WO2025174427A1

WO2025174427A1 - Eliminating spectral distortion in fluorescence measurements of high optical density samples

Info

Publication number: WO2025174427A1
Application number: PCT/US2024/054550
Authority: WO
Inventors: Xuan YE; Zygmunt Gryczynski; Luca CERESA; Bong Lee
Original assignee: Texas Christian University; ExxonMobil Technology and Engineering Co
Current assignee: Texas Christian University; ExxonMobil Technology and Engineering Co
Priority date: 2024-02-12
Filing date: 2024-11-05
Publication date: 2025-08-21
Anticipated expiration: 2026-08-12

Abstract

A method may include: introducing a slurry catalyst mixture into a sample chamber, where the slurry catalyst mixture comprises a multi-component catalyst and a carrier fluid, wherein the multi-component catalyst comprises a first activated catalyst and a second activated catalyst; illuminating the slurry catalyst mixture in the sample chamber; capturing a spectrum of the slurry catalyst mixture, wherein the spectrum comprises at least one spectrum selected from the group consisting of UV-Vis spectrum, emission spectrum, and combinations thereof; correcting the spectrum using an inner filter effects model to form a corrected spectrum of the slurry catalyst mixture; and determining a calculated ratio of an amount of the first activated catalyst and an amount of the second activated catalyst in the multi-component catalyst from the corrected spectrum of the slurry catalyst mixture by fitting the spectrum of the slurry catalyst mixture to a single component spectrum of the first activated catalyst and a single component spectrum of the second activated catalyst, using spectral deconvolution.

Description

ELIMINATING SPECTRAL DISTORTION IN FLUORESCENCE MEASUREMENTS OF HIGH OPTICAL DENSITY SAMPLES

FIELD

[0001] This disclosure relates to methods to correct for inner filter effects in spectroscopic characterization of supported multi-component catalyst slurry mixtures.

BACKGROUND

[0002] Supported multi-component catalysts are widely used in commercial scale polymer production as multi-component catalysts enable the production of multi-modal polymer resins. Supported dual-component catalysts include a support with two types of active sites disposed thereon. The relative contribution to polymerization between the first and second active sites determines the composition of the resulting multi-modal polymer resin, where the relative contribution of each active site is dependent upon the ratio of the active sites on the supported dual-component catalyst.

[0003] A method of producing a supported dual-component catalyst may include reacting a first catalyst component containing a precursor for the first type of active site and a second catalyst component containing a precursor for the second type of active site at conditions suitable to transform at least a portion of the precursor of the first and second ty pe of active site to the activated form (activated catalyst) to form the supported dual-component catalyst. The mole ratio of the two types of active sites on the supported catalyst does not necessarily equal the mole ratio of the two precursors used in the preparation of the supported catalyst. There are likely several reasons for the disparity⁷, including that the two precursors may have different activation energies, sometimes referred to as activation efficiency, thereby leading to a disparate activation for the two catalyst precursors used during the catalyst preparation. Even if the mole ratio of the two catalyst precursors is kept constant during catalyst production, the mole ratio of the resulting two types of active sites on the supported catalyst may⁷ vary due to variability⁷ in relative activation energy⁷ in catalyst preparation.

[0004] The ratio of the active sites on a supported catalyst can be indirectly evaluated by a polymerization test such as in a pilot plant or lab-scale reactor followed by analysis of the resultant polymer. However, this technique is time consuming and does not allow for feedback to a catalyst production process or a commercial polymer production process. Without knowledge of the ratio of the active sites in the dual-component catalyst, it is generally not possible to determine the composition of the polymer resin product in advance of using the dual-component catalyst in a polymerization run. Ideally, the dual-component catalyst would be characterized to determine the ratio of active sites in advance of using the dual-component catalyst in a polymerization application such that the catalyst response in the reactor as well as the composition of the resin product can be more readily controlled.

[0005] One method to evaluate active sites in the supported multi-component catalyst is to capture a UV-Vis spectrum and/or emission spectrum from a supported catalyst and performing spectral deconvolution on the captured spectrum to determine the contribution of each active sites to the captured spectrum which correlates to the molar ratio of each of the active sites in the supported catalyst. Spectrophotometric methods of evaluating supported multi-component catalysts have certain drawbacks including weak signal from the sample which complicates implementing the method in a production reactor.

[0006] Supported multi-component catalysts tend to have high optical densities and are highly scattering. Therefore, the excitation light is highly attenuated as the excitation light passes through the sample chamber containing the catalysts. This effect is known as the primary inner filter effect. The spectrophotometric detection channel is focused on the center of the sample chamber and effectively the majority of emission signal is detected from the center of the sample chamber. The attenuation of excitation light effectively reduces the number of excited fluorophores in the center of the sample chamber thereby affecting the overall intensity of recovered spectrum. The primary inner filter effect tends to exacerbate in more concentrated solutions. Spectrographic characterization of supported multi-component catalysts is also affected by secondary inner filter effects where the absorption/excitation spectra and the emission spectra of supported multicomponent catalysts have significant overlap. This overlap in absorption/excitation/emission spectra results in the emission of light emerging from the center of the sample chamber being reabsorbed by the catalyst slurry which affects the recovered spectrum not only in the overall intensity but also in the profile of the measured emission spectrum. Molar ratio measurement of active sites obtained from spectral deconvolution of a captured spectrum which have been modified by primary and/or secondary inner filter effects can vary from the actual molar ratio of active sites on the supported catalyst, especially when the optical density and scattering of the sampled material is high and additionally so when the concentration of the optically dense material is high.

[0007] References of potential interest in this regard include: US Patent Nos. 6,194,223; 6,723,804; 7,456,021; 7,904,271; 8,843,324; 10,679,734; and 11,170,874; as well as EP1713840, EP3071950, EP3655756, WO2014/062643; Babushkin, Dmitrii et al., “Novel Zirconocene Hydride Complexes in Homogeneous and in SiO2-Supported Olefin-Polymerization Catalysts Modified with Diisobutylaluminum Hydride or Triisobutylaluminum,” Macromolecular Chemistry and Physics 209 (12), 1210-1219 (2008); and Velthoen, Marjolein et al., “Insights into the activation of silica-supported metallocene olefin polymerization catalysts by methylaluminoxane”. Catalysis Today 334, 223-230 (2019), Gryczynski et. al., “Practical Fluorescence Spectroscopy”, CRS Press, Taylor and Francis Group, Boca Raton, London, New York, 2020, Kimball et. al. “On the origin and correction for inner filter effects in fluorescence Part I: primary inner filter effect-the proper approach for sample absorbance correction.” Methods Appl. Fluoresc. 2020, 8, 033002. Ceresa et. al.. “On the origin and correction for inner filter effects in fluorescence. Part II: secondary inner filter effect -the proper use of front-face configuration for highly absorbing and scattering samples.” Methods Appl. Fluoresc. 2021, 9, 035005, and Ye et. al. “Structural Characterization and Spatial Mapping of Active Site on Supported Metallocene Catalysts for Olefin Polymerization: A Luminescence-based Approach”, ACS Catalysis. 2023, 13, 12197-12212.

SUMMARY

[0008] Disclosed herein is an example method comprising: introducing a slurry catalyst mixture into a sample chamber, where the slurry’ catalyst mixture comprises a multi-component catalyst and a carrier fluid, wherein the multi-component catalyst comprises a first activated catalyst and a second activated catalyst; illuminating the slurry catalyst mixture in the sample chamber; capturing a spectrum of the slurry' catalyst mixture, wherein the spectrum comprises at least one spectrum selected from the group consisting of UV-Vis spectrum, emission spectrum, and combinations thereof; correcting the spectrum using an inner filter effects model to form a corrected spectrum of the slurry catalyst mixture; and determining a calculated ratio of an amount of the first activated catalyst and an amount of the second activated catalyst in the multicomponent catalyst from the corrected spectrum of the slurry catalyst mixture by fitting the spectrum of the slurry catalyst mixture to a single component spectrum of the first activated catalyst and a single component spectrum of the second activated catalyst, using spectral deconvolution.

[0009] Further disclosed herein is an example method comprising: contacting a base catalyst mixture and a trim catalyst solution to form a contact product comprising a post-trim multicomponent catalyst, wherein the base catalyst mixture comprises a first catalyst, a second catalyst, a support, an activator, and a carrier, wherein the trim catalyst solution comprises additional second catalyst, and a solvent, and wherein the post-trim multi-component catalyst comprises a first active catalyst corresponding to the first catalyst and a second active catalyst corresponding to the second catalyst; generating a spectrum of the post-trim multi-component catalyst; correcting the spectrum of the post-trim multi-component catalyst using an inner filter effects model to form a corrected spectrum the post-trim multi-component catalyst; determining a calculated ratio of an amount of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst from the corrected spectrum the post-trim multi-component catalyst by fitting the spectrum of the post-trim multi-component catalyst to a single component spectrum of the first active catalyst and a single component spectrum of the second active catalyst using spectral deconvolution; comparing the calculated ratio to a target ratio of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst and adjusting a flow rate of the trim catalyst solution such that the calculated ratio of amount of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst is closer to the target ratio; introducing the post-trim multi-component catalyst and one or more olefins into a polymerization reactor; and polymerizing the one or more olefins in the presence of the post-trim multicomponent catalyst to produce a polymer product.

[0010] Further disclosed herein is an example system comprising: an optical probe comprising: alight source; a UV-vis detector; a fluorescence detector; a sample chamber comprising an optical path, a first collimating lens positioned at a first end of the sample chamber and a second collimating lens positioned at a second end of the sample chamber such that the first collimating lens and the second collimating lens are in the optical path; an excitation arm configured to transport light from the light source through the first collimating lens to the optical path; an emission arm configured to transport emission light from the optical path through the first collimating lens to the fluorescence detector; and an optical cable configured to transport light from the optical path though the second collimating lens to the UV-vis detector; wherein the sample chamber is configured to hold a post-trim multi-component catalyst mixture, and wherein the optical probe is configured to illuminate the post-trim multi-component catalyst mixture in the sample chamber and generate a spectrum of the post-trim multi-component catalyst mixture; and a control system configured to: receive the spectrum of the post-trim multi-component catalyst mixture; correct the spectrum of the post-trim multi-component catalyst mixture using an inner filter effects model to form a corrected spectrum of the post-trim multi-component catalyst mixture determine a calculated ratio of an amount of the first activated catalyst and the second activated catalyst in the post-trim multi-component catalyst mixture from the corrected spectrum of the post-trim multi-component catalyst mixture by fitting the spectrum of the post-trim multicomponent catalyst mixture to a single component spectrum of the first activated catalyst and a single component spectrum of the second activated catalyst using spectral deconvolution; compare the calculated ratio of the amount of the first activated catalyst and the second activated catalyst in the multimodal catalyst to a set point ratio of the amount of the first activated catalyst and the second activated catalyst in the multimodal catalyst; and adjust a flow rate of a trim catalyst solution such that the calculated ratio of amount of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst is closer to the set point ratio.

[0011] These and other features and attributes of the disclosed methods and systems of the present disclosure and their advantageous applications and/or uses will be apparent from the detailed description which follows.

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] To assist those of ordinary skill in the relevant art in making and using the subject matter hereof, reference is made to the appended drawings, wherein:

[0013] FIG. 1 is a schematic of a gas-phase reactor system in accordance with certain embodiments of the present disclosure.

[0014] FIG. 2A is a schematic illustration of primary inner filter effects on fluorescence measurements in square geometry.

[0015] FIG. 2 B is. a schematic illustration of secondary inner filter effects on fluorescence measurements in square geometry.

[0016] FIG. 3 A is a schematic illustration of an optical probe in accordance with certain embodiments of the present disclosure.

