Method for determining the activity of activated chemically-treated solid oxides in olefin polymerization

Abstract

Methods for determining the catalytic activity of activated chemically-treated solid oxides using color measurement techniques are described, and these methods are integrated into transition metal based catalyst preparation processes and systems, and into olefin polymerization processes and related polymerization reactor systems.

Description

Field of the Invention

[0001] The present disclosure relates to methods for determining the catalytic activity of activated chemically-treated solid oxides, and integration of these methods into related catalyst preparation processes and systems, polymerization processes, and reactor systems. Background of the Invention

[0003] The catalyst system for the polymerization based on ethylene often uses activators, such as chemically treated solid oxides. However, there is no discernible physical difference between fully activated, partially activated or unactivated chemically treated solid oxides. Routinely, the procedure for evaluating the quality or catalytic activity of chemically treated solid oxides is to test its performance in the polymerization experiment in the laboratory reactor. Although this is very helpful to prevent the use of a large amount of inconsistent or low-quality chemically treated solid oxide activators in commercial polymerization reactors, the turnaround time of such laboratory experiments is too long to be accepted. Therefore, it will be advantageous to determine the catalytic activity of chemically treated solid oxides within a much shorter time frame. The present invention is generally directed to these purposes. Summary of the invention

[0004] This summary is provided to introduce a series of concepts further described below in the detailed description in a simplified form. This summary is not intended to determine the necessary or essential features of the claimed subject matter. This summary is also not intended to limit the scope of the claimed subject matter.

[0005] Disclosed herein is a method for determining the catalytic activity of an activated chemically treated solid oxide. According to one aspect of the invention, one such method may include: (i) combining a sample of the activated chemically treated solid oxide with a solution of a color indicator compound to form a treated solid support, (ii) measuring the color of the treated solid support (performed with any suitable color measuring instrument / device), and (iii) generating a color value (such as R+G+B) of the treated solid support, and correlating the color value with a standard to determine the catalytic activity of the activated chemically treated solid oxide.

[0006] In another aspect, a process for preparing a catalyst composition is disclosed, and in this aspect, the process may include: (I) determining the catalytic activity of an activated chemically-treated solid oxide, wherein the catalytic activity is determined via any method disclosed herein, (II) contacting a transition metal compound, the activated chemically-treated solid oxide, and an optional co-catalyst (e.g., in a catalyst preparation vessel) to form the catalyst composition, and (III) adjusting the relative amount of at least one component of the catalyst composition based on the catalytic activity of the activated chemically-treated solid oxide (or based on the determined catalytic activity).

[0007] In yet another aspect, a process for operating a polymerization reactor system is disclosed, and in this aspect, the process may include: (I) determining the catalytic activity of an activated chemically-treated solid oxide, wherein the catalytic activity is determined via any of the methods disclosed herein, (II) contacting a catalyst system comprising a transition metal compound, the activated chemically-treated solid oxide, and an optional co-catalyst with an olefin monomer and an optional olefin comonomer in a reactor within the polymerization reactor system under polymerization reaction conditions to produce an olefin polymer, and (III) when the catalytic activity of the activated chemically-treated solid oxide has reached a predetermined level, adjusting the flow rate of the activated chemically-treated solid oxide entering the reactor (or adjusting the flow rate of the chemically-treated solid oxide based on the determined activity).

[0008] In addition, various activation systems, catalyst preparation systems, and polymerization reactor systems are disclosed herein. One such activation system may include: (a) an activation vessel configured to calcine a raw (or unactivated) chemically treated solid oxide to form an activated chemically treated solid oxide, (b) an activator storage vessel configured to receive the activated chemically treated solid oxide from the activation vessel and further configured to introduce the activated chemically treated solid oxide into a catalyst preparation vessel, and (c) an analytical system configured to determine the catalytic activity of the activated chemically treated solid oxide before introducing the activated chemically treated solid oxide into the catalyst preparation vessel.

[0009] A representative catalyst preparation system may include: (a) a catalyst preparation vessel, which is configured to contact a transition metal compound, an activated chemically-treated solid oxide, and an optional co-catalyst to form a catalyst composition, (b) an activator feed stream, which is configured to introduce the activated chemically-treated solid oxide into the catalyst preparation vessel, (c) a transition metal compound feed stream, which is configured to introduce the transition metal compound into the catalyst preparation vessel, (d) a catalyst system feed stream, which is configured to remove the catalyst composition from the catalyst preparation vessel (e.g., and introduce the catalyst composition into a reactor, if desired), and (e) an analytical system (e.g., including a color analyzer), which is configured to determine the catalytic activity of the activated chemically-treated solid oxide before introducing the activated chemically-treated solid oxide into the catalyst preparation vessel.

[0010] A representative polymerization reactor system may include: (A) a reactor configured to contact a catalyst system with an olefin monomer and an optional olefin comonomer under polymerization reaction conditions to produce an olefin polymer, (B) a catalyst preparation vessel configured to contact a transition metal compound, an activated chemically-treated solid oxide, and an optional co-catalyst to form the catalyst system, and (C) an analytical system (e.g., including a color analyzer) configured to determine the catalytic activity of the activated chemically-treated solid oxide before introducing the activated chemically-treated solid oxide into the catalyst preparation vessel.

[0011] Both the foregoing summary of the invention and the following detailed description provide examples and are merely illustrative. Therefore, the foregoing summary of the invention and the following detailed description should not be considered restrictive. In addition, in addition to the features or variations set forth herein, other features or variations may also be provided. For example, certain aspects may be directed to various feature combinations and sub-combinations described in the detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] The following drawings form part of this specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in conjunction with the detailed description presented herein.

[0013] Figure 1 A schematic block diagram of a polymerization reactor system consistent with aspects of the present invention is shown.

[0014] Figure 2 A schematic block diagram of a catalyst preparation system consistent with aspects of the present invention is shown.

[0015] Figure 3 A schematic block diagram of an activation system consistent with aspects of the present invention is shown.

[0016] Figure 4 Photographs of the differently color treated solid oxides of Example 1 are presented.

[0017] Figure 5 A plot of normalized catalytic activity versus color value for the chemically-treated solid oxide of Example 1 is presented.

[0018] definition

[0019] In order to more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to the present disclosure. If a term is used in the present disclosure but is not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2nd edition (1997) can be applied, as long as the definition does not conflict with any other disclosure or definition applied herein, or any claim applying the definition is unclear or invalid. If any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0020] In this article, the features of the subject matter are described so that within a particular aspect, combinations of different features are conceivable. For each aspect and / or feature disclosed herein, all combinations that do not adversely affect the systems, compositions, processes and / or methods described herein are considered, with or without explicit description of a particular combination. In addition, unless otherwise expressly stated, any aspect and / or feature disclosed herein may be combined to describe creative features consistent with the present disclosure.

[0021] In this disclosure, although systems, processes and methods are often described in terms of “comprising” various components, devices, or steps, the systems, processes and methods may also “consist essentially of” or “consist of” the various components, devices, or steps, unless otherwise stated.

[0022] The terms "a", "an", and "the" are intended to include plural alternatives, such as at least one. For example, unless otherwise indicated, disclosure of "a polymerization reactor" or "a transition metal compound" is meant to encompass one polymerization reactor or one transition metal compound, or a combination of more than one polymerization reactor or more than one transition metal compound.

[0023] For any particular compound or group disclosed herein, unless otherwise indicated, any name or structure (general or specific) presented is intended to encompass all conformational isomers, positional isomers, stereoisomers, and mixtures thereof that may result from a particular set of substituents. Unless otherwise indicated, the name or structure (general or specific) also encompasses all enantiomers, diastereomers, and other optical isomers (if any) in enantiomeric or racemic form that the skilled person will recognize, as well as mixtures of stereoisomers. For example, a general reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane; and a general reference to butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl.

[0024] The term "about" means that the amount, size, formula, parameter, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller as necessary, reflecting tolerances, conversion factors, rounding, measurement errors, etc., and other factors known to those skilled in the art. In general, whether or not explicitly stated, the amount, size, formula, parameter, or other quantity or characteristic is "about" or "approximately". The term "about" also encompasses amounts that vary due to different equilibrium conditions of compositions resulting from a particular initial mixture. Whether or not modified by the term "about", the claims include equivalents of the stated amounts. The term "about" may mean within 10% of the reported value, preferably within 5% of the reported value.

[0025] Various numerical ranges are disclosed herein. When any type of range is disclosed or claimed, it is intended to disclose or claim each possible number that such range can reasonably cover, including the endpoints of the range and any sub-ranges and combinations of sub-ranges contained therein, unless otherwise specified. As a representative example, the present disclosure states that in some aspects, polymerization conditions may include a polymerization temperature in the range of about 60°C to about 115°C. By disclosing that the temperature may be in the range of about 60°C to about 115°C, it is intended to state that the temperature may be any temperature in the range, and for example may be equal to about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 105°C, about 110°C, or about 115°C. In addition, the temperature may be in any range of about 60°C to about 115°C (for example, the temperature may be in the range of about 70°C to about 110°C), and this is also included in any combination of ranges between about 60°C and about 115°C. In addition, in all cases where "about" is disclosed for a particular value, the value itself is disclosed. Thus, a disclosure of a temperature range from about 60°C to about 115°C also discloses a temperature range from 60°C to 115°C (e.g., the temperature may be in the range of 70°C to 110°C), and this also includes any combination of ranges between 60°C and 115°C. Likewise, all other ranges disclosed herein should be interpreted in a manner similar to this example.

[0026] The term "polymer" is generally used herein to include olefin homopolymers, copolymers, terpolymers, etc., as well as alloys and blends thereof. The term "polymer" also includes impact, block, graft, random and alternating copolymers. Copolymers can be derived from olefin monomers and an olefin comonomer, and terpolymers can be derived from olefin monomers and two olefin comonomers. Therefore, "polymer" covers copolymers and terpolymers. Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization and terpolymerization. Therefore, ethylene polymers will include ethylene homopolymers, ethylene copolymers (e.g., ethylene / α-olefin copolymers), ethylene terpolymers, etc., and blends or mixtures thereof. Therefore, ethylene polymers cover polymers often referred to as LLDPE (linear low density polyethylene) and HDPE (high density polyethylene) in the art. As an example, ethylene copolymers can be derived from ethylene and comonomers, such as 1-butene, 1-hexene or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer can be classified as ethylene / 1-hexene copolymers. If any and unless otherwise indicated, the term "polymer" also includes all possible geometric configurations, and such configurations may include isotactic, syndiotactic and atactic symmetries. The term "polymer" is also intended to include polymers of all molecular weights, and includes lower molecular weight polymers or oligomers.

[0027] Unless otherwise indicated, the term "contacting" is used herein to describe systems, compositions, processes and methods in which components are contacted or combined together in any order, in any manner and for any length of time. For example, the components can be combined by blending or mixing using any suitable technique.

[0028] Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the typical methods, devices, and materials are described herein.

[0029] All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which might be used in connection with the presently described invention. DETAILED DESCRIPTION

[0030] When a commercial polymerization reactor operator has doubts about the quality and activity or productivity of a chemically treated solid oxide activator, a sample is typically shipped to a catalyst laboratory and then tested in a laboratory or bench-scale reactor. This process can often take 3-5 days, and therefore real-time control, monitoring, and troubleshooting in a commercial polymerization plant is time-consuming and impractical.

[0031] Therefore, an important object of the present invention is a non-polymeric method for evaluating the catalytic activity of a chemically treated solid oxide. In this article, catalytic activity data can be quickly turned around (e.g., in one hour or less), and testing scheme is cheap and can be implemented on-site at a manufacturing plant.

[0032] Methods for determining catalytic activity

[0033] Aspects of the present invention relate to methods for determining the catalytic activity of activated chemically treated solid oxides. Such methods may include the following (or consist essentially of the following, or consist of the following): (i) a sample of the activated chemically treated solid oxide is combined with a solution of a color indicator compound to form a solid support for treatment, (ii) the color of the solid support for treatment is measured, and (iii) the color value of the solid support for treatment is generated, and the color value is associated with a standard to determine the catalytic activity of the activated chemically treated solid oxide. Typically, the features of the methods disclosed herein (e.g., chemically treated solid oxides, color indicator compounds, solutions, color values, and standards, etc.) are described independently herein, and these features can be combined in any combination to further describe the disclosed methods. In addition, unless otherwise stated, other process steps may be performed before, during, and / or after any step listed in the disclosed method.

[0034] In step (i), the sample of the chemically treated solid oxide of activation is combined with the solution of the color indicator compound to form the solid support for processing. Usually, the solution comprises the color indicator compound and a hydrocarbon solvent. Typical hydrocarbon solvents may include but are not limited to propane, hexamethylene, isobutane, normal butane, normal pentane, isopentane, neopentane, normal hexane, toluene, etc., and combinations thereof. On the one hand, the hydrocarbon solvent may include pentane, hexane, heptane, benzene, toluene or dimethylbenzene, etc., and mixtures or combinations thereof.

