comprising the following components: a Group 4, 5 or 6 transition metal oxides, alkoxides and halides, or titanium, zirconium or vanadium oxides, alkoxides and halides; and optionally a magnesium compound, internal and / or external electron donors (alcohols, ethers, siloxanes, etc.), an alkyl aluminum or boron alkyl and alkyl halides, and inorganic oxide carrier.

[0103] 常规类型的过渡金属催化剂是本领域公知的那些传统齐格勒_纳塔催化剂。 [0103] The conventional-type transition metal catalysts are those known in the art _ Traditional Ziegler Natta catalysts. 常规类型的过渡金属催化剂的实例在US专利Nos. 4,115,639,4,077,904,4,482,687,4,564,60 5,4,721,763,4,879,359和4,960,741中有述。 Examples of conventional-type transition metal catalysts in US Patent Nos. 4,115,639,4,077,904,4,482,687,4,564,60 5,4,721,763,4,879,359 and 4,960,741 there is described. 可以在本发明中使用的常规类型的过渡金属催化剂化合物包括元素周期表的3-17族,或4-12族,或4-6族的过渡金属化合物。 Conventional-type transition metal catalyst compounds may be used in the present invention include Group 3-17 of the periodic table, or a Group 4-12, or a Group 4-6 transition metal compound.

[0104] 这些常规类型的过渡金属催化剂可以用通式MRx来表示,其中M是3-17族金属,或4-6族金属,或4族金属,或钛;R是卤素或烃氧基;以及χ是金属M的化合价。 [0104] These conventional-type transition metal catalysts may be represented by the formula MRx, where M is a Group 3-17 metal, or a Group 4-6 metal, metal, or 4, or titanium; R is halo, or alkoxy; and χ is the valence of the metal M. R的实例包括烷氧基,苯氧基,溴离子,氯离子和氟离子。 Examples of R include alkoxy, phenoxy, bromide, chloride and fluoride ions. 其中M是钛的常规类型的过渡金属催化剂的实例包括TiCl4, TiBr4, Ti (OC2H5) 3C1,Ti (OC2H5) Cl3, Ti (OC4H9) 3C1,Ti (OC3H7) 2C12,Ti (OC2H5) 2Br2, TiCl 3. 1/3A1C13 和Ti (OC12H25) Cl3O Wherein M is an instance of titanium conventional-type transition metal catalysts include TiCl4, TiBr4, Ti (OC2H5) 3C1, Ti (OC2H5) Cl3, Ti (OC4H9) 3C1, Ti (OC3H7) 2C12, Ti (OC2H5) 2Br2, TiCl 3 . 1 / 3A1C13 and Ti (OC12H25) Cl3O

[0105] 可用于本发明实施方案的基于镁/钛电子给体配合物的常规类型的过渡金属催化剂化合物例如在US专利No S. 4,302,565和4,302,566中有述。 [0105] may be used in embodiments of the present invention are described for example in US Patent No S. 4,302,565 and 4,302,566 based on magnesium / titanium electron-donor complexes of conventional-type transition metal catalyst compounds thereof. 还考虑了由Mg/Ti/Cl/ THF衍生的催化剂,它们是本领域的那些普通技术人员所公知的。 Also contemplated by the catalyst Mg / Ti / Cl / THF are derived, which are those of ordinary skill in the art. 制备这种催化剂的一般方法的一个例子包括以下步骤:将TiCl4溶于THF中,使用Mg将该化合物还原为TiCl3,添加MgCl2,再除去溶剂。 Examples of a general method for preparing such a catalyst comprising the steps of: TiCl4 in THF, the use of the compound is reduced to TiCl3 was Mg, add MgCI2, and remove the solvent.

[0106] 用于上述常规类型的过渡金属催化剂化合物的常规类型的助催化剂化合物可以用通式M3M4vX2。 [0106] a conventional type used for the above conventional-type transition metal catalyst compound cocatalyst compounds can be represented by the formula M3M4vX2. R\_。 R \ _. 表示,其中M3是元素周期表的1-3和12-13族的金属;M4是元素周期表的1族金属;ν是0-1的数值;各X2是任何卤素;c是0-3的数值;各R3是单价烃基或氢;b 是1-4的数值;和其中bc是至少1。 , Where M3 is a metal of the Periodic Table and Group 1-312-13; M4 is a metal of the Periodic Table of Elements; v is a value of 0-1; each X2 is any halogen; C is 0-3 value; each R3 is a monovalent hydrocarbon radical or hydrogen; B is a number from 1 to 4; and wherein bc is at least 1. 用于上述常规类型的过渡金属催化剂的其它常规类型的有机金属助催化剂化合物具有通式M3R3k,其中M3是ΙΑ、IIA、IIB或IIIA族金属,例如锂,钠,铍,钡,硼,铝,锌,镉和镓;k等于1、2或3,取决于M3的化合价,该化合价进而通常取决于M3所属的特定的族;以及各R3可以是包括烃基和含有13-16族元素如氟、铝或氧或它们的组合的烃基的任何单价基团。 Other conventional-type transition metal catalysts of the above conventional-type organometallic cocatalyst compounds having the general formula M3R3k, wherein M3 is ΙΑ, IIA, IIB or IIIA metal, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium, and gallium; K equals 1, 2 or 3, depending on the valency of M3 which valency in turn normally depends upon the particular group M3 belongs; and each R3 may be a hydrocarbyl group containing a group 13-16 element such as fluorine, a hydrocarbyl aluminum or oxygen or any combination thereof monovalent group.