[0017] FIG. 3B is a cross section of bifurcated optical fiber in accordance with certain embodiments of the present disclosure.

[0018] FIG. 3C is a cross section of a sample chamber including two collimating lenses in accordance with certain embodiments of the present disclosure.

[0019] FIG. 4A is an illustration of a front-facing emission measurement without a collimating lens in accordance with certain embodiments of the present disclosure.

[0020] FIG. 4B is an illustration of a UV-vis spectrographic measurement without a collimating lens in accordance with certain embodiments of the present disclosure.

[0021] FIG. 4C is an illustration of a front-facing emission measurement with a collimating lens in accordance with certain embodiments of the present disclosure.

[0022] FIG. 4D is an illustration of a UV-vis spectrographic measurement with two collimating lenses in accordance with certain embodiments of the present disclosure.

[0023] FIG. 5 is a cross section schematic illustrating the interior of the sample chamber including collimating lenses in accordance with certain embodiments of the present disclosure.

[0024] FIG. 6 is a schematic illustration of an optical probe in accordance with certain embodiments of the present disclosure. [0025] FIG. 7 is a graph of experimentally detected emission intensity as a function of the distance in accordance with certain embodiments of the present disclosure.

[0026] FIG. 8 A is a normalized absorption and emission spectra of Rhodamine B in ethanol in accordance with certain embodiments of the present disclosure.

[0027] FIG. 8B is a graph of absorption spectra of Rhodamine B in ethanol in accordance with certain embodiments of the present disclosure.

[0028] FIG. 8C is a spectrogram showing normalized emission spectra of Rhodamine B in ethanol predicted by an inner filter effect model in accordance with certain embodiments of the present disclosure.

[0029] FIG. 8D is a spectrogram showing normalized emission spectra of Rhodamine B in ethanol predicted by an inner filter effect model in accordance with certain embodiments of the present disclosure.

[0030] FIG. 9A is spectrogram of the results of a UV-vis absorption test in accordance with certain embodiments of the present disclosure.

[0031] FIG. 9B is spectrogram of the results of a spectral emission test in accordance with certain embodiments of the present disclosure.

[0032] FIG. 9C is a normalized spectrogram of the results of a spectral emission test in accordance with certain embodiments of the present disclosure.

[0033] FIG. 9D is a normalized spectrogram with correction for inner filter effects in accordance with certain embodiments of the present disclosure.

DETAILED DESCRIPTION

[0034] Disclosed herein are methods to correct for inner filter effects in spectroscopic characterization in front-face configuration of supported multi-component catalyst slurry mixtures. Spectroscopic characterization of supported multi-component catalyst slurry mixtures is disclosed in International Patent Application No. PCT/US2023/027544 filed July 12, 2023, the disclosure of which is incorporated herein in its entirety by reference.

[0035] Gas-phase polymerization in a fluidized bed is an industrial process used in polymerizing ethylene and ethylene comonomers to produce polyethylene polymer and copolymer compositions. It is generally known in the art that a polyolefin's composition distribution (CD) and molecular weight distribution (MWD) affect attributes of the polyolefin. To reduce or to avoid certain trade-offs among desirable attributes, bimodal polymers have become increasingly important in the polyolefins industry. Catalyst design and support technology have allowed for the development of single-reactor bimetallic (dual component) catalyst systems capable of producing bimodal polyethylene. The active sites’ composition (i.e., the mole ratio of the two types of active sites) in dual-component catalyst system, often differs from the mole ratio of the two catalyst precursor used in making the dual-component catalyst. A supported catalyst is added to a diluent to form a catalyst slurry and pumped to a polymerization reactor. A catalyst solution can be added (i.e., “trimmed”) to the catalyst slurry to adjust one or more properties “in-situ” of polymer being formed in a reactor.

[0036] However, such “trim” processes are limited because the post-trim catalyst slurry is typically not able to be fully characterized before introduction into the polymerization reactor. When the optical density' of the post-trim catalyst slurry is relatively low or the concentration of supported multi-component catalyst in the post-trim catalyst slurry is relatively low, the spectral distortion from inner filter effects tends to also be low resulting in a spectrogram that can be more accurately deconvoluted to recover the molar ratios of the active sites. However, since most commercial applications utilize supported multi-component catalysts with relatively high optical densities and at relatively high concentration, the spectra obtained from spectroscopic characterization can deviate from the true steady-state fluorescence spectra and may not strongly correlate to the molar ratios of the active sites.

[0037] As will be disclosed in further detail below, the present methods utilize an in-line spectral measurement device in a front-face configuration where the device is configured to capture a UV- vis spectra and a fluorescence spectrum of a supported multi-component catalyst. The device comprises a sample chamber with two collimating lenses disposed on either side of the sample chamber in the excitation light beam path. The method further includes using the as-measured “distorted” fluorescence spectrum and the acquired UV-vis spectrum in a mathematical inner filter effect model which corrects for the inner filter effect throughout the full wavelength region and yielding the true fluorescence spectrum free of distortion. Spectral deconvolution is then performed on the true fluorescence spectrum and the ratio of active sites in the supported multicomponent catalyst is calculated. Based on the ratio of active sites, the catalyst solution can be trimmed into the catalyst slurry to achieve a desired ratio of active sites in the post-trim catalyst slurry entering the polymerization reactor.

[0038] As used herein, the indefinite article “a” or “an” shall mean “at least one” unless specified to the contrary or the context clearly indicates otherwise. Thus, embodiments using “an alphaolefin” include embodiments where one, two or more alpha-olefins are used, unless specified to the contrary' or the context clearly indicates that only one alpha-olefin is used.

[0039] As used herein, “wt.%” means percentage by weight, “vol%” means percentage by volume, “mol%” means percentage by mole, “ppm” means parts per million, and “ppm wt” and “wppm” are used interchangeably and mean parts per million on a weight basis. All concentrations herein, unless otherw ise stated, are expressed on the basis of the total amount of the composition in question.

[0040] An ‘'olefin” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as including an olefin, e.g, ethylene and at least one C3 to C20 ot-olefm, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35 wt.% to 55 wt.%. it is understood that the repeating unit/mer unit or simply unit in the copolymer is derived from ethylene in the polymerization reaction and the derived units are present at 35 wt.% to 55 wt.%, based on a weight of the copolymer. For the purposes of the present disclosure, ethylene shall be considered an a-olefin.

[0041] A '‘polymer” has two or more of the same or different repeating units/mer units or simply units. A “homopolymer” is a polymer having units that are the same. A “copolymer” is a polymer having tw o 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” as used to refer to units indicates that the units differ from each other by at least one atom or are different isomerically. The definition of copolymer, as used herein, includes terpolymers and the like. Likewise, the definition of polymer, as used herein, includes homopolymers, copolymers, and the like. Furthermore, the terms “polyethylene copolymer"’, “ethylene copolymer"’, and “ethylene-based polymer” are used interchangeably to refer to a copolymer that includes at least 50 mol% of units derived from ethylene.

[0042] Nomenclature of elements and groups thereof used herein are pursuant to the NEW NOTATION published in HAWLEYS CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition, John Wiley & Sons, Inc., (1997) (reproduced there with permission from IUPAC), unless reference is made to the Previous IUPAC form noted with Roman numerals (also appearing in the same), or unless otherwise noted.

[0043] As used herein, the term “slurry catalyst mixture” refers to a contact product that includes at least one catalyst compound and a carrier fluid (e.g.. mineral oil), and optionally one or more of an activator, a co-activator, and a support. In a preferred embodiment, the slurry catalyst mixture includes a contact product that includes at least two catalyst compounds and the carrier fluid (e.g., mineral oil), and optionally one or more of an activator, a co-activator, and a support. [0044] As used herein, the term “catalyst system” refers to a combination of at least one catalyst compound, an optional activator, an optional co-activator, and an optional support material. As such, in some embodiments the catalyst system can include only a single catalyst compound when the optional activator, the optional co-activator, and the optional support material are not present. In other embodiments, the catalyst system can include only two or more catalyst compounds when the optional activator, the optional co-activator, and the optional support material are not present. For the purposes of the present disclosure, when catalyst systems are described as including neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers. Catalyst systems, catalysts, and activators of the present disclosure are intended to embrace ionic forms in addition to the neutral forms of the compounds/components.

[0045] A metallocene catalyst is an organometallic compound with at least one 7t-bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and more frequently two rebound cyclopentadienyl moieties or substituted cyclopentadienyl moieties bonded to a transition metal. In the description herein, the metallocene catalyst may be described as a catalyst precursor, a pre-catalyst compound, metallocene catalyst compound or a transition metal compound, and these terms are used interchangeably. An “anionic ligand" is a negatively charged ligand which donates one or more pairs of electrons to a metal ion. For purposes of the present disclosure, in relation to metallocene catalyst compounds, the term “substituted” means that a hydrogen group has been replaced with ahydrocarbyl group, a heteroatom, or a heteroatom containing group. For example, methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group.

[0046] “Alkoxides” include an oxygen atom bonded to an alkyl group that is a Ci to Cio hydrocarbyl. The alkyl group may be straight chain, branched, or cyclic. The alkyl group may be saturated or unsaturated. In at least one embodiment, the alkyl group may comprise at least one aromatic group.

[0047] “Asymmetric” as used in connection with the instant indenyl compounds means that the substitutions at the 4 positions are different, or the substitutions at the 2 positions are different, or the substitutions at the 4 positions are different and the substitutions at the 2 positions are different. [0048] The properties and performance of polyethylene compositions can be advanced by the combination of (1) varying one or more reactor conditions such as reactor temperature, hydrogen concentration, comonomer concentration, and so on; and (2) selecting and feeding a dual catalyst system having a first catalyst and second catalyst; the dual catalyst system may advantageously be trimmed as needed with additional first and/or second catalyst. Such catalyst trim processes provide for ready adjustment of polyethylene properties by permitting on-the-fly adjustment of ratios of first and second catalyst in the dual catalyst system fed to the reactor.

[0049] In various embodiments in accordance with the present disclosure, the slurry catalyst mixture can include a first catalyst compound that can be a “high molecular weight component” and a second catalyst compound that can be a “low molecular weight component.'’ In other words, the first catalyst can provide primarily for a high molecular-weight portion of the polymer and the second catalyst can provide primarily for a low molecular weight portion of the polymer (e.g., the first catalyst tends to produce relatively higher-molecular-weight polymer chains; while the second catalyst tends to produce relatively lower-molecular-weight polymer chains). In at least one embodiment, a dual catalyst system can be present in a catalyst pot of a reactor system, and a molar ratio of the first catalyst compound to the second catalyst compound of the dual catalyst system can be from 99: 1 to 1 :99, such as from 90: 10 to 10:90, such as from 85: 15 to 50:50, such as from 75:25 to 50:50, such as from 60:40 to 40:60. Consistent with the above note regarding trim catalyst systems, the first catalyst compound and/or the second catalyst compound can be added to a polymerization process as a trim catalyst 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 are each a metallocene catalyst compound.

GAS PHASE REACTOR

[0050] FIG. 1 is a schematic of a gas-phase reactor system 100, showing the addition of at least two catalysts, at least one of which is added as a trim catalyst. The catalyst slurry mixture from catalyst pot 106 and solution catalyst mixture from trim pot 108 can be mixed in-line. For example, the solution catalyst mixture and catalyst slurry mixture can be mixed by utilizing a mixer such as static mixer 109 or an agitating vessel. Alternatively, any suitable mixer may be used including mixing in a conduit, mixing using a mixing apparatus, or mixing in a continuously agitated tank, for example. Any mixer capable of contacting the solution catalyst mixture and catalyst slurry mixture can be used. Gas phase reactor system 100 includes optic probe 150 to analyze the mixture of the catalyst slurry mixture from catalyst pot 106 and solution catalyst mixture from trim pot 108.

