Process for modifying supported catalyst during polymerization of olefins by delivering catalyst solution under pressure

Abstract

A polymerization process can include introducing a catalyst slurry comprising a supported catalyst to a line in fluid communication with a mixing unit; directing the catalyst solution to the mixing unit via a pressurizable fluid distribution system comprising a first pressure vessel and a second pressure vessel in parallel with each other and in fluid communication with the mixing unit, the first pressure vessel operating in an online mode when the second pressure vessel is in an offline mode; at least partially filling the first pressure vessel with a first portion of the catalyst solution; pressurizing the first pressure vessel to deliver a first portion of the catalyst solution to the mixing unit; contacting the catalyst slurry with a catalyst solution in a line or in a mixing unit to obtain a modified catalyst slurry; feeding the modified catalyst slurry to a polymerization reactor; and polymerizing to obtain a polyolefin.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 592450, filed October 23, 2023, entitled “METHODS FOR MODIFYING ASUPPORTED CATALYST DURING OLEFIN POLYMERIZATION THROUGH PRESSURIZED DELIVERYOF A CATALYST SOLUTION”, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to methods for polymerizing one or more olefins, and more specifically, to methods for polymerizing one or more olefins using enhanced supported catalyst blending techniques prior to polymerization. Background Technology

[0004] Gas-phase polymerization can be used to polymerize ethylene or ethylene comonomers with one or more olefins. Gas-phase polymerization processes carried out in fluidized beds are particularly cost-effective. One or more olefin monomers and catalyst particles containing an activated catalyst compound can be introduced into a polymerization reactor, where the olefin monomers (one or more) can polymerize in the presence of the catalyst particles to produce polyolefin products, preferably in fine-particle form.

[0005] During polymerization, catalyst particles (i.e., supported catalysts) may begin to overheat, especially when the catalytic compounds on the catalyst particles exhibit aggressive kinetic characteristics. When catalyst particles overheat, polymer particles within the reactor may begin to clump together, which can lead to eventual polymer buildup within the reactor. As used herein, the term "flakes" refers to the buildup of polymer within the reactor (sometimes also called agglomeration or clumping), which in some cases can lead to process failures and even reactor shutdowns.

[0006] Overheating of catalyst particles can be mitigated by altering the ratio of one or more catalyst compounds on the particles. For maximum process flexibility, catalyst particles can be modified in situ before being fed to the polymerization reaction without process downtime. In some instances, a catalyst solution can be contacted with the catalyst particles to introduce additional catalyst compounds and / or different catalyst compounds onto the particles. The catalyst solution that introduces additional and / or different catalyst compounds onto the catalyst particles may be referred to as a “trim catalyst” or “trim catalyst solution” because the catalyst solution modifies the properties of the original catalyst particles. Unfortunately, in-situ modification of catalyst particles in the aforementioned manner can lead to suboptimal catalyst activation and ongoing process control challenges, including the agglomeration of the resulting polymer. Short and / or variable contact times between the catalyst particles and the catalyst solution can be particularly problematic because it can result in multiple supported catalysts with diverse polymerization properties.

[0007] Some references of potential interest in this field include: U.S. Patent Nos. 10,927,205 and 6,956,089; U.S. Patent Publications Nos. 2022 / 0033536 and 2022 / 0033537; and International Patent Publication No. WO2022 / 174202. Summary of the Invention

[0008] In various aspects, the method of this disclosure includes: providing a catalyst slurry comprising a supported catalyst, wherein the supported catalyst comprises a support material, at least one catalyst compound, and at least one activator; introducing the catalyst slurry into a pipeline in fluid communication with a mixing unit; providing a catalyst solution comprising a first catalyst compound already contained on the supported catalyst or a second catalyst compound different from the first catalyst compound; introducing the catalyst solution into a pressurized fluid distribution system in fluid communication with the mixing unit, wherein the pressurized fluid distribution system comprises at least one first pressure vessel and at least one second pressure vessel connected in parallel with each other, and wherein at least one first pressure vessel operates in an online mode while at least one second pressure vessel is in an offline mode, and at least one first pressure vessel and at least one second pressure vessel are switchable between online and offline modes; at least partially filling at least one first pressure vessel with a first portion of the catalyst solution; pressurizing at least one first pressure vessel such that the pressurized fluid distribution system supplies the first portion of the catalyst solution from the at least one first pressure vessel to the mixing unit; and in the pipeline, an inline inline mixer (an inline) within the pipeline. In a mixer, a mixing unit, or any combination thereof, a catalyst solution is contacted with a catalyst slurry to obtain a modified catalyst slurry, wherein the modified catalyst slurry incorporates at least a portion of a first catalyst compound or a second catalyst compound from the catalyst solution onto a supported catalyst; the modified catalyst slurry is fed into a polymerization reactor; and α-olefins are polymerized in the polymerization reactor under polymerization reaction conditions to obtain polyolefins.

[0009] In some or other aspects, the method of this disclosure includes: providing a catalyst slurry comprising a supported catalyst, wherein the supported catalyst comprises a support material, at least one catalyst compound, and at least one activator; providing a catalyst solution comprising a first catalyst compound already contained on the supported catalyst or a second catalyst compound different from the first catalyst compound; and directing the catalyst solution to a pressurized fluid distribution system, wherein the pressurized fluid distribution system comprises at least one first pressure vessel and at least one second pressure vessel connected in parallel with each other, and wherein at least one first pressure vessel operates in an online mode while at least one second pressure vessel is in an offline mode, and at least one first pressure vessel and at least one second pressure vessel... The apparatus can switch between online and offline modes; at least partially fill at least one first pressure vessel with a first portion of a catalyst solution; pressurize at least one first pressure vessel such that a pressurizable fluid distribution system supplies the first portion of the catalyst solution to a pipeline downstream of at least one first pressure vessel; introduce a catalyst slurry into the pipeline; contact the catalyst solution with the catalyst slurry in the pipeline to obtain a modified catalyst slurry, wherein the modified catalyst slurry incorporates at least a portion of a first catalyst compound or a second catalyst compound from the catalyst solution onto a supported catalyst; feed the modified catalyst slurry into a polymerization reactor; and polymerize α-olefins in the polymerization reactor under polymerization reaction conditions to obtain polyolefins.

[0010] These and other features and properties of the disclosed methods and their advantageous applications and / or uses will become apparent from the following detailed description. Attached Figure Description

[0011] To assist those skilled in the art in making and using this subject matter, reference is made to the accompanying drawings. These drawings are included to illustrate certain aspects of this disclosure and should not be considered an exclusive configuration. The disclosed subject matter is capable of considerable modifications, alterations, combinations, and equivalents in form and function, as will occur to those skilled in the art who benefit from this disclosure.

[0012] Figure 1 This is a block diagram of a gas-phase reactor system, in which the mixing of catalyst slurry and catalyst solution can be carried out in a mixing unit.

[0013] Figure 2 This is a block diagram of a gas-phase reactor system, in which the mixing of catalyst slurry and catalyst solution can be carried out in a pipeline upstream of the mixing unit.

[0014] Figure 3 This is a block diagram of a gas-phase reactor system, in which the mixing of catalyst slurry and catalyst solution can be carried out in an online pipeline mixer upstream of the mixing unit. Detailed Implementation

[0015] This invention relates to a method for polymerizing one or more olefins, and more specifically, to a method for polymerizing one or more olefins using a supported catalyst blending technique enhanced prior to polymerization.

[0016] As mentioned above, catalyst particles (i.e., supported catalysts) can be modified in situ prior to polymerization, for example, to reduce polymer agglomeration. However, in-situ modification of catalyst particles can lead to ineffective catalyst activation and persistent difficulties in the polymerization process. Ineffective mixing between the catalyst slurry and the catalyst solution, including short mixing contact times and inconsistent delivery rates of the catalyst solution, can also contribute to these difficulties.

[0017] The aforementioned problems can be addressed through the various features disclosed herein. In particular, this disclosure provides increased and / or less varied contact time between catalyst particles and catalyst solution in the catalyst slurry during the production of modified supported catalysts. As part of accomplishing the foregoing, this disclosure utilizes a pressurized fluid distribution system, as further described below, which can provide more stable flow and customizable flow rates of the catalyst solution, thereby offering additional process advantages. As a result of the robust techniques for modifying supported catalysts according to the disclosure herein, more consistent polymerization performance can be achieved.

[0018] definition

[0019] Various specific embodiments, versions, and examples of the invention will now be described, including preferred embodiments and definitions adopted herein for understanding the claimed invention. While specific preferred embodiments are given in the following detailed description, those skilled in the art will understand that these embodiments are merely exemplary and that the invention may be practiced in other ways. For the purpose of determining infringement, the scope of the invention will refer to any one or more of the appended claims, including their equivalents, and elements or limitations equivalent to the recited elements or limitations. Any reference to “invention” may refer to one or more of the inventions defined by the claims, but not necessarily all of them.

[0020] As used herein, the indefinite article “a” or “an” shall mean “at least one” unless otherwise stated or clearly indicated by the context. Thus, embodiments using “α-olefin” include embodiments in which one, two or more α-olefins are used, unless otherwise stated or clearly indicated by the context.

[0021] Unless otherwise stated, all figures indicating quantities in this disclosure should be understood to be modified by the term "about" in all cases. It should also be understood that precise numerical values ​​used in the specification and claims constitute specific embodiments.

[0022] The term “A and / or B” as used in this article with the word “and / or” is intended to include “A and B”, “A or B”, “A” and “B”.

[0023] As used herein, “wt%” means weight percentage, “volume%” means volume percentage, “molar%” means molar percentage, “ppm” means parts per million, and “ppm wt” and “wppm” are used interchangeably and mean parts per million based on weight. Unless otherwise stated, all concentrations herein are based on the total amount of the compositions discussed.

[0024] For the purposes of this disclosure, the nomenclature of the elements is based on the new notation of the periodic table provided in Hawley's Condensed Chemical Dictionary, 16th Edition, John Wiley & Sons, Inc. (2016), Appendix V, unless otherwise stated.

[0025] As used herein, the terms “optional” or “optionally” mean that the event or situation subsequently described occurs or does not occur (or that an element exists or does not exist), and the description includes instances where the event or situation occurs and instances where the event or situation does not occur.

[0026] A "reactor" is any type of container or holding device with one or more reactors and / or one or more reaction zones in any configuration, in which similar polymers are produced. The term "gas-phase polymerization" refers to the production of polymers in a gas-phase reactor, where monomers react in the reaction zone of the reactor in the gas phase. In gas-phase polymerization, the monomers do not necessarily have to be supplied to the reactor in the gas phase. Instead, the monomers can be supplied in the gas phase, liquid phase (condensed phase), or a mixture of gas and liquid phases.

[0027] "alkoxide" includes compounds with alkyl groups (which are C1-C6). 10 An alkyl group is bonded to an oxygen atom (alkyl group). The alkyl group can be straight-chain, branched, or cyclic. The alkyl group can be saturated or unsaturated. In at least one embodiment, the alkyl group may contain at least one aromatic group.

[0028] The terms “antistatic agent,” “continuous additive,” “continuous auxiliary agent,” and “scale inhibitor” are used interchangeably and refer to compounds or mixtures of compounds, such as solids and / or liquids, that can be used to reduce fouling in reactors during polymerization. Fouling in reactors can be caused by polymer buildup within the reactor. Fouling can manifest itself through any number of phenomena, including flaking of reactor walls, blockage of inlet and outlet lines, formation of large aggregates, or other forms of polymer buildup within the reactor that may lead to reactor shutdown. Antistatic agents can be used as part of the catalyst composition or introduced directly into the reactor independently of the catalyst composition. In some embodiments, the antistatic agent may be contained on a support also loaded with one or more catalysts.

[0029] The term “catalyst” is used interchangeably with the terms “catalyst compound”, “catalyst precursor”, “transition metal compound”, “transition metal complex” and “precatalyst”.

[0030] A “catalyst system” is a combination of one or more catalyst compounds, activators, optional co-activators, and optional support materials. For the purposes of this disclosure, when a catalyst system is described as comprising a neutral, stable form of a component, it is fully understood by those skilled in the art that the ionic form of the component is the form in which it reacts with the monomer to produce a polymer. The catalyst systems, catalysts, and activators of this disclosure are intended to include, in addition to the neutral form of the compound / component, an ionic form.

[0031] The terms “group”, “radical”, and “substituent” are used interchangeably in this document.

[0032] The term "hydrocarbon" refers to a class of compounds having hydrogen atoms bonded to carbon, and includes saturated hydrocarbon compounds, unsaturated hydrocarbon compounds, and mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds with different numbers of carbon atoms. The term "C"... n "" refers to a hydrocarbon (one or more) or hydrocarbon group having n carbon atoms (one or more) per molecule or per group, where n is a positive integer. Such hydrocarbon compounds can be one or more of the following: linear, branched, cyclic, acyclic, saturated, unsaturated, aliphatic, or aromatic.

[0033] The terms “hydrocarbyl radical,” “hydrocarbyl group,” or “hydrocarbyl” are used interchangeably and are defined as a group consisting only of hydrogen and carbon atoms and having at least one unfilled valence position when removed from the parent compound.

[0034] The term “optionally substituted” means that the hydrocarbon or hydrocarbon group may be unsubstituted or substituted. Unless otherwise specified as explicitly unsubstituted, any hydrocarbon group herein may be optionally substituted. The term “substituted” means that at least one hydrogen atom in the parent hydrocarbon group has been replaced by at least a non-hydrogen group, such as a hydrocarbon group, a heteroatom, or a heteroatom-containing group.