[0107] MA [0107] MA

[0108] 聚合可以采用以上催化剂以及选自乙烯和一种或多种从1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯或1-癸烯中选择的α -烯烃中的单体进行。 [0108] With the above polymerization catalyst, and may be selected from one or more of ethylene and 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene or 1-decene selected of α - olefins monomers.

[0109] 为了更好地理解本发明,提供与在本发明的实施中进行实际试验有关的以下实施例: [0109] For a better understanding of the present invention, there is provided the actual test in the embodiment of the present invention is related to the following Example:

[0110] 实施例 [0110] Example

[0111] 本文所述的聚合反应在内径0. 57米和床高4. 0米的连续中试规模气相流化床反应器中进行。 [0111] The polymerization reactions described herein the inner diameter 0.57 m and 4.0 m high bed in a continuous pilot-scale gas phase fluidized bed reactors. 该流化床由聚合物颗粒组成。 The fluidized bed consisting of polymer particles. 乙烯和氢气的气体原料流与液体共聚单体一起在混合T形装置内混合,并在反应器床以下引入到再循环气体管道内。 With ethylene and hydrogen gas feed stream with the liquid comonomer in the T-shaped mixing device for mixing, and introduced into the reactor in the recycle gas duct below the bed. 采用己烯作为共聚单体。 Using hexene as comonomer. 控制乙烯、氢气和共聚单体的各自流量以保持固定组成目标。 Controlling ethylene, hydrogen and comonomer are each composed of a fixed flow rate to maintain a target. 控制乙烯浓度以保持恒定的乙烯分压。 Ethylene concentration controlled to maintain a constant ethylene partial pressure. 控制氢气以保持恒定的氢气与乙烯摩尔比。 Controlling the hydrogen to maintain a constant hydrogen to ethylene mole ratio. 通过在线气相色谱仪测定所有气体的浓度以确保相对恒定的再循环气流的组成。 The concentrations of all the gases was measured by on-line gas chromatograph to ensure relatively constant composition in the recycle stream.

[0112] 使用提纯的氮气作为载体将固体催化剂直接注入到流化床中。 [0112] using purified nitrogen as a carrier for the solid catalyst is injected directly into the fluidized bed. 调节它的速率以保持恒定的生产速率。 Adjust its speed to maintain a constant production rate. 通过让补充原料和再循环气体连续流过反应区而使生长聚合物颗粒的起反应的床保持在流化状态。 Supplementary materials and by having a continuous flow of recycle gas through the reaction zone of the growing polymer particles of the reactive bed is maintained in a fluidized state. 使用0.6-0. 9米/秒的表观气体速度来达到该目的。 Use superficial gas velocity 0.6-0. 9 m / second to achieve the object. 反应器在2170kPa的总压力下工作。 Reactor was operated at a total pressure of 2170kPa. 为了保持恒定的反应器温度,连续上调或下调再循环气体的温度以适应由于聚合导致的产热速率的任何改变。 To maintain a constant reactor temperature, the temperature of the continuous upward or downward from the recycle gas to accommodate any changes in the rate of heat generation due to the polymerization.

[0113] 通过以等于颗粒产物形成速率的速率排出床的一部分而使流化床保持在恒定高度(4.0米)。 [0113] withdrawing a portion of the bed of particles by a rate equal to the rate of product formation in the fluidized bed is maintained at a constant height (4.0 meters). 产物形成速率(聚合物生产速率)在50-70kg/h的范围内。 Rate of product formation (the polymer production rate) is in the range 50-70kg h /. 产物经由系列阀门半连续地排放到固定容积的腔室内,同时还回排放到反应器中。 The product semi-continuously via a series of valves to discharge a fixed volume chamber, and also discharged back into the reactor. 这使得可以高度有效地排出产物,同时将大部分的未反应的气体再循环到反应器中。 This makes it possible to highly efficiently discharged product, while most of the unreacted gas is recycled to the reactor. 将该产物吹扫,以除去夹带的烃类并用小股湿化氮气蒸汽处理,以钝化任何痕量的残留催化剂。 The product was purged to remove entrained hydrocarbons and treated with humidified nitrogen shares a small steam treatment, to inactivate any remaining traces of the catalyst. [0114] 图1是中试规模流化床反应器和静电测量仪器的大致位置的示意图。 [0114] FIG. 1 is a schematic view of the approximate location of the pilot-scale fluidized bed reactor and an electrostatic measuring instrument.

[0115] 来自静电探针的读数以电流的形式测定。 [0115] readings from the static probe is measured as a current. 该电流通过Keithley6517A型静电计(以电流方式工作)测定。 This current is measured by Keithley6517A type electrometer (operating in current mode). 同时采用6517A型静电计中的扫描卡收集多个探针的数据。 While using the data type 6517A electrometer probe scanning a plurality of card collection. 每一探针的数据以125个读数/秒的速度收集,每6秒报告平均值。 Each probe data at a rate of 125 readings / second collection, reporting average every 6 seconds. 作为替代方案,将所述探针连接于专用Keithley 485型皮可安培计。 Alternatively, the probe type is connected to a dedicated Keithley 485 picoammeter. 在该替代情况下,每一个静电探针连续连接于该计量表,该表每5秒钟报告电流的“点”或瞬时值。 In this alternative case, each of the electrostatic probe is continuously connected to the metering table that "point" every 5 seconds or instantaneous value of the current report. 两种类型的电流计报告的数据在计算机日志中记录,并用于产生如图4-7所示的曲线。 Data reported galvanometer two types of records in a computer log, and used to generate the curve shown in Figure 4-7.