[0051] Catalyst pot 106 contains a first catalyst slurry mixture. First catalyst slurry mixture can be prepared by any suitable method including by mixing particles of the first catalyst with mineral oil, for example. The catalyst pot 106 can be an agitated holding tank configured to keep the solids concentration homogenous. In at least one embodiment, the catalyst pot 106 can be maintained at an elevated temperature, such as from 30 °C to 80 °C. Alternatively, from 30°C to 40°C. from 40 °C to 50 °C, from 50 °C to 60°C, from 60 °C to 80°C, or any ranges therebetween. Elevated temperature can be obtained by electrically heat tracing the catalyst pot 106 using, for example, a heating blanket. Maintaining the catalyst pot 106 at an elevated temperature can further reduce or eliminate solid residue formation on vessel walls which could otherwise slide off of the walls and cause plugging in downstream delivery lines. In at least one embodiment, catalyst pot 106 can have a volume from 0.5 m³ to 8.0 m³. Alternatively, from 0.5 m³ to 1.0 m³, 1.0 m³ to 2.0 m³, 2.0 m³ to 3.0 m³. 3.0 m³ to 4.0 m³, 4.0 m³ to 5.0 m³, 5.0 m³ to 6.0 m³, 6.0 m³ to 7.0 m³, 7.0 m³ to 8.0 m³, or any ranges therebetween.

[0052] In at least one embodiment, the catalyst pot 106 can be maintained at pressure of 1.0 bar to 4.0 bar. Alternatively, from 1.0 bar to 1.5 bar, 1.5 bar to 2.0 bar, 2.0 bar to 2.5 bar, 2.5 bar to 3.0 bar, 3.0 bar to 3.5 bar, 3.5 bar to 4.0 bar, or any ranges therebetween. In at least one embodiment, piping 130 and piping 140 of the gas-phase reactor system 100 can be maintained at an elevated temperature, such as from 30 °C to 80 °C. Alternatively, from 30°C to 40°C, from 40 °C to 50 °C, from 50 °C to 60°C, from 60 °C to 80°C, or any ranges therebetween. Elevated temperature can be obtained by electrically heat tracing the piping 130 and or the piping 140 using, for example, a heating blanket. Maintaining the piping 130 and/or the piping 140 at an elevated temperature can provide the same or similar benefits as described for an elevated temperature of catalyst pot 106.

[0053] A solution catalyst mixture, prepared by mixing a solvent and at least one second catalyst and/or activator, can be placed in another vessel, such as a trim pot 108. Trim pot 108 can have a volume of 0.5 m³ to 1.0 m³, 1.0 m³ to 2.0 m³, 2.0 m³ to 3.0 m³, 3.0 m³ to 4.0 m³, 4.0 m³ to 5.0 m³, 5.0 m³ to 6.0 m³, 6.0 m³ to 7.0 m³, 7.0 m³ to 8.0 nF, or any ranges therebetween. The trim pot 108 can be maintained at an elevated temperature, such as from 30 °C to 80 °C. Alternatively, from 30°C to 40°C, from 40 °C to 50 °C, from 50 °C to 60°C, from 60 °C to 80°C, or any ranges therebetween. The trim pot 108 can be heated by electrically heat tracing the trim pot 108, for example, via a heating blanket. Maintaining the trim pot 108 at an elevated temperature can provide reduced or eliminated foaming in piping 130 and or piping 140 when the catalyst slurry mixture from catalyst pot 106 is combined in-line (also referred to herein as “on-line"’) with the solution catalyst mixture from trim pot 108.

[0054] The catalyst slurry mixture can then be combined in-line with the solution catalyst mixture to form a slurry/solution catalyst mixture or final catalyst composition. A nucleating agent 107, such as silica, alumina, fumed silica or any other particulate matter can be added to the slurry and/or the solution in-line or in catalyst pot 106 or trim pot 108. Similarly, additional activators or catalyst compounds can be added in-line. For example, a second catalyst slurry mixture that includes a different catalyst can be introduced from a second cat pot (which may include wax and mineral oil). The two catalyst slurry' mixtures can be used as the catalyst system with or without the addition of a solution catalyst mixture from the trim pot 108. In embodiments, the solution catalyst mixture is analyzed by optic probe 150 as will be described in detail below. Optic probe 150 outputs a signal 154 to controller 152. Controller 152 may include a computer system. microcontrollers, programmable logic controller, or any other control system capable of monitoring and adjusting process variables within gas-phase reactor system 100. Controller 152 also may include other devices to carry out the control, including sensors, actuators, and a control algorithm.

[0055] Signal 154 can include data which represents a spectrum of the catalyst present in slurry catalyst mixture which controller 152 utilizes to determine the ratio of two active catalysts present in the catalyst. The spectral deconvolution of the spectrum of the catalyst to determine the ratio of the types of active catalyst sites will be discussed in detail below. The ratio can be compared to a target ratio or setpoint ratio to see if the slurry catalyst mixture is within specifications and if not, the controller 152 can output a signal 156 to adjust an amount of solution catalyst mixture from trim pot which is mixed in static mixer 109. The ratio of active sites in the slurry catalyst mixture can be adjusted in real time to control the polymerization process in fluidized bed reactor 122. [0056] The catalyst slurry mixture and solution catalyst mixture can be mixed in-line. For example, the solution catalyst mixture and catalyst slurry mixture can be mixed by utilizing a mixer such as static mixer 109 or an agitating vessel. The mixing of the catalyst slurry mixture and the solution catalyst mixture should be sufficient enough to allow the catalyst compound in the solution catalyst mixture to disperse in the catalyst slurry mixture such that the catalyst component, originally in the solution, migrates to the supported activator originally present in the slurry. The combination can form a uniform dispersion of catalyst compounds on the supported activator forming the catalyst composition. The length of time that the slurry and the solution can be contacted can be in a range of 1 minute to 4 hours. Alternatively, from 1 minute to 10 minutes, 10 minutes to 30 minutes, 30 minutes to 1 hour, 1 hour to 1.5 hours, 1.5 hours to 2 hours, 2 hours to 2.5 hours, 2.5 hours to 3 hours, 3 hours to 3.5 hours, 3.5 hours to 4 hours, or any ranges therebetween.

[0057] In at least one embodiment, static mixer 109 of the gas-phase reactor system 100 can be maintained at an elevated temperature, such as from 30 °C to 80 °C. Alternatively, from 30°C to 40°C, from 40 °C to 50 °C, from 50 °C to 60°C, from 60 °C to 80°C, or any ranges therebetween. The elevated temperature of the static mixer 109 can be obtained by electrically heat tracing static mixer 109 using, for example, a heating blanket. Maintaining static mixer 109 at an elevated temperature can provide reduced or eliminated foaming in static mixer 109 and can promote mixing of the catalyst slurry mixture and catalyst solution (as compared to lower temperatures) which reduces run times in the static mixer and for the overall polymerization process.

[0058] In another embodiment, an aluminum alkyl, an ethoxylated aluminum alkyl, an aluminoxane, an anti-static agent or a borate activator, such as a Ci to Cis alkyl aluminum (for example tri-isobutyl aluminum, trimethyl aluminum or the like), a Ci to C15 ethoxylated alkyl aluminum or methyl aluminoxane, ethyl aluminoxane, isobutylaluminoxane, modified aluminoxane or the like can be added to the mixture of the slurry/solution catalyst mixture in line. The alkyds, antistatic agents, borate activators and/or alumin oxanes can be added from an alkyd vessel 110 directly to the combination of the solution catalyst mixture and the catalyst slurry' mixture, or can be added via an additional alkane (such as hexane, heptane, and or octane) carrier stream, for example, from a carrier vessel 112. The additional alkyls, antistatic agents, borate activators and/or aluminoxanes may⁷ be present at up to 500 ppm, at 1 to 300 ppm, at 10 ppm to 300 ppm, or at 10 to 100 ppm. A carrier gas 114 such as nitrogen, argon, ethane, propane, and the like, can be added in-line to the mixture of the slurry and the solution. In embodiments, the carrier gas can be added at the rate of 0.5 kg/hr to 45 kg/hr. Alternatively, from 0.5 kg/hr to 1.0 kg/hr, 1.0 kg/hr to 10 kg/hr, 10 kg/hr to 20 kg/hr, 20 kg/hr to 30 kg/hr, 30 kg/hr to 45 kg/hr, or any ranges therebetween.

[0059] In at least one embodiment, a liquid carrier stream can be introduced into the combination of the solution catalyst mixture and the catalyst slurry mixture. The mixture of the solution, the slurry and the liquid carrier stream can pass through a mixer or length of tube for mixing before being contacted with a gaseous carrier stream. Similarly, a comonomer 116, such as hexene, another alpha-olefin, or diolefin, may be added in-line to the mixture of the slurry' and the solution. [0060] In one embodiment, a gas stream 126, such as cycle gas, or recycle gas 124, monomer, nitrogen, or other materials can be introduced into an injection nozzle 148 that can include a support tube 128 that can at least partially surround an injection tube 120. The slurry/solution catalyst mixture can be passed through the injection tube 120 into fluidized bed reactor 122. In at least one embodiment, the injection tube may aerosolize the slurry /solution mixture. Any number of suitable tubing sizes and configurations may be used to aerosolize and/or inject the slurry/solution mixture.

[0061] Fluidized bed reactor 122 can include a reaction zone 132 and a velocity reduction zone 134. The reaction zone 132 can include a bed 136 that can include growing polymer particles, formed polymer particles and a minor amount of catalyst particles fluidized by the continuous flow of the gaseous monomer and diluent to remove the heat of polymerization through the reaction zone. Optionally, a portion of the recycle gas 124 can be cooled and compressed to form liquids that can increase the heat removal capacity⁷ of the circulating gas stream when readmitted to the reaction zone. A suitable rate of gas flow can be readily determined by experimentation. Make-up of gaseous monomer to the circulating gas stream can be at a rate equal to the rate at which particulate polymer product and monomer associated therewith is withdrawn from the reactor and the composition of the gas passing through the reactor can be adjusted to maintain an essentially steady state gaseous composition within the reaction zone. The gas leaving the reaction zone 132 can be passed to the velocity reduction zone 134 where entrained particles can be removed, for example, by slowing and falling back to the reaction zone 132. If desired, finer entrained particles and dust can be removed in a separation sy stem 138. Such as a cyclone and/or fines filter. The recycle gas 124 can be passed through a heat exchanger 144 where at least a portion of the heat of polymerization can be removed. The gas can then be compressed in a compressor 142 and returned to the reaction zone 132. To promote formation of particles in fluidized bed reactor 122, a nucleating agent 118, such as fumed silica, can be added directly into fluidized bed reactor 122. Conventional trim polymerization processes include introducing a nucleating agent into the polymerization reactor. Furthermore, when a metallocene catalyst or other similar catalyst is used in the gas phase reactor, oxygen or fluorobenzene can be added to fluidized bed reactor 122 directly or to the gas stream 126 to control the polymerization rate.

[0062] FIG. 1 is not limiting, as additional solution catalyst mixtures and/or catalyst slurry mixtures can be used. For example, a catalyst slurry’ mixture can be combined with two or more solution catalyst mixtures having the same or different catalyst compounds and or activators. Likewise, the solution catalyst mixture can be combined with two or more catalyst slurry mixtures each having the same or different supports, and the same or different catalyst compounds and or activators. Similarly, two or more catalyst slurry mixtures can be combined with two or more solution catalyst mixtures, for example in-line, where the catalyst slurry mixtures each include the same or different supports and can include the same or different catalyst compounds and or activators and the solution catalyst mixtures can include the same or different catalyst compounds and or activators. For example, the catalyst slurry mixture can contain a supported activator and two different catalyst compounds, and two solution catalyst mixtures, each containing one of the catalysts in the slurry', and each can be independently combined, in-line, with the slurry.