[0035] "Olefin" is a linear, branched, or cyclic compound having at least one double bond between carbon and hydrogen. When a polymer or copolymer is referred to as containing an olefin, such as ethylene and / or at least one C3-C... 20 In the case of α-olefins, the olefins present in such polymers or copolymers are in a polymeric form of olefin. For example, when a copolymer is claimed to have an "ethylene" content of about 35% to about 55% by weight, it should be understood that the repeating / monomer units or simple units in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are present at about 35% to about 55% by weight, based on the weight of the copolymer. For the purposes of this disclosure, ethylene should be considered as an α-olefin.

[0036] A “polymer” has two or more repeating units / monomer units or simple units (monomer units) that are the same or different. A “homopolymer” is a polymer having the same units. A “copolymer” is a polymer having two or more units that are different from each other. A “terpolymer” is a polymer having three units that are different from each other. The term “different” used to refer to units indicates that the units are different from each other at at least one atom or are isomerically different. As used herein, the definition of copolymer includes terpolymers, etc. Similarly, as used herein, the definition of polymer includes homopolymers, copolymers, etc. Furthermore, the terms “polyethylene copolymer,” “ethylene copolymer,” and “ethylene-based polymer” are used interchangeably to refer to copolymers containing at least 50 mol% units derived from ethylene. Polyolefin polymers include polymeric forms of one or more olefin monomers.

[0037] The term "characteristic mass transfer time" refers to the timescale in which diffusion occurs. Once multiple (e.g., 2, 3, 4, 5, or even more) characteristic mass transfer times have elapsed, diffusion-based mixing can be considered complete. The mixing unit in the method of this disclosure can extend the contact time between the catalyst solution and the catalyst slurry beyond the characteristic mass transfer time for interparticle diffusion. By extending the contact time beyond the characteristic mass transfer time, additional time is available for the catalyst compound to diffuse from the catalyst solution onto the supported catalyst (intraparticle diffusion) and for catalyst activation to take place. The time for mass transfer can be reduced to less than the time achieved solely by diffusion (e.g., by using a mechanically stirred mixing tank).

[0038] Polymerization processes and systems, and activation of catalyst compounds

[0039] When using a supported catalyst containing one or more catalyst compounds, it may be necessary to modify the final supported catalyst by introducing additional catalyst compounds (one or more) onto the supported catalyst, for example, to alter the kinetic characteristics during polymerization or to change the composition or characteristics of the polymer being produced. The introduced additional catalyst compounds (one or more) can increase the loading of catalyst compounds already present on the supported catalyst and / or introduce different catalyst compounds not yet present on the supported catalyst. One way to modify a supported catalyst is by contacting (i) the supported catalyst in a catalyst slurry with (ii) a catalyst solution containing one or more of the catalyst compounds, thereby producing a modified supported catalyst in a modified catalyst slurry. Compared to the original (before contact) catalyst slurry, the modified catalyst slurry may have a different loading of at least one catalyst compound on the support material. When the modified catalyst slurry is produced in situ in the manner described above, the kinetic characteristics and / or contact time of the modified catalyst slurry are desiredly controlled with specified precision. Otherwise, insufficient kinetic control may lead to rheological changes in the catalyst slurry and / or catalyst solution, such as thermal oscillations and pressure differentials, which can cause disturbances within the catalyst system and potentially result in polymer flocculing and other problems. Insufficient activation may also occur with newly introduced catalyst compounds (one or more), preventing sufficient modification of catalyst properties during polymerization. For example, overly aggressive kinetics, if not modified sufficiently, can lead to polymer flocculing within the reactor. Alternatively or additionally, if the supported catalyst is not sufficiently modified and / or is underactivated, substandard polymers may be produced during polymerization. Inconsistent and / or short contact times between catalyst particles and the catalyst solution can also contribute to these and other problems.

[0040] Unrestricted by theory or mechanism, it is believed that catalyst compounds introduced from a catalyst solution into a supported catalyst may undergo suboptimal activation due to limited diffusion into the interior of the support material, thereby contacting the catalyst compounds with a co-loaded activator within the support material. The activation of catalyst compounds introduced from the catalyst solution can be enhanced by increasing the contact time between the catalyst slurry containing the supported catalyst and the catalyst solution before the modified catalyst slurry, generated from the contact between the catalyst slurry and the catalyst solution, enters the polymerization reactor. Highly variable contact times can also be problematic, as the original catalyst particles may undergo more or less modification or activation than desired, potentially leading to the formation of unwanted polymer products (e.g., by continuously feeding a supported catalyst with unintentionally varying amounts of activated catalyst compounds, and possibly also by inconsistent contact times over time). The enhanced catalyst activation resulting from the increased and less varied contact time between the catalyst solution and the catalyst slurry according to the methods disclosed herein can provide improved performance during gas-phase polymerization reactions using modified supported catalysts. Furthermore, the controlled delivery of catalyst solution using the pressurized fluid distribution system described herein can additionally contribute to enhanced activation of one or more catalyst compounds and improved reliability of the activation process. At the very least, enhanced catalyst activation can reduce flaking within the gas-phase polymerization reactor and improve the reliability and / or reproducibility of the polymerization process. Various methods for increasing the contact time between the catalyst slurry and the catalyst solution, any of which can be combined with the pressurized fluid distribution system described herein, can provide improved polymerization performance and are further described in detail herein. According to more specific examples, the increased contact time between the catalyst slurry and the catalyst solution can at least exceed the characteristic mass transfer mixing time.

[0041] The pressurized fluid distribution system described herein offers additional benefits related to increased contact time between the catalyst solution and the catalyst slurry. Specifically, pressurized fluid distribution can replace one or more pumps conventionally used in systems for producing modified catalyst slurries. For example, a diaphragm pump can be a type of conventional pump that can be replaced by the pressurized fluid distribution system disclosed herein. Systems containing conventional pumps are prone to blockage by solid buildup during operation, and the catalyst solution can sometimes degas, particularly in the pump head, which can lead to operability problems. Furthermore, the flow rate of conventional pumps is not easily controlled, and some types of pumps can generate pulsating flow at the point where contact occurs between the catalyst solution and the catalyst slurry. Pulsating flow is particularly prevalent in diaphragm pumps and peristaltic pumping systems. While systems containing conventional pumps are generally satisfactory, any of the aforementioned issues can adversely affect the successful formation of modified catalyst slurries in some cases. The pressurized fluid distribution system described herein can overcome one or more of these difficulties to facilitate the formation of modified catalyst slurries with improved reliability during the polymerization process, thereby providing improved and more consistent performance.

[0042] While this disclosure provides for enhancing slurry catalyst activation by enabling more effective contact between the supported catalyst and the catalyst solution, it should be understood that consistent delivery of the modified supported catalyst to the reactor is also a factor in achieving good polymerization performance. For example, when a modified supported catalyst is introduced through multiple lines, maintaining consistent delivery rates across the lines can preserve improved polymerization performance. Providing consistent delivery rates of the modified supported catalyst through multiple lines may include individually heating or cooling the lines to control viscosity and delivery rates, or using pinch valves or other flow control devices to slow down the delivery rate in a single line as needed.

[0043] To better understand embodiments of this disclosure, reference is now made to the accompanying drawings illustrating a polymerization process and reactor system in which a modified catalyst slurry is produced and fed into a polymerization reactor, preferably a gas-phase polymerization reactor. Those skilled in the art will understand that elements such as pumps, heat exchangers, valves, vents, and similar system components may be present in the depicted process and reactor system, but such elements have sometimes been omitted for clarity. Furthermore, elements with similar structures and functions in multiple figures will be referred to using common reference numerals herein, and for brevity, such elements will be described in detail only upon their first appearance.

[0044] Figure 1This is a block diagram of a gas-phase reactor system 100, in which a mixing unit is used to mix the catalyst slurry and the catalyst solution. As shown, a first catalyst-containing mixture can be introduced as a catalyst slurry into a first vessel 102, the first catalyst-containing mixture containing a supported catalyst in a suitable support liquid. The first vessel 102 can optionally be a stirred-hold vessel configured to maintain a substantially constant solid concentration of the supported catalyst in the catalyst slurry. Alternatively, the first vessel 102 can be maintained at an elevated temperature, for example, from about 30°C, 40°C, or 43°C to about 45°C, 60°C, or 75°C. The elevated temperature can be obtained by electrically heating the first vessel 102, for example, using a heating blanket. Maintaining the first vessel 102 at an elevated temperature can further reduce or eliminate the formation of solid residues on the walls of the first vessel 102, which could otherwise slide off the walls and cause blockages and other problems in downstream delivery lines. The first vessel 102 can have a volume sufficient to support the required operating time, for example, about 0.5 m³. 3 Approximately 15m 3 or about 3m 3 Approximately 12m 3 or about 6m 3 Approximately 10m 3 The volume. In at least one embodiment, the first container 102 may have a volume of approximately 0.75 m³. 3 1.15m 3 1.5m 3 1.9m 3 or 2.3m 3 up to 3m 3 3.8m 3 5.7m 3 6.8m 3 7.6m 3 12.8m 3 Or 14.0m 3 The volume, for example, is approximately 1.9m³. 3 From approximately 12.8m 3 or about 2.3m 3 To approximately 6.8m 3 or approximately 5.7m 3 up to 7.6m 3 It should be understood that the volume of the first container 102 can be selected based on the catalyst consumption rate. In a non-limiting example, the volume of the first container 102 can be selected to provide an operating time of at least about 12 hours, for example, about 12 hours to about 96 hours, or about 12 hours to about 72 hours, or about 12 hours to about 48 hours, or about 12 hours to about 24 hours, or about 24 hours to about 72 hours, or about 48 hours to about 96 hours.

[0045] The supported catalyst may comprise a support material, at least one activator, and at least one catalyst compound (e.g., it may comprise two, three, or more catalyst compounds, each of which is different from the others; or the supported catalyst may comprise a single catalyst compound). The first catalyst-containing mixture may comprise a catalyst slurry.

[0046] A second catalyst-containing mixture (comprising (i) one or both of a first catalyst compound already present on a supported catalyst and (ii) a second catalyst compound different from the first catalyst compound) can be introduced into a second container 106. The second catalyst-containing mixture may contain a catalyst solution (e.g., a trimmed catalyst solution) containing one or both of the first and second catalyst compounds just mentioned dissolved in a suitable solvent. The second container 106 may have a volume sufficient to support the required operating time, for example, about 0.3 m³. 3 Approximately 10m 3 or about 1m 3 Approximately 7m 3 or about 2m 3 Approximately 5m 3 The volume. In at least one embodiment, the second container 106 for the catalyst solution may have a volume of approximately 0.38 m³. 3 0.75m 3 1.15m 3 1.5m 3 1.9m 3 or 2.3m 3 Any low value in approximately 3m 3 3.8m 3 5.7m 3 or 7.6m 3 Any high value in, for example, about 1.5m 3 Approximately 3.8m 3 or about 2.3m 3 Approximately 3.8m 3 or about 2.3m 3 Approximately 3m 3The volume of the second container 106 is within a certain range. It should be understood that the volume of the second container 106 can be selected based on the catalyst consumption rate and the length of time that the catalyst solution and catalyst slurry need to be kept in contact. In a non-limiting example, the volume of the second container 106 can be selected to provide an operating time of at least about 12 hours, for example, about 12 hours to about 96 hours, or about 12 hours to about 72 hours, or about 12 hours to about 48 hours, or about 12 hours to about 24 hours, or about 24 hours to about 72 hours, or about 48 hours to about 96 hours. The second container 106 for the catalyst solution can be maintained at an elevated temperature, for example, about 30°C, 40°C, or 43°C to about 45°C, 60°C, or 75°C, which can be obtained by electrically heating the second container 106 using, for example, a heating blanket. Maintaining the second container 106 at an elevated temperature can help reduce or eliminate foaming when the catalyst slurry and catalyst solution are combined according to the description herein.

[0047] The catalyst slurry is transported from the first container 102 to the mixing unit 101 via line 104, and the catalyst solution is transported to the mixing unit 101 via line 108 after passing through the pressurized fluid distribution system 118 discussed below. Figure 1 As shown, the catalyst solution can be directly passed to the mixing unit 101, or as... Figure 2 and Figure 3 It is carried out indirectly as shown and discussed later.

[0048] Still referencing Figure 1 The catalyst solution is supplied from the second container 106 via a pressurized fluid distribution system 118 comprising a plurality of pressure vessels 120a and 120b in fluid communication with the pipeline 108. Pressure vessels 120a and 120b may each have a volume smaller than that of the second container 106. In at least one embodiment, pressure vessels 120a and 120b may each have a volume of approximately 1 m³. 3 Approximately 2m 3 or approximately 0.75m 3 To approximately 1.5m 3The volume. As used herein, the term "pressure vessel" refers to a vessel maintained at a pressure above atmospheric pressure under its normal operating conditions. For pressure vessels 120a and 120b, the catalyst solution contained therein can be dispensed under pressure to mixing unit 101, as described below. Pressure vessels 120a and 120b are arranged in parallel with each other such that when pressure vessel 120b is in offline mode, pressure vessel 120a can operate in online mode, and online and offline modes can be switched between pressure vessels 120a and 120b. That is, when pressure vessel 120b operates in online mode, pressure vessel 120a can be in offline mode, and vice versa. The term "online mode" refers to the operating state in which a given pressure vessel is pressurized and supplies catalyst solution to line 108. The term "offline mode" refers to the operating state in which a given pressure vessel does not supply catalyst solution to line 108. Pressure vessels may be pressurized or unpressurized in offline mode. Although Figure 1 Individual examples of pressure vessels 120a and 120b have been depicted, but it should be appreciated that pressure vessel 120a may represent a group of two or more first pressure vessels 120a connected in parallel with each other, and pressure vessel 120b may similarly represent a group of two or more second pressure vessels 120b connected in parallel with each other, wherein the two groups operate in such a manner that one group is in an online mode and the other group is in an offline mode.