[0116] 图4示出了在中试规模气相反应器上由Univation Technologies, LLC在市场上供应的金属茂催化剂XCAT EZ 100的拱顶结皮事件。 [0116] FIG. 4 shows on a pilot-scale gas phase reactor by a Univation Technologies, metallocene catalyst, XCAT EZ LLC supplied in the market dome skinning event 100. 在该图的顶部的六条描记线(trace) 示出了拱顶内的表层热电偶读数(壁温度)。 At the top of the figure six traces (the trace) shows skin thermocouple readings (wall temperatures) in the dome. 如本领域所公知的那样,结皮(和在该情况下拱顶结皮)用表层热电偶读数的快速增高(或尖峰)来表示。 As it is well known in the art as the crust (crust and dome in this case) with a rapid increase skin thermocouple readings (or spike) below. 在拱顶结皮事件之前,再循环管道静电读数显示了急剧升高,随后突然下降。 Before vault event crust, electrostatic recirculation line readings show a sharp rise, followed by a sudden drop. 测定的输送(再循环)管道静电的下降被认为是从该反应器转移出的固体的速率下降的结果。 Descending transporting (recycling) pipe static measurement is believed to result from the decrease rate of the reactor is transferred out of the solid. 固体转移速率下降似乎与拱顶结皮的形成一致。 The solid appears to decrease the transfer rate consistent with the formation of crusts dome.

[0117] 图5示出了在中试规模气相反应器上用XCAT EZ 100金属茂催化剂的4个连续拱顶结皮事件。 [0117] FIG. 5 shows four successive dome event crust with XCAT EZ 100 metallocene catalyst on the pilot-scale gas phase reactor. 在该图顶部的六条描记线示出了拱顶内的表层热电偶读数。 In the top six traces shown in FIG skin thermocouple readings vault. 相应的刻度在右边显示。 The corresponding scale is displayed on the right. 拱顶结皮由表层热电偶读数的快速升高(或尖峰)来表示。 Rapidly rises from the surface crust dome thermocouple readings (or spike) below. 四个事件的每一个形成了大小足以堵塞产物排放口和干扰流化的拱顶结皮。 Each of sufficient size to plug the formation of a product discharge port and interfere with fluidization dome skinning four events. 在四个事件的每一个中,操作人员不得不关停反应器进行清洗。 In each of the four events, the operator has to shut down the reactor for cleaning.

[0118] 再循环管道携带静电读数用图5中的底部描记线来表示。 [0118] carrying the electrostatic recirculation line readings represented in Fig. 5 bottom traces. 相应的刻度在左边显示。 The corresponding scale is displayed on the left. 在每一个拱顶结皮事件之前,注意到了再循环管道静电的急剧升高。 Before each event a dome crust, noticed a sharp increase in the recirculation line static electricity. 在第一、第三和第四个事件中,再循环管道静电达到了200皮安。 In the first, third and fourth events, electrostatic recirculation line reached 200 pico-ampere. 在第二个事件中,再循环管道静电峰达到了95皮安。 In the second incident, the recirculation duct static peak of 95 pico-ampere.

[0119] 图6示出了图5的相同拱顶结皮事件,其中增加了分配板静电探针的读数用于比较。 [0119] FIG. 6 shows the same dome event crust FIG. 5, which increases the distribution plate electrostatic probe readings for comparison. 从图中可以看出,在拱顶结皮事件之前,分配板静电探针显示了一些响应,但该响应不显著,并且是不一致的。 As can be seen from the figure, before skinning dome event, the distributor plate static probes showed some response, but the response was not significant, and is inconsistent. 因为分配板探针与相同的夹带细粒接触,所以我们预期它们会显示与再循环管道探针相等(和成比例)的响应。 Because the probe distribution plate in contact with the same entrained fines, so we expect that they will show equality (and proportional) to the recirculation duct probe response. 该差别的原因是未知的。 The reason for this difference is unknown.

[0120] 图7显示了金属茂催化剂XCAT HP 100催化剂的反应器壁结皮事件,该催化剂由Univation Technologies, LLC在市场上供应。 [0120] Figure 7 shows a metallocene catalyst, XCAT HP 100 catalyst reactor wall crusts event, the catalyst Technologies, LLC supplied by Univation in the market. 在该情况下,于结皮事件之前,观察到了两个分配板探针的显著响应。 In this case, before skinning an event, a significant response was observed distribution plate two probes.

[0121] 图7还提供了对于我们先前描述的测量问题的极好说明,即常规反应器静电探针没有在使用金属茂催化剂的结皮事件之前提供有意义的指示。 [0121] Figure 7 also provides an excellent explanation for the measurement problem we have previously described, i.e., a conventional reactor static probes do not provide a meaningful indication prior to use skinning event metallocene catalysts. 如由该图中的反应器描记线所示,在壁结皮事件之前(或期间),常规反应器静电探针没有响应。 As the figure by the reactor trace shown by the line, before skinning wall event (or period), the conventional reactor static probe does not respond.