[0035] Any suitable color indicator compound can be used herein.Usually, suitable color indicator compounds are included in the color of the activated chemically treated solid oxide after contacting with the activated chemically treated solid oxide, but do not change the color of the unactivated chemically treated solid oxide after contacting with the unactivated chemically treated solid oxide.On the one hand, the color indicator compound can be an electron-rich compound, and on the other hand, the color indicator compound can be an unsaturated compound, and on the other hand, the color indicator compound can be both electron-rich and unsaturated.Preferably, but not necessarily, it is advantageous in the case where the color indicator compound is colorless (and therefore, the color indicator solution containing solvent and the color indicator compound is colorless).

[0036] Illustrative and non-limiting examples of suitable color indicator compounds contemplated herein may include the following nitrogen-containing compounds:

[0037]

[0038] etc., and combinations thereof.

[0039] Other illustrative and non-limiting examples of suitable color indicator compounds contemplated herein may include the following compounds that do not contain nitrogen atoms:

[0040]

[0041]

[0042] etc., and combinations thereof.

[0043] In step (i), the sample of the activated chemically treated solid oxide is combined with the solution of the color indicator compound in any suitable container or reservoir, and illustrative examples of the container or reservoir may include a flask, a wide-mouth bottle, a test tube or a flow cell device. Other suitable sample chambers can be used in step (i). Representative flow cell devices considered herein (for combining the sample of the activated chemically treated solid oxide with the solution of the color indicator compound to form a treated solid support) can be configured to separate the solid (treated solid support) to the bottom portion of the flow cell device, and to allow any liquid to occupy the upper portion of the flow cell device (the solid settles due to its higher density), and the bottom portion of the flow cell device can be configured to easily measure the color of the treated solid support (with a suitable color measurement instrument / device).

[0044] The time and temperature conditions in step (i) are not particularly limited, but ambient / room temperature is typically used for convenience. The contact time in step (i) - before measuring the color in step (ii) - is a period of time sufficient for the color indicator compound to interact / react with the activated chemically-treated solid oxide, and for convenience, is often in the range of 1 minute to 4 hours, but is not limited thereto.

[0045] The color of the solid carrier of treatment is measured in step (ii), and this can be done with any suitable color measuring instrument or device. Non-limiting examples include smart phones, spectrophotometers, colorimeters, etc. If necessary, the solid carrier of treatment of coloration (i.e., solid) can be separated from any liquid present before color measurement, and this can be done using various techniques, such as screening, filtering, centrifugation, etc., and including a combination of two or more of these techniques, and any other suitable technique for removing solids or particulates from the liquid portion.

[0046] In step (iii), a color value of the treated solid support is generated, and the color value is then correlated with a standard to determine the catalytic activity of the activated chemically treated solid oxide. Any numerical representation of the color of the treated solid support can be used as the color value; for example, the color value can be the sum of R+G+B (red+green+blue). The R+G+B color model is an additive color model in which red, green, and blue light are added together in various ways to reproduce a variety of colors. The name of the model comes from the first letters of the three additive primary colors (red, green, and blue). The main purpose of the RGB color model is for the sensing, representation, and display of images in electronic systems (such as televisions and computers), but it is also used in conventional photography. In fact, if a picture is input into a photoshop program (such as Adobe), the program will output the red, green, and blue information of any point on the picture. Color picker is another commonly used program that can be used to extract red, green, and blue data from a picture or photograph.

[0047] The color value of the solid oxide of treatment is associated with a standard, and the standard may include a calibration curve. The association step may be performed manually or may be performed automatically. If a calibration curve is used, these calibration curves may be generated by any program known to those skilled in the art, and its non-limiting illustration is shown in the following examples. Therefore, the step of associating the color value with the standard may include any suitable method for converting the color value into the catalytic activity of the activated chemically treated solid oxide.

[0048] The step of correlating may include any suitable method or technique for converting the color value to the catalytic activity of the activated chemically-treated solid oxide. The step of correlating may be performed manually, or may be configured to automatically convert the color value data - for example, via a mathematical model - to the catalytic activity of the activated chemically-treated solid oxide.

[0049] In some cases, actual color values ​​can be generated, which can be collected or output, viewed on a display or computer screen, or printed in hard copy form. In other cases, color values ​​are generated, but not collected or output in a viewable form. For example, data from color measurements can be directly converted (or automatically converted) to the catalytic activity of the activated chemically-treated solid oxide by correlation with a standard (such as a calibration curve or a mathematical model).

[0050] Polymerization reactor system

[0051] Various polymerization reactor systems and processes for operating or controlling such systems are disclosed and described herein. For example, on the one hand, a process for operating a polymerization reactor system may include: (I) determining the catalytic activity of an activated chemically treated solid oxide, wherein the catalytic activity is determined via any method described herein, (II) contacting a catalyst system comprising a transition metal compound, an activated chemically treated solid oxide, and an optional cocatalyst with an olefin monomer and an optional olefin comonomer in a reactor within the polymerization reactor system under polymerization reaction conditions to produce an olefin polymer, and (III) when the catalytic activity of the activated chemically treated solid oxide has reached a predetermined level, adjusting the flow rate of the activated chemically treated solid oxide into the reactor. Therefore, the flow rate (or feed rate) of the chemically treated solid oxide can be manually and / or automatically adjusted based on the determined activity. Generally, the features of the process for operating a polymerization reactor system disclosed herein (e.g., chemically treated solid oxide, transition metal compound, catalyst system, olefin monomer, olefin comonomer, reactor, method for determining catalytic activity, and flow rate control of chemically treated solid oxide, etc.) are described independently herein, and can be combined in any combination to further describe the disclosed process. Furthermore, unless otherwise stated, other steps may be performed before, during and / or after any steps recited in the disclosed processes.

[0052] Step (I) involves determining the catalytic activity of the activated chemically treated solid oxide using a color measurement technique. Therefore, the specific features associated with step (I) may be the same as those disclosed and described herein when it relates to a method for determining the catalytic activity of an activated chemically treated solid oxide.

[0053] In step (II), a catalyst system comprising a transition metal compound, an activated chemically treated solid oxide and an optional cocatalyst is contacted with an olefin monomer and an optional olefin comonomer in a reactor in a polymerization reactor system under polymerization reaction conditions to produce an olefin polymer. On the one hand, the catalyst system does not contain a cocatalyst, and on the other hand and more often, the catalyst system contains a cocatalyst. Similarly, in some aspects, only a transition metal compound is present in the catalyst system, and in other aspects, two or more transition metal compounds are present in the catalyst system.

[0054] The process disclosed herein is applicable to various situations that may be interested in the catalytic activity of the activated chemically treated solid oxide. For example, when the catalytic activity of the activated chemically treated solid oxide has reached a predetermined level, the flow rate of the activated chemically treated solid oxide entering the reactor can be adjusted. According to historical conditions and current conditions in, for example, a polymerization reactor system, a person skilled in the art can easily determine the predetermined level. As a non-limiting example, the predetermined level can be a certain percentage of the catalytic activity of the activated chemically treated solid oxide (for example, exceeding the catalytic activity considered to be allowed during normal high-quality production) that has been reduced. For example, the target catalytic activity of the activated chemically treated solid oxide can be 95% of the maximum activity (which is converted into 95% of the maximum polymer productivity based on g / g of the activated chemically treated solid oxide), and for normal high-quality production, the predetermined control lower limit and upper limit can be 90% and 100% respectively. If the measured activity of the activated chemically-treated solid oxide is 75%, the feed rate of the activated chemically-treated solid oxide to the catalyst preparation vessel (and therefore to the polymerization reactor) can be increased to increase the amount of "active" chemically-treated solid oxide in the polymerization reactor, so that the overall productivity in the reactor is increased due to the increased amount of chemically-treated solid oxide added.

[0055] The flow rate in step (III) is controlled by adjusting the flow rate of the activated chemically-treated solid oxide to the catalyst preparation vessel on the one hand, by adjusting the relative flow rates (ratio of activated chemically-treated solid oxide: transition metal compound) to the catalyst preparation vessel on the other hand, by adjusting the flow rate of the catalyst system leaving the catalyst preparation vessel and entering the reactor on the other hand, or on the other hand by any combination of these techniques.

[0056] As an example, if the catalytic activity of the activated chemically-treated solid oxide is below the target activity, the flow rate of the activated chemically-treated solid oxide into the reactor can be increased by increasing the relative flow rates (ratio of activated chemically-treated solid oxide: transition metal compound) to the catalyst preparation vessel. This can be accomplished, for example, by increasing the feed rate of the activated chemically-treated solid oxide to the catalyst preparation vessel while keeping the feed rate of the transition metal compound to the catalyst preparation vessel constant.

[0057] Optionally, the disclosed process for operating a polymerization reactor system may also include - based on the catalytic activity of the activated chemically treated solid oxide - controlling the flow rate of the transition metal compound into the reactor; additionally or alternatively, controlling the flow rate of the cocatalyst into the reactor; additionally or alternatively, controlling the ethylene concentration in the reactor; or additionally or alternatively, controlling the polymerization temperature in the reactor. As a non-limiting illustration, if the catalytic activity of the activated chemically treated solid oxide is below a particular target value, the ethylene concentration in the reactor may be increased to compensate for the lower activity of the activated chemically treated solid oxide. Similarly, the polymerization temperature may be increased to compensate for the lower activity of the activated chemically treated solid oxide.

[0058] In another aspect of the present invention, a polymerization reactor system is provided, and in this aspect, the polymerization reactor system may include: (A) a reactor, the reactor being configured to contact a catalyst system with an olefin monomer and an optional olefin comonomer under polymerization reaction conditions to produce an olefin polymer, (B) a catalyst preparation container, the catalyst preparation container being configured to contact a transition metal compound, an activated chemically treated solid oxide and an optional cocatalyst to form a catalyst system, and (C) an analysis system, the analysis system being configured to determine the catalytic activity of the activated chemically treated solid oxide before the activated chemically treated solid oxide is introduced into the catalyst preparation container. Generally, the features of any polymerization reactor system disclosed herein (e.g., polymerization reactor, catalyst system, olefin monomer (and olefin comonomer, if any), polymerization conditions, olefin polymer, catalyst preparation container and analysis system, etc.) are described independently herein, and these features can be combined in any combination to further describe the disclosed polymerization reactor system. In addition, unless otherwise specified, in addition to the reactor, catalyst preparation container and analysis system, other devices or reactor system components may also be present in the disclosed polymerization reactor system. Additionally, in certain aspects contemplated herein, the catalyst system can be contacted with an olefin monomer and an olefin comonomer in a polymerization reactor (eg, contacted with ethylene and an α-olefin comonomer, such as 1-hexene).

[0059] First, the analysis system may include any analysis system or device configured to determine the catalytic activity of the activated chemically treated solid oxide before the activated chemically treated solid oxide is introduced into the catalyst preparation vessel. For example, the analysis system may include a suitable color measuring instrument or color analyzer, such as a smart phone, a spectrophotometer, a colorimeter, etc. In one aspect of the present invention, the analysis system may include: a color analyzer for measuring the color of the activated chemically treated solid oxide after contacting the activated chemically treated solid oxide with a color indicator solution; and a computer system for generating a color value (e.g., R+G+B) of the treated solid support, and for associating the color value with a standard to determine the catalytic activity of the activated chemically treated solid oxide. The computer system may be "built-in" or integrated with the color analyzer, or the computer system may be external, so that the external computer system obtains the output of the color analyzer and determines the catalytic activity. As described herein, the standard may include a calibration curve, and the association step may include any suitable technique for converting the color value into the catalytic activity of the activated chemically treated solid oxide, such as a mathematical model.

[0060] The catalyst preparation container may include any container or equipment capable of contacting two or more components of the catalyst system (e.g., mixing or blending) to form a catalyst system. The catalyst preparation container may be a mixing tank or other suitable stirred tank or container. The catalyst system may be transferred to the reactor from the catalyst preparation container as required. Often, in the catalyst preparation container, a transition metal compound (e.g., one, two, or three) and an activated chemically treated solid oxide are contacted, or alternatively, a transition metal compound (e.g., one, two, or three), an activated chemically treated solid oxide and a co-catalyst are contacted to form a catalyst system. Multi-component catalyst preparation containers and methods are disclosed in, for example, U.S. Patent No. 7,615,596 (e.g., pre-contactor), which is incorporated herein by reference in its entirety.

[0061] Optionally, the polymerization reactor system may also include a controller, which is configured to control the flow rate of the activated chemically treated solid oxide entering the reactor based on or according to the catalytic activity determined by the analytical system. Therefore, the polymerization reactor system may include a reactor, a catalyst preparation container, an analytical system and a controller. The controller that may include any suitable processing unit or computer system can be used to analyze the data about the catalytic activity of the activated chemically treated solid oxide, and adjust the flow rate of the activated chemically treated solid oxide entering the reactor system based on the determined activity. On the other hand, the controller may be programmed with an algorithm to control the flow rate of the activated chemically treated solid oxide entering the reactor system based on the catalytic activity determined by the analytical system. As an example, if the catalytic activity determined by the analytical system is too low, the flow rate may be increased by the controller.