[0049] Furthermore, the pressurized fluid distribution system 118 may optionally include one or more feed containers 122 in a pipeline located between the second container 106 and pressure vessels 120a and 120b, such that the one or more feed containers 122 can provide a stable supply of catalyst solution to pressure vessels 120a and 120b during operation of system 100. Advantageously, the one or more feed containers 122 can facilitate the refilling or replacement of the second container 106 without interrupting the supply of catalyst solution to pressure vessels 120a and 120b. For example, when the second container 106 is offline, such as during refilling or maintenance, catalyst solution can be supplied to one or more of pressure vessels 120a and 120b by the one or more feed containers 122. In another instance, when the second container 106 is replaced with another second container 106 containing additional catalyst solution, or if the second container 106 is otherwise disconnected from the feed containers 122, the one or more feed containers 122 can continue to supply catalyst solution to one or more of pressure vessels 120a and 120b.

[0050] The fluid capacity of pressure vessels 120a and 120b and / or one or more feed vessels 122 may vary depending on factors such as the size of the second vessel 106, the flow rate of the catalyst solution (for mixing with the catalyst slurry) in the pipeline 108, and the frequency at which pressure vessels 120a and 120b circulate between their corresponding online and offline modes.

[0051] The introduction of catalyst solution into pressure vessels 120a and 120b can be managed via corresponding inlet valves 124a and 124b. As shown, inlet valve 124a regulates the supply of catalyst solution to pressure vessel 120a, and inlet valve 124b regulates the supply of catalyst solution to pressure vessel 120b. Similarly, outlet valve 125a regulates the discharge of catalyst solution from the first pressure vessel 120a, and outlet valve 125b regulates the discharge of catalyst solution from the second pressure vessel 120b. Inlet valves 124a / 124b and outlet valves 125a / 125b can be any type of valve providing on / off performance; however, valves providing metered flow rates can also be used.

[0052] Typically, the catalyst solution is supplied one at a time to pressure vessels 120a and 120b via the second container 106 or one or more feed containers 122. An exception is during the initial start-up / loading of system 100, during which pressure vessels 120a and 120b may optionally be loaded simultaneously, followed by pressurization of one of pressure vessels 120a or 120b and entry into its corresponding online mode. Since pump pulsation does not propagate downstream from pressure vessels(one or more) 120a and / or 120b, any type of conventional pump (not shown) can supply the catalyst solution from the second container 106 or one or more feed containers 122 to pressure vessels(one or more) 120a and / or 120b. Alternatively, the second container 106 or one or more feed containers 122 can be pressurized with gas to push the catalyst solution to pressure vessels 120a and / or 120b. When loading the catalyst solution, pressure vessels 120a and / or 120b may be at least partially depressurized and then subsequently pressurized according to further description herein. During the entire process of filling the corresponding pressure vessel 120a or 120b with the catalyst solution, outlet valves 125a and 125b are normally closed. Exhaust ports (not shown) on each of the pressure vessels 120a and 120b may be opened to prevent pressure buildup during catalyst solution filling. After the catalyst solution has been filled into pressure vessels 120a and / or 120b, the exhaust ports may be closed. Once one of the pressure vessels 120a or 120b is at least partially filled with catalyst solution, preferably completely filled, it is selected to initially supply the catalyst solution to line 108 (i.e., in online mode), and the other of the pressure vessels 120a or 120b is selected to be in offline mode. For example, if pressure vessel 120a is selected to supply the catalyst solution to mixing unit 101, pressure vessel 120a is pressurized with gas from gas supply 130a via line 131a, preferably an inert gas such as nitrogen. Once properly pressurized, outlet valve 125a is opened to discharge the catalyst solution. The pressure head supplied by the gas can be kept constant during the discharge of the catalyst solution from pressure vessel 120a (e.g., by keeping the valve in line 131a open to allow continued gas flow into pressure vessel 120a), or the gas pressure in pressure vessel 120a can be allowed to decrease during the discharge of the catalyst solution therefrom. If the gas pressure is allowed to decrease during the discharge of the catalyst solution from pressure vessel 120a, the change in flow rate can be attributed to the use of one or more control valves 126 downstream of pressure vessel 120a (discussed separately below). That is, one or more control valves 126 can be adjusted to maintain the flow rate at a substantially constant level. Such adjustment can be performed automatically or manually.

[0053] When it is necessary to switch pressure vessel 120a to offline mode and pressure vessel 120b to online mode, pressure vessel 120b can be pressurized similarly using gas from gas supply 130b via pipeline 131a. Further details regarding the switching of pressure vessels 120a and 120b between their respective online and offline modes will be discussed later. Although... Figure 1 Individual gas supplies 130a and 130b and corresponding pipelines 131a and 131b are shown, but it should be understood that individual gas supplies may also suitably supply gas to pipelines 131a and 131b for pressurizing one of pressure vessels 120a and 120b at a given time.

[0054] When pressure vessel 120a is operating in online mode, outlet valve 125a is open, and the catalyst solution enters line 108 and subsequently into mixing unit 101. As the volume of catalyst solution in pressure vessel 120a decreases, a second portion of the catalyst solution can be introduced into pressure vessel 120b when it is in offline mode (if the catalyst solution was not pre-filled during system 100 startup). To do this, inlet valve 124b and vent (not shown) can be opened to allow the catalyst solution to flow from second container 106 or one or more feed containers 122 to pressure vessel 120b. Once pressure vessel 120b is fully or partially filled with catalyst solution, preferably fully filled, inlet valve 124b and vent (not shown) are closed, and pressure vessel 120b is pressurized using gas supplied from gas supply 130b via line 131b. At this point, pressure vessel 120b is ready to switch to the corresponding online mode as pressure vessel 120a switches to the corresponding offline mode. There are no particular restrictions on the timing of filling the catalyst solution into pressure vessel 120b, except that the filling must be completed before pressure vessel 120a needs to be switched to the corresponding offline mode.

[0055] Once the catalyst solution in pressure vessel 120a is depleted or nearly depleted (e.g., less than 10% or less than 5% of the catalyst solution remains), outlet valve 125a can be closed and outlet valve 125b can be opened (e.g., before closing outlet valve 125a, or simultaneously or nearly simultaneously with closing outlet valve 125a), thereby switching pressure vessel 120a to offline mode and pressure vessel 120b to online mode. A check valve (not shown) can be used to prevent backflow. Once pressure vessel 120b is in online mode, it now supplies catalyst solution to line 108 without interrupting the flow of catalyst solution. Once pressure vessel 120a no longer supplies catalyst solution to line 108, pressure vessel 120a can be depressurized and subsequently refilled with catalyst solution in a manner similar to that described above for pressure vessel 120b. For example, pressure vessel 120a can be at least partially refilled in offline mode with a third portion of catalyst solution while pressure vessel 120b is operating in online mode and supplying a second portion of the catalyst solution to the mixing unit. Then pressure vessels 120a and 120b can continue to switch between the corresponding online and offline modes, cycling as many times as needed.

[0056] In one or more embodiments, the decision to switch pressure vessel 120a or pressure vessel 120b to a corresponding offline mode can be based on the volume of the remaining catalyst solution in pressure vessel 120a or pressure vessel 120b (e.g., the volume reaches a predetermined depletion threshold, such as about 10% or less of the vessel volume, or about 5% or less of the vessel volume). For example, the volume of the catalyst solution can be monitored visually or via one or more sensors (not shown) (e.g., volume sensors, level sensors, etc.). Alternatively, the flow rate of the catalyst solution from pressure vessel 120a or pressure vessel 120b can be monitored, and the decision to switch to the corresponding offline mode can be based on the vessel volume and the amount of residual volume expected to remain based on the flow rate of the catalyst solution, again keeping the residual volume above the predetermined depletion threshold.

[0057] The pressure within pressure vessels 120a and 120b can be suitably high to facilitate the distribution of the catalyst solution to line 108. In non-limiting examples, the pressure can be about 300 psi or higher, or about 400 psi or higher, or about 500 psi or higher, for example in the range of about 300 psi to about 500 psi, or about 500 psi to about 600 psi. The pressure can also be at least the operating pressure in polymerization reaction 114. Preferably, the pressure can be supplied with an inert gas, such as nitrogen, helium, argon, or any combination thereof. Other inert gases may be supplied alternatively, depending on specific process requirements. Optionally, the inert gas can be purified to reduce or remove contaminants, such as oxygen, water, sulfur compounds, etc., that may cause poisoning of one or more components of the catalyst slurry or catalyst solution.

[0058] Furthermore, the pressurizable fluid distribution system 118 may include one or more control valves 126 located downstream of pressure vessels 120a and 120b and configured to manage or regulate the flow of catalyst solution to line 108. For example, it may be desirable to overpressure the in-line pressure vessel (e.g., pressure vessel 120a) to facilitate transport therefrom, but the selected pressure may result in excessive flow and / or reduced flow as the overpressure decreases. One or more control valves 126 may facilitate the desired flow to accommodate the overpressure, or, if the flow from the in-line pressure vessel (e.g., pressure vessel 120a) should be changed, one or more control valves 126 may be used to maintain the flow at a desired level. By limiting the flow, one or more control valves 126 may also help mitigate foaming of the catalyst solution as it is delivered to the catalyst slurry. In various embodiments, one or more control valves 126 may be remotely controlled via, for example, wireless connection to one or more computer devices. Suitable examples of one or more control valves 126 may include metering valves, such as needle valves or shut-off valves.

[0059] According to embodiments of this disclosure, a catalyst solution delivered under gas pressure can adsorb the amount of gas required to achieve equilibrium in the headspace of an online pressure vessel to facilitate its distribution. If the pressure of the resulting combined liquid stream drops below a defined threshold and exceeds the equilibrium solubility of the dissolved gas (e.g., dissolved nitrogen) at a lower pressure, the catalyst slurry and catalyst solution may suffer from foaming. Bubble formation and foaming can damage various components of system 100 and may lead to ineffective modification of the supported catalyst. By utilizing one or more control valves 126 to maintain a low ratio of catalyst solution to catalyst slurry, the released gas can be adequately absorbed by the catalyst slurry, which is not at equilibrium gas solubility conditions. That is, by promoting a relatively low flow rate, one or more control valves 126 can limit the amount of releasable gas to the amount that can be absorbed by the catalyst slurry. Furthermore, the distance between one or more control valves 126 and the location where the catalyst solution contacts the catalyst slurry can be minimized to limit the location where non-equilibrium gas release may occur.

[0060] The catalyst solution is provided directly or indirectly to the mixing unit 101. Figure 1 (As shown in the diagram, it is provided directly). The mixing unit 101 can be a mechanically stirred mixing tank, a static mixer, or a mixing block. Preferably, the mixing unit is a mechanically stirred mixing tank to provide a longer contact time. A static mixer or mixing block can provide a total contact time of about 1-2 minutes between the catalyst solution and the catalyst slurry (when the resulting modified catalyst is delivered to the polymerization reactor 114 via line 112). The contact time within the static mixer or mixing block itself can be in the range of only a few seconds.

[0061] By utilizing a mechanically stirred mixing tank as mixing unit 101 (or as part of mixing unit 101), more thorough (higher quality) and longer-lasting mixing can be achieved than is feasible using a static mixer or mixing block alone. Mixing unit 101, including a mechanically stirred mixing tank, may include one or more impellers or other internal components to facilitate agitation and mixing therein. For example, one or more impellers may be present in the mechanically stirred mixing tank, defined as a slanted-blade turbine. In addition to the volume and construction of the mechanically stirred mixing tank, the rotational rate of one or more impellers may affect the residence time of the catalyst slurry and catalyst solution in mixing unit 101. A suitable mechanically stirred mixing tank may be characterized by sufficient volume and construction to provide a contact time at least approximately 5 minutes longer than that produced by a single mixing block or static mixer. In a non-limiting example, the mixing unit 101, including a mechanically stirred mixing tank, can provide a contact time of approximately 20, 22, 25, 27, 28, or 30 minutes to approximately 30, 33, 35, 37, 38, 39, 40, 42, 45, or 50 minutes between the catalyst slurry and the catalyst solution therein (considering a range from any of the aforementioned lower to any of the aforementioned higher ends, e.g., 30 to 40 minutes). In addition to the increased contact time, the mixing unit 101, including a mechanically stirred mixing tank, can improve the mixing quality to a degree exceeding that of just diffusion-limited methods. Unconstrained by theory or mechanism, mechanical stirring can provide greater homogenization of the catalyst solution throughout the catalyst slurry and reduce the thickness of the mass transfer boundary layer on the catalyst particles, thereby allowing for faster mass transfer of the catalyst from the catalyst solution to the catalyst particles for activation.

[0062] The mixing unit 101 may be a mechanically stirred mixing tank having a total volume of, for example, about 10 L to about 30 L, or about 10 L to about 20 L, or about 15 L to about 25 L, or about 20 L to about 30 L. Volumes within the aforementioned ranges, combined with the design and construction of the mechanically stirred mixing tank, are sufficient to provide a contact time of about 30-40 minutes within the tank. It should be understood that, depending on the catalyst feed rate, the volume can be adjusted upwards or downwards from the aforementioned range to maintain the contact time within the desired specified range. Variations in catalyst productivity (kg catalyst / kg polymer) and / or production rate (kg / hr polymer production) may further cause the volume of the mechanically stirred mixing tank to increase or decrease to achieve the desired contact time and / or mixing quality.