[0122] 图8示出了图7的壁结皮数据,其中增加了再循环管道携带静电用于比较。 [0122] FIG. 8 shows a view of the wall 7 of the skinning data, which increases the recirculation line for comparison with electrostatically. 从该图可以看出,再循环管道探针在壁结皮事件之前没有提供显著的响应。 As can be seen from this figure, the probe does not provide recirculation duct significant response prior to the wall skinning event. 来自该探针的唯一的显著响应发生在壁结皮形成之后。 The only significant response from the probe occurs after the wall is formed crust. 这指示应该监测存在于反应器系统中的所有探针,因为一些探针可能没有记录到静电,而其它探针可能记录到静电,从而能够通过使用连续性添加剂来控制。 This indicates that all probes should be monitored is present in the reactor system, because some of the probes may not have the electrostatic recording, and electrostatic other probes may be recorded, it can be controlled by the use of continuity additives.

[0123] 所述实验数据提供了一些重要和出乎意料的结果:再循环管道携带静电探针在使用金属茂催化剂的拱顶结皮事件之前提供了有意义的响应。 [0123] The experimental data provides some important and unexpected results: the recirculation pipe carrying the electrostatic probes provide a meaningful response prior to the dome using a metallocene catalyst skinning event. 所述分配板探针明显没有提供拱顶结皮的预先指示。 The distributor plate probes do not provide significant advance indication dome skinning.

[0124] 相反,在壁结皮的情况下,分配板探针在使用金属茂催化剂的壁结皮事件之前提供了有意义的响应,但再循环管道探针明显没有。 [0124] In contrast, in the case where the wall of the crust, the distributor plate probes provide meaningful responses prior to a wall using a metallocene catalyst crust events, but no significant recirculation duct probes. 虽然这些结果与拱顶结皮的发现相反,但本发明显然提供了对于使用金属茂催化剂的拱顶和壁结皮问题的解决方案。 Although these results contrast with the dome crust discoveries, the present invention clearly provides a solution to the use of a dome wall of a metallocene catalyst and skinning problems. 在再循环管道和分配板(或等同物)这两个位置上测量携带静电,这些测量值与静电控制装置结合使用以保持携带静电在大约零的水平。 Electrostatic measurements carried in the recirculation piping and distribution plate (or equivalent) on these two positions, the measurements used in combination with static control means to maintain the level of static electricity carried approximately zero.

[0125] 为了确定将携带静电保持在大约零水平的有效控制方式,对作为在己烷中的溶液或作为在矿物油中的固体淤浆的多种连续性添加剂进行了测试。 [0125] In order to determine the effective electrostatic carrying approximately zero control level, serving as a solution in hexane or as a solid slurry in mineral oil various continuity additives were tested. 将固体淤浆用于不溶性组分(硬脂酸铝),而将己烷溶液用于油酸铝和以商标0CTASTAT 3000和0CATSTAT 2000 由Associated OctelCompany出售的商购产品。 The solid slurry was used for the insoluble components (aluminum stearate), while a hexane solution of oleic acid and aluminum under the trademark 0CTASTAT 3000 0CATSTAT 2000 and sold by Associated OctelCompany of available products. 油酸铝溶液按0. 40%浓度制备;0CTASTAT 2000和3000溶液浓度是0. 53wt%。 Aluminum oleate solution concentration was prepared as 0.40%; solution concentration 0CTASTAT 2000 and 3000 are 0. 53wt%. 这些溶液使用有效范围为100-1200cc/hr的正排量泵进给到反应区。 The effective range of solution used 100-1200cc / hr of a positive displacement pump fed to the reaction zone. 硬脂酸铝淤浆通过将固体硬脂酸铝加入到已经在80-100° F下用氮气脱气24小时的矿物油中来制备。 Aluminum stearate slurry by mixing the solid aluminum stearate was added to the already prepared degassed with nitrogen for 24 hours mineral oil at 80-100 ° F. 所得淤浆浓度是5.66wt%。 The resulting slurry concentration was 5.66wt%. 采用Ι-lOOcc/hr的有效泵抽范围,将该淤浆进给到反应区。 Using Ι-lOOcc / hr effective pumping range of the pump, the slurry fed to the reaction zone. 还采用异戊烷作为反应器进料管道的冲洗物。 Isopentane also be employed as the reactor feed conduit rinsed.

[0126] 中试规模聚合反应器的数据指示,几种添加剂的单独添加和独立控制能够同时控制和减轻流化床反应器的拱顶和下段的结皮。 [0126] Pilot scale data indicative of a polymerization reactor, and to add several additives can simultaneously separate and minimize the fluidized bed reactor dome and a lower crust independent control. 许多连续性添加剂是相对不溶的,所以如上所述,它们作为矿物油中的淤浆进给。 Many of the continuity additives are relatively insoluble, so that as described above, they are as a mineral oil slurry feed. 将可溶性物料溶于己烷中,再直接进给到反应器中。 The soluble material was dissolved in hexane, and then fed directly into the reactor.