[0062] Depending on the requirements of the reactor system, the controller can be operated as needed, at set time intervals, or continuously. Therefore, it is contemplated that the catalytic activity of the activated chemically treated solid oxide can be continuously monitored and / or adjusted and / or controlled. Therefore, in particular aspects consistent with the present invention, the polymerization reactor system and controller can be operated in real time or near real time, so that the catalytic activity of the activated chemically treated solid oxide can be determined, and the determined activity can be used instantly or nearly instantly to adjust the flow rate or feed rate of the activated chemically treated solid oxide.

[0063] The controller or computing device can be implemented using a personal computer, a network computer, a server, a mainframe or other similar microcomputer-based workstation. The controller or computing device may include any computer operating environment, such as a handheld device, a multiprocessor system, a microprocessor-based or programmable transmitter electronic device, a minicomputer, a mainframe computer, etc. The controller or computing device may also be implemented in a distributed computing environment where tasks are performed by a remote processing device. In addition, the controller or computing device may include a mobile terminal, such as a smart phone, a cellular phone, a cellular phone using a wireless application protocol (WAP), a personal digital assistant (PDA), an intelligent pager, a portable computer, a handheld computer, a conventional phone, a wireless fidelity (Wi-Fi) access point, or a fax machine. The aforementioned systems and devices are examples, and the controller or computing device may include other systems or devices. The controller or computing device may also be implemented via a system on a chip (SOC), in which each and / or many of the components described above may be integrated onto a single integrated circuit. Such a SOC device may include one or more processing units, a graphics unit, a communication unit, a system virtualization unit, and various application functions, all of which may be integrated (or "burned") onto a chip substrate as a single integrated circuit. Other controller methods and apparatus will be apparent to those skilled in the art in view of this disclosure.

[0064] The controller of the system disclosed herein can control the flow rate of the activated chemically-treated solid oxide into or within the polymerization reactor system by any method that provides precise and nearly instantaneous control based on the catalytic activity of the activated chemically-treated solid oxide.

[0065] The systems disclosed herein are applicable to a wide variety of situations in which the catalytic activity of the activated chemically treated solid oxide may be of interest. For example, the controller may also be configured to control the flow rate of the transition metal compound into the reactor, and / or the flow rate of the cocatalyst into the reactor, and / or the ethylene concentration in the reactor, and / or the polymerization temperature in the reactor based on or according to the catalytic activity determined by the analytical system.

[0066] Figure 1 A representative polymerization reactor system 100 consistent with aspects of the present invention is shown in . The polymerization reactor system 100 includes a catalyst preparation vessel 160, a reactor 170, an analysis system 180, and a controller 190. The analysis system 180 may include a color analyzer and a computer system as described herein. Figure 1 The polymerization reactor system 100 includes an activator feed stream 155 (at Figure 1 Not shown, but in Figure 2 Separate feed streams to the catalyst preparation vessel for the other catalyst components are shown in FIG. Figure 1 As shown, sample stream 158 from activator feed stream 155 is submitted to analysis system 180 to determine the catalytic activity of the activated chemically-treated solid oxide before it enters catalyst preparation vessel 160. Polymerization reactor system 100 includes catalyst system feed stream 165 from catalyst preparation vessel 160 to reactor 170. Other feed streams such as monomer / comonomer (e.g., ethylene and α-olefin comonomer), hydrogen, diluent, etc. to the reactor are not fed in the reactor. Figure 1 However, those skilled in the art will recognize their existence.

[0067] Information or data 185 from the analysis system 180 regarding the catalytic activity of the activated chemically-treated solid oxide can be provided to the controller 190, which can then control or adjust 195 the flow rate of the activated chemically-treated solid oxide into the reactor (e.g., into the catalyst preparation vessel), the flow rate of the transition metal compound and / or the co-catalyst into the reactor (e.g., into the catalyst preparation vessel), the ethylene concentration in the reactor, and / or the polymerization temperature in the reactor. For example, if the activity determined by the analysis system 180 is too low or below a target value, the controller 190 can increase the feed rate of the activated chemically-treated solid oxide 155 to the catalyst preparation vessel 160 (and therefore to the reactor 170). As another example, if the catalytic activity is too low or below a target value, the controller 190 can increase the ethylene concentration in the reactor.

[0068] The disclosed polymerization reactor system and its operation method are intended to cover any olefin polymerization process using any / all types of polymerization reactors and polymerization reaction conditions. As used herein, "polymerization reactor" includes any polymerization reactor capable of polymerizing (including oligomerization) olefin monomers and comonomers (one or more than one comonomer, if used) to produce homopolymers, copolymers, terpolymers, etc. Various types of polymerization reactors include those that can be referred to as slurry reactors, gas phase reactors, solution reactors, high pressure reactors, tubular reactors, autoclave reactors, etc., including those of their combinations. The polymerization conditions of various reactor types are well known to those skilled in the art. The gas phase reactor may include a fluidized bed reactor or a graded horizontal reactor. The slurry reactor may include a vertical or horizontal loop. The high pressure reactor may include an autoclave or a tubular reactor. These reactor types can generally be operated continuously. Continuous processes can use intermittent or continuous polymer product discharge. The polymerization reactor system and process may also include partial or complete direct recycling of unreacted monomers, unreacted comonomers and / or diluents.

[0069] The polymerization reactor system disclosed herein may include a type of polymerization reactor or multiple reactors of the same or different types. For example, the polymerization reactor system may include a solution reactor, a gas phase reactor, a slurry reactor, or a combination of two or more of these reactors. Producing polymers in multiple reactors may include several stages in at least two separate polymerization reactors interconnected by a transfer device, and the transfer device makes it possible to transfer the polymer produced by the first polymerization reactor to the second reactor. The polymerization conditions in one reactor may be different from the operating conditions of other reactors. Alternatively, the polymerization in multiple reactors may include manually transferring polymers from one reactor to a subsequent reactor to continue polymerization. The multi-reactor system may include any combination, including but not limited to a combination of multiple loop reactors, multiple gas phase reactors, a loop reactor and a gas phase reactor, a combination of multiple high-pressure reactors or a high-pressure reactor with a loop reactor and / or a gas phase reactor. Multiple reactors can be operated in series, in parallel, or in a manner that has both.

[0070] According to one aspect, the polymerization reactor system may include at least one loop slurry reactor, for example, including a vertical or horizontal loop. Monomer, diluent, catalyst and optional comonomer can be continuously fed to the loop reactor where polymerization occurs. Typically, a continuous process may include continuously introducing monomer / comonomer, catalyst and diluent into a polymerization reactor, and continuously removing a suspension comprising polymer particles and diluent from this reactor. The reactor effluent may be flashed to remove solid polymer from a liquid comprising diluent, monomer and / or comonomer. A variety of techniques may be used for this separation step, including but not limited to: flashing that may include any combination of heating and decompression, separation by cyclone action in a cyclone separator or hydrocyclone separator, or separation by centrifugation.

[0071] Typical slurry polymerization processes (also referred to as particle form processes) are disclosed, for example, in U.S. Pat. Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, 6,833,415, and 8,822,608, each of which is incorporated herein by reference in its entirety.

[0072] Suitable diluents used in the slurry polymerization include, but are not limited to, the monomers being polymerized and hydrocarbons that are liquid under the reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, normal butane, normal pentane, isopentane, neopentane, and normal hexane. Some loop polymerizations can occur under bulk conditions without the use of a diluent, such as can be used in bulk polymerization of propylene to form a polypropylene homopolymer.

[0073] According to another aspect, the polymerization reactor system may include at least one gas phase reactor (e.g., a fluidized bed reactor). Such a reactor system may employ a continuous recycle stream containing one or more monomers, which is continuously circulated through a fluidized bed under polymerization conditions in the presence of a catalyst. The recycle stream may be taken out of the fluidized bed and recycled back into the reactor. At the same time, the polymer product may be taken out from the reactor, and new or fresh monomers may be added to replace the polymerized monomers. Such a gas phase reactor may constitute a process for the multi-step gas phase polymerization of olefins, wherein the olefins are polymerized in gas phase in at least two independent gas phase polymerization zones, while the catalyst-containing polymer formed in the first polymerization zone is fed to the second polymerization zone. A type of gas phase reactor is disclosed in U.S. Patent Nos. 5,352,749, 4,588,790, 5,436,304, 7,531,606, and 7,598,327, each of which is incorporated herein by reference in its entirety.

[0074] According to another aspect, the polymerization reactor system may include a high pressure polymerization reactor, for example, a tubular reactor or an autoclave reactor. The tubular reactor may have several zones in which fresh monomers, initiators or catalysts are added. The monomers may be entrained in an inert gas stream and introduced into one zone of the reactor. Initiators, catalysts and / or catalyst components may be entrained in a gas stream and introduced into another zone of the reactor. The gas streams may be mixed to polymerize. Heat and pressure may be appropriately used in such high pressure polymerization reactors to obtain optimal polymerization reaction conditions.

[0075] According to another aspect, the polymerization reactor system may include a solution polymerization reactor, wherein the monomer / comonomer may be contacted with the catalyst composition by suitable stirring or other means. A carrier comprising an inert organic diluent or excess monomer may be used. If desired, the monomer / comonomer may be contacted with the catalytic reaction product in the gas phase in the presence or absence of a liquid material. The polymerization zone may be maintained at a temperature (e.g., up to 150° C. to 180° C.) and pressure that will result in the formation of a polymer solution in the reaction medium. Stirring may be used to obtain better temperature control and maintain a uniform polymerization mixture throughout the polymerization zone. The exothermic heat of polymerization may be dissipated by appropriate means.

[0076] In some aspects, the polymerization reactor system may include any combination of the following: a raw material feed system, a feed system for catalyst and / or catalyst components, and / or a polymer recovery system, including a continuous system. In other aspects, a suitable reactor system may include systems for raw material purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, loading, laboratory analysis, and process control.

[0077] The polymerization conditions that can be monitored, adjusted and / or controlled to achieve efficiency and provide desired polymer properties may include, but are not limited to, reactor temperature, reactor pressure, catalyst system flow rate into the reactor, monomer (and comonomer, if used) flow rate into the reactor, monomer concentration in the reactor, olefin polymer output rate, recycle rate, hydrogen flow rate (if used), reactor cooling state, etc. The polymerization temperature may affect catalyst productivity, polymer molecular weight and molecular weight distribution. According to the Gibbs Free Energy Equation, a suitable polymerization temperature may be any temperature below the depolymerization temperature. Typically, depending on the type of polymerization reactor, polymer grade, etc., this includes about 60°C to about 280°C, such as about 60°C to about 185°C, about 60°C to about 115°C, or about 130°C to about 180°C. In some reactor systems, the polymerization reactor temperature may generally be in the range of about 70°C to about 110°C, or about 125°C to about 175°C.

[0078] Suitable pressures will also vary depending on the reactor and polymerization type. The pressure for liquid phase polymerization in a loop reactor may typically be less than 1000 psig (6.9 MPa). The pressure for gas phase polymerization may typically be in the range of 200 psig to 500 psig (1.4 MPa to 3.4 MPa). High pressure polymerization in a tubular reactor or autoclave reactor may typically be carried out at about 20,000 psig to 75,000 psig (138 MPa to 517 MPa). The polymerization reactor may also be operated in a supercritical region, which typically occurs at higher temperatures and pressures (e.g., above 92° C. and 700 psig (4.83 MPa)). Operation above the critical point (supercritical phase) of the pressure / temperature diagram may provide advantages for the polymerization process.

[0079] The concentration of reactants entering the polymerization reactor can be controlled to produce resins with certain physical and mechanical properties. The proposed end-use product to be formed from the polymer resin and the method of ultimately forming the product can determine the desired polymer properties and attributes. Mechanical properties include tensile, flexural, impact, creep, stress relaxation and hardness tests. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystalline melting temperature, stereoregularity, crack growth, long chain branching and rheological measurements.

[0080] Aspects contemplated herein also relate to and encompass polymers (or oligomers) produced by any polymerization reactor system and method disclosed herein. Articles may be formed from and / or may include polymers (or oligomers) produced according to the systems and methods described herein.

[0081] Catalyst system

[0082] The methods, processes and systems disclosed herein are applicable to any catalyst system suitable for the polymerization of olefin monomers, but are not limited thereto. In this article, "catalyst system" may also be referred to as "catalyst composition," and these terms are used interchangeably. In the catalyst system (or catalyst composition), the transition metal compound may include (or each transition metal compound may independently include, if there are two or more transition metal compounds in the catalyst system) a transition metal (one or more than one) from Groups 3 to 12 of the periodic table of the elements (Chemical and Engineering News, 63 (5), 27, 1985). In one aspect, the transition metal compound may include (or each transition metal compound may independently include) a transition metal of Group 3, 4, 5 or 6, or a combination of two or more transition metals. In some aspects, the transition metal compound may include (or each transition metal compound may independently include) chromium, vanadium, titanium, zirconium, hafnium or a combination thereof, or in other aspects may include chromium, titanium, zirconium, hafnium or a combination thereof. Thus, the transition metal compound may contain (or each transition metal compound may independently contain) chromium, or titanium, or zirconium, or hafnium, alone or in combination.