[0063] The reactor temperature of the fluid bed process can be in a range of 30 °C to 200 °C. Alternatively, from 30 °C to 40 °C, 40 °C to 50 °C, 50 °C to 80 °C, 80 °C to 100 °C, 100 °C to 150 °C, 150 °C to 200 °C, or any ranges therebetween. In general, the reactor temperature can be operated at a suitable temperature taking into account the sintering temperature of the polymer product within the reactor. Thus, the upper temperature limit in various embodiments can be the melting temperature of the polyethylene copolymer produced in the reactor. However, higher temperatures can result in narrower molecular weight distributions that can be improved by the addition of a catalyst, or other co-catalysts. [0064] Hydrogen gas can be used in the polymerization process to help control or otherwise adjust the final properties of the polyolefin. Using certain catalyst systems, increasing concentrations (partial pressures) of hydrogen can increase a flow index such as the melt index of the polyethylene polymer. The melt index can thus be influenced by the hydrogen concentration. The amount of hydrogen in the polymerization can be expressed as a mole ratio relative to the total polymerizable monomer, for example, ethylene, or a blend of ethylene and hexene or propylene. The amount of hydrogen used in the polymerization process can be an amount necessary to achieve the desired melt index of the final polyolefin polymer. For example, the mole ratio of hydrogen to total monomer (H2:monomer) can be 0.0001 or greater, 0.0005 or greater, or 0.001 or greater. Further, the mole ratio of hydrogen to total monomer (H2:monomer) can be 10 or less, 5 or less, 3 or less, or 0. 10 or less. A range for the mole ratio of hydrogen to monomer can include any combination of any upper mole ratio limit with any lower mole ratio limit described herein. The amount of hydrogen in the reactor at any time can range to up to 5,000 ppm, up to 4,000 ppm in another embodiment, up to 3,000 ppm, or from 50 ppm to 5,000 ppm, or from 50 ppm to 2,000 ppm in another embodiment. 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. Further, the ratio of hydrogen to total monomer (H2:monomer) can be 0.00001 : 1 to 2: 1, 0.005: 1 to 1.5:1, or 0.0001 : 1 to 1: 1. The one or more reactor pressures in a gas phase process (either single stage or two or more stages) can vary from 690 kPa, 1.379 kPa, or 1,724 kPa to 2,414 kPa, 2.759 kPa, or 3,448 kPa.

[0065] The gas phase reactor can be capable of producing from 10 kg per hour (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 to 45,500 kg/hr of polymer.

[0066] In embodiments, the polymer product can have a melt index ratio (MIR) ranging from 10 to less than 300, or, in many embodiments, from 20 to 66, such as 25 to 55. The melt index (MI, 12) can be measured in accordance with ASTM D-1238-20.

[0067] The polymer product can have a density ranging from 0.89 g/cm³, 0.90 g/cm³, 0.91 g/cm³, or 0.92 g/cm³ to 0.93 g/cm³, 0.95 g/cm³. 0.96 g/cm³, or 0.97 g/cm³. Density can be determined in accordance with ASTM D-792-20. The polymer can have a bulk density, measured in accordance with ASTM D-1895-17 method B, of from 0.25 g/cm³ to 0.5 g/cm³. For example, the bulk density of the polymer can be from 0.30 g/cm³, 0.32 g/cm³, or 0.33 g/cm³ to 0.40 g/cm¹, 0.44 g/cm³, or 0.48 g/cm³.

[0068] Polymerization process according to various embodiments can include contacting one or more olefin monomers with a catalyst slurry mixture that can include mineral oil and catalyst particles. The one or more olefin monomers can be ethylene and/or propylene and the polymerization process can include heating the one or more olefin monomers and the catalyst system to 70°C or more to form ethylene polymers or propylene polymers.

[0069] Monomers useful herein include substituted or unsubstituted C2 to C40 alpha olefins, such as C2 to C20 alpha olefins, such as C2 to C12 alpha olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In at least one embodiment, the monomer can include ethylene and one or more optional comonomers selected from propylene or C4 to C40 olefins, such as C4 to C20 olefins, such as Ce to C12 olefins. The C4 to C40 olefin monomers may be linear, branched, or cyclic. The C4 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.

[0070] In some embodiments, the C2 to C40 alpha olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbomene, norbomadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene. nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1 -hydroxy -4-cyclooctene, 1 -acetoxy -4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbomene, norbomadiene, and their respective homologs and derivatives, such as norbomene, norbomadiene. and di cyclopentadiene. [0071] In at least one embodiment, one or more dienes can be present in the polymer product at up to 10 wt.%, such as at 0.00001 to 1.0 wt.%, such as 0.002 to 0.5 wt.%, such as 0.003 to 0.2 wt.%, based upon the total weight of the composition. In at least one embodiment 500 ppm or less of diene is added to the polymerization, such as 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.

[0072] Diene monomers include any hydrocarbon structure, such as C4 to C30, having at least two unsaturated bonds, where at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). The diene monomers can be selected from alpha, omega-diene monomers (z.e. di-vinyl monomers). The diolefin monomers are linear di-vinyl monomers, such as those containing from 4 to 30 carbon atoms. Examples of dienes can include, but are not limited to, butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene. octacosadiene, nonacosadiene, triacontadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9- decadiene, 1.10-undecadiene, 1,11 -dodecadiene, 1,12-tridecadiene. 1,13-tetradecadiene, and low molecular weight poly butadienes (Mw less than 1000 g/mol). Cyclic dienes include cyclopentadiene, vinylnorbomene, norbomadiene, ethylidene norbomene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.

[0073] In at least one embodiment, the catalyst disclosed herein can be capable of producing ethylene polymers having an Mw from 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. In at least one embodiment, the catalyst disclosed herein can be capable of producing ethylene polymers having a melt index (MI) of 0.6 or greater g/10 min, such as 0.7 or greater g/10 min, such as 0.8 or greater g/10 min, such as 0.9 or greater g/10 min, such as 1.0 or greater g/10 min, such as 1.1 or greater g/10 min, such as 1.2 or greater g/10 min.

[0074] ‘‘Catalyst productivity ’' is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and can be expressed by the following formula: P/(T x W) and expressed in units of gPgcat^hr'¹. In at least one embodiment, the productivity of the catalysts disclosed herein can be at least 50 g(polymer)/g(cat)/hour, such as 500 or more g(polymer)/g(cat)/hour, such as 800 or more g(polymer)/g(cat)/hour, such as 5,000 or more g(polymer)/g(cat)/hour, such as 6,000 or more g(polymer)/g(cat)/hour.

PROCESS FOR MAKING SLURRY CATALYST MIXTURE

[0075] A container or vessel can be used to produce or otherwise make the slurry catalyst mixture. One or more mineral oils can be introduced into the vessel. The mineral oil can be heated within the vessel to a temperature of 30 °C to 100 °C. Alternatively, from 30°C to 40°C, from 40 °C to 50 °C, from 50 °C to 60°C, from 60 °C to 80°C, from 80 °C to 100°C or any ranges therebetween to produce a heated mineral oil. A moisture concentration of the heated mineral oil can be reduced to produce a dried mineral oil. For instance, moisture concentration of the heated mineral oil can be reduced by at least one of: (i) passing a first inert gas through the heated mineral oil. (ii) passing a second inert gas through a headspace of the vessel, (hi) subjecting the heated mineral oil to a vacuum, and (iv) adding an aluminum-containing compound to the heated mineral oil. In various embodiments, two or more, three or more, or four or more of the above may be employed in combination; for instance, a combination of (i) and (ii) may be employed per some embodiments; and/or a combination of (iii) and (iv) in particular embodiments. [0076] Regarding (i) and (ii), the first and/or second inert gases can independently be or include, but are not limited to, nitrogen, carbon dioxide, argon, or any mixture thereof. Amounts of first and/or second inert gas (passed through the mineral oil or into the head space of the vessel) can be gauged in terms of volumetric turnovers (where each turnover equals the volume of the vessel), and can range from a low of 5, 10, 15, or 20 volumetric turnovers to 30, 40, 45, 50, 55, or 60 volumetric turnovers (with ranges from any low to any high contemplated). Vessel volume is not limited but may for instance range from a low of any one of 0.75. 1.15. 1.5, 1.9, or 2.3 m³ to a high of 3, 3.8, 5.7, or 7.6 m³. Regarding (iii), the heated mineral oil can be subjected to a vacuum, i.e., a pressure of < 101 kPa-absolute, < 75 kPa-absolute, < 60 kPa-absolute, or < 55 kPa-absolute. Vacuum pressures in various embodiments may range from a low of any one of 0.67, 1, 10. 15, or 20 kPa-absolute to a high of any one of 30, 40, 55, 60, 65, or 80 kPa-absolute. with ranges from any foregoing low end to any foregoing high end contemplated herein. The heated mineral oil can be subjected to the vacuum for at time period of 1 hr, 2, hr, 3 hr, 4 hr, or 5 hr to 6 hr, 8 hr, 10 hr, 12 hr, 24 hr, or longer. Regarding (iv), the aluminum-containing compound can be or can include, but is not limited to, a compound represented by the formula AlR(3-a)X_a, where R is a branched or straight chain alkyl, cycloalkyl, heterocycloalkyl, aryl, or a hydride radical having from 1 to 30 carbon atoms, X is a halogen, and a is 0, 1, or 2. For instance, the aluminum-containing compound can be or can include tri-hexyl-aluminum, triethylaluminum, trimethylaluminum, triisobutylaluminum, di-isobutylaluminum bromide, di-isobutylaluminum hydride, methyl aluminoxane, modified methyl aluminoxane, ethylaluminoxane, isobutylaluminoxane, or any mixture thereof. The modified methyl aluminoxane can be produced by the hydrolysis of trimethylaluminum and a higher trialkydaluminum, such as triisobut laluminum. Modified methyl aluminoxanes are generally more soluble in aliphatic solvents and more stable during storage. There are a variety of well-known processes for preparing aluminoxanes and modified aluminoxanes.

[0077] In some embodiments, the moisture concentration of the dried mineral oil can be < 100 ppmw, < 85 ppmw, < 70 ppmw, < 60 ppmw, < 55 ppmw, < 50 ppmw, < 45 ppmw, < 40 ppmw, < 35 ppmw, < 30 ppmw. < 25 ppmw, or < 20 ppmw, as measured according to ASTM D1533-12. In some embodiments, the dried mineral oil can have a density of 0.85 g/cm³, 0.86 g/cm³, or 0.87 g/cm³ to 0.88 g/cm³, 0.89 g/cm³, or 0.9 g/cm³ at 25°C according to ASTM D4052-18a. In some embodiments, the dried mineral oil can have a kinematic viscosity at 40°C of 50 cSt, 75 cSt, or 100 cSt to 150 cSt, 200 cSt, 250 cSt, or 300 cSt according to ASTM D341-20el. In some embodiments, the dried mineral oil can have an average molecular weight of 250 g/mol. 300 g/mol, 350 g/mol, 400 g/mol, 450 g/mol, or 500 g/mol to 550 g/mol, 600 g/mol, 650 g/mol, 700 g/mol, or 750 g/mol according to ASTM D2502-14(2019)el.