[0063] Besides volume, other mechanically stirred mixing vessels suitable for use within mixing unit 101 as disclosed herein include, but are not limited to, any type of stirred mixing vessel described in the Handbook of Industrial Mixing (2004, edited by Paul, Atiemo-Obeng, and Kresta). The vessel defining a mechanically stirred mixing vessel can include any suitable shape, such as primarily cylindrical as well as various types of vessel heads and bottoms (e.g., flat, ellipsoidal, or conical). Depending on the impeller selection, baffles may optionally be used to prevent solid rotation and enhance axial mixing. In some embodiments, the vessel of the mechanically stirred mixing vessel may be graded with horizontal baffles to provide multiple connected chambers. In any embodiment, the vessel of the mechanically stirred mixing vessel can be vertical, horizontal, or inclined. In any embodiment, impellers (one or more), axially or inclined, centered or eccentric, or any combination thereof, may be mounted on the top, bottom, or sides of the vessel. Each impeller (e.g., one, two, three, four, or even more impellers of the same or different types) can be any of axial flow, radial flow, mixing flow, close contact, spiral band, or any combination thereof. Impellers (one or more) can be sized at different ratios to the container diameter, located at different heights from the bottom of the container, and can be of different types to influence different mixing patterns in different sections of the mechanically stirred mixing tank. Inlet and outlet locations can be situated at different points within the mechanically stirred mixing tank depending on the desired mixing performance. The liquid level within the mechanically stirred mixing tank can be manipulated from partially full to completely full (e.g., no or limited vapor space).

[0064] In one non-limiting example, the mechanically stirred mixing tank can be a cylindrical container with a conical bottom (with a taper of about 15 degrees) and separated from the impeller shaft by an agitator axially spaced from the impeller by two inclined turbine blades. Catalyst slurry and catalyst solution can be loaded into the top of the liquid-filled mechanically stirred mixing tank, and the effluent can be extracted from the bottom, with a direct line from inlet to outlet passing through the space of the impeller.

[0065] It should also be understood that in some process configurations (not shown), mixing unit 101 can be eliminated, in which case contact between the catalyst solution and the catalyst slurry can occur in line 104 or 112.

[0066] By contacting the catalyst slurry with the catalyst solution in mixing unit 101, a modified catalyst slurry containing the modified supported catalyst is obtained, and then transported to polymerization reactor 114 via line 112. Optionally, one or more static mixers 115 may be located within line 112, which can provide additional contact time for mixing if needed. Although line 112 is in Figure 1While depicted as a single pipeline, it should be understood that pipeline 112 may alternatively comprise multiple parallel pipelines to deliver the modified catalyst slurry to the polymerization reactor 114 at multiple locations and / or at different flow rates. For example, pipeline 112 may comprise one, two, three, four, five, six, or more parallel pipelines, each operating independently of the others and having independent thermal control relative to each other. Furthermore, other components may be delivered to the polymerization reactor 114 via pipeline 112 (or multiple pipelines 112), or combined with the modified catalyst slurry in one or more pipelines and / or introduced into one or more separate pipelines that do not contain the modified catalyst slurry. Such other components are discussed in more detail below.

[0067] It should be understood that while this document describes modified catalyst slurries containing at least two catalyst compounds, modified catalyst slurries may contain a single catalyst compound (the first catalyst compound) if suitable for a particular process (e.g., where the supported catalyst contains catalyst compounds deposited thereon, and the catalyst solution contains the same catalyst compounds, such that controlling the amount of catalyst solution mixed with the catalyst slurry effectively controls the amount of deposited catalyst compounds). Similarly, modified catalyst slurries may alternatively contain three or more catalyst compounds, depending on specific process requirements (e.g., one, two, or three compounds may be present on the supported catalyst of the catalyst slurry, or one or two catalyst compounds, or even all three catalyst compounds, may be added via the catalyst solution to provide on-the-fly control of the compound ratios).

[0068] The polymerization reactor 114 may include a reaction zone and a rate-reduction zone. The reaction zone may include a bed and a diluent to remove the heat of polymerization through the reaction zone. The bed may contain growing polymer particles, formed polymer particles, and a small amount of catalyst particles fluidized by a continuous flow of gaseous monomers. An olefin feed (gas, liquid, or liquid-gas) may be provided to and recycled within the polymerization reactor 114. Optionally, some of the recycled feed may be cooled and compressed to form a liquid (e.g., in the case where the gas contains induced condensate (ICAs)), which can improve the heat removal capacity of the recycled feed when it is returned to the reaction zone. The rate at which olefin monomers are replenished to the recycled feed may be equal to the rate at which particulate polymer products and associated monomers are extracted from the reactor, and the composition of the feed through the reactor may be adjusted to maintain a substantially steady-state gaseous composition within the reaction zone. The gas exiting the reaction zone may proceed to the rate-reduction zone, where entrained particles may be removed, for example, by slowing down and falling back into the reaction zone below the rate-reduction zone. If necessary, finer entrained particles and dust can be removed in a separation system (e.g., a cyclone separator and / or a fine powder filter). The recirculated stream can pass through a heat exchanger, where at least a portion of the heat of polymerization can be removed and / or the recirculated stream can be compressed and returned to the reaction zone.

[0069] In another suitable process configuration of this disclosure, the contact time between the catalyst solution and the catalyst slurry can be increased by contacting the catalyst slurry with the catalyst solution in a pipeline upstream of the mixing unit 101. In this case, the increased contact time in the pipeline can facilitate the typically shorter contact time in a static mixer or mixing block, although a mechanically stirred mixing tank can also be used in this configuration. Figure 2 This is a block diagram of a gas phase reactor system 200, in which the mixing of catalyst slurry and catalyst solution can be carried out in a pipeline upstream of mixing unit 101, which may advantageously be or include a static mixer or mixing block, thereby providing a simpler mixing solution at a lower cost compared to mechanically stirred mixing tanks.

[0070] like Figure 2 As shown, the catalyst slurry is again supplied from the first container 102 to the line 104, and the catalyst solution is again supplied from the second container 106 to the line 108 after passing through the pressurized fluid distribution system 118. Unlike Figure 1The catalyst solution in line 108 is supplied directly to mixing unit 101 as in the example above. At least a portion of the catalyst solution in line 108 is diverted to line 104 via line 212 (i.e., a "jumpover line"), wherein premixing of the catalyst slurry and catalyst solution can take place in the downstream portion 104a of line 104 before entering mixing unit 101. All catalyst solution in line 108 need not be diverted to line 104 via line 212, and alternatively, a portion of the catalyst solution may be selectively directed to mixing unit 101. Preferably, the entire catalyst solution in line 108 is directed to line 104 for mixing with the catalyst slurry in the line before entering mixing unit 101. Optionally, if desired, one or more static mixers or mixing blocks 302 may be additionally placed in line 104a upstream of mixing unit 101 to provide additional contact time for mixing, such as... Figure 3 As shown in system 300.

[0071] Therefore, the pressurized fluid distribution system 118 can supply the catalyst solution upstream of the mixing unit 101 to the line 104, directly to the mixing unit 101, or any combination thereof. The downstream section 104a includes a portion of the line 104 located between the mixing unit 101 and the junction of the line 212 and the line 104. A slurry pump (in...) Figure 2 or Figure 3(Not shown) may be located immediately upstream of downstream section 104a to maximize contact time in downstream section 104a and facilitate transport of catalyst slurry and catalyst solution to mixing unit 101. In a non-limiting example, the catalyst slurry and catalyst solution may have a contact time of at least about 5 minutes (or at least about 6 minutes, e.g., at least about 7 minutes) in downstream section 104a, and the contact time may be further adjusted by selecting the location where line 212 intersects with line 104. The total (combined) contact time of catalyst slurry and catalyst solution in downstream section 104a and mixing unit 101 may be at least about twice the contact time obtained in the absence of downstream section 104a of line 104 (e.g., when catalyst slurry and catalyst solution are directly introduced to mixing unit 101) and / or the total contact time may be increased by at least about 4 minutes compared to the contact time obtained in the absence of downstream section 104a of line 104 (e.g., when catalyst slurry and catalyst solution are directly introduced to mixing unit 101). In a more specific, non-limiting instance, when a downstream portion 104a of line 104 is present, the total contact time within the downstream portion 104a and mixing unit 101 may be at least about 6 minutes, or at least about 7 minutes (e.g., in the range of 6, 7, or 8 minutes to 7, 8, 9, or 10 minutes; considering the range from any of the aforementioned low points to any of the aforementioned high points, provided that the high end is greater than the low end; e.g., 6-7 minutes). Further increases in contact time can be achieved by introducing a static mixer or mixing block 302 into line 104, as described above for system 300. Figure 3 ).

[0072] Modified catalyst slurry can be introduced into the polymerization reactor via a single line in contact with the fluid in the polymerization reactor, or via two or more lines (e.g., 2, 3, 4, or more lines) in contact with the fluid in the polymerization reactor. It is also contemplated that multiple modified catalyst slurries with different compositions can be introduced via two or more lines in contact with the fluid in the polymerization reactor. Such lines may include dedicated equipment for transporting the modified catalyst slurry / multiple slurries through the lines and into the polymerization reactor. Examples of such dedicated equipment include, but are not limited to, pinch valves, nozzles (such as jet nozzles and solid flow nozzles), temperature controllers, the like, and any combination thereof. Dedicated equipment can be used to control the homogeneity of the catalyst entering the polymerization reactor. The lines (one or more) entering the polymerization reactor can be temperature-controlled either upstream of the dedicated equipment or within the equipment itself. Therefore, temperature control can help regulate the viscosity of the modified catalyst slurry and limit temperature variations within the polymerization reactor caused by the modified catalyst slurry / multiple slurries entering the polymerization reactor at different rates. When multiple pipelines exist, each pipeline can be operated using independent flow control and / or independent temperature control.

[0073] More generally, a modified catalyst slurry and one or more olefins, as well as other potential feed streams, can be introduced into a polymerization reactor, preferably a gas-phase reactor, and more preferably a fluidized bed gas-phase polymerization reactor. A modified catalyst slurry can be obtained by combining an initial catalyst slurry containing a supported catalyst (comprising at least one catalyst compound) with a catalyst solution containing a first catalyst compound (already contained on the supported catalyst) and / or a second catalyst compound (not yet contained on the supported catalyst). More generally, the supported catalyst may contain one, two, or three (or even more) different catalyst compounds; and the catalyst solution may contain one or more catalyst compounds, any of which may be either (i) the same as one of the catalyst compounds in the supported catalyst; or (ii) different from any of the catalyst compounds in the supported catalyst. In addition to at least one catalyst compound, the supported catalyst may also contain at least one activator on a support material. The catalyst slurry and catalyst solution may each contain a support liquid suitable for transporting the supported catalyst and the catalyst compound (one or more) therein, and contact between the supported catalyst of the catalyst slurry and the catalyst compound (one or more) of the catalyst solution can be carried out therein. The support liquid in the catalyst slurry and the support liquid in the catalyst solution can be the same or different. By contacting the catalyst slurry with the catalyst solution, different catalyst compounds can be introduced onto the support material and / or the loading of at least one catalyst compound on the support material can be increased. After contacting the activator on the support material, a modified catalyst slurry with regulated activity for polymerization is obtained. In a non-limiting example, as a direct result of the increased contact time between the catalyst slurry and the catalyst solution disclosed herein, the modified catalyst slurry is less prone to flaking during polymerization. The contact time can be further selected to reduce the degree of polymer flaking to the desired extent.

[0074] Therefore, the method of this disclosure may include: providing a catalyst slurry comprising a supported catalyst, the supported catalyst comprising a support material, at least one catalyst compound, and at least one activator; leading the catalyst slurry to a pipeline in fluid communication with a mixing unit; providing a catalyst solution comprising a first catalyst compound already contained on the supported catalyst or a second catalyst compound different from the first catalyst compound; leading the catalyst solution to a pressurized fluid distribution system in fluid communication with the mixing unit, the pressurized fluid distribution system comprising at least one first pressure vessel and at least one second pressure vessel connected in parallel with each other, wherein at least one first pressure vessel operates in an online mode and at least one second pressure vessel is in an offline mode, and at least one first pressure vessel and at least one second pressure vessel are in an offline mode. The second pressure vessel can be switched between online and offline modes; at least one first pressure vessel is at least partially filled with a first portion of the catalyst solution; the at least one first pressure vessel is pressurized such that a pressurizable fluid distribution system supplies the first portion of the catalyst solution from the at least one first pressure vessel to a mixing unit; the catalyst solution is contacted with a catalyst slurry in a pipeline, in an online pipeline mixer in a pipeline, in a mixing unit, or any combination thereof to obtain a modified catalyst slurry, the modified catalyst slurry incorporating at least a portion of a first catalyst compound or a second catalyst compound from the catalyst solution onto a supported catalyst; the modified catalyst slurry is fed to a polymerization reactor; and α-olefins are polymerized in the polymerization reactor under polymerization reaction conditions to obtain polyolefins. In a particular example, the polymerization reactor may be a fluidized bed gas-phase polymerization reactor.