[0083] In certain aspects of the invention, the transition metal compound may include (or each transition metal compound may independently include) any suitable non-metallocene compound. Generally, the methods, processes and systems disclosed herein are most suitable for transition metal compounds, such as non-metallocene compounds, wherein such transition metal compounds are suitable for use in olefin polymerization processes, such as ethylene-based polymerization processes.

[0084] Illustrative and non-limiting examples of suitable transition metal compounds contemplated herein may include the following compounds (R and R' = halide or C1-C 18 Hydrocarbyl, n=integer from 0 to 4, Ph=phenyl, tBu=tert-butyl, py=pyridine):

[0085]

[0086]

[0087] Alternatively or additionally, in some aspects, the transition metal compound may include (or each transition metal compound may independently include) a metallocene compound. On the one hand, the transition metal compound may include (or at least one transition metal compound in the catalyst system may include) an unbridged metallocene compound. For example, the metallocene compound may include an unbridged zirconium or hafnium-based metallocene compound and / or an unbridged zirconium and / or hafnium-based binuclear metallocene compound. On the other hand, the metallocene compound may include an unbridged zirconium-based or hafnium-based metallocene compound containing two indenyls or cyclopentadienyls and indenyls. On the other hand, the metallocene compound may include an unbridged zirconium-based or hafnium-based metallocene compound containing two indenyls. On the other hand, the metallocene compound may include an unbridged zirconium-based or hafnium-based metallocene compound containing two indenyls. On the other hand, the metallocene compound may include an unbridged zirconium-based or hafnium-based metallocene compound containing cyclopentadienyls and indenyls.

[0088] In one aspect, the metallocene compound may include an unbridged zirconium-based metallocene compound containing two indenyl groups or a cyclopentadienyl group and an indenyl group, while in another aspect, the metallocene compound may include a dinuclear unbridged metallocene compound having an alkenyl linking group.

[0089] Illustrative and non-limiting examples of unbridged metallocene compounds suitable for use as transition metal compounds described herein may include the following compounds (Ph = phenyl, stereochemistry not shown):

[0090]

[0091]

[0092] etc., and combinations thereof.

[0093] The transition metal compound is not limited to unbridged metallocene compounds such as those described above, or suitable unbridged metallocene compounds disclosed in U.S. Pat. Nos. 7,199,073, 7,226,886, 7,312,283 and 7,619,047, which are incorporated herein by reference in their entirety. For example, the transition metal compound may include unbridged dinuclear metallocene compounds such as those described in U.S. Pat. Nos. 7,919,639 and 8,080,681, the disclosures of which are incorporated herein by reference in their entirety. Illustrative and non-limiting examples of dinuclear metallocene compounds suitable for use in the present invention may include the following compounds (stereochemical structures not shown):

[0094]

[0095] etc., and combinations thereof.

[0096] In various aspects of the invention, the transition metal compound may include (or at least one transition metal compound in the catalyst system may include) a bridged metallocene compound. For example, the bridged metallocene compound may include a bridged zirconium or hafnium-based metallocene compound. On the other hand, the bridged metallocene compound may include a bridged zirconium or hafnium-based metallocene compound with an alkenyl substituent. On the other hand, the bridged metallocene compound may include a bridged zirconium or hafnium-based metallocene compound with an alkenyl substituent and a fluorenyl group. On the other hand, the bridged metallocene compound may include a bridged zirconium or hafnium-based metallocene compound with an alkenyl substituent and a fluorenyl group. On a further aspect, the bridged metallocene compound may include a bridged zirconium or hafnium-based metallocene compound with a cyclopentadienyl group and a fluorenyl group, and an alkenyl substituent on the bridging group and / or the cyclopentadienyl group.

[0097] In one aspect, the bridged metallocene compound may include a single atom bridged metallocene compound having a fluorenyl group. In another aspect, the bridged metallocene compound may include a single atom bridged metallocene compound having a fluorenyl group and a cyclopentadienyl group or an indenyl group. In yet another aspect, the bridged metallocene compound may include a single atom bridged metallocene compound having a fluorenyl group and a cyclopentadienyl group. In yet another aspect, the bridged metallocene compound may include a single atom bridged metallocene compound having a fluorenyl group and an indenyl group.

[0098] In these and other aspects, the bridged metallocene compound can contain an aryl substituent (e.g., phenyl) on the bridging atom. Additionally or alternatively, the bridged metallocene compound can contain an alkenyl substituent, for example, on the bridging atom and / or on the fluorenyl group and / or on the cyclopentadienyl or indenyl group.

[0099] Illustrative and non-limiting examples of suitable bridged metallocene compounds contemplated herein may include the following compounds (Me = methyl, Ph = phenyl, t-Bu = tert-butyl, stereochemistry not shown):

[0100]

[0101]

[0102] etc., and combinations thereof.

[0103] Other examples of bridged metallocene compounds suitable for use as described herein may include, but are not limited to, the following compounds (stereochemistry not shown):

[0104]

[0105] etc., and combinations thereof.

[0106] The transition metal compounds are not limited to bridged metallocene compounds such as those described above. Other suitable bridged metallocene compounds are disclosed in U.S. Pat. Nos. 7,026,494, 7,041,617, 7,226,886, 7,312,283, 7,517,939, 7,619,047, 8,288,487, 8,329,834, 8,629,292 and 9,040,642, all of which are incorporated herein by reference in their entirety.

[0107] In a particular aspect of the invention, the catalyst system can contain two metallocene compounds, for example, two different unbridged metallocene compounds, two different bridged metallocene compounds, or a bridged metallocene compound and an unbridged metallocene compound. When there are two transition metal compounds (or two metallocene compounds), the weight ratio of the first compound to the second compound (first: second) can typically be in the range of about 50: 1 to about 1: 50, about 10: 1 to about 1: 10, about 5: 1 to about 1: 5, about 4: 1 to about 1: 4, about 3: 1 to about 1: 3, about 2: 1 to about 1: 2, about 1.5: 1 to about 1: 1.5, or about 1.2: 1 to about 1: 1.2.

[0108] In addition to the transition metal compound, the catalyst system may also include an activated chemically treated solid oxide (one or more) and an optional cocatalyst. Illustrative cocatalysts may include, but are not limited to, aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum (e.g., alkylaluminum) compounds, and the like, and combinations thereof. Representative organoaluminum compounds may include, but are not limited to, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, ethoxydiethylaluminum, diethylaluminum chloride, and the like, including combinations thereof.

[0109] The cocatalysts that can be used for the catalyst system of the present invention are not limited to the cocatalysts described above. Other suitable cocatalysts are well known to those skilled in the art, including, for example, those disclosed in U.S. Patent Nos. 3,242,099, 4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, 7,294,599, 7,601,665, 7,884,163, 8,114,946 and 8,309,485, which are incorporated herein by reference in their entirety.

[0110] Chemically treated solid oxide

[0111] The present invention encompasses various catalyst compositions that may contain chemically treated solid oxides. In one aspect, the chemically treated solid oxide may include a solid oxide treated with an electron-withdrawing anion. Alternatively, in another aspect, the chemically treated solid oxide may include a solid oxide treated with an electron-withdrawing anion, the solid oxide containing a Lewis acidic metal ion. Non-limiting examples of suitable chemically treated solid oxides are disclosed in, for example, U.S. Patent Nos. 7,294,599, 7,601,665, 7,884,163, 8,309,485, 8,623,973 and 8,703,886, which are incorporated herein by reference in their entirety.

[0112] Solid oxides may encompass oxide materials such as alumina, "mixed oxides" thereof such as silica-alumina, coatings of one oxide on another oxide, and combinations and mixtures thereof. Mixed oxides such as silica-alumina may be single or multiple chemical phases in which more than one metal is combined with oxygen to form a solid oxide. Examples of mixed oxides that may be used alone or in combination to form a chemically treated solid oxide may include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, alumina-titania, alumina-zirconia, zinc aluminate, alumina-boria, silica-boria, aluminum phosphate-silica, titania-zirconia, and the like. As described in U.S. Pat. No. 7,884,163, solid oxides used herein may also encompass oxide materials such as silica-coated alumina.

[0113] Therefore, on the one hand, the solid oxide may include silica, alumina, silica-alumina, silica-coated alumina, aluminophosphate, aluminum phosphate, heteropolytungstate, titania, silica-titania, zirconium oxide, silica-zirconia, magnesium oxide, boron oxide, zinc oxide, any mixed oxide thereof, or any combination thereof. On the other hand, the solid oxide may include alumina, silica-alumina, silica-coated alumina, aluminophosphate, aluminum phosphate, heteropolytungstate, titania, silica-titania, zirconium oxide, silica-zirconia, magnesium oxide, boron oxide, or zinc oxide, and any mixed oxide thereof, or any mixture thereof. On the other hand, the solid oxide may include silica, alumina, titania, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, any mixed oxide thereof, or any combination thereof. On the other hand, the solid oxide may include silica, alumina, titania, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, any mixed oxide thereof, or any combination thereof. On the other hand, the solid oxide may include silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-boron oxide, or any combination thereof. In yet another aspect, the solid oxide can comprise alumina, silica-alumina, silica-coated alumina, or any mixture thereof; alternatively, alumina; alternatively, silica-alumina; or alternatively, silica-coated alumina.

[0114] The alumina solid oxide material of silica-alumina or silica coating that can be used can have the silica content of about 5 weight % to about 95 weight %.On the one hand, the silica content of these solid oxides can be the silica of about 10 weight % to about 80 weight %, or the silica of about 20 weight % to about 70 weight %.On the other hand, the scope of the silica content of such materials can be the silica of about 15 weight % to about 60 weight %, or the silica of about 25 weight % to about 50 weight %.The solid oxide considered herein can have any suitable surface area, pore volume and particle size, as recognized by those skilled in the art.

[0115] The electron-withdrawing component used to treat the solid oxide can be an anion that increases the Lewis or Bronsted properties of the solid oxide after treatment (compared to a solid oxide not treated with at least one electron-withdrawing anion). Any component of acidity. According to one aspect, the electron-withdrawing component may be an electron-withdrawing anion derived from a salt, acid or other compound (such as a volatile organic compound) that serves as a source or precursor of an electron-withdrawing anion. Examples of electron-withdrawing anions may include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trifluoromethanesulfonate, fluorozirconate, fluorotitanate, phosphotungstate, tungstate, molybdate, etc., including mixtures and combinations thereof. In addition, other ions or nonionic compounds serving as sources of these electron-withdrawing anions may also be used. In some aspects provided herein, it is contemplated that the electron-withdrawing anion may be or may include fluoride, chloride, bromide, phosphate, trifluoromethanesulfonate, bisulfate or sulfate, etc., or any combination thereof. In other aspects, the electron-withdrawing anion can include sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trifluoromethanesulfonate, fluorozirconate, fluorotitanate, etc., or combinations thereof. However, in other aspects, the electron-withdrawing anion can include fluoride and / or sulfate.

[0116] Based on the weight of the chemically treated solid oxide, the chemically treated solid oxide can generally contain about 1 wt % to about 25 wt % of electron-withdrawing anions. In specific aspects provided herein, based on the total weight of the chemically treated solid oxide, the chemically treated solid oxide can contain about 1 wt % to about 20 wt %, about 2 wt % to about 20 wt %, about 3 wt % to about 20 wt %, about 2 wt % to about 15 wt %, about 3 wt % to about 15 wt %, about 3 wt % to about 12 wt %, or about 4 wt % to about 10 wt % of electron-withdrawing anions.

[0117] In one aspect, the chemically-treated solid oxide (whether in activated or unactivated form) can include fluorided alumina, chlorided alumina, brominated alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, fluorided-chlorinated silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, and the like, and any mixtures or combinations thereof. On the other hand, the chemically treated solid oxide employed in the catalyst system described herein may be or may include a fluorinated solid oxide and / or a sulfated solid oxide, non-limiting examples of which may include fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, fluorinated silica-coated alumina, sulfated silica-coated alumina, and the like, and combinations thereof. In yet another aspect, the chemically treated solid oxide may include fluorinated alumina; alternatively, chlorided alumina; alternatively, sulfated alumina; alternatively, fluorinated silica-alumina; alternatively, sulfated silica-alumina; alternatively, fluorinated silica-zirconia; alternatively, chlorided silica-zirconia; alternatively, sulfated silica-coated alumina; alternatively, fluorinated-chlorinated silica-coated alumina; or alternatively, fluorinated silica-coated alumina. In some aspects, the chemically treated solid oxide may include a fluorinated solid oxide, while in other aspects, the chemically treated solid oxide may include a sulfated solid oxide.