[0078] Once the dried mineral oil has been produced, catalyst particles can be introduced into the dried mineral oil to produce a mixture. The mixture can be mixed, blended, stirred, or otherwise agitated for at least 2 hours to remove at least a portion of any gas that can be present within the pores of the catalyst particles, to produce the slurry catalyst mixture. In some embodiments, the mixture can be agitated for 2 hours, 2.5 hours. 3 hours, 3.5 hours. 4 hours, 4.5 hours, 5 hours, or more to produce the slurry catalyst mixture. In some embodiments, the temperature of the mixture can be maintained at a temperature of 50°C, 55°C, 60°C, or 65°C to 75°C, 80°C, 85°C, or 90°C during agitation of the mixture. In other embodiments, the temperature of the mixture can be allowed to cool down. For example, the mixture can be allowed to cool down to a temperature of 45°C, 40°C, 35°C, or 30°C during agitation of the mixture.

[0079] In some embodiments, the vessel can include one or more mixing apparatus that can be configured to mix, blend, stir, or otherwise agitate the mixture within the vessel. In some embodiments, the mixing apparatus can be a rotatable mixing apparatus. Suitable rotatable mixing apparatus can include one or more blades or impellers configured to agitate one or more components of the slurry catalyst mixture within the vessel when rotated. The rotatable mixing apparatus can be rotated at 40 rotations per minute (rpm), 50 rpm, 75 rpm, or 100 rpm to 150 rpm, 175 rpm, 200 rpm. 225 rpm, or 250 rpm. In other embodiments, the mixture can be agitated via ultrasonic waves. In still other embodiments, the mixture can be agitated by moving the vessel, e.g., rolling the vessel or rotating the vessel back and forth an axis thereof.

[0080] The mineral oil may also be agitated during introduction into the vessel; during heating of the mineral oil; during reduction of the moisture concentration in the mineral oil; and/or during introduction of the catalyst particles to the mineral oil.

[0081] The mineral oil in the slurry catalyst mixture can also be referred to as a diluent. In some embodiments, in addition to the mineral oil, the slurry catalyst mixture can also include one or more additional diluents. Additional diluents can be or can include, but are not limited to, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof.

[0082] In some embodiments, the slurry catalyst mixture can have a solids content of 1 wt.% to 40 wt.%. Alternatively, from 1 wt.% to 5 wt.%, from 5 wt.% to 10 wt.%, from 10 wt.% to 15 wt.%, from 15 wt.% to 20 wt.%, from 20 wt.% to 25 wt.%, from 25 wt.% to 30 wt.%, from 35 wt.% to 40 wt.%, or any ranges therebetween. [0083] Although wax has heretofore been considered necessary for many slurry catalyst mixtures, e.g., for stability’ (especially for storage and transport), it is noted that slurry catalyst mixtures of various embodiments herein may advantageously omit the wax. Thus, according to such embodiments, the slurry catalyst mixture can be free of any wax having a melting point, at atmospheric pressure, of > 25°C, based on a total weight of the slurry catalyst mixture. More generally, the slurry catalyst mixture can include < 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, at atmospheric pressure, of > 25°C, based on a total w eight of the slurry' catalyst mixture. As used herein, the term “wax” includes a petrolatum also known as petroleum jelly or petroleum wax. Petroleum w axes include paraffin waxes and microcrystalline waxes, which include slack wax and scale wax. In at least one embodiment, the w ax, if present, can have a density (at 100°C) of 0.7 g/cm³, 0.73 g/cm³, or 0.75 g/cm³ to 0.87 g/cm³, 0.9 g/cm³, or 0.95 g/cm³. The wax, if present, can have a kinematic viscosity at 100°C of 5 cSt, 10 cSt, or 15 cSt to 25 cSt, 30 cSt, or 35 cSt. The w ax, if present, can have a melting point, at atmospheric pressure, of 25°C, 35°C. or 50°C to 80°C, 90°C. or 100°C. The wax, if present can have a boiling point of 200°C or greater, 225°C or greater, or 250°C or greater.

[0084] The term “wax” also refers to or otherwise includes any wax not considered a petroleum wax, which include animal waxes, vegetable waxes, mineral fossil or earth waxes, ethylenic polymers and polyol ether-esters, chlorinated naphthalenes, and hydrocarbon type waxes. Animal waxes can include beeswax, lanolin, shellac wax. and Chinese insect wax. Vegetable waxes can include carnauba, candelilla, bayberry, and sugarcane. Fossil or earth waxes can include ozocerite, ceresin, and montan. Ethylenic polymers and polyol ether-esters include polyethylene glycols and methoxypolyethylene glycols. The hydrocarbon ty pe waxes include waxes produced via Fischer- Tropsch synthesis.

[0085] Once the slurry catalyst mixture has been produced, the slurry catalyst mixture can be transferred from the vessel into a catalyst pot or cat pot configured to introduce the slurry' catalyst mixture into a gas phase polymerization reactor, such as the gas phase polymerization reactor described in FIG. 1. As such, in various embodiments, the vessel can be located on-site at a manufacturing facility that includes a gas phase polymerization reactor. By making the slurry catalyst mixture on-site at the manufacturing facility, the use of slurry catalyst cylinders to transport the slurry’ catalyst mixture can be avoided because the slurry' catalyst mixture, upon preparation, can be introduced into the catalyst pot or “cat pot” from which the slurry catalyst mixture can be introduced into the gas phase polymerization reactor. In some embodiments, bymaking the slurry' catalyst mixture on-site at the manufacturing facility, the slurry catalyst mixture can be introduced into the gas phase polymerization reactor within a time period of < 180 minutes,

< 150 minutes. < 125 minutes. < 100 minutes. < 80 minutes, < 60 minutes, < 50 minutes, or < 40 minutes upon initiation of agitation of the mixture. In other embodiments, by making the slurry catalyst mixture on-site at the manufacturing facility’, the slurry catalyst mixture can be introduced into the gas phase polymerization reactor within a time period of < 180 minutes, < 150 minutes,

< 125 minutes. < 100 minutes, < 80 minutes, < 60 minutes, < 50 minutes, or < 40 minutes upon ceasing or stopping agitation of the mixture.

[0086] Although, as noted above, wax advantageously may be omitted where storage and/or transport stability’ are not required for certain catalyst mixtures, it was surprisingly discovered that wax and/or additional diluent in certain catalyst mixtures can aid in the polymerization process in certain cases, e.g., depending on identity(ies) of catalyst compound(s) in the slurry catalyst mixture. Thus, surprisingly, even when one would otherwise think that omitting wax or other diluents is desired (e.g., because there is no need for added storage/transportation stability ), it is found that certain catalyst slurries should include w ax or other diluents. Thus, processes according to various embodiments may include identifying slurry catalyst mixture(s) for which wax and/or additional diluent is desired and including wax in such slurry catalyst mixture(s) (preferably also while not including wax and/or additional diluent in slurry catalyst mixtures where no processing advantage is obtained by the presence of the w ax and/or diluent).

[0087] Accordingly, polymerization processes per some embodiments can include, at a first time, introducing a carrier gas, one or more olefins, and a first slurry catalyst mixture into a polymerization reactor. The first slurry catalyst mixture can include a contact product of one or more catalysts selected from a first group of catalysts, a first support, a first activator, a first mineral oil, and a wax having a melting point, at atmospheric pressure, of > 25°C. The first slurry catalyst mixture can include > 1 wt.% of the wax, based on a total weight of the first slurry catalyst mixture. The one or more olefins can be polymerized in the presence of the first catalyst within the polymerization reactor to produce a first polymer product.

[0088] Then, a second time after the first time, a second slurry’ catalyst mixture can be introduced into the polymerization reactor. This can occur, e.g., as part of a grade transition or the like in a polymer production campaign (e.g.. first slurry catalyst mixture may be stopped before, dunng, or soon after introduction of the second slurry catalyst mixture). The second slurry catalyst mixture can include a contact product of one or more catalysts selected from a second group of catalysts, a second support, a second activator, and a second mineral oil. The one or more catalysts selected from the second group of catalysts are preferably different from the one or more catalysts selected from the first group of catalysts; how ever, the first and second supports, activators, and/or mineral oils can be the same or different. The second si urn- catalyst mixture, contrary to the first slurry catalyst mixture, can be free of or include < 1 wt.% of any wax having a melting point, at atmospheric pressure, of> 25°C, based on a total weight of the slurry catalyst mixture. The second slurry catalyst mixture can in particular be produced according to process described above, entailing removing of moisture from the slurry catalyst mixture. The polymerization process can also include polymerizing the one or more olefins in the presence of the second catalyst within the polymerization reactor to produce a second polymer product. In some embodiments, the carrier gas can be or can include, but is not limited to, nitrogen, argon, ethane, propane, or any mixture thereof. In some embodiments, the one or more olefins can be or can include one more substituted or unsubstituted C2 to C40 alpha olefins, as further described below.

[0089] In particular, it is believed that catalysts in the first group of catalysts and those of the second group of catalysts will preferably have different bulk densities; this aids in identifying which slu - catalyst mixtures may benefit from wax and/or additional diluent, and which will not. For instance, the one or more catalysts in the first group of catalysts can have a bulk densify of > 0.43 g/cm³, > 0.44 g/cm³, or > 0.45 g/cm³. On the other hand, the one or more catalysts in the second group of catalysts can have a bulk densify of < 0.45 g/cm³, < 0.44 g/cm³, < 0.43 g/cm³, < 0.42 g/cm³, < 0.41 g/cm³, or < 0.40 g/cm³. Put in other words, in various embodiments, the bulk densify of the one or more catalyst in the first group of catalysts is greater than the bulk densify of the one or more catalysts in the second group of catalysts.

CATALYST PARTICLES

[0090] The catalyst or catalyst compounds can be or can include, but are not limited to, one or more metallocene catalyst compounds. In some embodiments, the catalyst can include at least a first metallocene catalyst compound and a second metallocene catalyst compound, where the first and second metallocene catalyst compounds have different chemical structures from one another. Metallocene catalyst compounds can include catalyst compounds having one or more Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to at least one Group 3 to Group 12 metal atom, and one or more leaving group(s) bound to the at least one metal atom. In further embodiments, the catalyst further includes a third and/or a fourth metallocene catalyst compound where the third and fourth metallocene catalyst compounds have different chemical structures from one another and different chemical structures than the first and second metallocene catalyst compounds.

[0091] Also suitable are catalyst systems employing a mix of two metallocene catalysts, and in particular, a mix of (1) a bis-cyclopentadienyl hafnocene (preferably a bridged bis- cyclopentadienyl hafnocene) and (2) a zirconocene, such as an indenyl-cyclopentadienyl zirconocene (preferably an unbridged indenyl-cyclopentadienyl zirconocene).

[0092] In embodiments, the metallocene catalyst compounds include a hafnocene. Suitable hafnocenes can include bridged or unbridged hafhocenes, preferably bridged hafnocenes, such as bis(n-propylcyclopentadienyl)hafnium dichloride, bis(n-propylcyclopentadienyl)hafnium dimethyl, (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)hafhium dichloride, (n- propylcyclopentadienyl, pentamethylcyclopentadienyl)hafnium dimethyl. (n- propyl cy cl opentadieny 1 , tetrarnethylcyclopentadienyl)hafnium dichloride, (n- propylcyclopentadienyl, tetramethylcyclopentadi enyl)hafnium dimethyl, bis(cyclopentadienyl)hafnium dimethyl, bis(n-butylcyclopentadienyl)hafnium dichloride, bis(n- butylcyclopentadienyl)hafnium dimethy l, and bis( 1 -methyl-3-n-butylcyclopentadienyl )hafhium dimethyl, and combinations thereof.