[0075] The implementation of cross-line, mechanically stirred mixing tanks, inline pipeline mixers, or mixing blocks, or any combination thereof, can increase contact time and significantly reduce the amount of polymer flakes in the polymerization reactor. For example, the polymer flake rate in the polymerization reactor can be ≤0.3%. In various embodiments, the polymer flake rate can be ≤0.3%, ≤0.27%, ≤0.25%, ≤0.23%, ≤0.2%, ≤0.17%, ≤0.15%, ≤0.13%, ≤0.1%, ≤0.09%, ≤0.8%, ≤0.07%, ≤0.06%, ≤0.05%, or ≤0.04%. The polymer flake rate refers to the percentage by mass of flake polymer produced relative to the total amount of polymer produced over a given time length. Reducing the polymer flake rate can reduce the frequency of flake removal downstream of the reactor. For example, accumulated polymer flakes may not need to be removed by a collection box connected to the polymerization reactor for up to 48 hours, or up to about 36 hours, or up to about 24 hours, or up to about 12 hours, or up to about 6 hours.

[0076] Catalyst slurry, catalyst solution and modified catalyst slurry

[0077] Catalyst slurries and modified catalyst slurries may comprise at least one catalyst compound on a support liquid and a supported catalyst. Optionally, the catalyst slurry may also comprise one or more waxes, mineral oils, induced condensers, or any combination thereof. In some embodiments, the support liquid may be, or may comprise, but is not limited to, one or more mineral oils and / or one or more waxes, optionally in further combination with an induced condenser.

[0078] It should also be noted that some components present within the polymerization reactor may be fed into the polymerization reactor via a modified catalyst slurry (e.g., optional induced condenser, support fluid, such as nitrogen), or may be introduced into the polymerization reactor additionally or alternatively via other means. For example, in gas-phase polymerization processes, particularly in fluidized bed gas-phase polymerization processes, the induced condenser may be provided to the process in the circulating gas flowing upward through the fluidized bed in the polymerization reactor, or it may be provided in other streams that are not modified catalyst slurry or circulating gas. Circulating gas may refer to a gaseous stream containing olefin feed that circulates through the reactor and is replenished with additional olefins as needed.

[0079] In some embodiments, the catalyst slurry or modified catalyst slurry may contain 1 wt%, 5 wt%, 8 wt%, or 10 wt% to 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, or 40 wt% solids based on the total weight of the catalyst slurry or modified catalyst slurry. The solids include one or more catalyst compounds, support material, activator, and any other solid components (one or more), if present. If wax is present in the support liquid, it is considered a liquid component rather than a solid component. For example, if the catalyst slurry or modified catalyst slurry contains a first catalyst, a second catalyst, a support, an activator, and a support liquid comprising mineral oil and wax, the solid components include the first and second catalysts, the support, and the activator; and the liquid components include mineral oil and wax.

[0080] The modified catalyst slurry may include a first catalyst compound and a second catalyst compound, wherein the first catalyst compound is capable of producing a high molecular weight polymer and the second catalyst compound is capable of producing a low molecular weight polymer. In other words, the first catalyst compound may be a catalyst that primarily produces high molecular weight polymer chains, and the second catalyst compound may primarily produce low molecular weight polymer chains, which may depend on the catalyst structure and the polymerization reaction may occur under specific polymerization conditions. Therefore, in some instances, the polymer product produced by the modified catalyst slurry under polymerization conditions may comprise both high molecular weight and low molecular weight polymers. The two catalyst compounds may be present in the modified catalyst slurry in molar ratios of the first catalyst compound to the second catalyst compound of 99:1 to 1:99, 90:10 to 10:90, 85:15 to 15:85, 75:25 to 25:75, 60:40 to 40:60, or 55:45 to 45:55. In some embodiments, the first catalyst compound and / or the second catalyst compound may also be added to the catalyst slurry as a catalyst from a catalyst solution to adjust the molar ratio of the first catalyst compound to the second catalyst compound. In at least one embodiment, the first catalyst compound and the second catalyst compound may each be a different metallocene catalyst, as described below.

[0081] The terms "slurry catalyst" or "catalyst slurry" each refer to a contact product comprising a dispersed supported catalyst, which includes at least one catalyst compound on a support material, a support liquid, an activator, and optionally a co-activator. In certain embodiments, the slurry catalyst may comprise two catalyst compounds, such as two different metallocene catalyst compounds, particularly after the formation of the modified catalyst slurry. For example, the modified slurry catalyst may comprise a supported catalyst, which may contain at least one first metallocene and a second metallocene that are structurally different from each other. Further disclosure of suitable catalyst compounds is provided below.

[0082] One or more induced condensing agents (ICAs) can be introduced into the polymerization reactor; such ICAs can improve the productivity of the polymer product. ICAs can be present in a catalyst slurry, a catalyst solution, or a modified catalyst slurry obtained by contacting the catalyst slurry with the catalyst solution. Alternatively, at least a portion of the ICA can be combined with the modified catalyst slurry in a line leading from a mixing unit, or the ICA can be introduced into the polymerization reactor independently of the catalyst slurry. The ICA can condense under polymerization conditions within the polymerization reactor. Introducing ICA into the polymerization reactor is commonly referred to as operating the reactor in “condensation mode.” ICAs can be non-reactive in the polymerization process, but their presence can improve the productivity of the polymer product. In some embodiments, the ICA agent can be, or may contain, but is not limited to, one or more alkanes. Illustrative alkanes can be, or may contain, but are not limited to, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, n-heptane, n-octane, or any mixture thereof. Further details regarding ICAs can be found in U.S. Patent Nos. 5,352,749; 5,405,922; 5,436,304; and 7,122,607; and International Patent Application Publication No. WO 2005 / 113615(A2). As described above, such ICAs (one or more) can be added to the modified catalyst slurry in a pipeline; this can be the primary source of ICA supplied to the reactor, or added to the modified catalyst slurry in addition to any other ICA introduced into the reactor, for example, via recirculated gas introduced into the polymerization reactor. The induced condenser can be introduced into the modified catalyst slurry at a rate or average rate (when using multiple pipelines) of approximately 0.4 kg / hr, 1 kg / hr, 5 kg / hr, or 8 kg / hr to 11 kg / hr, 23 kg / hr, or 45 kg / hr per pipeline.

[0083] When the catalyst slurry or modified catalyst slurry also contains an inducing condenser, the inducing condenser may account for 30 to 90% by weight of the catalyst slurry or modified catalyst slurry, for example, 30, 35, 40, 45 or 50% to 60, 70, 80 or 90% by weight of the catalyst slurry or modified catalyst slurry. In some embodiments, when the catalyst slurry or modified catalyst slurry contains mineral oil and wax in addition to the induced condenser, the mineral oil may account for a low of 8, 15, 20, or 25% by weight to a high of 40, 50, 60, or 68% by weight of the catalyst slurry or modified catalyst slurry, the wax may account for a low of 2, 5, or 7% by weight to a high of 10, 12, or 15% by weight of the catalyst slurry or modified catalyst slurry, and the induced condenser may account for a low of 30, 40, 45, or 50% by weight to a high of 60, 70, 80, or 90% by weight of the catalyst slurry or modified catalyst slurry, each based on the total mass of the catalyst slurry or modified catalyst slurry.

[0084] The presence of wax can increase the viscosity of mixtures containing catalysts (e.g., catalyst slurries or modified catalyst slurries). The term "wax" as used herein includes wax pastes, also known as petroleum pastes or petroleum waxes. Petroleum waxes include paraffin waxes and microcrystalline waxes, which include porous paraffin waxes and flake waxes. Commercially available waxes include SONO JELL. ® Paraffin, for example, is available from SONOJELL, Sonneborn, LLC. ® 4 and SONOJELL ® 9. In at least one embodiment, the wax, if present, may have a concentration of 0.7 g / cm³. 3 0.73g / cm 3 Or 0.75g / cm 3 Up to 0.87 g / cm 3 0.9g / cm 3 or 0.95g / cm 3 The density (at 100°C). If the wax is present, it may have a kinematic viscosity at 100°C of 5 cSt, 10 cSt, or 15 cSt to 25 cSt, 30 cSt, or 35 cSt. If the wax is present, it may have a melting point of 25°C, 35°C, or 50°C to 80°C, 90°C, or 100°C. If the wax is present, it may have a boiling point of 200°C or higher, 225°C or higher, or 250°C or higher.

[0085] It should be understood that the term "wax" also refers to or additionally includes any wax not considered petroleum wax, including animal waxes, plant waxes, fossil or terrestrial waxes, vinyl polymers and polyol ether esters, chlorinated naphthalene, and hydrocarbon waxes. Animal waxes may include beeswax, lanolin, shellac wax, and Chinese insect wax. Plant waxes may include palm wax, candelilla wax, laurel wax, and sugarcane wax. Fossil or terrestrial waxes may include ozocerite, pure ozocerite, and lignite wax. Vinyl polymers and polyol ether esters include polyethylene glycol and methoxy polyethylene glycol. Hydrocarbon waxes include waxes synthesized via Fischer-Tropsch synthesis.

[0086] In some embodiments, the catalyst slurry, catalyst solution, or modified catalyst slurry may be free of any wax having a melting point of ≥25°C. In other embodiments, the catalyst slurry, catalyst solution, or modified catalyst slurry may contain ≤3 wt%, ≤2.5 wt%, ≤2 wt%, ≤1.5 wt%, ≤1 wt%, ≤0.9 wt%, ≤0.8 wt%, ≤0.7 wt%, ≤0.6 wt%, ≤0.5 wt%, ≤0.4 wt%, ≤0.3 wt%, ≤0.2 wt%, or ≤0.1 wt% of any wax having a melting point of ≥25°C, based on the total mass of the catalyst slurry, catalyst solution, or modified catalyst slurry.

[0087] In various embodiments, alkylaluminum, ethoxylated alkylaluminum, aluminoxane, antistatic agents (e.g., those mentioned in paragraphs

[0078] -

[0082] of WO 2022 / 174202) or borate (ester) activators, such as C1-C1, may be added to the modified catalyst slurry in the pipeline. 15 Alkyl aluminum (e.g., triisobutylaluminum, imethyl aluminum, etc.), C1-C 15 Ethoxylated alkyl aluminum or methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, modified aluminoxane, etc. For example, alkyl compounds, antistatic agents, borate (ester) activators, and / or aluminoxanes can be added directly to the modified catalyst slurry from a container in a pipeline. Additional alkyl compounds, antistatic agents, borate (ester) activators, and / or aluminoxanes can be present in amounts of 1 ppm, 10 ppm, 50 ppm, 75 ppm, or 100 ppm to 200 ppm, 300 ppm, 400 ppm, or 500 ppm. In some embodiments, optional support fluids, such as molecular nitrogen, argon, ethane, propane, etc., can be added to the modified catalyst slurry in a pipeline. The support fluid, such as molecular nitrogen, can be introduced through the pipeline at a rate (or average rate, when multiple pipelines are used) of approximately 0.4 kg / hr, 1 kg / hr, 5 kg / hr, or 8 kg / hr to 11 kg / hr, 23 kg / hr, or 45 kg / hr per pipeline. In other embodiments, the carrier fluid can be introduced via pipeline at a rate or average rate of approximately 5 kg / hr, 7 kg / hr, 9 kg / hr or 10 kg / hr to 11 kg / hr, 13 kg / hr or 15 kg / hr per pipeline (when multiple pipelines are used).

[0088] In some implementation schemes (not directly shown) Figure 1 , Figure 2 or Figure 3 In this process, after mixing the catalyst solution and catalyst slurry, a support fluid, such as molecular nitrogen, monomer, or other material, can be introduced into the modified catalyst slurry. This introduction can be made along a line guiding the gas-phase polymerization reactor or at an injection nozzle within the reactor, the injection nozzle potentially including a support tube that at least partially surrounds the nozzle. The modified catalyst slurry can then be introduced into the polymerization reactor through the injection nozzle. In various embodiments, the injection nozzle atomizes the resulting catalyst-containing mixture. Any number of suitable tube sizes and configurations can be used to atomize and / or inject the slurry / solution mixture.

[0089] In some configurations, the support fluid may be directly or indirectly separated from or otherwise derived from a recirculating gas (e.g., all or part of the recirculating gas). In this case, where the recirculating gas is used as the support fluid, those skilled in the art will understand that such a recirculating gas may also contain an induced condenser. The recirculating gas may contain at least a portion of the polymerization feed recycled through the gas-phase polymerization reactor.

[0090] In some embodiments, based on the total weight of the modified catalyst slurry, the modified catalyst slurry may contain one or more catalyst compounds ranging from 1 wt%, 5 wt%, 10 wt%, or 15 wt% to 25 wt%, 30 wt%, 35 wt%, or 40 wt%. The aforementioned weight percentages do not include the support material on which the catalyst is placed. In such embodiments, the total amount of modified catalyst slurry introduced into the polymerization reactor may be at a flow rate of ≥0.1 kg / hr per cubic meter of polymerization reactor volume, ≥0.11 kg / hr per cubic meter of polymerization reactor volume, ≥0.12 kg / hr per cubic meter of polymerization reactor volume, ≥0.13 kg / hr per cubic meter of polymerization reactor volume, or ≥0.14 kg / hr per cubic meter of polymerization reactor volume, up to 0.2 kg / hr per cubic meter of polymerization reactor volume, 0.3 kg / hr per cubic meter of polymerization reactor volume, 0.4 kg / hr per cubic meter of polymerization reactor volume, or 0.5 kg / hr per cubic meter of polymerization reactor volume.