[0118] Various processes can be used to form chemically treated solid oxides useful in the present invention. Methods of contacting the solid oxide with an electron-withdrawing component, suitable electron-withdrawing components and amounts added, impregnation with a metal or metal ion (e.g., zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, etc., or combinations thereof), and various calcination procedures and conditions are disclosed, for example, in U.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6 , 388,017, 6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894, 6,667,274, 6,750,302, 7,294,599, 7,601,665, 7,884,163, and 8,309,485, which are incorporated herein by reference in their entirety. Other suitable processes and procedures for preparing chemically treated solid oxides (e.g., fluorinated solid oxides and sulfated solid oxides) are well known to those skilled in the art.

[0119] Olefin monomers and olefin polymers

[0120] The olefin monomers considered herein typically include olefin compounds with 2 to 30 carbon atoms per molecule and at least one olefinic double bond. Homopolymerization processes using single olefins (such as ethylene, propylene, butylene, hexene, octene, etc.) are encompassed, as well as copolymerization, homopolymerization, trimerization, and similar polymerization reactions using olefin monomers and at least one different olefinic compound. Polymerization processes herein are also intended to encompass oligomerization processes.

[0121] For example, any resulting ethylene copolymer or terpolymer may typically contain a large amount of ethylene (>50 mol%) and a small amount of comonomer (<50 mol%). Comonomers copolymerizable with ethylene often have from 3 to 20 carbon atoms in their molecular chain.

[0122] Acyclic, cyclic, polycyclic, terminal (α), internal, straight chain, branched, substituted, unsubstituted, functionalized and non-functionalized olefins can be used. For example, typical unsaturated compounds that can be polymerized to produce olefin polymers may include but are not limited to ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, four common octenes (e.g., 1-octene), four common nonenes, five common decenes, etc., or a mixture of two or more of these compounds. Cyclic and bicyclic olefins including but not limited to cyclopentene, cyclohexene, norbornene, norbornadiene, etc., may also be polymerized as described herein. Styrene may also be used as a monomer or comonomer. On the one hand, olefin monomers may include C2-C 24 Olefins; alternatively, C2-C 12 Olefins; alternatively, C6-C 24 Olefins; alternatively, C2-C 10 α-olefins; alternatively, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene or styrene; alternatively, ethylene, propylene, 1-butene, 1-hexene or 1-octene; alternatively, ethylene or propylene; alternatively, ethylene; or alternatively, propylene.

[0123] When copolymer (or alternatively, terpolymer) is needed, olefin monomer may include ethylene or propylene copolymerized with at least one comonomer, for example. According to one aspect, olefin monomer in polymerization process may include ethylene. In this regard, the example of suitable olefin comonomer may include but is not limited to propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, etc., or a combination thereof. According to another aspect, olefin monomer may include ethylene, and olefin comonomer may include alpha-olefin, and in another aspect, comonomer may include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof; or alternatively, olefin comonomer may include 1-butene, 1-hexene, 1-octene, or a combination thereof.

[0124] Typically, based on the total weight of monomers and comonomers, the amount of comonomers introduced into the polymerization reactor to produce copolymers can be about 0.01 weight percent (wt%) to about 50 weight percent comonomers. According to another aspect, based on the total weight of monomers and comonomers, the amount of comonomers introduced into the polymerization reactor can be about 0.01 weight percent to about 40 weight percent comonomers. In yet another aspect, based on the total weight of monomers and comonomers, the amount of comonomers introduced into the polymerization reactor can be about 0.1 weight percent to about 35 weight percent comonomers. In yet another aspect, based on the total weight of monomers and comonomers, the amount of comonomers introduced into the polymerization reactor can be about 0.5 weight percent to about 20 weight percent comonomers.

[0125] According to one aspect, at least one monomer / reactant may be ethylene, and thus the polymerization reaction may be a homopolymerization involving only ethylene, or a copolymerization with different acyclic, cyclic, terminal, internal, linear, branched, substituted or unsubstituted olefins. In addition, the methods disclosed herein are intended to include olefins as well as diene compounds, including but not limited to 1,3-butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, and the like.

[0126] The olefin polymers encompassed herein may include any polymer (or oligomer) produced by any olefin monomer (and optional comonomer) described herein. For example, the olefin polymer may include ethylene homopolymers, propylene homopolymers, ethylene copolymers (e.g., ethylene / 1-butene, ethylene / 1-hexene, or ethylene / 1-octene), propylene random copolymers, propylene block copolymers, etc., including combinations thereof. In addition, in certain aspects, the olefin polymer (or oligomer) may include olefin dimers, olefin trimers, or olefin tetramers, and mixtures or combinations thereof. Thus, the olefin polymer encompasses C6-C 24 Olefins (or C6-C 24 α-olefins, or 1-hexene, or 1-octene, or 1-decene, or 1-dodecene, or 1-tetradecene, or 1-hexadecene).

[0127] Catalyst preparation

[0128] The disclosed method for determining the catalytic activity of the activated chemically treated solid oxide can also be used in the process of preparing the catalyst composition. A process for preparing the catalyst composition may include: (I) determining the catalytic activity of the activated chemically treated solid oxide, wherein the catalytic activity is determined via any method described herein, (II) contacting the transition metal compound, the activated chemically treated solid oxide and an optional co-catalyst (e.g., in a catalyst preparation container) to form a catalyst composition, and (III) adjusting the relative amount of at least one component of the catalyst composition based on the catalytic activity of the activated chemically treated solid oxide (or based on the determined catalytic activity). Therefore, the flow rate (or feed rate) of the components of the catalyst composition can be manually and / or automatically adjusted based on the determined activity. Generally, the features of the process for preparing the catalyst composition disclosed herein (e.g., chemically treated solid oxide, transition metal compound, co-catalyst, method for determining catalytic activity and flow rate control of catalyst system components, etc.) are described independently herein, and can be combined in any combination to further describe the disclosed process. In addition, unless otherwise specified, other steps may be performed before, during and / or after any step listed in the disclosed process.

[0129] Step (I) involves determining the catalytic activity of the activated chemically treated solid oxide using a color measurement technique. Therefore, the specific features associated with step (I) may be the same as those disclosed and described herein when it relates to a method for determining the catalytic activity of an activated chemically treated solid oxide.

[0130] In step (II), the catalyst composition is formed by a transition metal compound, an activated chemically treated solid oxide and an optional promoter. In one aspect, the catalyst composition does not contain a promoter, while in another aspect and more often, the catalyst composition contains a promoter. Likewise, in some aspects, only one transition metal compound is present in the catalyst composition, while in other aspects, two or more transition metal compounds are present in the catalyst composition.

[0131] The catalyst composition can be formed by combining the corresponding components in any order or in any manner. For example, in step (II), a mixture of a transition metal compound and a co-catalyst can be contacted with an activated chemically treated solid oxide in a diluent. The diluent can be any hydrocarbon solvent disclosed herein, but is not limited thereto. In another example, in step (II), a first solution of a transition metal compound and a second solution of a co-catalyst can be contacted with an activated chemically treated solid oxide. As described above, the first solution and the second solution can utilize any suitable hydrocarbon solvent, but are not limited thereto.

[0132] The processes disclosed herein are applicable to a wide variety of situations in which the catalytic activity of the activated chemically treated solid oxide may be of interest. For example, when the catalytic activity of the activated chemically treated solid oxide is too low, the relative amount of the activated chemically treated solid oxide may be adjusted (increased) in step (III) - relatively more activated chemically treated solid oxide may be fed into the catalyst preparation vessel. Thus, the total amount of "active" chemically treated solid oxide in the catalyst preparation vessel increases due to the increase in the relative amount of chemically treated solid oxide.

[0133] Optionally, the disclosed process for preparing the catalyst composition may further include - based on the catalytic activity of the activated chemically-treated solid oxide - adjusting the relative amount of the transition metal compound and / or the promoter in step (III). For example, a relatively high concentration of transition metal compound in the catalyst composition may be used to compensate for the lower catalytic activity of the activated chemically-treated solid oxide.

[0134] In another aspect of the present invention, a catalyst preparation system is provided, and in this aspect, the catalyst preparation system may include: (a) a catalyst preparation vessel, the catalyst preparation vessel being configured to contact a transition metal compound, an activated chemically-treated solid oxide, and an optional co-catalyst to form a catalyst composition, (b) an activator feed stream, the activator feed stream being configured to introduce the activated chemically-treated solid oxide into the catalyst preparation vessel, (c) a transition metal compound feed stream, the transition metal compound feed stream being configured to introduce the transition metal compound into the catalyst preparation vessel, (d) a catalyst system feed stream, the catalyst system feed stream being configured to remove the catalyst composition from the catalyst preparation vessel (for example, and introduce the catalyst composition into a reactor, if desired), and (e) an analytical system, the analytical system being configured to determine the catalytic activity of the activated chemically-treated solid oxide before introducing the activated chemically-treated solid oxide into the catalyst preparation vessel.

[0135] Typically, the features of any catalyst preparation system disclosed herein (e.g., catalyst preparation container, activator feed stream, transition metal compound feed stream, catalyst system feed stream and analysis system, etc.) are described independently herein, and these features can be combined in any combination to further describe the disclosed catalyst preparation system. In addition, unless otherwise stated, other devices or catalyst preparation system components may be present in the disclosed catalyst preparation system. For example, the catalyst preparation system may also include a cocatalyst feed stream configured to introduce a cocatalyst into the catalyst preparation container. Alternatively, the cocatalyst feed stream can be combined (pre-contact) with the activator feed stream, and then the resulting pre-contact mixture can be fed into the catalyst preparation container.

[0136] First, the analysis system may include any analysis system or device configured to determine the catalytic activity of the activated chemically treated solid oxide before the activated chemically treated solid oxide is introduced into the catalyst preparation vessel. For example, the analysis system may include a suitable color measuring instrument or color analyzer, such as a smart phone, a spectrophotometer, a colorimeter, etc. In one aspect of the present invention, the analysis system may include: a color analyzer for measuring the color of the activated chemically treated solid oxide after contacting the activated chemically treated solid oxide with a color indicator solution; and a computer system for generating a color value (e.g., R+G+B) of the treated solid support, and for associating the color value with a standard to determine the catalytic activity of the activated chemically treated solid oxide. The computer system may be "built-in" or integrated with the color analyzer, or the computer system may be external, so that the external computer system obtains the output of the color analyzer and determines the catalytic activity. As described herein, the standard may include a calibration curve, and the association step may include any suitable technique for converting the color value into the catalytic activity of the activated chemically treated solid oxide, such as a mathematical model. Furthermore, the analysis system may further comprise a washing system configured to clean the color analyzer after a measurement cycle (and before the next measurement cycle).

[0137] The catalyst preparation container may include any container or equipment capable of contacting two or more components of the catalyst system (e.g., mixing or blending) to form a catalyst composition. The catalyst preparation container may be a mixing tank or other suitable stirred tank or container. The catalyst composition may be transmitted to the reactor from the catalyst preparation container via the catalyst system feed stream as required. Often, in the catalyst preparation container, a transition metal compound (e.g., one, two, or three) and an activated chemically treated solid oxide are contacted, or alternatively, a transition metal compound (e.g., one, two, or three), an activated chemically treated solid oxide and a co-catalyst are contacted to form a catalyst system. Multi-component catalyst preparation containers and methods are disclosed in, for example, U.S. Patent No. 7,615,596 (e.g., pre-contactor), which is incorporated herein by reference in its entirety. On the one hand, for example, only one transition metal compound is present in (a). In another aspect, two or more transition metal compounds are present in (a), and (c) comprises a single feed stream for introducing the mixture of transition metal compounds into the catalyst preparation vessel, or (c) comprises separate transition metal compound feed streams for introducing each transition metal compound individually into the catalyst preparation vessel.

[0138] The catalyst preparation system may also include (f) a controller configured to control the flow rate of the activator feed stream and / or the flow rate of the transition metal compound feed stream (and / or the flow rate of the co-catalyst, if used) entering the catalyst preparation vessel based on or according to the catalytic activity determined by the analytical system. For the catalyst preparation system, any features or options for the controller may be the same as those disclosed herein for the polymerization reactor system, or for the process of operating the polymerization reactor system. Thus, based on the catalytic activity determined by the analytical system, the flow rate of the activator feed stream flowing into the catalyst preparation vessel may be increased or decreased; additionally or alternatively, the flow rate of the transition metal compound feed stream may be increased or decreased; and additionally or alternatively, the flow rate of the co-catalyst feed stream may be increased or decreased.

[0139] Adjustments to the relative amounts of specific catalyst components can be readily determined by one skilled in the art based on, for example, historical and current conditions in the catalyst preparation vessel and the overall composition (eg, desired composition) of the catalyst composition.

[0140] As disclosed herein, the transition metal compound (or each transition metal compound independently) can include any suitable transition metal compound, whether a non-metallocene compound, a bridged metallocene compound, or an unbridged metallocene compound, etc. Likewise, the cocatalyst (when present) can include any suitable cocatalyst or any cocatalyst disclosed herein. In a particular aspect of the invention, the cocatalyst can include an organoaluminum compound, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and the like.