[0093] Other suitable hafnocene compounds include, but are not limited to, rac/meso Me₂Si(Me₃SiCH₂Cp)₂HfMe₂; racMe₂Si(Me₃SiCH₂Cp)₂HfMe₂; rac/meso

Ph₂Si(Me₃SiCH₂Cp)₂HfMe₂; rac/meso (CH₂)₃ Si(Me? SiCH₂Cp)₂HfMe₂; rac/meso

(CH₂)₄Si(Me3SiCH₂Cp)₂HfMe₂; rac/meso (C6F₅)2Si(Me₃SiCH₂Cp)₂HfMe₂: rac/meso

(CH₂)₃ I ( Me? SiCH₂Cp)₂ZrMe₂; rac/meso Me₂Ge(Me₃ SiCH₂Cp)₂HfMe₂; rac/meso

Me₂Si(Me₂PhSiCH₂Cp)₂HfMe₂; rac/meso Ph₂Si(Me₂PhSiCH₂Cp)₂HfMe₂;

Me₂Si(Me4Cp)(Me₂PhSiCH₂Cp)HfMe₂, and combinations thereof.

[0094] As noted above, suitable catalyst compounds also or instead may include a zirconocene, such as an unbridged zirconocene including, but not limited to, bis(indenyl)zirconium di chloride, bis(indenyl)zirconium dimethyl, bis(tetrahydro-l -indeny l)zirconium dichloride, bis(tetrahydro-l- indenyl)zirconium dimethyl. rac/meso-bis(l-ethylindenyl)zirconium dichloride, rac/meso-bis(l- ethylindenyl)zirconium dimethyl, rac/meso-bis(l-methylindenyl)zirconium dichloride, rac/meso- bis(l -methylin denyl)zirconium dimethyl, rac/meso-bis(l-propylindenyl)zirconium dichloride, rac/meso-bis(l -propylindenyl)zirconium dimethyl, rac/meso-bis(l-butylindenyl)zirconium dichloride, rac/meso-bis(l-butylindenyl)zirconium dimethyl, meso-bis(lethylindenyl) zirconium dichloride, meso-bis(l-ethylindenyl) zirconium dimethyl, (l-methylindenyl)(pentamethyl cyclopentadienyl) zirconium dichloride, (1 -methylin denyl)(pentamethyl cyclopentadienyl) zirconium dimethyl, and combinations thereof.

SLURRY CATALYST MIXTURE INCLUDING ACTIVATORS AND SUPPORTS

[0095] As noted above, the slurry catalyst mixture can include one or more activators and/or supports in addition to one or more catalysts. The term “activator” refers to any compound or combination of compounds, supported or unsupported, which can activate a single site catalyst compound or component, such as by creating a cationic species of the catalyst component. For example, this can include the abstraction of at least one leaving group (the 'X' group in the single site catalyst compounds described herein) from the metal center of the single site catalyst compound/component. The activator may also be referred to as a “co-catalysf. For example, the slurry catalyst mixture can include two or more activators (such as aluminoxane and a modified aluminoxane) and a catalyst compound, or the slurry catalyst mixture can include a supported activator and more than one catalyst compound. In particular embodiments, the slurry catalyst mixture can include at least one support, at least one activator, and at least two catalyst compounds. For example, the slurry' can include at least one support, at least one activator, and two different catalyst compounds that can be added separately or in combination to produce the slurry’ catalyst mixture. In some embodiments, a mixture of a support, e.g., silica, and an activator, e.g., aluminoxane, can be contacted with a catalyst compound, allowed to react, and thereafter the mixture can be contacted with another catalyst compound, for example, in a trim system.

[0096] The molar ratio of metal in the activator to metal in the catalyst compound in the slurry' catalyst mixture can be 1000: 1 to 0.5: 1, 300: 1 to 1: 1, 100: 1 to 1: 1, or 150: 1 to 1 : 1. The slurry’ catalyst mixture can include a support material which can be any inert particulate earner material known in the art, including, but not limited to, silica, fumed silica, alumina, clay, talc or other support materials such as disclosed above. In one embodiment, the slurry’ can include silica and an activator, such as methyl aluminoxane ("MAO"), modified methyl aluminoxane ("MM AO), as discussed further below. In embodiments, activators include aluminoxane compounds, modified aluminoxane compounds, and ionizing anion precursor compounds that abstract a reactive, a- bound, metal ligand making the metal compound cationic and providing a charge-balancing noncoordinating or weakly coordinating anion.

[0097] As noted above, one or more organo-aluminum compounds such as one or more alkylaluminum compounds can be used in conjunction with the aluminoxanes. For example, alkydaluminum species that can be used include diethylaluminum ethoxide, diethylaluminum chloride, and/or disobutylaluminum hydride. Examples of trialkylaluminum compounds include, but are not limited to, trimethylaluminum, triethylaluminum ("TEAL), triisobutylaluminum “TiBAl), tri-n-hexylaluminum, tri-n-octylaluminum, tri propyl aluminum, tributylaluminum, and the like.

[0098] Suitable supports include, but are not limited to, active and inactive materials, synthetic or naturally occurring zeolites, as well as inorganic materials such as clays and/or oxides such as silica, alumina, zirconia, titania, silica-alumina, cerium oxide, magnesium oxide, or combinations thereof. In particular, the support may be silica-alumina, alumina and/or a zeolite, particularly alumina. Silica-alumina may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.

[0099] In some embodiments, at least a portion of the slurry catalyst mixture can be contacted with a solution catalyst mixture to produce or otherwise form a slurry/solution catalyst mixture.

SOLUTION CATALYST MIXTURE - TRIM SOLUTION

[0100] The solution catalyst mixture can include a solvent and only catalyst compound(s), such as a metallocene, or can also include an activator. In some embodiments, the solution catalyst mixture can be or can include, but is not limited to, a contact product of a solvent/diluent and the first catalyst or the second catalyst. In some embodiments, the slurry/solution catalyst mixture can be introduced into the gas phase polymerization reactor. In at least one embodiment, the catalyst compound(s) in the solution catalyst mixture can be unsupported.

[0101] The solution catalyst mixture, if used, can be prepared by dissolving the catalyst compound and optional activators in a liquid solvent. In some embodiments, the liquid solvent can be an alkane, such as a Cs to C30 alkane, or a Cs to C10 alkane. Cyclic alkanes such as cyclohexane and aromatic compounds such as toluene can also be used. Mineral oil can be used as a solvent alternatively or in addition to other alkanes such as one or more Cs to C30 alkanes. The mineral oil in the solution catalyst mixture, if used, can have the same properties as the mineral oil that can be used to make the slurry catalyst mixture described above. The solvent employed should be liquid under the conditions of polymerization and relatively inert. In one embodiment, the solvent utilized in the solution catalyst mixture can be different from the diluent used in the slurry catalyst mixture. In another embodiment, the solvent utilized in the solution catalyst mixture can be the same as the diluent, i.e., the mineral oil(s) and any additional diluents used in the slurry catalyst mixture.

[0102] If the solution catalyst mixture includes both the catalyst and an activator, the ratio of metal in the activator to metal in the catalyst in the solution catalyst mixture can be 1000: 1 to 0.5: 1, 300: 1 to 1 : 1, or 150: 1 to 1 : 1. In various embodiments, the activator and catalyst can be present in the solution catalyst mixture at up to 90 wt.%, at up to 50 wt.%, at up to 20 wt.%, such as at up to 10 wt.%, at up to 5 wt.%. at less than 1 wt.%, or between 100 ppm and 1 wt.%. based on the weight of the solvent, the activator, and the catalyst. The one or more activators in a solution catalyst mixture, if used, can be the same or different as the one or more activators used in a slurry catalyst mixture.

[0103] The solution catalyst mixture can include any one of the catalyst compound(s) of the present disclosure. As the catalyst is dissolved in the solution, a higher solubility can be desirable. Accordingly, the catalyst in the solution catalyst mixture can often include a metallocene, which may have higher sol ubi li ty than other catalysts. In the polymerization process any of the above described solution catalyst mixtures can be combined with any of the slurry catalyst mixtures described above. In addition, more than one solution catalyst mixture can be utilized.

CONTINUITY ADDITIVE - STATIC CONTROL AGENT

[0104] In gas-phase polyethylene production processes, it can be desirable to use one or more static control agents to help facilitate the regulation of static levels within the reactor. The continuity additive is a chemical composition that, when introduced into the fluidized bed within the reactor, can influence or drive static charge (negative, positive, or to zero) in the fluidized bed. The continuity additive used can depend, at least in part, on the nature of the static charge, and the choice of static control agent can vary depending, at least in part, on the polymer being produced and/or the single site catalyst compounds being used. In some embodiments, the continuity additive or static control agent can be introduced into the reactor in an amount of 0.05 ppm to 200 ppm. Alternatively, from 0.05 ppm to 2 ppm, 5 ppm, 10 ppm, or 20 ppm to 50 ppm, 75 ppm, 100 ppm, 150 ppm, 200 ppm.

[0105] In some embodiments, the continuity additive can be or can include aluminum stearate. The continuity additive can be selected for its ability to receive the static charge in the fluidized bed without adversely affecting productivity. Other suitable continuity additives can be or can include, but are not limited to, aluminum distearate, ethoxylated amines, and combinations thereof. In embodiments the continuity additive includes a mixture of a polysulfone copolymer, a polymeric polyamine, and oil soluble sulfonic acid. Any of the continuity additives can be used either alone or in combination.

[0106] In some embodiments, the continuity additive can include fatty' acid amines, amidehydrocarbon or ethyoxylated-amide compounds, carboxylate compounds such as arylcarboxylates and long chain hydrocarbon carboxylates, and fatty acid-metal complexes; alcohols, ethers, sulfate compounds, metal oxides and other compounds known in the art. Some specific examples of control agents can be or can include, but are not limited to, 1,2-diether organic compounds, magnesium oxide, glycerol esters, ethoxylated amines (e g., N,N-bis(2- hydroxyethyl)octadecylamine), alkyl sulfonates, and alkoxylated fatty acid esters, chromium N- oleylanthranilate salts, calcium salts of a Medialan acid and di-tert-butylphenol, an a-olefin- acrylonitrile copolymer and polymeric polyamine, sorbitan-monooleate, glycerol monostearate, methyl toluate, dimethyl maleate, dimethyl fumarate, triethylamine, 3,3-diphenyl-3-(imidazol-l- yl)-propin, and like compounds. In some embodiments, another continuity additive can include a metal carboxylate salt, optionally, with other compounds. [0107] In some embodiments, the continuity additive can include an extracted metal carboxylate salt can be combined with an amine containing agent such an extracted carboxylate metal salt. For example, the extracted metal carboxylate salt can be combined with antistatic agents such as fatty amines, such as a blend of ethoxylated stearyl amine and zinc stearate, or a blend of ethoxylated stearyl amine, zinc stearate and octadecyl-3, 5 -di -tert-butyl-4-hydroxyhydrocinnamate.

[0108] Other continuity additives can include ethyleneimine additives such as polyethyleneimines having the following general formula: -(CH2-CH2-NH)n-, where n can be from 10 to 10,000. The polyethyleneimines can be linear, branched, or hyper branched (e.g., forming dendritic or arborescent polymer structures). The polyethyleneimines can be a homopolymer or copolymer of ethyleneimine or mixtures thereof (referred to as polyethyleneimine(s) hereafter). Although linear polymers represented by the chemical formula - (CH2 — CH2 — NH)n- can be used as the polyethyleneimine, materials having primary, secondary, and tertiary⁷ branches can also be used.