[0091] In some embodiments, to promote particle formation in the polymerization reactor, nucleating agents such as silica, alumina, vapor-deposited silica, or other suitable particulate matter can be added directly to the reactor. Alternatively, the nucleating agent may be present in the catalyst solution, catalyst slurry, and / or modified catalyst slurry, and optionally, the nucleating agent may also be introduced into the reactor. Advantageously, the nucleating agent may be optional in this disclosure, but may be included if desired. Preferably, the catalyst solution and catalyst slurry do not contain nucleating agents and / or do not contain nucleating agents when mixing the catalyst solution and catalyst slurry (i.e., if nucleating agents are present, they are introduced into the modified catalyst slurry in one or more lines downstream of any mixing unit (mechanically stirred mixing tank, static mixer, mixing block, etc.). For embodiments that do not contain nucleating agents, it has been found that high polymer bulk density (e.g., 0.4 g / cm³) can be obtained. 3(or greater), which is greater than the bulk density of polymers formed by conventional processes. Furthermore, when using metallocene catalysts or other similar catalysts in a gas-phase reactor, oxygen or fluorobenzene can be added directly to the polymerization reactor or added to the gas stream (containing the support fluid) in the pipeline to control the polymerization rate. Therefore, when a metallocene catalyst (sensitive to oxygen or fluorobenzene) is used in combination with another catalyst (insensitive to oxygen) in a gas-phase polymerization reactor, oxygen can be used to modify the metallocene polymerization rate relative to the polymerization rate of the other catalyst. For example, WO 1996 / 009328 discloses the addition of water or carbon dioxide to a gas-phase polymerization reactor for similar purposes.

[0092] Catalyst compounds

[0093] The methods disclosed herein can generally be carried out using any catalyst system, wherein once a modified supported catalyst has been formed, the catalyst system comprises at least one catalyst compound, preferably two or more catalyst compounds, located on a support. In a particular example, according to the disclosure herein, the supported catalyst in the support slurry may contain a first catalyst compound on the support, and a second catalyst compound, different from the first catalyst compound, may be delivered from a catalyst solution to the catalyst slurry to form a modified catalyst slurry.

[0094] As a specific example, the catalyst compound may comprise one or more metallocenes. In some embodiments, the catalyst may comprise first and second catalyst compounds, said first and second catalyst compounds being at least a first metallocene and a second metallocene, wherein said first and second metallocenes have chemical structures different from each other. The metallocene may comprise a structure having one or more Cp ligands (cyclopentadienyl and ligands similar to cyclopentadienyl isovalve) bonded to at least one metal atom from Group 3 to Group 12 and one or more leaving groups bonded to said at least one metal atom.

[0095] Suitable metallocene catalysts may include those described in U.S. Patent Application Publications 2019 / 0119413 and 2019 / 0119417, which are incorporated herein by reference. Also suitable are catalyst systems using mixtures of two metallocene catalysts, such as those described in U.S. Patent Application Publication 2020 / 0071437, for example, a mixture of (1) dicyclopentadienyl hafnium cadmium and (2) zirconium cadmium, such as indenyl-cyclopentadienyl zirconium cadmium. Additional details are provided below.

[0096] More specifically, the dicyclopentadienyl hafnium cadmium may be associated with one or more of the metallocenes of formula (A1) and / or (A2) as described in US2020 / 0071437; for example, those of formula (A1) as described in paragraphs

[0069] -

[0086] of US2020 / 0071437; or those of formula (A2) as described in paragraphs

[0086] -

[0101] of US2020 / 0071437, which are incorporated herein by reference.

[0097] Specific examples of hafnium according to formula (A1) include bis(n-propylcyclopentadienyl) hafnium dichloride, bis(n-propylcyclopentadienyl)dimethyl hafnium, (n-propylcyclopentadienyl, pentamethylcyclopentadienyl) hafnium dichloride, (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)dimethyl hafnium, (n-propylcyclopentadienyl, tetramethylcyclopentadienyl) hafnium dichloride, (n-propylcyclopentadienyl, tetramethylcyclopentadienyl)dimethyl hafnium, bis(cyclopentadienyl)dimethyl hafnium, bis(n-butylcyclopentadienyl)hafnium dichloride, bis(n-butylcyclopentadienyl)dimethyl hafnium, and bis(1-methyl-3-n-butylcyclopentadienyl)dimethyl hafnium.

[0098] Particularly useful hafnium compounds according to (A2) include one or more listed in paragraph

[0101] of US2020 / 0071437, which are also incorporated herein by reference, such as (relatively brief examples): racemic / meta-Me2Si(Me3SiCH2Cp)2HfMe2; racemic Me2Si(Me3SiCH2Cp)2HfMe2; racemic / meta-Ph2Si(Me3SiCH2Cp)2HfMe2; racemic / meta-(CH2)3Si(Me3SiCH2Cp)2HfMe2; racemic / meta-(CH2)4Si(M e3SiCH2Cp)2HfMe2; racemic / meta-(C6F5)2Si(Me3SiCH2Cp)2HfMe2; racemic / meta-(CH2)3Si(Me3SiCH2Cp)2ZrMe2; racemic / meta-Me2Ge(Me3SiCH2Cp)2HfMe2; racemic / meta-Me2Si(Me2PhSiCH2Cp)2HfMe2; racemic / meta-Ph2Si(Me2PhSiCH2Cp)2HfMe2; Me2Si(Me4Cp)(Me2PhSiCH2Cp)HfMe2; etc.

[0099] Therefore, in certain instances, the first catalyst compound on the support material may comprise a first metallocene, which is a hafnium cadmium, such as racemic / meta-dimethylsilylbis[((trimethylsilyl)methyl)cyclopentadienyl]dimethylhafnium. The second catalyst compound in the catalyst solution may comprise a second metallocene different from the first metallocene. The second metallocene may comprise zirconium cadmium, as described below.

[0100] Suitable catalyst compounds may include zirconium cyclopentadienylene, such as zirconium cyclopentadienylene of formula (B) as described in paragraphs

[0103] -

[0113] of US2020 / 0071437, the description of which is also incorporated herein by reference. Specific examples of suitable zirconium cyclopentadienylene may be any one or more of those listed in paragraph

[0112] of US2020 / 0071437, such as: bis(indenyl)zirconia, bis(indenyl)dimethylzirconia, bis(tetrahydro-1-indenyl)zirconia, bis(tetrahydro-1-indenyl)dimethylzirconia, racemic / meta-bis(1-ethylindenyl)zirconia, racemic / meta-bis(1-ethylindenyl)dimethylzirconia, racemic / meta-bis(1-methylindenyl) ... (1-methylindenyl) dimethylzirconium, racemic / meta-bis(1-propylindenyl)zirconium dichloride, racemic / meta-bis(1-propylindenyl) dimethylzirconium, racemic / meta-bis(1-butylindenyl)zirconium dichloride, racemic / meta-bis(1-butylindenyl) dimethylzirconium, meta-bis(1-ethylindenyl)zirconium dichloride, meta-bis(1-ethylindenyl) dimethylzirconium, (1-methylindenyl)(pentamethylcyclopentadienyl)zirconium dichloride, (1-methylindenyl)(pentamethylcyclopentadienyl) dimethylzirconium, or combinations thereof.

[0101] Therefore, in certain instances, the second catalyst compound may contain a second metallocene, which is a zirconium, such as racemic / meta-bis(1-methylindenyl)dimethylzirconium.

[0102] As described above, supported catalysts and / or modified supported catalysts may contain one or more activators and / or supports in addition to one or more catalyst compounds. The term "activator" refers to any compound or combination of compounds, whether supported or unsupported, capable of activating a single-site catalyst compound or component, for example, by generating a cationic substance of the catalyst component. This may include, for example, abstracting at least one leaving group from the metal center of a single-site catalyst compound / component. Activators may also be referred to as "co-catalysts." For example, a supported catalyst or modified supported catalyst within a slurry catalyst or modified slurry catalyst mixture may contain two or more activators (e.g., aluminoxanes and modified aluminoxanes) and at least one catalyst compound, such as a first catalyst compound and a second catalyst compound. In a particular embodiment, a slurry catalyst or modified slurry catalyst may contain at least one support, at least one activator, and at least two catalyst compounds. For example, a slurry may contain at least one support, at least one activator, and two different catalyst compounds, which may be added individually or in combination to produce a slurry catalyst or modified slurry catalyst. In some embodiments, a mixture of a support (e.g., silica) and an activator (e.g., aluminoxane) may be contacted with a catalyst compound to react it, and thereafter the mixture may be contacted with another catalyst compound from a catalyst solution to form a modified supported catalyst within a modified catalyst slurry as disclosed herein.

[0103] The molar ratio of the metal or noncoordinate anion in the activator of the slurry catalyst to the metal in one or more catalyst compounds can be from 1000:1 to 0.5:1, 300:1 to 1:1, 100:1 to 1:1, or 150:1 to 1:1. The support material for the supported catalyst can be any inert particulate support material known in the art, including but not limited to silica, vapor-deposited silica, alumina, clay, talc, or other support materials disclosed above. In one embodiment, the supported catalyst may comprise silica and an activator, such as methylaluminoxane (“MAO”), modified methylaluminoxane (“MMAO”), etc. Preferred activators typically include aluminoxane compounds, modified aluminoxane compounds, and ionized anion precursor compounds that engulf reactive, σ-bonded metal ligands to give the metal compound a positive charge and provide a charge-balanced noncoordinate or weakly coordinated anion. For example, suitable activators may include any aluminoxane activator and / or ionized / noncoordinated anionic activator described in paragraphs

[0118] -

[0128] of US2020 / 0071437, which is also incorporated herein by reference.

[0104] Suitable supports include, but are not limited to, active and inactive materials, synthetic or naturally occurring zeolites, and inorganic materials such as clay and / or oxides, such as silica, alumina, zirconium oxide, titanium oxide, silica-alumina, cerium oxide, magnesium oxide, or combinations thereof. In particular, the support can be silica-alumina, alumina, and / or zeolite, especially alumina. Silica-alumina can be naturally occurring or in the form of a gel-like precipitate or gel comprising a mixture of silica and metal oxides. Suitable supports may include any support material described in paragraphs

[0129] -

[0131] of US2020 / 0071437, the description of which is also incorporated herein by reference; wherein Al2O3, ZrO2, SiO2, and combinations thereof are particularly indicated.

[0105] catalyst solution

[0106] The catalyst solution may contain a solvent or diluent and only one or more catalyst compounds, such as metallocenes, or may also contain an activator. In certain instances, at least one catalyst compound in the catalyst solution may be unsupported. Preferably, the catalyst solution can be prepared by dissolving at least one catalyst compound and optionally an activator in a solvent or diluent. In some embodiments, the diluent or solvent may be an alkane, such as C5-C... 30 Alkanes or C5-C 10 Alkanes. Cycloalkanes such as cyclohexane and aromatic compounds such as toluene can also be used. Mineral oils can also be used in place of other alkanes, such as one or more C5-C6 hydrocarbons. 30 Alkanes may be used as diluents, or in addition to the aforementioned alkanes, as diluents. If mineral oil is used, the mineral oil in the catalyst solution may have the same properties as the mineral oil used to prepare the catalyst slurry.

[0107] The diluent or solvent used can be liquid and relatively inert under polymerization conditions. In one embodiment, the diluent used in the catalyst solution may be different from the diluent used in the catalyst slurry. In another embodiment, the solvent used in the catalyst solution may be the same as the diluent, i.e., the mineral oil (one or more) and any additional diluent used in the catalyst slurry. In some cases, hydrocarbon solvents may also act as inducing condensers during the polymerization reaction.

[0108] If the catalyst solution contains both a catalyst and an activator, the ratio of the metal or noncoordinate anion in the activator to the metal in the catalyst solution can be from 1000:1 to 0.5:1, 300:1 to 1:1, or 150:1 to 1:1. In various embodiments, based on the weight of the diluent, activator, and catalyst, the activator and catalyst can be present in quantities of up to about 90 wt%, up to about 50 wt%, up to about 20 wt%, for example up to about 10 wt%, up to about 5 wt%, less than 1 wt%, or 100 ppm to 1 wt%. If used, one or more activators in the catalyst solution can be the same as or different from one or more activators present in the catalyst slurry on the supported catalyst.

[0109] Polymerization conditions and polyolefin products

[0110] Once the modified catalyst slurry has been produced according to the above disclosure, it can be fed into a polymerization reaction in combination with an olefin feed under suitable polymerization conditions to obtain a polyolefin. In a non-limiting example, the olefin feed may contain at least one α-olefin to provide a polyolefin homopolymer or copolymer.

[0111] Preferably, the polymerization reaction can be carried out under gas-phase polymerization conditions. The monomers (one or more) introduced into the polymerization reaction under gas-phase polymerization conditions can be introduced in the gas phase, liquid phase, or a combination thereof. The reaction of the monomers (one or more) can be carried out in the gas phase within the reaction zone of the reactor. If desired, unreacted monomers (one or more) can be recycled through the reactor.

[0112] The monomers available in this article include substituted or unsubstituted C2-C monomers. 40 α-olefins, such as C2-C 20 α-olefins, such as C2-C 12 α-olefins, such as ethylene, propylene, butene, pentene, hexene, hepten, octene, nonene, decene, undecene, dodecene, and their isomers. In at least one embodiment, the monomer may include ethylene and a mixture selected from C3-C4. 40 Alkenes, such as C4-C 20 Alkenes, such as C6-C 12 One or more optional comonomers of an olefin. Suitable C4-C 40 Olefin monomers can be linear, branched, or cyclic. (C4-C) 40 Cyclic olefins can be tensioned or non-tensioned, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups. In at least one embodiment, the monomer may comprise ethylene and optionally a comonomer, said comonomer may comprise one or more C3-C... 40 Alkenes, such as C4-C 20 Alkenes, such as C6-C12 Olefins.