[0141] Figure 2 A representative catalyst preparation system 200 consistent with aspects of the present invention is shown in FIG. The catalyst preparation system 200 includes a catalyst preparation vessel 260, an analysis system 280, and a controller 290. Figure 2 Reactor 270 is also shown, and catalyst system feed stream 265 leaves catalyst preparation vessel 260 and passes through valve V210 before entering reactor 270. Catalyst preparation system 200 includes transition metal compound feed stream 252, cocatalyst feed stream 254, and activator feed stream 255 to catalyst preparation vessel 260. Figure 2 As shown, a sample stream 258 from the activator feed stream 255 from the activator mix tank 250 to the catalyst preparation vessel 260 can be submitted to the analysis system 280 to determine the catalytic activity of the activated chemically-treated solid oxide before it enters the catalyst preparation vessel 260.

[0142] The solid activated chemically treated solid oxide in the storage vessel 240 is transferred to the activator mixing tank 250 via pipeline 245 and valve V201, where the chemically treated solid oxide is typically combined with a small amount of diluent to form a flowable slurry consistency, or combined with a larger amount of diluent to form a slurry of diluted solids. The activator feed stream 255 leaves the mixing tank 250 and is usually transferred to the catalyst preparation vessel 260 through valves V202 and V203. By closing valve V203 and opening valve V204, a sample stream 258 is periodically obtained from the activator feed stream 255 for analysis (via analysis system 280).

[0143] Sample stream 258 passes through valve V205 and is passed into color analyzer and computer system 210, which may include any suitable sample chamber for containing samples during analysis. Here, sample stream 258-which contains activated chemically treated solid oxide-is combined with color indicator solution 206 via pipeline 208 and valves V207 and V208. After analysis, valve V207 is closed and valve V206 is opened to allow washing solution 202 to flow through pipeline 204 and valves V206 and V208 to wash or drain the sample chamber by washing or draining into disposal reservoir 205 through pipeline 215 and valve V209.

[0144] The information or data 285 regarding the catalytic activity from the analysis system 280 may be provided to the controller 290, which may then control or adjust 295 the flow rate of the activator feed stream 255, and / or the flow rate of the co-catalyst feed stream 254, and / or the flow rate of the transition metal feed stream 252 to the catalyst preparation vessel 260. Thus, the controller 290 controls or adjusts 285 the flow rate of the activator feed stream 255, the flow rate of the co-catalyst feed stream 254, and / or the flow rate of the transition metal compound feed stream 252 into the catalyst preparation vessel 260 based on or according to the catalytic activity determined by the analysis system 280. The controller 290 may further be configured to control the opening / closing function of the valves in the system, as well as their sequence, periodicity, and duration.

[0145] Activation system

[0146] Also contemplated herein are activation systems that can be utilized alone or in combination with the catalyst preparation systems and polymerization reactor systems described above. One such activation system can include: (a) an activation vessel configured to calcine a raw (or unactivated) chemically-treated solid oxide to form an activated chemically-treated solid oxide, (b) an activator storage vessel configured to receive the activated chemically-treated solid oxide from the activation vessel and further configured to introduce the activated chemically-treated solid oxide into the catalyst preparation vessel, and (c) an analytical system configured to determine the catalytic activity of the activated chemically-treated solid oxide prior to introducing the activated chemically-treated solid oxide into the catalyst preparation vessel.

[0147] Similar to the catalyst preparation system, the analysis system may include any analysis system or device configured to determine the catalytic activity of the activated chemically treated solid oxide before the activated chemically treated solid oxide is introduced into the catalyst preparation vessel. Therefore, the analysis system may include a suitable color measuring instrument or color analyzer, such as a smart phone, a spectrophotometer, a colorimeter, etc. In one aspect of the present invention, the analysis system may include: a color analyzer for measuring the color of the activated chemically treated solid oxide after contacting the activated chemically treated solid oxide with a color indicator solution; and a computer system for generating a color value (e.g., R+G+B) of the treated solid support, and for associating the color value with a standard to determine the catalytic activity of the activated chemically treated solid oxide. The computer system may be "built-in" or integrated with the color analyzer, or the computer system may be external, so that the external computer system obtains the output of the color analyzer and determines the catalytic activity. As described herein, the standard may include a calibration curve, and the association step may include any suitable technique for converting the color value into the catalytic activity of the activated chemically treated solid oxide, such as a mathematical model. Furthermore, the analysis system may further comprise a washing system configured to clean the color analyzer after a measurement cycle (and before the next measurement cycle).

[0148] The activation vessel can be a batch or continuous device for calcining the unactivated chemically treated solid oxide to form an activated chemically treated solid oxide. The operating conditions of such calcining devices / vessels are well known and described in many patents cited herein. For example, calcination can be performed in an ambient (air) atmosphere at a temperature of about 200° C. to about 900° C. (or about 400° C. to about 700° C., or about 350° C. to about 550° C.) for a period of 15 minutes to about 50 hours (or about 2 hours to about 20 hours, or about 1 hour to about 8 hours).

[0149] The activator storage container may include any container or device and can often be maintained under a controlled atmosphere, such as an inert atmosphere. The activation system may also include (d) a controller configured to control the flow rate of the activated chemically treated solid oxide from the activator storage container into the catalyst preparation container based on or according to the catalytic activity determined by the analytical system. In certain aspects, if the calcination step in the activation container is found to be inefficient, such that the catalytic activity of the activated chemically treated solid oxide is unacceptably low, the controller may prevent any flow from entering the catalyst preparation container, thereby preventing the generation of large amounts of substandard catalyst (and waste).

[0150] Figure 3 A representative activation system 300 consistent with aspects of the present invention is shown in FIG. Activation system 300 includes an activation container 330, an activation agent storage container 340, an analysis system 380, and a controller 390. Figure 3 The catalyst preparation system 200 is also shown in FIG. 1 , and the activator feed stream 345 leaves the activator storage container 340 and passes through valve V311 before it enters the catalyst preparation system 200. The original unactivated chemically treated solid oxide 320 is transferred to the activation container 330 through pipeline 325 and valve V301, where the unactivated chemically treated solid oxide is calcined under suitable conditions to form an activated chemically treated solid oxide. After passing through valve V302, the activated chemically treated solid oxide is transferred to the activator storage container 340 through pipeline 338 and valve V304.

[0151] like Figure 3 As shown, the sample stream 335 of the activated chemically treated solid oxide can be submitted to the analysis system 380 by valve V303 to determine the catalytic activity of the activated chemically treated solid oxide. This is achieved by periodically closing valve V304 and opening valve V303. Sample stream 335 passes through valve V303 and is transferred to the color analyzer and computer system 310, which may include any suitable sample chamber for accommodating samples during analysis. Here, sample stream 335-it contains the activated chemically treated solid oxide-is combined with color indicator solution 306 via pipeline 308 and valves V307 and V308. After analysis, close valve V307 and open valve V306 to allow washing solution 302 to flow through pipeline 304 and valves V306 and V308, to wash or empty the sample chamber by pipeline 315 and valve V309 to the disposal reservoir 305.

[0152] Information or data 385 about the catalytic activity from the analysis system 380 can be provided to the controller 390, which can then control or adjust 395 the flow rate of the activator feed stream 345 to the catalyst preparation system 200 (and the catalyst preparation vessel). A second sample stream 348 from the activator storage container of the activated chemically treated solid oxide can be submitted to the analysis system 380 through valve V310 to determine the catalytic activity of the activated chemically treated solid oxide entering the color analyzer and computer system 310 and its sample chamber. Similarly, information or data 385 about the catalytic activity of the second sample stream 348 from the analysis system 380 can be provided to the controller 390, which can then control or adjust 395 the flow rate of the activator feed stream 345 to the catalyst preparation system 200 (and the catalyst preparation vessel). Optionally, if the catalytic activity is found to be unsuitable, the contents of the activator storage vessel 340 may be recycled 342 to the activation vessel 330 via valve 305 for re-calcination / activation prior to its subsequent introduction into the catalyst preparation system 200 (catalyst preparation vessel). The controller 390 may further be configured to control the opening / closing function of the valves in the system, as well as their sequence, periodicity, and duration.

[0153] Example

[0154] The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the present invention in any way. After reading the description herein, various other aspects, modifications and equivalents thereof may be conceived by those of ordinary skill in the art without departing from the spirit of the present invention or the scope of the appended claims.

[0155] The polymerization experiments of Examples 1-4 were carried out in a 1-gallon stainless steel autoclave reactor for 30 minutes, and the reactor contained isobutane as a diluent. The solution of the metallocene compound was prepared by dissolving about 20 mg of the metallocene compound in 20 mL of toluene. Under isobutane purge, 0.4 mL of TIBA (1M in heptane), 100 mg of chemically treated solid oxide (CTSO) and metallocene solution (0.5 to 2 mg of metallocene compound) were loaded into the cold reactor through the loading port in this order. The reactor was closed and isobutane was added. The reactor was heated to the desired operating temperature of 90 ° C, and ethylene was then introduced into the reactor (1-hexene and hydrogen were not used). Ethylene was fed as needed to maintain a target pressure of 390 psig. Throughout the experiment, the reactor was maintained at the desired temperature by an automatic heating-cooling system. After the reactor was vented, purged and cooled, the resulting polymer product was dried under reduced pressure at 50 ° C. The structure of the metallocene compound used in Examples 1-4 is shown below (Me = methyl; t-Bu = tert-butyl):

[0156]

[0157] Example 1

[0158] Table 1 summarizes Example 1, where the chemically treated solid oxide (CTSO) was a sulfated alumina (14.7 wt% sulfate) activated / calcined at 600°C for 3 hours in dry nitrogen, with the exception of Example 1E, in which the sulfated alumina CTSO was not activated / calcined. The sulfated alumina was prepared as follows. A 300 m2 surface area 2 / g, alumina with a pore volume of 1.3 mL / g and an average particle size of 100 microns was calcined at 600°C for 15 minutes in air and then allowed to cool. Next, 100 g of the alumina was impregnated with 300 mL of water in which 15 g of concentrated sulfuric acid had been dissolved. The resulting wet powder was then vacuum dried at 100°C overnight. Calcination was performed at 600°C by fluidizing the sulfated alumina in dry nitrogen for 3 hours and then cooled to room temperature while still fluidized under nitrogen.

[0159] Examples 1A and 1E were tested for polymerization activity, and Examples 1B-1D were mixed with different amounts of water as shown in Table 1 and then tested for polymerization activity. Water was added to the sulfated alumina CTSO by injecting water into a nitrogen stream during fluidization at room temperature.

[0160] Additionally, approximately 300 mg samples of each CTSO were mixed with 3 mL of a heptane solution of butylated hydroxytoluene (BHT) (0.05 g BHT / mL) at room temperature for 1 hour. Figure 4 The resulting color of each treated solid oxide is shown in the photograph of , where Examples 1D-1E are white / off-white, Example 1C is yellow, Example 1B is yellow-orange, and Example 1A is reddish-orange. The color value (R+G+B) was determined for each example, and as shown in Table 1, there is a clear correlation between the treated solid oxide color, color value, and the catalytic activity of the CTSO in ethylene polymerization reactions. Figure 5 The correlation between the normalized catalytic activity and the color value of the chemically treated solid oxide is shown. Thus, a sample of the chemically treated solid oxide can be mixed with a color indicator solution and the resulting color value determined and then used Figure 5 Linear calibration curve or mathematical relationship in (statistical R 2 value of 0.97), the catalytic activity of the chemically-treated solid oxide can be determined without the need for polymerization experiments.

[0161] Example 2

[0162] Table 2 summarizes Example 2, where the chemically treated solid oxide (CTSO) was a fluorinated silica coated alumina (4.75 wt % fluoride) activated / calcined at 600°C for 3 hours in dry nitrogen, with the exception of Example 2E, in which the fluorinated silica coated alumina CTSO was not activated / calcined. The fluorinated silica coated alumina was prepared as follows. 400 mL of water and 100 g of silica coated alumina (40 wt % alumina, surface area 450 m 2 / g, pore volume of 1.3 mL / g, and average particle size of 35 microns) were mixed to make a slurry. Concentrated hydrofluoric acid solution (5 g HF) was mixed into the slurry, and the resulting slurry was then spray dried to a dry flowable powder. Calcination was performed at 600° C. by fluidizing the fluorinated silica-coated alumina in dry nitrogen for 3 hours, then cooling to room temperature while still fluidizing under nitrogen.

[0163] Examples 2A and 2E were tested for polymerization activity, and Examples 2B-2D were mixed with different amounts of water as shown in Table 2 and then tested for polymerization activity. Water was added to the fluorided silica-coated alumina CTSO by injecting water into a nitrogen stream during fluidization at room temperature.