END USES

[0109] The polymers produced by the processes disclosed herein and blends thereof can be useful in forming operations such as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding, and rotary molding. Films include blown or cast films formed by co-extrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc., in food-contact and non-food contact applications. Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc. Extruded articles include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.

[0110] Specifically, any of the foregoing polymers, such as ethylene copolymers or blends thereof, can be used in mono- or multi-layer blown, extruded, and/or shrink films. These films may be formed by any number of well-known extrusion or coextrusion techniques, such as a blown bubble film processing technique, wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form aflat film. Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. [0111] The polymers produced herein may be further blended with one or more second polymers and used in film, molded part and other typical applications. In one embodiment, the second polymer can be selected from ethylene homopolymer, ethylene copolymers, and blends thereof. Useful second ethylene copolymers can include one or more comonomers in addition to ethylene and can be a random copolymer, a statistical copolymer, a block copolymer, and/or blends thereof. The process of making the second ethylene polymer is not critical, as it can be made by slurry, solution, gas phase, high pressure or other suitable processes, and by using catalyst systems appropriate for the polymerization of polyethylene, such as Ziegler-Natta-type catalysts, chromium catalysts, metallocene-type catalysts, other appropriate catalyst systems or combinations thereof, or by free-radical polymerization.

OPTICAL PROBE CONFIGURATION

[0112] As discussed above, the mole ratio of the types of active sites on the multi-component catalyst do not necessarily equal the mole ratio of the two or more catalyst precursors used in the preparation of the supported catalyst due to the different activation energies and activation efficiencies. Spectral characterization methods can be utilized to evaluate the ratio of active sites but spectrophotometric methods of evaluating supported multi-component catalysts have certain drawbacks which lead to difficulty in implementing the method in a production reactor. One challenge for quantitative fluorescence spectroscopy is the spectral distortions caused by primary and/or secondary inner filter effects.

[0113] Catalyst slurries used in commercial polyethylene production reactors typically have catalyst loadings in the range of 15 pmol - 50 pmol metallocene (MCN) / g supported catalyst resulting in optical densities (absorbance) in a range 1 to 4 or higher. For quantitative fluorescence spectral analysis to accurately resolve the contribution of each active site to the overall spectra, industry guidelines typically call for high optical density samples to be diluted such that the absorbance is less than 0.1. However, diluting the catalyst slurry is usually not practical in a commercial application and diluting the catalyst slurry may affect the physicochemical properties of the final polymerized product.

[0114] The primary inner filter effect (1° IFE) occurs when a sample strongly absorbs the excitation light, causing non-uniform illumination along the light path. The stronger the sample absorbs a given incident light (i.e. higher optical density), the more severe the intensity attenuation becomes. The secondary' inner filter effect (2° IFE) occurs when the emitted light is reabsorbed by a sample as the light propagates through the sample towards the detector. The secondary' inner filter effect is manifested in samples where one fluorophores emission spectrum overlaps with the absorption spectrum of either the fluorophore itself, or another component in the sample. Both the primary and secondary inner filter effects are wavelength dependent. FIG. 2A is a schematic illustration of a square geometry spectrophotometry configuration and a graph of primary’ inner filter effects on fluorescence measurements with four hypothetic samples with increasing absorbance from 0.1 to 4 (in 10 mm path-length cuvette). FIG. 2B is a schematic illustration of secondary' inner filter effects on fluorescence measurements in square geometry⁷ with four hypothetic samples with increasing absorbance from 0. 1 to 4 (in 10 mm path-length cuvette). As can be seen for both excitation and emission spectra in FIG. 2A and FIG. 2B, increasing absorbance (A) greatly decreases the intensity⁷ of incident light (Id) of light traveling distance (d) where a distance of a few millimeters, depending on absorbance, results in large loss of incident light.

[0115] FIG. 3 A is a schematic illustration of an optic probe 300 for in-line measurement of a post-trim multi-component catalyst in accordance with certain embodiments of the present disclosure. Optic probe 300 enables in-line measurements of UV-Vis absorption, steady-state emission, time-resolved emission spectra, and time-resolved intensity decay (lifetime) of posttrim supported multi-component catalyst i.e. the fluorescence and/or phosphorescence lifetimes of the catalyst slurry' mixture. The optic probe comprises tunable light source 302, bifurcated optical fiber 304, sample chamber 306, optical fiber 308, UV-vis detector 310, optional filter 314, and fluorescence detector 312. Post-trim catalyst slurry⁷ is introduced into sample chamber 306 as indicated by arrow 340 while light from tunable light source 302 is guided into the sample chamber using bifurcated optical fiber 304. The post-trim catalyst slurry exits sample chamber 306 and as indicated by arrow 318 and is directed to a fluidized bed reactor such as fluidized bed reactor 122 in FIG. 1.

[0116] Tunable light source 302 can include a continuum tunable light source for UV-Vis spectrometry, a laser light source for steady-state emission spectra, and/or a pulsed laser light source for intensity decays and time-resolved emission spectra. The post-trim catalyst slurry is illuminated by the light in sample chamber 306 which causes the catalyst slurry in sample chamber 306 to fluoresce. The light passing through sample chamber 306 from tunable light source 302 as well as the additional generated light from the fluorescence of the catalyst slurry’ is directed into UV-vis detector 310 through optical fiber 308. In embodiments, UV-vis detector 310 is configured to detect UV-Vis range wavelengths such as wavelengths in the range of 200 nm to 1100 nm. Additionally, generated light as well as reflected light is directed through bifurcated optical fiber 304 into optional filter 314 and through to fluorescence detector 312. Optional filter 314 can include a long pass filter which blocks excitation light from reaching fluorescence detector 312. Optional filter 314 can be selected to allow light to pass through if its wavelength is above a given threshold such as a 500 nm long-pass filter. In embodiments, fluorescence detector 312 is configured to detect wavelengths in the range of 250 nm to 1100 nm. for example. In embodiments where the tunable light source 302 includes a laser light source, fluorescence detector 312 is equipped with diffraction element (e.g. diffraction grating) and array type sensor allowing for wavelength resolved detection.

[0117] FIG. 3B is a cross section of bifurcated optical fiber 304 showing excitation arm 316 for transmitting light from tunable light source 302 to sample chamber 306 and emission arm 324 for transmitting light from sample chamber 306 to fluorescence detector 312. Each of excitation arm 316 and emission arm 324 can include a single optical fiber or a bundle of optical fibers.

[0118] FIG. 3C is a cross section of sample chamber 306. As shown in FIG. 3C, sample chamber 306 includes a first collimating lens 320 and a second collimating lens 322 positioned distance at “1” from each other at opposite ends of sample chamber 306. Bifurcated optical fiber 304 is positioned on one end of sample chamber 306 such that excitation light from tunable light source 302 is transmitted through excitation arm 316 and directed through first collimating lens 320 into sample chamber 306. Collimated excitation light entering sample chamber 306 illuminates the post-trim catalyst slurry flowing through sample chamber 306 and the incident collimated excitation light is at least partially absorbed by the post trim-catalyst slurry thereby attenuating the collimated excitation light traversing sample chamber 306. The attenuated collimated excitation light enters second collimating lens 322 and is transmitted by optical fiber 308 to UV- vis detector 310. Additionally, incident collimated light from excitation arm 316 causes fluorophores in the post-trim catalyst slurry to fluoresce thereby emitting light in sample chamber 306. Reflected incident collimated light and emitted light from fluorophores is transmitted back through first collimating lens 320 and into emission arm 324. From first collimating lens 320, Reflected incident collimated light and emitted light is transmitted through emission arm 324 of bifurcated optical fiber 304 to optional filter 314. Optional filter 314 may include a long pass filter which filters wavelengths of light corresponding to the reflected and scattered excitation light from tunable light source 302.

[0119] The in-line measurements of UV-Vis and steady-state emission spectra of the catalyst slurry stream are enabled by the use of appropriate light sources and corresponding UV-vis and spectral detector. The distance between the two optic fibers in optic probe 300 can be varied to accommodate various flow rates of catalyst slu ' and to allow for variable optical path. In embodiments, the distance between the fibers (‘T’ in FIG. 3C) can van' from 0.1 mm to 10 mm, for example. Alternatively, from 0. 1 mm to 0.5 mm, from 0.5 mm to 1 mm, from 1 mm to 5 mm, from 5 mm to 10 mm, or any ranges therebetween. [0120] The configuration of the optic probe which includes dual collimating lens at each end of the sample chamber allows for inner filter effect correction which improves the accuracy of the radiometric quantification of the active sites in the post-trim supported multi-component catalyst slurry. FIG. 4A illustrates emission measurement without a collimating lens. As shown in FIG. 4A, in the absence of a collimating lens, the emerging laser light 400 from excitation arm 316 forms a cone and the density of the laser beam intensity (i.e. photon counts per mm²) measured depends on the distance from the fiber tip. In embodiments where the excitation arm and emission arm of the bifurcated optical fiber are identical, the detected emission 402 transported through emission arm 324 will only emerge from the overlapping area of both excitation and emission cones. The size of the overlapping area depends on the distance X’ from the tip of the fiber.

[0121] FIG. 4B illustrates UV-vis measurement without a collimating lens. As shown in FIG. 4B, in the absence of a collimating lens the emerging light 404 from excitation arm 316 forms a cone and the beam intensity measured depends on the distance from the fiber tip. As a result, a relatively low amount of light is captured by optical fiber 308. The energy of the excitation beam is quickly distributed on a circle surface and the efficiency for light collection quickly drops as the fiber distance increases. The configuration without collimating lens is therefore considered non-ideal for the absorbance measurement and the correction for the inner filter effects.

[0122] FIG. 4C illustrates an embodiment where a collimating lens is used in front-face emission measurement. As shown in FIG. 4C, first collimating lens 320 shapes the emerging laser light 400 from excitation arm 316 to form a cylinder. Effectively the overlapping area between the excitation and emission cones stays constant throughout each distance “X” over the length “1” of the sample chamber.

[0123] FIG. 4D illustrates an embodiment where two collimating lenses are used in UV-vis measurement. As shown in FIG. 4D, first collimating lens 320 shapes emerging light 404 from excitation arm 316 to form a uniform emission cylinder across the sample chamber. Second collimating lens 322 shapes the light traversing the sample chamber such that optical fiber 308 can collect a majority of emerging light 404 from excitation arm 316. In the UV-vis measurement, the receiving fiber can collect most of the light from the excitation arm, and the only attenuating factor for the excitation beam is by the sample’s absorption and/or scattering. Light intensity measurements with both the reference solvent/diluent and the sample of interest allow the UV-vis spectrum to be calculated. The configuration with collimating lens is therefore considered beneficial for measuring light attenuation (absorption) and for the correction of inner filter effects. [0124] For a chosen excitation wavelength, if the sample absorbs strongly at the wavelength (i.e., high optical density at the given wavelength), the intensity of the excitation light will decrease as it penetrates the sample through the primary inner filter effect. If the sample also absorbs strongly at the wavelengths of the emission, then the intensity of the emission light at these wavelengths will decrease as it travels through the sample on the way to the detector by the secondary inner filter effect. The secondary inner filter effect is wavelength dependent.

[0125] FIG. 5 is a cross section schematic illustrating the interior of the sample chamber including collimating lenses. In FIG. 5, “f ’ is the focal length of first collimating lens 320, point “A” is the focal distance, and angle ”[>’’ is the collection angle and cylindncal angle. The fraction rrd of collected emission will be proportional to ratio of fiber tip surface (—² ) to a surface area of a sphere or radius f (nf²).