[0127] 用XCAT HP 200和XCAT EZ 100金属茂催化剂体系测试下列化合物: [0127] The following compounds were tested with the XCAT HP 200 and XCAT EZ 100 metallocene catalyst systems:

[0128] 油酸铝(溶液) [0128] Aluminum oleate (solution)

[0129] 硬脂酸铝(淤浆) [0129] Aluminum stearate (slurry)

[0130] 0CTASTAT 3000 (溶液) [0130] 0CTASTAT 3000 (solution)

[0131] 0CTASTAT 2000 (溶液) [0131] 0CTASTAT 2000 (solution)

[0132] AS_990(淤浆) [0132] AS_990 (slurry)

[0133] ATMER 163 (溶液) [0133] ATMER 163 (solution)

[0134] 进行两个系列试验,一个用XCAT HP 200金属茂催化剂,另一个用XCATEZ 100金属茂催化剂。 [0134] for two series of tests, one with XCAT HP 200 metallocene catalyst, other metallocene catalyst with XCATEZ 100. XCAT HP 200金属茂催化剂试验程序通过采用催化剂与二硬脂酸铝(基于催化剂重量的3%)的干混物的运行来开始。 XCAT HP 200 metallocene catalyst test procedure is started by using the catalyst with aluminum distearate (3% based on the weight of the catalyst) of the dry blend operation. 然后起动添加剂进料,并按制度操作反应器。 Additive feed was then started, according to the operation of the reactor system. 然后将所述催化剂切换到其中不存在二硬脂酸铝的一种情况(称为“单纯催化剂”),假设没有可操作性问题,同时仍将添加剂加入到反应器中。 The catalyst was then switched to one where the aluminum distearate (referred to as "pure catalyst") is not present, assuming no operability problems while still additives are added to the reactor. 经由单独的连续性添加剂进料管道,添加剂的进料速率分阶段增加到大约20ppm(重量)。 Via a separate continuity additive feed line, the feed rate of the additive stages increased to about 20ppm (by weight). 最终步骤是将添加剂流量减小至单纯催化剂时的零。 The final step is to reduce the additive flow to zero when a pure catalyst. XCAT EZ 100金属茂催化剂试验在评价计划用于工业测试的催化剂的可操作性的尝试过程中进行。 It is workable process of trying XCAT EZ 100 metallocene catalyst test in the evaluation plan for the testing of industrial catalysts. 在该情况下,响应冷表层热电偶读数(即偏离正常温度的负值)添加AS-990,以便用XCAT EZ 100金属茂催化剂进行连续操作。 In this case, in response to cold skin thermocouple readings (i.e., negative deviation from the normal temperature) was added AS-990, for continuous operation with XCAT EZ 100 metallocene catalyst. 产生正的结果的添加剂是: Additives that produce a positive result:

[0135] 硬脂酸铝 [0135] Aluminum stearate

[0136] AS-990 [0136] AS-990

[0137] 油酸铝 [0137] Aluminum oleate

[0138] 0CTASTAT 2000 [0138] 0CTASTAT 2000

[0139] 在这些试验过程中观察到了几个重要发现。 [0139] observed in these tests several important discoveries. 当使用单纯催化剂,不单独添加连续性添加剂时,产生了冷表层温度读数。 When the catalyst is used alone, without adding a separate continuity additive, cold skin temperature readings produced. 在一些情况下,这些值渐进性变得更糟,直到它们自身突然逆转并导致结皮事件。 In some cases, these values ​​become progressively worse, until they suddenly reversed itself and lead to skinning events. 用共混的催化剂/连续性添加剂,也观察到了较高的携带静电水平。 With the blended catalyst / continuity additive, also observed a higher level with electrostatically. 通过添加较高水平的连续性添加剂,通常通过单独添加连续性添加剂(与催化剂和连续性添加剂的共混物分开),减少了携带静电。 By adding higher levels of the continuity additive, generally by adding a separate continuity additive (and the catalyst blend separate continuity additive), decreased electrostatically charged. 增高的携带静电水平对应于增高的反应器静电水平。 Increased level corresponds to the electrostatically charged electrostatic horizontal reactor increased. 当连续性添加剂流量增加时,携带静电降低。 When increasing the continuity additive flow, reduce static electricity carry. 最终,两个结皮事件以携带静电的渐进性降低和随后携带静电突然增加为特征。 Eventually, the two events crust to carry the progressive lowering of static electricity and then suddenly increased to carry the electrostatic characteristics. 采用“单纯”催化剂的运行促成了这些结皮事件。 A "pure" run catalysts contributed to these events crust. 在此时,发生了表层热电偶偏离和结皮。 At this point, skin thermocouple deviation and occurrence of skinning. 虽然该现象的确切机理不明,但似乎催化剂被吸引到壁上,如由携带静电下降所证实的。 Although the exact mechanism of this phenomenon is unknown, but it seems to be attracted to the walls of a catalyst, such as a decline in carry-static confirmed. 当发生表层温度偏离时,催化剂明显被释放且携带静电突然增加。 When the surface temperature deviation occurs, the catalyst is released and significantly electrostatically charged suddenly increases.