[0164] In addition, approximately 300 mg samples of each CTSO were mixed with 3 mL of a heptane solution of butylated hydroxytoluene (BHT) (0.05 g BHT / mL) at room temperature for 1 hour. Color values ​​(R+G+B) were determined for each example, and as shown in Table 2, there is a clear correlation between the color of the treated solid oxide, the color value, and the catalytic activity of the CTSO in ethylene polymerization reactions. The data from Table 2 can be used to construct a similar Figure 5 2 to illustrate the correlation between the normalized catalytic activity and color value of the chemically treated solid oxide. Therefore, a sample of the chemically treated solid oxide can be mixed with a color indicator solution and the resulting color value can be determined, and then the catalytic activity of the chemically treated solid oxide can be determined using a linear calibration curve or mathematical relationship based on the data in Table 2 without the need for polymerization experiments.

[0165] Example 3

[0166] Table 3 summarizes Example 3, in which the chemically treated solid oxide (CTSO) was a sulfated alumina (14.7 wt % sulfate) activated / calcined at 300°C to 700°C in dry nitrogen for 3 hours in a manner similar to Example 1, with the exception of Example 3F, in which the sulfated alumina CTSO was not activated / calcined. Examples 3A-3F were tested for polymerization activity, and approximately 300 mg samples of each CTSO were also mixed with 3 mL of a heptane solution of butylated hydroxytoluene (BHT) (0.05 g BHT / mL) at room temperature for 1 hour. Color values ​​(R+G+B) were determined for each example, and as shown in Table 3, there is a clear correlation between color value, activation temperature, and the catalytic activity of the CTSO in ethylene polymerization reactions. The data from Table 3 can be used to construct a method similar to Figure 5 3 to illustrate the correlation between the normalized catalytic activity and color value of the chemically treated solid oxide. Therefore, a sample of the chemically treated solid oxide can be mixed with a color indicator solution and the resulting color value can be determined, and then the catalytic activity of the chemically treated solid oxide can be determined using a linear calibration curve or mathematical relationship based on the data in Table 3 without the need for polymerization experiments.

[0167] Example 4

[0168] Table 4 summarizes Example 4, in which the chemically treated solid oxide (CTSO) was a fluorinated silica-coated alumina (4.75 wt % fluoride) activated / calcined at 300°C to 700°C in dry nitrogen for 3 hours in a manner similar to Example 2, with the exception of Example 4F, in which the CTSO was not activated / calcined. Examples 4A-4F were tested for polymerization activity, and approximately 300 mg samples of each CTSO were also mixed with 3 mL of a heptane solution of butylated hydroxytoluene (BHT) (0.05 g BHT / mL) at room temperature for 1 hour. Color values ​​(R+G+B) were determined for each example, and as shown in Table 4, there is a clear correlation between color value, activation temperature, and the catalytic activity of the CTSO in ethylene polymerization reactions. The data from Table 4 can be used to construct a similar Figure 5 4 to illustrate the correlation between the normalized catalytic activity and color value of the chemically treated solid oxide. Therefore, a sample of the chemically treated solid oxide can be mixed with a color indicator solution and the resulting color value can be determined, and then the catalytic activity of the chemically treated solid oxide can be determined using a linear calibration curve or mathematical relationship based on the data in Table 4 without the need for polymerization experiments.

[0169] Table 1. Summary of Example 1.

[0170]

[0171] Table 2. Summary of Example 2.

[0172]

[0173] Table 3. Summary of Example 3.

[0174]

[0175]

[0176] Table 4. Summary of Example 4.

[0177]

[0178] The present invention has been described above by reference to many aspects and specific embodiments. A person skilled in the art will appreciate many variations based on the foregoing specific embodiments. All such obvious variations are within the full intended scope of the appended claims. Other aspects of the present invention may include, but are not limited to, the following (each aspect is described as "comprising / including...", but alternatively, may be "consisting essentially of..." or "consisting of...", unless otherwise specifically stated):

[0179] Aspect 1. A method for determining the catalytic activity of an activated chemically-treated solid oxide, the method comprising:

[0180] (i) combining a sample of the activated chemically-treated solid oxide with a solution of a color indicator compound to form a treated solid support;

[0181] (ii) measuring the color of the treated solid support (using any suitable color measuring instrument / device); and

[0182] (iii) generating a color value for said treated solid support and correlating said color value to a standard to determine said catalytic activity of said activated chemically-treated solid oxide.

[0183] Aspect 2. The method of aspect 1, wherein the solution comprises the color indicator compound and a solvent, such as a hydrocarbon solvent.

[0184] Aspect 3. The method of aspect 2, wherein the hydrocarbon solvent comprises any suitable hydrocarbon compound or any hydrocarbon compound disclosed herein, such as pentane, hexane, heptane, benzene, toluene or xylene, and mixtures or combinations thereof.

[0185] Aspect 4. A process for preparing a catalyst composition, the process comprising:

[0186] (I) determining the catalytic activity of the activated chemically-treated solid oxide, wherein the catalytic activity is determined by the method of any one of aspects 1-3;

[0187] (II) contacting a transition metal compound, the activated chemically-treated solid oxide, and an optional promoter (e.g., in a catalyst preparation vessel) to form the catalyst composition; and

[0188] (III) adjusting the relative amount of at least one component of the catalyst composition based on the catalytic activity of the activated chemically-treated solid oxide (or based on the determined catalytic activity).

[0189] Aspect 5. The process of aspect 4, wherein the relative amount of the activated chemically-treated solid oxide is adjusted in step (III).

[0190] Aspect 6. The process according to aspect 4 or 5, wherein the relative amount of the transition metal compound and / or the co-catalyst is adjusted in step (III).

[0191] Aspect 7. The process of any one of aspects 4-6, wherein in step (II) the transition metal compound and the promoter are contacted with a mixture of the activated chemically-treated solid oxide in a diluent.

[0192] Aspect 8. The process of any one of aspects 4-7, wherein in step (II) the first solution of the transition metal compound and the second solution of the promoter are contacted with the activated chemically-treated solid oxide.

[0193] Aspect 9. A process for operating a polymerization reactor system, the process comprising:

[0194] (I) determining the catalytic activity of the activated chemically-treated solid oxide, wherein the catalytic activity is determined by the method of any one of aspects 1-3;

[0195] (II) contacting a catalyst system comprising a transition metal compound, the activated chemically-treated solid oxide, and an optional cocatalyst with an olefin monomer and an optional olefin comonomer in a reactor within the polymerization reactor system under polymerization reaction conditions to produce an olefin polymer; and

[0196] (III) adjusting the flow rate of the activated chemically-treated solid oxide into the reactor when the catalytic activity of the activated chemically-treated solid oxide has reached a predetermined level (or adjusting the flow rate of the chemically-treated solid oxide based on the determined activity).

[0197] Aspect 10. A process as described in Aspect 9, wherein the flow rate in step (III) is controlled by adjusting the flow rate of the activated chemically-treated solid oxide to the catalyst preparation vessel, and / or by adjusting the relative flow rate to the catalyst preparation vessel (ratio of activated chemically-treated solid oxide: transition metal compound), and / or by adjusting the flow rate of the catalyst system leaving the catalyst preparation vessel and entering the reactor.

[0198] Aspect 11. A process as described in Aspect 9 or 10, wherein the process further comprises controlling the flow rate of the transition metal compound entering the reactor, the flow rate of the co-catalyst entering the reactor, the ethylene concentration in the reactor, the polymerization temperature in the reactor, or any combination thereof based on the catalytic activity of the activated chemically-treated solid oxide.

[0199] Aspect 12. The process of any one of aspects 4-11, wherein the co-catalyst is present in step (II).

[0200] Aspect 13. The process of any one of aspects 4-12, wherein only one transition metal compound is present in step (II).

[0201] Aspect 14. The process of any one of aspects 4-12, wherein two or more transition metal compounds are present in step (II).

[0202] Aspect 15. A method or process as described in any of the preceding aspects, wherein the sample of the activated chemically-treated solid oxide is combined with the solution of the color indicator compound in any suitable container or reservoir, such as a flask, jar, test tube, or flow cell apparatus.

[0203] Aspect 16. The method or process of any of the preceding aspects, wherein the color value is the sum of R+G+B.

[0204] Aspect 17. The method or process of any of the preceding aspects, wherein the standard comprises a calibration curve.

[0205] Aspect 18. The method or process of any of the preceding aspects, wherein the correlating step comprises any suitable method of converting the color value to the catalytic activity of the activated chemically-treated solid oxide.

[0206] Aspect 19. An activation system, comprising:

[0207] (a) an activation vessel configured to calcine a raw (or unactivated) chemically-treated solid oxide to form an activated chemically-treated solid oxide;

[0208] (b) an activator storage vessel configured to receive the activated chemically-treated solid oxide from the activation vessel and further configured to introduce the activated chemically-treated solid oxide into a catalyst preparation vessel; and

[0209] (c) an analytical system configured to determine the catalytic activity of the activated chemically-treated solid oxide prior to introducing the activated chemically-treated solid oxide into the catalyst preparation vessel.

[0210] Aspect 20. A system as described in Aspect 19, wherein the analysis system includes: a color analyzer configured to measure the color of the activated chemically treated solid oxide after contacting the activated chemically treated solid oxide with a color indicator solution; and a computer system for generating a color value of the treated solid support and for correlating the color value with a standard to determine the catalytic activity of the activated chemically treated solid oxide.

[0211] Aspect 21. The system of aspect 19 or 20, wherein the analysis system further comprises a washing system configured to clean the color analyzer after a measurement cycle.

[0212] Aspect 22. A system as described in any of Aspects 19-21, wherein the activation system further comprises (d) a controller configured to control the flow rate of the activated chemically-treated solid oxide from the activator storage container into the catalyst preparation container based on or in accordance with the catalytic activity determined by the analytical system.

[0213] Aspect 23. The system of any of Aspects 20-22, wherein the standard comprises a calibration curve.

[0214] Aspect 24. The system of any of Aspects 20-23, wherein the correlating step comprises any suitable technique for converting the color value to the catalytic activity of the activated chemically-treated solid oxide.

[0215] Aspect 25. A catalyst preparation system, comprising:

[0216] (a) a catalyst preparation vessel configured to contact a transition metal compound, an activated chemically-treated solid oxide, and an optional promoter to form a catalyst composition;

[0217] (b) an activator feed stream configured to introduce the activated chemically-treated solid oxide into the catalyst preparation vessel;

[0218] (c) a transition metal compound feed stream configured to introduce the transition metal compound into the catalyst preparation vessel;

[0219] (d) a catalyst system feed stream configured to remove the catalyst composition from the catalyst preparation vessel (e.g., and introduce the catalyst composition into a reactor, if desired); and

[0220] (e) an analytical system configured to determine the catalytic activity of the activated chemically-treated solid oxide prior to introducing the activated chemically-treated solid oxide into the catalyst preparation vessel.

[0221] Aspect 26. The system of aspect 25, wherein the catalyst preparation system further comprises a co-catalyst feed stream configured to introduce the co-catalyst into the catalyst preparation vessel.

[0222] Aspect 27. A system as described in Aspect 25 or 26, wherein the catalyst preparation system further includes (f) a controller configured to control the flow rate of the activator feed flow, and / or the flow rate of the transition metal compound feed flow (and / or the flow rate of the co-catalyst, if used) entering the catalyst preparation vessel based on or in accordance with the catalytic activity determined by the analysis system.

[0223] Aspect 28. The system of any of aspects 25-27, wherein only one transition metal compound is present in (a).

[0224] Aspect 29. A system as described in any of Aspects 25-27, wherein two or more transition metal compounds are present in (a), and (c) comprises a single feed stream for introducing the mixture of transition metal compounds into the catalyst preparation vessel, or (c) comprises separate transition metal compound feed streams for introducing each transition metal compound into the catalyst preparation vessel separately.

[0225] Aspect 30. A system as described in any of Aspects 25-29, wherein the analytical system comprises: a color analyzer for measuring the color of the activated chemically treated solid oxide after contacting the activated chemically treated solid oxide with a color indicator solution; and a computer system for generating a color value of the treated solid support and for correlating the color value with a standard to determine the catalytic activity of the activated chemically treated solid oxide.

[0226] Aspect 31. The system of any of Aspects 25-30, wherein the analysis system further comprises a washing system configured to clean the color analyzer after a measurement cycle.

[0227] Aspect 32. The system of Aspect 30 or 31, wherein the standard comprises a calibration curve.

[0228] Aspect 33. The system of any of Aspects 30-32, wherein the correlating step comprises any suitable technique for converting the color value to the catalytic activity of the activated chemically-treated solid oxide.

[0229] Aspect 34. A polymerization reactor system, comprising:

[0230] (A) a reactor configured to contact the catalyst system with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer;

[0231] (B) a catalyst preparation vessel configured to contact a transition metal compound, an activated chemically-treated solid oxide, and an optional promoter to form the catalyst system; and

[0232] (C) an analytical system configured to determine the catalytic activity of the activated chemically-treated solid oxide prior to introducing the activated chemically-treated solid oxide into the catalyst preparation vessel.