[0113] In some implementations, C2-C 40 α-olefin monomers and optional comonomers (one or more) include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, their substituted derivatives and isomers, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene and their respective homologues and derivatives, such as norbornene, norbornadiene and dicyclopentadiene.

[0114] In at least one embodiment, one or more dienes may be present in the polymer product at a maximum of 10% by weight, for example, from 0.00001% to 1.0% by weight, or from 0.002% to 0.5% by weight, or from 0.003% to 0.2% by weight, based on the total weight of the composition. In at least one embodiment, 500 ppm or less of diene is added to the polymerization, for example, 400 ppm or less, such as 300 ppm or less. In other embodiments, at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.

[0115] Diene monomers include any hydrocarbon structure having at least two unsaturated bonds, such as C4-C. 30At least two of the unsaturated bonds are readily incorporated into the polymer by stereo-oriented or non-stereo-oriented catalysts (one or more). The diene monomer may be selected from α,ω-diene monomers (i.e., divinyl monomers). The diene monomer is a linear divinyl monomer, for example, those containing 4-30 carbon atoms. Examples of dienes include butadiene, pentadiene, hexadiene, heptadecadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, heptadecanadiene, octadecadiene, nonadecanadiene, eicosadiene, icosadiene, icosadiene, icosadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecanadiene, octadecadiene, nonadecanadiene, triadecadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tetadecanadiene, 1,13-tetradecadiene, and low molecular weight polybutadiene (Mw < 1000 g / mol). Cyclic dienes include cyclopentadiene, vinyl norbornene, norbornene, ethylidene norbornene, divinylbenzene, dicyclopentadiene, or dienes containing more polycyclic rings with or without substituents at various ring positions.

[0116] The temperature within the polymerization reactor can be greater than 30°C, 40°C, 50°C, 90°C, 100°C, 110°C, 120°C, 150°C, or higher. Typically, the reactor can be operated at a suitable temperature, taking into account the sintering temperature of the polymer product produced within the reactor. Therefore, in one embodiment, the upper temperature limit can be the melting point of the polymer product produced within the reactor. However, higher temperatures can lead to a narrower molecular weight distribution, which can be further improved by adding a catalyst or other co-catalyst.

[0117] In some implementations, hydrogen can be used in the polymerization process to help control or modulate the final properties of the polyolefin, as described, for example, in the "Polypropylene Handbook," pp. 76-78 (Hanser Publishers, 1996). With certain catalyst systems, an increased hydrogen concentration (partial pressure) can increase the flow index, such as the melt index of polyethylene polymers. Therefore, the melt index can be affected by the hydrogen concentration. The amount of hydrogen in the polymerization can be expressed as a molar ratio relative to the total polymerizable monomers (e.g., ethylene, or a mixture of ethylene and hexene or propylene).

[0118] The amount of hydrogen used in the polymerization process can be the amount necessary to achieve the desired melt index of the final polyolefin polymer. For example, the molar ratio of hydrogen to total monomer (H2:monomer) can be 0.0001 or greater, 0.0005 or greater, or 0.001 or greater. Furthermore, the molar ratio of hydrogen to total monomer (H2:monomer) can be 10 or less, 5 or less, 3 or less, or 0.10 or less. The range of the molar ratio of hydrogen to monomer can include any combination of any upper and lower molar ratio limits described herein. At any time, the amount of hydrogen in the reactor can be up to 5,000 ppm, in another embodiment up to 4,000 ppm, up to 3,000 ppm, or 50 ppm to 5,000 ppm, or in another embodiment 50 ppm to 2,000 ppm. The amount of hydrogen in the reactor can be from 1 ppm, 50 ppm, or 100 ppm to 400 ppm, 800 ppm, 1,000 ppm, 1,500 ppm, or 2,000 ppm, based on weight. Furthermore, the ratio of hydrogen to total monomers (H2:monomers) can be from 0.00001:1 to 2:1, 0.005:1 to 1.5:1, or 0.0001:1 to 1:1. The pressure of one or more reactors in the gas-phase process (single-stage, two-stage, or more stages) can be from 690 kPa, 1,379 kPa, or 1,724 kPa to 2,414 kPa, 2,759 kPa, or 3,448 kPa.

[0119] The polymerization reactor is capable of producing polymers at rates greater than 10 kg / hr, greater than 455 kg / hr, greater than 4,540 kg / hr, greater than 11,300 kg / hr, greater than 15,900 kg / hr, greater than 22,700 kg / hr, or greater than 29,000 kg / hr up to 45,500 kg / hr, up to 70,000 kg / hr, up to 100,000 kg / hr, or up to 150,000 kg / hr.

[0120] In some embodiments, the polymer product may have a melt index ratio (I0) of 10 to less than 300, or in many embodiments, a melt index ratio (I0) of 20 to 66. 21.6 / I 2.16 Melt index (I) 2.16 Melt flow index (I2) can be measured according to ASTM D-1238-13, condition E (190℃, 2.16kg), and is also referred to as "I2 (190℃ / 2.16kg)". 21.6 It can be measured according to ASTM D-1238-13, condition F (190℃, 21.6kg), and is also known as "I". 21.6 (190℃ / 21.6kg)

[0121] In some embodiments, the polymer product may have a concentration of 0.89 g / cm³. 3 0.90g / cm 3 or 0.91g / cm 3 Up to 0.95 g / cm 3 0.96g / cm 3 or 0.97g / cm 3 The density. The density can be determined according to ASTM D-792-20. In some embodiments, the polymer product may have a density of 0.25 g / cm³. 3 up to 0.5 g / cm 3 The bulk density. For example, the bulk density of a polymer can be 0.30 g / cm³. 3 0.32g / cm 3 , or 0.33g / cm 3 Up to 0.40 g / cm 3 0.44 g / cm 3 or 0.48 g / cm 3 Bulk density can be measured according to ASTM D-1895-17 Method B.

[0122] In some embodiments, the polymerization process may include contacting one or more olefin monomers with a modified catalyst slurry, which may comprise mineral oil and a supported catalyst. The one or more olefin monomers may be ethylene and / or propylene, and the polymerization process may include heating the one or more olefin monomers and the catalyst system to 70°C or higher to form an ethylene polymer, a propylene polymer, or an ethylene-propylene copolymer.

[0123] In at least one embodiment, the catalyst and method disclosed herein are capable of producing ethylene polymers having a weight-average molecular weight (Mw) of 40,000 g / mol, 70,000 g / mol, 90,000 g / mol, or 100,000 g / mol to 200,000 g / mol, 300,000 g / mol, 600,000 g / mol, 1,000,000 g / mol, or 1,500,000 g / mol. Mw can be determined using gel permeation chromatography (GPC). For GPC data, differential refractive index (DRI) method is preferred for Mn, while light scattering (LS) is preferred for Mw and Mz. GPC can be performed on a Waters 150C GPC instrument equipped with a DRI detector. The GPC column can be calibrated by running a series of narrow polystyrene standards. The molecular weight of polymers other than polystyrene is routinely calculated using the Mark Houwink coefficient of the polymer to be tested.

[0124] The ethylene polymer may have a melt index (MI) of 0.2 g / 10 min or higher, such as 0.4 g / 10 min or higher, 0.6 g / 10 min or higher, 0.7 g / 10 min or higher, 0.8 g / 10 min or higher, 0.9 g / 10 min or higher, 1.0 g / 10 min or higher, 1.1 g / 10 min or higher, or 1.2 g / 10 min or higher. In some embodiments, the upper limit of the MI of the ethylene polymer may be any one of 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, or 5.5 g / 10 min. In some or other embodiments, the ethylene polymer may have a melt index of up to about 25 g / 10 min, or up to about 50 g / 10 min, or up to about 100 g / 10 min.

[0125] "Catalyst productivity" is a measure of how many grams of polymer (P) are produced in a time period T hours using a polymerization catalyst containing W grams of catalyst (cat); and can be expressed as: P / (T×W), with gPgcat. -1 hr -1 The units are expressed as [units]. In at least one embodiment, the catalyst disclosed herein can have a yield of at least 50 g Pgcat. -1 hr -1 Or larger, such as 500g Pgcat -1 hr -1 Or larger, such as 800gPgcat -1 hr -1 Or larger, such as 5,000g Pgcat -1 hr -1 Or larger, such as 6,000g Pgcat -1 hr -1 Or larger.

[0126] While a gas-phase polymerization process has been described above, it should be understood that other polymerization processes known in the art can also be used to produce polymer products. In some embodiments, any suspension polymerization, homogeneous polymerization, bulk polymerization, solution polymerization, slurry polymerization, and / or other gas-phase polymerization processes known in the art can be used. Such methods can be carried out in batch, semi-batch, or continuous modes. A homogeneous polymerization process is defined as a process in which at least about 90% by weight of the product is soluble in the reaction medium. A bulk process is defined as a process in which the monomer concentration in all feeds leading to the reactor is 70% by volume or greater. Alternatively, the reaction medium may be free of or contain no solvents or diluents (except for small amounts, or amounts, typically present with the monomer as a support for a catalyst or other additive; e.g., propane in propylene).

[0127] In some embodiments, the polymerization process can be a slurry polymerization process, preferably a continuous slurry loop polymerization process. A single slurry loop reactor, or multiple reactors in parallel or series, can be used (although, to achieve a unimodal molecular weight distribution, it is preferable to use either a single reactor or multiple reactors (e.g., in parallel) with the same catalyst, feed, and reaction conditions, such that the polymer product is considered to be produced in a single reaction step). As used herein, the term "slurry polymerization process" means a polymerization process in which a supported catalyst is used and monomers are polymerized on supported catalyst particles in a liquid medium (containing, for example, an inert diluent and unreacted polymerizable monomers), such that a two-phase composition comprising a polymer solid and a liquid is circulated within the polymerization reactor. Typically, a slurry tank or a slurry loop reactor can be used; in certain embodiments herein, a slurry loop reactor is preferred. In such a process, the reaction diluent, dissolved monomers (one or more), and catalyst can be circulated in a loop reactor at a relatively high pressure during the polymerization reaction. The resulting solid polymer is also circulated within the reactor. A slurry of polymer and liquid media can be collected in one or more settling legs of a slurry loop reactor, from which the slurry is periodically discharged into a flash chamber, where the mixture can be flashed to a relatively low pressure; alternatively, in other instances, a single-point discharge process can be used to move the slurry to the flash chamber. Flashing results in the substantially complete removal of the liquid media from the polymer, and the vaporized polymeric diluent (e.g., isobutane) can then be recompressed to condense the recovered diluent into a liquid form suitable for recovery back to the reactor as a liquid diluent.

[0128] Slurry polymerization processes can include those described in U.S. Patent No. 6,204,344. Other non-limiting examples of slurry processes include continuous loop processes or stirred tank processes. Additionally, other examples of slurry processes include those described in U.S. Patent No. 4,613,484. In yet another embodiment, the polymerization process can be a multi-stage polymerization process, in which one reactor operates in a slurry phase, fed into a reactor operating in a gas phase, as described in U.S. Patent No. 5,684,097.

[0129] Unless otherwise stated, all figures used in this specification and related claims to indicate quantities of components, properties such as molecular weight, reaction conditions, etc., should be understood to be modified by the term "about" in all cases. Therefore, unless indicated to the contrary, the numerical parameters listed in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained through embodiments of the invention. At least, and without attempting to limit the application of the doctrine of equivalence to the scope of the claims, each numerical parameter should be interpreted based on the number of significant figures reported and by applying common rounding techniques.

[0130] This document presents one or more illustrative embodiments comprising one or more inventive elements. For clarity, not all features of the physical embodiments are described or shown in this application. It should be understood that in developing a physical embodiment comprising one or more elements of the invention, numerous embodiment-specific decisions must be made to achieve the developer's objectives, such as compliance with system-related, business-related, governmental-related, and other constraints that change with the embodiment and vary over time. While the developer's efforts may be time-consuming, such efforts are a routine task for those skilled in the art who benefit from this disclosure.

[0131] Although compositions and methods are described herein with the term “comprising” various components or steps, compositions and methods may also be “substantially composed of various components and steps” or “consisting of various components and steps”.

[0132] Additional implementation plan

[0133] This disclosure also relates to the following non-restrictive implementations.

[0134] Implementation Plan 1. A method comprising:

[0135] A catalyst slurry comprising a supported catalyst is provided, wherein the supported catalyst comprises a support material, at least one catalyst compound, and at least one activator;

[0136] The catalyst slurry is led to a pipeline in fluid communication with the mixing unit;

[0137] A catalyst solution is provided, which contains a first catalyst compound already contained on a supported catalyst or a second catalyst compound different from the first catalyst compound;

[0138] The catalyst solution is directed to a pressurized fluid distribution system in fluid communication with the mixing unit, the pressurized fluid distribution system comprising at least one first pressure vessel and at least one second pressure vessel connected in parallel with each other;

[0139] Wherein, when at least one second pressure vessel is in offline mode, at least one first pressure vessel operates in online mode, and at least one first pressure vessel and at least one second pressure vessel can switch between online mode and offline mode;

[0140] At least one first pressure vessel is filled at least partially with a first portion of the catalyst solution;

[0141] At least one first pressure vessel is pressurized such that a pressurized fluid distribution system supplies a first portion of the catalyst solution from the at least one first pressure vessel to the mixing unit;

[0142] The catalyst solution is contacted with a catalyst slurry in a pipeline, in an online pipeline mixer, in a mixing unit, or any combination thereof to obtain a modified catalyst slurry, the modified catalyst slurry incorporating at least a portion of a first catalyst compound or a second catalyst compound from the catalyst solution onto a supported catalyst.