[0140] 在多种连续性添加剂的试验过程中且对流化床反应器的拱顶进行目测。 [0140] and the dome of the fluidized bed reactor during the test was visually more continuity additives. 在用催化剂/连续性添加剂共混物运行时,总是存在拱顶结皮。 In the run with the catalyst / continuity additive blend, the dome is always present crust. 当提高添加剂水平时(一般通过单独的进料管道),拱顶被渐进性清理,直至它被完全清理到裸露金属壁为止。 When the level of enhancing additives (generally through a separate feed line), the dome is progressive clean until it is completely clean until bare metal wall. 对于硬脂酸铝, 这需要基于生产速率的按重量计10-15ppm(ppmw)的总浓度。 For aluminum stearate, this required a total concentration based on production rate by weight 10-15ppm (ppmw) of. 当将硬脂酸铝与催化剂共混时,生产率制约因素将硬脂酸盐的浓度限制至6ppm (重量),按共混物的百分率计(这是大致的水平,但在该水平以上,共混物变得难以处理,因此在现今的物料和给料装置的情况下提出了实际限制)。 When the aluminum stearate is blended with the catalyst, productivity constraints limit the concentration of the salt to acid of 6 ppm (weight), according to the blend percentage basis (which is substantially level, but above that level, total mix becomes difficult to handle, thus proposes a practical limit at the current situation and material feed means). 更高活性的金属茂催化剂导致了甚至更低的水平,即在共混物中最多包含3-4ppmw,证明了需要单独添加该添加剂。 Higher activity metallocene catalyst resulted in even lower levels, i.e., up to 3-4ppmw contained in the blend, the additive proved necessary to add separately.

[0141] 在中试装置聚合反应中,用XCAT EZ 100金属茂催化剂进行测试受到了拱顶结皮事件的干扰。 [0141] In the polymerization pilot plant were tested by the interference event with the dome crust XCAT EZ 100 metallocene catalyst. 然而,本发明使用连续性添加剂AS-990的示例消除了冷表层温度读数,并且消除了结皮。 However, the example using the continuity additive AS-990 of the present invention to eliminate cold skin temperature readings and eliminate taking skin. 例如,在将AS-990在矿物油中的淤浆进给到反应器中以消除分配板和扩展段中的冷表层温度读数时,平稳进行了10天运行而没有任何操作性问题出现。 For example, when the AS-990 in mineral oil slurry is fed into the reactor to eliminate cold skin temperature readings in the distribution plate and extended segment, a 10-day run smoothly without any operability problems. 床中的AS-990 水平(来自附加进料)平均大约10-30ppm(基于床重)。 AS-990 levels (from the additional feed) averaged about 10-30ppm bed (based on bed weight).

[0142] 试图不用AS-990的试验导致了表层温度偏离。 [0142] do not try to test AS-990 led to the surface temperature deviation.

[0143] 图9示出了在本发明的实施中中试装置聚合反应的数据。 [0143] FIG. 9 shows data in the embodiment of the present invention, the polymerization pilot plant. 数据覆盖了13天的时间。 Data coverage 13 days.

[0144] 曲线顶部的各个线条是反应器的表层温度。 [0144] respective lines top curve is the surface temperature of the reactor. 显示阶跃变化的下部虚线是连续性添加剂的流量。 Displaying a step change in flow rate is the lower dashed line continuity additive. 手工记录流量,该流量在0-20ppm范围内变化。 Manually record traffic, which varies within the range of 0-20ppm. 点1示出了当试验单纯催化剂时对表层温度的影响,它显示了冷表层温度读数的形成。 Point 1 shows the effect of the test when the temperature of the surface layer of the catalyst alone, it shows the formation of cold skin temperature readings. 当增加油酸铝流量时,冷表层温度读数消除。 When the aluminum oleate flow increases, eliminate cold skin temperature readings. 流量的进一步增加引起再次形成冷表层温度读数。 Further increase in traffic caused by the formation of cold surface temperature readings again. 这证明该添加剂有最佳的水平。 This proves that the additive has the best level.

[0145] 点2示出了切断油酸铝流入和用单纯催化剂运行的结果。 [0145] Point 2 shows the result of the aluminum oleate and running inflow catalyst by simple cutting. 这证明减少该添加剂具有与增加该添加剂不同的效果-没有冷表层温度读数,而是表层温度偏移。 This has proven to reduce the additive increased the additive effect different - no cold skin temperature readings but a skin temperature excursion. 这证实了需要最佳水平的添加剂。 This confirms the optimum level of additive required. 总之,用二硬脂酸铝的试验是非常稳定的,没有发现冷表层温度偏移。 In short, aluminum distearate test is very stable, and no cold skin temperature excursions. 在点3处,将所引入的催化剂切换为单纯催化剂,这导致了再次形成冷表层温度,但没有正的表层温度偏移。 At point 3, the catalyst introduced into the catalyst as a simple switch, which results in the formation of cold surface temperature again, but no positive skin temperature excursions.

[0146] 点4示出了0CTASTAT 2000的结果。 [0146] Point 4 shows results of 0CTASTAT 2000. 该添加剂与油酸铝相似,具有最佳水平。 This is similar to the aluminum oleate additive, with the best level. 一旦连续性添加剂的流量增加太多,开始形成冷表层温度。 Once the flow of continuity additive is increased too much cold skin temperatures started to form.

[0147] 图10的曲线对应于图9中的曲线,但在该情况下,示出了三种不同的静电测量结果。 Curve [0147] FIG 10 corresponds to the curve in FIG. 9, but in this case, shows three different static measurements. 标记为反应器静电1的顶部由线是使用电流探针测定的反应器静电的曲线,标记为反应器静电2的中部曲线是使用电压探针的反应器静电的曲线,以及底部曲线是携带静电的曲线。 Top labeled reactor static 1 by the line is measured using a current probe reactor static curve, the middle labeled reactor static curve 2 is a plot of the reactor static using a voltage probe, and the bottom curve is electrostatically charged curve. 携带静电按绝对值测定。 In absolute determination to carry static electricity. 虚线是如上所述的连续性添加剂的流量。 The dashed line is the flow of the continuity additives as described above.