[0233] Aspect 35. The system of aspect 34, wherein the co-catalyst is present in (B).

[0234] Aspect 36. The system of aspect 34 or 35, wherein only one transition metal compound is present in (B).

[0235] Aspect 37. The system of aspect 34 or 35, wherein two or more transition metal compounds are present in (B).

[0236] Aspect 38. A system as described in any of Aspects 34-37, wherein the analysis system comprises: a color analyzer for measuring the color of the activated chemically treated solid oxide after contacting the activated chemically treated solid oxide with a color indicator solution; and a computer system for generating a color value of the treated solid support and for correlating the color value with a standard to determine the catalytic activity of the activated chemically treated solid oxide.

[0237] Aspect 39. The system of Aspect 38, wherein the standard comprises a calibration curve.

[0238] Aspect 40. The system of Aspect 38 or 39, wherein the correlating step comprises any suitable technique for converting the color value to the catalytic activity of the activated chemically-treated solid oxide.

[0239] Aspect 41. A system as described in any of Aspects 34-40, wherein the reactor system further includes (D) a controller configured to control the flow rate of the activated chemically-treated solid oxide entering the reactor based on (or in accordance with) the catalytic activity determined by the analytical system.

[0240] Aspect 42. A system as described in Aspect 41, wherein the controller is also configured to control the flow rate of the transition metal compound entering the reactor, and / or the flow rate of the co-catalyst (if used) entering the reactor, the ethylene concentration in the reactor, the polymerization temperature in the reactor, or any combination thereof based on or in accordance with the catalytic activity determined by the analysis system.

[0241] Aspect 43. The process or system of any one of Aspects 9-18 or 34-42, wherein the reactor system comprises one reactor.

[0242] Aspect 44. The process or system of any of Aspects 9-18 or 34-42, wherein the reactor system comprises two or more reactors.

[0243] Aspect 45. The process or system of any of Aspects 9-18 or 34-44, wherein the reactor system comprises a solution reactor, a gas phase reactor, a slurry reactor, or a combination thereof.

[0244] Aspect 46. The process or system of any of Aspects 9-18 or 34-45, wherein the reactor system comprises a loop slurry reactor.

[0245] Aspect 47. A process or system as described in any of Aspects 9-18 or 34-46, wherein the polymerization reaction conditions include a polymerization reaction temperature in the range of about 60°C to about 185°C, about 60°C to about 115°C, or about 130°C to about 180°C, and any suitable reaction pressure, for example, from about 200 to about 1000 psig.

[0246] Aspect 48. A process or system as described in any one of aspects 9-18 or 34-47, wherein the olefin monomer comprises C2-C 24 Olefins.

[0247] Aspect 49. The process or system of any of aspects 9-18 or 34-48, wherein the olefin monomer comprises propylene.

[0248] Aspect 50. The process or system of any of aspects 9-18 or 34-48, wherein the olefin monomer comprises ethylene.

[0249] Aspect 51. The process or system of any of Aspects 9-18 or 34-48, wherein the catalyst system is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

[0250] Aspect 52. The process or system of any of Aspects 9-18 or 34-48, wherein the olefin polymer comprises an ethylene homopolymer, an ethylene copolymer, a propylene homopolymer, or a propylene-based copolymer.

[0251] Aspect 53. The process or system of any of Aspects 9-18 or 34-48, wherein the olefin polymer comprises an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, or an ethylene / 1-octene copolymer.

[0252] Aspect 54. The process or system of any one of aspects 4-18 or 25-53, wherein the transition metal compound (or at least one of the two or more transition metal compounds) comprises any suitable non-metallocene compound.

[0253] Aspect 55. The process or system of any one of Aspects 4-18 or 25-53, wherein the transition metal compound (or at least one of the two or more transition metal compounds) comprises any suitable metallocene compound.

[0254] Aspect 56. A process or system as described in any of Aspects 4-18 or 25-53, wherein the transition metal compound (or at least one of the two or more transition metal compounds) comprises chromium, vanadium, titanium, zirconium, hafnium, or a combination thereof.

[0255] Aspect 57. The process or system of any of aspects 4-18 or 25-53, wherein two transition metal compounds are present, one of which is a bridged metallocene compound and the other of which is an unbridged metallocene compound.

[0256] Aspect 58. A method, process or system as described in any of Aspects 1-57, wherein the (activated or unactivated) chemically-treated solid oxide comprises fluorided alumina, chlorided alumina, brominated alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, fluorided-chlorinated silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.

[0257] Aspect 59. A method, process or system as described in any of Aspects 1-57, wherein the (activated or unactivated) chemically-treated solid oxide comprises fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, fluorided-chlorided silica-coated alumina, sulfated silica-coated alumina, or any combination thereof.

[0258] Aspect 60. The method, process, or system of any of Aspects 1-57, wherein the (activated or unactivated) chemically-treated solid oxide comprises a fluorided solid oxide and / or a sulfated solid oxide.

[0259] Aspect 61. The method, process or system of any of aspects 1-60, wherein the color indicator compound comprises any suitable compound or any compound disclosed herein.

[0260] Aspect 62. The method, process or system of any one of aspects 1-61, wherein the color indicator compound is an electron-rich compound.

[0261] Aspect 63. The method, process or system of any one of aspects 1-62, wherein the color indicator compound is an unsaturated compound.

[0262] Aspect 64. A method, process or system as described in any of Aspects 1-63, wherein the color indicator compound includes any compound that changes the color of the activated chemically-treated solid oxide after contact with the activated chemically-treated solid oxide, but does not change the color of the unactivated chemically-treated solid oxide after contact with the unactivated chemically-treated solid oxide.

[0263] Aspect 65. The method, process or system of any one of aspects 1-64, wherein the color indicator compound is colorless.

Claims

1. A method for determining the catalytic activity of an activated chemically-treated solid oxide, the method comprising: (i) combining a sample of the activated chemically-treated solid oxide with a solution of a color indicator compound to form a treated solid support; (ii) measuring the color of the treated solid support; as well as (iii) generating a color value for the treated solid support and correlating the color value to a standard to determine the catalytic activity of the activated chemically-treated solid oxide; wherein the activated chemically-treated solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, silica-titania, zirconia, silica-zirconia, magnesia, boria, zinc oxide or any combination thereof.

2. The method of claim 1, wherein: The solution comprises the color indicator compound and a hydrocarbon solvent; and The activated chemically-treated solid oxide comprises a fluorided solid oxide and / or a sulfated solid oxide.

3. The method of claim 1, wherein the standard comprises a calibration curve.

4. The method of claim 1, wherein the color indicator compound: changing the color of the activated chemically-treated solid oxide after contacting with the activated chemically-treated solid oxide; and The color of the unactivated chemically-treated solid oxide is not changed after contacting with the unactivated chemically-treated solid oxide.

5. A process for preparing a catalyst composition, the process comprising: (I) performing the method as claimed in claim 1; (II) contacting a transition metal compound, the activated chemically-treated solid oxide, and an optional promoter to form the catalyst composition; as well as (III) adjusting the relative amount of at least one component of the catalyst composition based on the catalytic activity of the activated chemically-treated solid oxide.

6. The process of claim 5, wherein the relative amount of the activated chemically-treated solid oxide is adjusted in step (III) and / or the relative amount of the transition metal compound is adjusted in step (III).

7. The process of claim 5, wherein: The transition metal compound, the activated chemically-treated solid oxide, and the promoter are contacted in step (II); and The transition metal compound includes a metallocene compound.

8. A process for operating a polymerization reactor system, the process comprising: (I) performing the method as claimed in claim 1; (II) contacting a catalyst system comprising a transition metal compound, the activated chemically-treated solid oxide, and an optional cocatalyst with an olefin monomer and an optional olefin comonomer in a reactor within the polymerization reactor system under polymerization conditions to produce an olefin polymer; as well as (III) adjusting the flow rate of the activated chemically-treated solid oxide into the reactor when the catalytic activity of the activated chemically-treated solid oxide has reached a predetermined level.

9. The process of claim 8, wherein the process further comprises controlling the flow rate of the transition metal compound entering the reactor, the flow rate of the cocatalyst entering the reactor, the ethylene concentration in the reactor, the polymerization temperature in the reactor, or any combination thereof based on the catalytic activity of the activated chemically-treated solid oxide.

10. The process of claim 8, wherein: The co-catalyst is present in step (II); and The olefin monomer includes ethylene.

11. The process of claim 8, wherein the olefin polymer comprises an ethylene homopolymer and / or an ethylene / α-olefin copolymer.

12. The process of claim 8, wherein the polymerization reactor system comprises one or two reactors, at least one of which is a loop slurry reactor.

13. A polymerization reactor system, comprising: (A) a reactor configured to contact the catalyst system with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer; (B) a catalyst preparation vessel configured to contact a transition metal compound, an activated chemically-treated solid oxide, and an optional promoter to form the catalyst system; as well as (C) an analytical system configured to determine the catalytic activity of the activated chemically-treated solid oxide prior to introducing the activated chemically-treated solid oxide into the catalyst preparation vessel; wherein the analysis system comprises: a color analyzer for measuring the color of the activated chemically-treated solid oxide after contacting the activated chemically-treated solid oxide with a color indicator solution; and a computer system for generating a color value and for correlating the color value with a standard to determine the catalytic activity of the activated chemically-treated solid oxide; and The activated chemically-treated solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, silica-titania, zirconia, silica-zirconia, magnesia, boria, zinc oxide or any combination thereof.

14. The system of claim 13, wherein said analytical system further comprises a vessel for contacting said activated chemically-treated solid oxide with said color indicator solution.

15. The system of claim 13, wherein the reactor system further comprises (D) a controller configured to control a flow rate of the activated chemically-treated solid oxide into the reactor based on the catalytic activity determined by the analytical system.

16. The system of claim 15, wherein the controller is further configured to control a flow rate of the transition metal compound into the reactor, a flow rate of the cocatalyst into the reactor, an ethylene concentration in the reactor, a polymerization temperature in the reactor, or any combination thereof based on the catalytic activity determined by the analytical system.

17. A catalyst preparation system, comprising: (a) a catalyst preparation vessel configured to contact a transition metal compound, an activated chemically-treated solid oxide, and an optional promoter to form a catalyst composition; (b) an activator feed stream configured to introduce the activated chemically-treated solid oxide into the catalyst preparation vessel; (c) a transition metal compound feed stream configured to introduce the transition metal compound into the catalyst preparation vessel; (d) a catalyst system feed stream configured to withdraw the catalyst composition from the catalyst preparation vessel; as well as (e) an analytical system configured to determine the catalytic activity of the activated chemically-treated solid oxide prior to introducing the activated chemically-treated solid oxide into the catalyst preparation vessel; as well as wherein the analysis system comprises: a color analyzer for measuring the color of the activated chemically-treated solid oxide after contacting the activated chemically-treated solid oxide with a color indicator solution; and a computer system for generating a color value and for correlating the color value with a standard to determine the catalytic activity of the activated chemically-treated solid oxide; and The activated chemically-treated solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, silica-titania, zirconia, silica-zirconia, magnesia, boria, zinc oxide or any combination thereof.

18. The system of claim 17, wherein the catalyst preparation system further comprises a co-catalyst feed stream configured to introduce the co-catalyst into the catalyst preparation vessel.

19. A system as described in claim 18, wherein the catalyst preparation system further includes (f) a controller, which is configured to control the flow rate of the activator feed flow, and / or the flow rate of the transition metal compound feed flow, and / or the flow rate of the co-catalyst feed flow entering the catalyst preparation container based on the catalytic activity determined by the analysis system.

20. An activation system, comprising: (a) an activation vessel configured to calcine an unactivated chemically-treated solid oxide to form an activated chemically-treated solid oxide; (b) an activator storage vessel configured to receive the activated chemically-treated solid oxide from the activation vessel and further configured to introduce the activated chemically-treated solid oxide into a catalyst preparation vessel; as well as (c) an analytical system configured to determine the catalytic activity of the activated chemically-treated solid oxide prior to introducing the activated chemically-treated solid oxide into the catalyst preparation vessel; as well as wherein the analysis system comprises: a color analyzer configured to measure the color of the activated chemically-treated solid oxide after contacting the activated chemically-treated solid oxide with a color indicator solution; and a computer system for generating a color value and for correlating the color value with a standard to determine the catalytic activity of the activated chemically-treated solid oxide; and The activated chemically-treated solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, silica-titania, zirconia, silica-zirconia, magnesia, boria, zinc oxide or any combination thereof.

21. The system of claim 20, wherein the analysis system further comprises a washing system configured to clean the color analyzer after a measurement cycle.

22. The system of claim 20, wherein the activation system further comprises (d) a controller configured to control a flow rate of the activated chemically-treated solid oxide from the activator storage vessel into the catalyst preparation vessel based on the catalytic activity determined by the analytical system.

23. The system of claim 22, wherein the computer system includes a calibration curve and / or a mathematical model.

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