[0143] The modified catalyst slurry is fed into the polymerization reactor; and

[0144] α-olefins are polymerized in a polymerization reactor under polymerization reaction conditions to obtain polyolefins.

[0145] Implementation Scheme 2. The method according to Implementation Scheme 1, wherein the polymerization reactor is a fluidized bed gas-phase polymerization reactor.

[0146] Implementation Scheme 3. The method according to Implementation Scheme 1 or Implementation Scheme 2, wherein the catalyst solution comprises at least a second catalyst compound.

[0147] Implementation Scheme 4. The method according to any one of Implementation Schemes 1-3, wherein the second catalyst compound is also present on the supported catalyst.

[0148] Implementation Scheme 5. The method according to any one of Implementation Schemes 1-3, wherein the second catalyst compound is not present on the supported catalyst.

[0149] Implementation Scheme 6. The method according to any one of Implementation Schemes 1-5, wherein the first catalyst compound comprises a first metallocene and the second catalyst compound comprises a second metallocene different from the first metallocene.

[0150] Implementation Scheme 7. The method according to any one of Implementation Schemes 1-6, wherein the pressurized fluid distribution system supplies a first portion of the catalyst solution to the pipeline at a location upstream of the mixing unit or the online pipeline mixer, directly to the mixing unit, or any combination thereof.

[0151] Implementation Scheme 8. The method according to any one of Implementation Schemes 1-7 further includes:

[0152] While at least one first pressure vessel in online mode is supplying a first portion of the catalyst solution to a pipeline, mixing unit, or any combination thereof, at least one second pressure vessel in offline mode is at least partially filled with a second portion of the catalyst solution.

[0153] Implementation Scheme 9. The method according to any one of Implementation Schemes 1-7, wherein, before initially supplying a first portion of the catalyst solution to the mixing unit by at least one first pressure vessel, at least one second pressure vessel is at least partially filled with a second portion of the catalyst solution.

[0154] Implementation Scheme 10. The method according to Implementation Scheme 8 or Implementation Scheme 9 further includes:

[0155] While maintaining at least one second pressure vessel in offline mode, pressurize at least one second pressure vessel containing a second portion of the catalyst solution;

[0156] By switching at least one first pressure vessel to offline mode while simultaneously switching at least one second pressure vessel to online mode, a second portion of the catalyst solution is supplied to a pipeline, mixing unit, or any combination thereof; and

[0157] Depressurize at least one primary pressure vessel.

[0158] Implementation Scheme 11. The method according to Implementation Scheme 10 further includes:

[0159] While at least one second pressure vessel in online mode supplies a second portion of the catalyst solution to a pipeline, mixing unit, or any combination thereof, at least one first pressure vessel in offline mode is at least partially refilled with a third portion of the catalyst solution.

[0160] Implementation Scheme 12. The method according to any one of Implementation Schemes 1-11 further includes:

[0161] The flow rate of the catalyst solution from the pressurized fluid distribution system to the pipeline, mixing unit, or any combination thereof is controlled via a control valve located downstream of at least one first pressure vessel and at least one second pressure vessel.

[0162] Implementation Scheme 13. The method according to any one of Implementation Schemes 1-12, wherein pressurization is performed using gas.

[0163] Implementation Scheme 14. The method according to Implementation Scheme 13, wherein the gas comprises an inert gas.

[0164] Implementation Scheme 15. The method according to Implementation Scheme 13 or Implementation Scheme 14, wherein the gas has a pressure of at least about 300 psi.

[0165] Implementation Scheme 16. The method according to any one of Implementation Schemes 1-15, wherein the mixing unit comprises a mechanically stirred mixing tank, a static mixer, a mixing block, or any combination thereof.

[0166] Implementation Scheme 17. The method according to any one of Implementation Schemes 1-16, wherein the α-olefin comprises ethylene and optionally one or more α-olefin comonomers.

[0167] Implementation Scheme 18. The method according to any one of Implementation Schemes 1-17, wherein the catalyst slurry further comprises mineral oil, wax, induced condenser, or any combination thereof.

[0168] Implementation Scheme 19. The method according to Implementation Scheme 18, wherein the induced condenser is present and comprises propane, isobutane, isopentane, isohexane, or any combination thereof.

[0169] Implementation Scheme 20. The method according to any one of Implementation Schemes 1-19, wherein the at least one activator comprises aluminum oxane.

[0170] Implementation Scheme 21. A method comprising:

[0171] A catalyst slurry comprising a supported catalyst is provided, wherein the supported catalyst comprises a support material, at least one catalyst compound, and at least one activator;

[0172] A catalyst solution is provided, which contains a first catalyst compound already contained on a supported catalyst or a second catalyst compound different from the first catalyst compound;

[0173] The catalyst solution is directed to a pressurized fluid distribution system, which includes at least one first pressure vessel and at least one second pressure vessel connected in parallel with each other.

[0174] Wherein, when at least one second pressure vessel is in offline mode, at least one first pressure vessel operates in online mode, and at least one first pressure vessel and at least one second pressure vessel can switch between online mode and offline mode;

[0175] At least one first pressure vessel is filled at least partially with a first portion of the catalyst solution;

[0176] At least one first pressure vessel is pressurized such that a pressurizable fluid distribution system supplies a first portion of the catalyst solution to a pipeline located downstream of at least one first pressure vessel.

[0177] The catalyst slurry is led to the pipeline;

[0178] The catalyst solution is brought into contact with the catalyst slurry in a pipeline to obtain a modified catalyst slurry, wherein at least a portion of a first catalyst compound or a second catalyst compound from the catalyst solution is incorporated onto a supported catalyst.

[0179] The modified catalyst slurry is fed into the polymerization reactor; and

[0180] α-olefins are polymerized in a polymerization reactor under polymerization reaction conditions to obtain polyolefins.

[0181] Therefore, the present invention is well suited to achieving the aforementioned objects and advantages, as well as those inherent therein. The specific examples and constructions disclosed above are merely illustrative, as modifications and equivalents can be made to the invention in ways that will be readily apparent to those skilled in the art who have benefited from its teachings. Furthermore, no limitation is intended to be imposed on the details of the constructions or designs shown herein, except as set forth in the claims below. Therefore, it is apparent that the specific illustrative examples disclosed above can be altered, combined, or modified, and all such variations are considered to be within the scope and spirit of the invention. The inventions illustratively disclosed herein can be suitably practiced in the absence of any elements not specifically disclosed herein and / or any optional elements disclosed herein. While compositions and methods are described using the terms “comprising,” “containing,” or “including” various components or steps, compositions and methods may also be described as “consistently of various components and steps” or “consisting of various components and steps.” All numerical values ​​and ranges disclosed above can vary by a certain amount. Whenever a numerical range with a lower and upper limit is disclosed, any numerical value falling within the range and any included range are specifically disclosed. In particular, the range of each value disclosed herein (in the form of "about a to about b", or equivalently "about a to b" or equivalently "about ab") should be understood as listing each numerical value and range included within a wider range of values. Furthermore, the terms in the claims have their ordinary, naive meanings unless otherwise explicitly and clearly defined by the patentee. Additionally, the indefinite articles "a" or "an" used in the claims are defined herein as meaning one or more of the elements they introduce.

Claims

1. A method comprising: A catalyst solution is provided, which contains a first catalyst compound already contained on a supported catalyst or a second catalyst compound different from the first catalyst compound; The catalyst solution is directed to a pressurized fluid distribution system in fluid communication with the mixing unit, the pressurized fluid distribution system comprising at least one first pressure vessel and at least one second pressure vessel connected in parallel with each other; Wherein, when at least one second pressure vessel is in offline mode, at least one first pressure vessel operates in online mode, and at least one first pressure vessel and at least one second pressure vessel can switch between online mode and offline mode; At least one first pressure vessel is filled at least partially with a first portion of the catalyst solution; At least one first pressure vessel is pressurized such that a pressurized fluid distribution system supplies a first portion of the catalyst solution from the at least one first pressure vessel to the mixing unit; A catalyst slurry comprising a supported catalyst is provided, wherein the supported catalyst comprises a support material, at least one catalyst compound, and at least one activator; The catalyst slurry is led to a pipeline in fluid communication with the mixing unit; The catalyst solution is contacted with a catalyst slurry in a pipeline, in an online pipeline mixer, in a mixing unit, or any combination thereof to obtain a modified catalyst slurry, the modified catalyst slurry incorporating at least a portion of a first catalyst compound or a second catalyst compound from the catalyst solution onto a supported catalyst. The modified catalyst slurry is fed into the polymerization reactor; and Polymerization of one or more α-olefin monomers in a polymerization reactor under polymerization reaction conditions to obtain polyolefins.

2. The method according to claim 1, wherein the polymerization reactor is a fluidized bed gas-phase polymerization reactor.

3. The method according to claim 1 or claim 2, wherein the catalyst solution comprises at least a second catalyst compound.

4. The method according to claim 3, wherein the second catalyst compound is also present on the supported catalyst.

5. The method according to claim 3, wherein the second catalyst compound is not present on the supported catalyst.

6. The method according to claim 1 or any one of claims 2-5, wherein the first catalyst compound comprises a first metallocene and the second catalyst compound comprises a second metallocene different from the first metallocene.

7. The method according to claim 1 or any one of claims 2-6, wherein the pressurized fluid distribution system supplies a first portion of the catalyst solution to the pipeline at a location upstream of the mixing unit or the online pipeline mixer, directly to the mixing unit, or any combination thereof.

8. The method according to claim 1 or any one of claims 2-7, further comprising: While at least one first pressure vessel in online mode is supplying a first portion of the catalyst solution to a pipeline, mixing unit, or any combination thereof, at least one second pressure vessel in offline mode is at least partially filled with a second portion of the catalyst solution.

9. The method according to claim 1 or any one of claims 2-8, wherein, Before the first portion of the catalyst solution is initially supplied to the pipeline, mixing unit, or combination thereof by at least one first pressure vessel, at least one second pressure vessel is at least partially filled with the second portion of the catalyst solution.

10. The method of claim 8, further comprising: While maintaining at least one second pressure vessel in offline mode, pressurize at least one second pressure vessel containing a second portion of the catalyst solution; By switching at least one first pressure vessel to offline mode while simultaneously switching at least one second pressure vessel to online mode, a second portion of the catalyst solution is supplied to a pipeline, mixing unit, or any combination thereof; and Depressurize at least one primary pressure vessel.

11. The method of claim 10, further comprising: While at least one second pressure vessel in online mode supplies a second portion of the catalyst solution to a pipeline, mixing unit, or any combination thereof, at least one first pressure vessel in offline mode is at least partially refilled with a third portion of the catalyst solution.

12. The method according to claim 1, further comprising: The flow rate of the catalyst solution from the pressurized fluid distribution system to the pipeline, mixing unit, or any combination thereof is controlled via a control valve located downstream of at least one first pressure vessel and at least one second pressure vessel.

13. The method of claim 1, wherein pressurization is performed using a gas, optionally wherein the gas is an inert gas.

14. The method of claim 13, wherein the gas has a pressure of at least about 300 psi.

15. The method according to claim 1 or any one of claims 2-14, wherein the mixing unit comprises a mechanically stirred mixing tank, a static mixer, a mixing block, or any combination thereof.

16. The method according to claim 1 or any one of claims 2-15, wherein the one or more α-olefin monomers comprise ethylene and optionally one or more α-olefin comonomers.

17. The method according to claim 1 or any one of claims 2-16, wherein the catalyst slurry further comprises mineral oil, wax, induced condenser, or any combination thereof.

18. The method of claim 17, wherein the induced condenser is present and comprises propane, isobutane, n-butane, isopentane, n-pentane, isohexane, n-hexane, or any combination thereof.

19. The method according to claim 1 or any one of claims 2-18, wherein the at least one activator comprises aluminoxane.

20. A method comprising: A catalyst solution is provided, which contains a first catalyst compound already contained on a supported catalyst or a second catalyst compound different from the first catalyst compound; The catalyst solution is directed to a pressurized fluid distribution system, which includes at least one first pressure vessel and at least one second pressure vessel connected in parallel with each other. Wherein, when at least one second pressure vessel is in offline mode, at least one first pressure vessel operates in online mode, and at least one first pressure vessel and at least one second pressure vessel can switch between online mode and offline mode; At least one first pressure vessel is filled at least partially with a first portion of the catalyst solution; At least one first pressure vessel is pressurized such that a pressurizable fluid distribution system supplies a first portion of the catalyst solution to a pipeline located downstream of at least one first pressure vessel. A catalyst slurry comprising a supported catalyst is provided, wherein the supported catalyst comprises a support material, at least one catalyst compound, and at least one activator; The catalyst slurry is led to the pipeline; The catalyst solution is brought into contact with the catalyst slurry in a pipeline to obtain a modified catalyst slurry, wherein at least a portion of a first catalyst compound or a second catalyst compound from the catalyst solution is incorporated onto a supported catalyst. The modified catalyst slurry is fed into the polymerization reactor; and α-olefins are polymerized in a polymerization reactor under polymerization reaction conditions to obtain polyolefins.

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