[0148] 携带静电在点1、3和4处的冷表层温度形成期间下降,虽然在点3处的程度更低。 [0148] 1,3 electrostatically charged during formation and cold point temperature of the surface 4 decreases, though at a lower extent at point 3. 这些带圆圈的点示出了含有二硬脂酸铝的共混催化剂的添加。 The circled points shows the addition of blended catalyst containing aluminum distearate. 在图9中的所有其它时候, 进给单纯催化剂。 In FIG. 9 all other times, the feeding of the catalyst alone. 这证明,当仅仅进给单纯的催化剂时,与进给单纯的催化剂并同时独立添加连续性添加剂相比,携带静电增高。 This proves that, when only a simple catalyst feed, and feed at the same time simple and independent of catalyst added continuity additive compared with electrostatically increased.

[0149] 图11和12示出了与以上那些类似的曲线,但使用GGT^Si1TAT®。 [0149] FIGS. 11 and 12 illustrate curves similar to those above, but using GGT ^ Si1TAT®. 在图η和12 中,点1对应于大约5ppm(重量)的0CTASTAT 3000的浓度(反应器中的总量),形成了低携带静电和冷表层温度。 12 and in FIG η, corresponding to a concentration of about 1 point (total in the reactor) 5ppm (by weight) of 0CTASTAT 3000, forming a low surface temperature and cold electrostatically charged. 然而,当增加0CTASTAT 3000的流量(5ppm以上)时,冷表层温度消失,这再次证明需要最佳的添加剂水平(添加剂量用虚线示出)。 However, when increasing the flow rate of 0CTASTAT 3000 (5ppm or more), the cold skin temperatures disappeared, which demonstrated again the need optimum level of additive (additive amounts shown in dashed lines). 在图11和12中,在点2 处,反应器用单纯催化剂和大约41ppm浓度的0CATSTAT3000进行试验。 In FIGS. 11 and 12, at point 2, the reactor catalyst alone and about 41ppm 0CATSTAT3000 concentration tested. 然后停止0CTASTAT 流入。 Then stop 0CTASTAT inflows. 立即开始形成冷表层温度,并且同时携带静电开始降低。 Immediately began to form a cold surface temperature, and at the same time carrying an electrostatic begins to decrease. 与许多其它连续性添加剂相反,立即发生了这种效应并且在冷表层温度形成方面没有滞后。 And forming a contrast to many other continuity additives, this effect occurred immediately there was no cold surface temperature hysteresis.

[0150] 图11和12证明,反应器(常规静电探针)静电不象携带静电测量结果那样容易与冷表层温度形成相关联。 [0150] FIGS. 11 and 12 demonstrate the reactor (conventional static probes) carrying an electrostatic image is not static measurement results as readily be formed associated with the cold surface temperature. 虽然反应器静电显示了对应于反应器条件变化的一些小的变化, 但反应器静电变化不象携带静电变化那样大。 Although reactor static show some small changes corresponding to the variator reaction conditions, the reactor static but does not change the electrostatic image bearing changes as large. 另外,这证明了渐进性冷表层温度(如果留下太长时间)怎样能够转变为正的表层温度偏移。 In addition, this proves progressive cold surface temperature (if left too long) how can be transformed into a positive surface temperature shift. 而且,这证明携带静电与冷表层温度一起降低,直至达到临界水平,在该临界水平时,它开始快速增高,随后是表层温度的大的偏移,这需要关停反应器。 And, proving that carry static and cold surface temperature decreases along until it reaches a critical level, when the critical level, it began to rapidly increase, followed by a large offset surface temperature, which requires shutting down the reactor.

[0151] 虽然参考特定实施方案说明了本发明,但本领域普通技术人员清楚,本发明本身提供了在这里没必要说明的变化。 [0151] While the embodiment described with reference to particular embodiments of the present invention, those of ordinary skill in the art apparent, the present invention provides in itself need not be described herein changes. 为此,那么应该仅仅参考所附权利要求书来确定本发明的真正范围。 To this end, it should be used only with reference to the appended claims for determining the true scope of the invention.

Claims (9)

  1. 以防止或逆转由至少一种烯烃的聚合反应所产生的聚合物的结皮的量将至少一种连续性添加剂引入到反应器系统中的方法,其中该聚合反应在反应器系统中进行,该反应器系统包括流化床反应器,夹带区,用于引入能够生产聚合物的催化剂体系的催化剂进给装置,至少一个用于与催化剂混合物独立地引入至少一种连续性添加剂的连续性添加剂进给装置,用于监测夹带区中的静电活性水平的装置,该方法包括:(a)让该至少一种烯烃与催化剂体系在流化床反应器中在聚合条件下接触;(b)在聚合反应开始之前、期间或之后的任何时间将该至少一种连续性添加剂引入到反应器系统中,其中该至少一种连续性添加剂包括一种或多种选自烷氧基化胺、羧酸盐、聚砜类、聚合多胺、磺酸类或它们的组合中的化合物;(c)监测夹带区中的静电活性水平,其中该夹带区 Amount of polymer crust prevent or reverse by the polymerization of at least one olefin produced at least one continuity additive into a reactor system, wherein the polymerization reaction is carried out in the reactor system, the the reactor system comprises a fluidized bed reactors, entrainment zone, a catalyst is capable of producing a polymer catalyst system for introducing the feed device, at least one continuity additive is introduced independently of the at least one continuity additive into the catalyst mixture to the apparatus, means for monitoring levels of electrostatic activity in the entrainment zone, the method comprising: (a) Have an olefin with the catalyst system under polymerization conditions in the fluidized bed reactor at least; (b) in the polymerization before starting the reaction, any time during or after the at least one continuity additive introduced into the reactor system, wherein the at least one continuity additive comprises one or more compounds selected from alkoxylated amines, carboxylic acid salts , polysulfones, polyamine compounds, sulfonic acids or combinations thereof in the polymerization; (c) monitoring the level of electrostatic activity in the entrainment zone, wherein the entrainment region 义为反应器系统的密相区以上或以下的任何区域;以及(d)调节引入到反应器系统中的该至少一种连续性添加剂的量,以便将夹带区中的静电活性水平保持在0或接近0。 It is defined as any region above the dense phase zone of the reactor system or less; and (d) introducing into the at least one adjustment amount of continuity additive in the reactor system to the level of electrostatic activity in the entrainment zone is maintained at 0 or close to zero.
  2. 2.如权利要求1所述的方法,其中该催化剂体系包括金属茂或常规过渡金属催化剂。 2. The method according to claim 1, wherein the catalyst system comprises a metallocene or a conventional transition metal catalyst.
  3. 3.如权利要求2所述的方法,其中该方法包括气相方法。 The method according to claim 2, wherein the method comprises a gas phase process.
  4. 4.如权利要求3所述的方法,其中连续生产聚合物。 4. The method according to claim 3, wherein the continuous production of polymers.
  5. 5.如权利要求4所述的方法,其中该单体包括乙烯或乙烯和一种或多种a-烯烃。 5. The method according to claim 4, wherein the monomers comprise ethylene or ethylene and one or more a- olefins.
  6. 6.如权利要求1所述的方法,其中该至少一种连续性添加剂包括乙氧基化硬脂胺。 6. The method according to claim 1, wherein the at least one continuity additive comprises ethoxylated stearyl amine.
  7. 7.如权利要求1所述的方法,其中该至少一种连续性添加剂包括硬脂酸铝。 7. The method according to claim 1, wherein the at least one continuity additive comprises aluminum stearate.
  8. 8.如权利要求1所述的方法,其中该至少一种连续性添加剂包括油酸铝。 8. The method according to claim 1, wherein the at least one continuity additive comprises aluminum oleate.
  9. 9.如权利要求1所述的方法,其中该至少一种连续性添加剂包括如下组分的混合物: 以该混合物的5-15wt%的浓度存在的1-癸烯-聚砜,以该混合物的5-15wt%的浓度存在的N-牛油-1,3-二氨基丙烷和表氯醇的反应产物,以该混合物的5-15wt%的浓度存在的十二烷基苯磺酸,以及以该混合物的60-80衬%的浓度存在的烃溶剂。 In this mixture polysulfone, - a concentration of 5-15wt% of the mixture of 1-decene present: The method as claimed in claim 1, wherein the at least one continuity additive comprises a mixture of the following components present in a concentration of 5-15wt% of the reaction product of N- tallow-1,3-diaminopropane and epichlorohydrin, at a concentration of 5-15wt% of the mixture of dodecylbenzene sulfonic acid present, as well as lining present in a concentration of 60-80% of the mixture of the hydrocarbon solvent.
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TW200902558A (en) 2007-02-16 2009-01-16 Univation Tech Llc Method for on-line monitoring and control of polymerization processes and reactors to prevent discontinuity events
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RU2549541C2 (en) * 2009-07-28 2015-04-27 Юнивейшн Текнолоджиз, Ллк Method of polymerisation with application of applied catalyst with constrained geometry
EP2510019A2 (en) * 2009-12-07 2012-10-17 Univation Technologies, LLC Methods for reducing static charge of a catalyst and methods for using the catalyst to produce polyolefins
CN104039840B (en) * 2011-12-31 2016-08-31 尤尼威蒂恩技术有限责任公司 Continuity additive polyolefin polymerization process
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1178222A (en) 1997-06-05 1998-04-08 联合碳化化学品及塑料技术公司 Process for controlling static in polymerizations utilizing metallocene catalysts
US6111034A (en) 1998-12-31 2000-08-29 Union Carbide Chemicals & Plastics Technology Corporation Static control in olefin polymerization
US20020132944A1 (en) 1999-12-15 2002-09-19 Agapiou Agapios K. Polymerization Process
EP1308464A1 (en) 2001-10-19 2003-05-07 BP Chemicals S.N.C. Process for the gas-phase (co-)polymerisation of olefins in a fluidised bed reactor

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5332706A (en) 1992-12-28 1994-07-26 Mobil Oil Corporation Process and a catalyst for preventing reactor fouling

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1178222A (en) 1997-06-05 1998-04-08 联合碳化化学品及塑料技术公司 Process for controlling static in polymerizations utilizing metallocene catalysts
US6111034A (en) 1998-12-31 2000-08-29 Union Carbide Chemicals & Plastics Technology Corporation Static control in olefin polymerization
US20020132944A1 (en) 1999-12-15 2002-09-19 Agapiou Agapios K. Polymerization Process
EP1308464A1 (en) 2001-10-19 2003-05-07 BP Chemicals S.N.C. Process for the gas-phase (co-)polymerisation of olefins in a fluidised bed reactor

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