[0126] In fluorescence spectroscopy, for an emitting point at focal distance A, the amount of light that lens will focus into the excitation fiber of bifurcated optical fiber 304 will be the light in the cubical angle below the ray, which becomes parallel to the optical axis after passing through first collimating lens 320, as indicated by the ray emitting from focal distance A. The diameter of the part of the lens that is able to collect emission light is equal to the diameter of the fiber (d). The collection angle equals to the cylindrical angle [3. Any light coming at angle larger than [3 will not be focused into the fiber. For emitting points at distance shorter than the focal distance such as point “B”, the collection angle will be equal to [3. As the emitting point moves closer to the lens, the surface area of the lens which is able to focus emission light into the fiber decreases proportionally to the distance square (X²). Effectively the collection efficiency between the lens surface and the lens focal point will be constant. For emitting points at longer distances than the focal distance such as point ‘"C” and point ‘"Cl”, the collection angle should decrease as the distance increases. The efficiency for collecting the emission signal for points beyond the focal distance will decrease slowly. For an emitting point in infinite distance, the maximum surface area of the lens to efficiently collect light into the fiber is proportional to D² (i.e., the surface area of the cylinder bottom). The above rationales are true for emitting points located on optical axis. While the efficiency for emission collection for emitting points that are off the optical axis will be smaller, the distance dependence will obey the same general rule as described above. Furthermore, the number of emitting points which are off the optical axis can be reduced by configuring and sizing the sample chamber such that a majority of the emitting points are located within the optical axis. Furthermore, the number of emitting points which are off the optical axis can be reduced by configuring and sizing the sample chamber such that a majority of the emitting points are located within the optical axis.

[0127] Thus, for emission measurement using the bifurcated fiber and a collimating lens as shown in FIG. 5, the observed emission intensity should stay constant up to the distance equal to the lens’ focal distance f, then slowly decrease as the distance between the emitting point and the lens increases. Further, when using a collimating lens and optical fiber to measure fluorescence signal of a thin sample such as where the path-length is in a range of 1 mm - 10 mm range, the signal perturbation due to geometrical factors is negligible. When the path length is short the fluorescence collection efficiency throughout the path length stays constant and results in a uniform excitation area such as in FIG. 4C allowing for correction of inner filter effects in measured emission spectra to recover the true emission spectra for high optical density samples. For a high optical density samples in a short path-length such as 1 - 2 mm, the largest contributor to excitation illumination and efficiency for fluorescence collection is the sample optical properties including absorption and scattering properties when the sample is placed within two focal distances from the lens.

INNER FILTER EFFECTS MODEL

[0128] A spectra correction method of inner filter effects using an optical probe as described above accounts for sample absorption of excitation light (primary inner filter effect) and reabsorption of emission light (secondary inner filter effect) and enables the reconstruction of the true emission spectrum from the as-measured emission spectrum. That is, the inner filter effects model can be used to reconstruct the true emission spectrum from the as-measured emission spectrum by accounting for primary and secondary⁷ inner filter effects. Most broadly, in some embodiments this can be accomplished by an inner filter effect model with output of an emission spectrum expressed as a function of either normalized or raw emission intensity against emission wavelengths. An example of this type of model (using raw emission intensity) is developed below. [0129] As the post-trim catalyst slurry is introduced into the sample chamber, the sample becomes illuminated with excitation light provided from the excitation arm of the bifurcated optical cable. As the excitation beam penetrates the sample, its intensity can be expressed as a function of the penetration depth x according to the Beer-Lambert Law as shown in Equation 1 where I(x) is intensity at penetration depth x, Io is initial intensity, c is the sample concentration, s is the extinction coefficient, Ae is the total absorbance of the sample at the excitation wavelength, and 1 is the total path length.

Equation 1

[0130] The fluorescence intensity observed from a given sample layer dx at distance x from the lens is proportional to the amount of light absorbed by the layer as shown in Equation 2. At any given distance x, the number of excited fluorophores AF can be calculated where dx is the thickness of the laver.

Equation 2

[0131] The total fluorescence signal detected is the sum of fluorescence intensity from all layers as shown in Equation 3 where 1 is the path length.

Equation 3

[0132] While Equation 3 is exact, for practical purposes, a numerical approximation method may be utilized to simplify calculation. The integral from Equation 3 can be divided into n layers where each layer has a thickness Ax = 1/n (sample thickness = 1) Equation 4 is the signal from the i^th layer within the sample. Equation 5 is the total fluorescence of the sample which is found by summing the contribution from each layer.

Equation 4

[0133] The fluorescence generated within each layer i will be attenuated as it travels back to the detection fiber by re-absorbance by the sample. Since the absorbance of the sample is w avelength dependent, the attenuation is also dependent on the wavelength. The wavelength dependency of absorption Af (Terns) causes deformation of the detected emission spectrum which is experimentally measured in UV-vis absorption spectroscopy of the sample. The detected wavelength dependent emission spectrum F(Xems) can be calculated by Equation 6 where Eo(Aems) is the true emission spectrum profile. Equation 6 can be rearranged to form Equation 7 which is the inner filter effect model for a specified wavelength. The full emission spectrum can be corrected by using the model of Equation 7 for each wavelength of interest such as wavelengths from 300 nm to 850 nm. Thus, by measuring the absorbance for a fixed sample thickness and emission spectrum, the true emission spectrum can be recovered free from the inner filter effects using Equation 7. Increasing the number of layers or decreasing the layer thickness will result in a more precise true emission spectrum. In embodiments for path lengths in the range of 1 mm to 10 mm the number of layers can be selected to be between 1 and 100, between 1 and 1000, between 1 and 10.000, or any ranges therebetween.

Equation 6

SPECTRAL DECONVOLUTION OF MULTI-COMPONENT CATALYST

[0134] As discussed above, the ratio of active sites in a multi-component catalyst does not necessarily correspond to the mole ratio of active catalyst precursor used to create the activated multi-component catalyst. The relative contribution in polymerization between the different types of active sites (i.e. composition of the resulting multi-modal polymer) depends on the mol ratio of the active sites on supported catalyst. In embodiments, it is assumed that for a particular type of active site, the spectral characteristics of the active sites remain the same with or without the presence of a second or subsequent type of active site. This assumption enables the spectrum of the supported multi-component catalyst to be considered as a linear combination of the spectra of the individual active sites. For a dual-component catalyst, Equation 8 shows the contribution of each active site A* and B* to the as measured spectrum. In further embodiments, the spectrum of the supported multi-component catalyst to be considered as a more complex combination of the individual spectra such as a polynomial, exponential, logarithmic, integral, derivative, or any other suitable form.

Equation 8 Spectrum^ A* , B*) — a Spectrum A*) + b Spectrum B*) + ^Background and Scatter)

[0135] In the spectral analysis of a dual-component catalyst, it is expected that the optimized ratio (that is a/b) of the two single-component spectra is proportional, but not necessarily equal, to the mol ratio of the two types of active sites on dual-component catalyst. This is because in the single-component catalyst, the exact concentration of the corresponding active site is not readily quantifiable. In addition, the response coefficients for the two types of active sites may differ, such as the extinction coefficient for absorption spectroscopy or quantum yield for emission spectroscopy are typically not equal for the two types of active sites. However, the catalyst performance in a polymerization reactor can still be predicted by the ratio of the spectra as the ratio of the spectra directly correlates to the relative quantity of active sites in the dual-component catalyst, as long as the same two single-component spectra are used as the basis for spectral deconvolution.

[0136] The 3-component deconvolution in Equation 8 can be simplified to a 2-component deconvolution method. The optical probe described above is utilized to capture the UV-vis and steady-state emission spectra of a control system of a catalyst slurry which does not contain A* or B*, i.e. a slurry without catalyst precursor containing support, solvent, static control agents, or other components described herein. The optical probe is further utilized to capture the UV-vis and steady-state emission spectra of a single-component system of a catalyst slurry containing only A* single-component spectra and a single-component system of a catalyst slurry containing only B*. The as-measured steady -state emission spectra of the control system, single-component A*, and single component B* are then corrected for inner filter effects using the inner filter effects model of Equation 7 and/or Equation 3 to yield a corrected emission spectra of the control system, single-component A*, and single component B*. By subtracting the corrected control spectrum from the corrected single-component A* spectrum and the corrected single-component B* spectrum, the background and scatter are removed from the corrected single-component A* spectrum and the corrected single-component B*. Next, the background/scatter-removed corrected emission spectra of the single-component A*, and single component B* are normalized by a normalization protocol such that the area under the curve is equal to 1 in the wavelengths of interest such as from 450 - 800 nm.

[0137] Thereafter, the optical probe can be used to measure the spectra from a multi-component catalyst slurry including A* and B*. The as-measured spectra are corrected using the inner filter effects model of Equation 7 and/or Equation 3. The corrected control spectrum can be subtracted from the corrected spectra to form a background/scatter-removed corrected spectra, which is then normalized to form a normalized, background/scatter-removed, corrected spectra.

[0138] A linear combination of the corrected single-component A* spectrum with background and scatter removed and the corrected single-component B* with background and scatter removed can then be fit to the background/scatter-removed corrected spectra. The single-component spectra can mathematically fit (i.e. curve fit) to solve for the coefficients a and b in Equation 8 which minimize the sum of the squares of offsets (residual) between the background/scatter-removed corrected spectra without background and scatter and the linear combination of the singlecomponent spectra. The coefficients a and b then represent the relative contribution of each active site type A* and B* and thus the molar ratio of each type of active site. IN-LINE MONITORING OF DUAL-COMPONENT CATALYST IN SLURRY

[0139] In-line monitoring of dual -component catalyst composition is highly desirable in processes where the catalyst composition can be adjusted in-line. One example of such process is the in-line trimming as described in FIG. 1 above. The in-line trimming process allows the base catalyst to react with one precursor, yielding a post-trim catalyst that features a different ratio of the two t pes of active sites (A* and B*) prior to entering the gas phase reactor. The relative ratio of the two types of active sites A* and B* in a post-trim catalyst, depends on the original ratio in base catalyst, the trim level (the amount of precursor B trimmed per gram of base catalyst), and the trim efficiency (the % of trimmed precursor B that was activated). In general, the trim efficiency is highly dependent on the in-line trimming condition, which is difficult to control and therefore difficult to accurately predict and control the ratio of the active sites in the post-trim catalyst. The capability to monitor post-trim catalyst composition in-line is highly desirable, because it allows early detection of any unexpected deviation in post-trim catalyst composition, preventing off-spec resin production.

[0140] One method of using the optical probe described herein is to continuously monitor a post trim catalyst slurry as the slurry is introduced into reactor. The UV-vis and fluorescence spectra of the post trim catalyst slurry is continually captured. The steady-state fluorescence emission spectra are continually corrected using the method described above. The corrected emission spectra are then deconvoluted using the method described above to derive the molar ratios of each of the active sites A* and B* in the post trim catalyst slurry. The calculated molar ratio can be compared to a target ratio and if the calculated molar ratio is not within a tolerance range of the target ratio, the trim level of precursor B can be adjusted such that the calculated molar ratio of active sites is closer to the target ratio.

ADDITIONAL EMBODIMENTS

[0141] Accordingly, the present disclosure may provide methods of spectroscopic characterization methods for supported catalyst in slurry. The methods and systems may include any of the various features disclosed herein, including one or more of the following statements. [0142] Statement 1. A method comprising: introducing a slurry catalyst mixture into a sample chamber, where the slurry catalyst mixture comprises a multi-component catalyst and a carrier fluid, wherein the multi-component catalyst comprises a first activated catalyst and a second activated catalyst; illuminating the slurry catalyst mixture in the sample chamber; capturing a spectrum of the slurry catalyst mixture, wherein the spectrum comprises at least one spectrum selected from the group consisting of UV-Vis spectrum, emission spectrum, and combinations thereof; correcting the spectrum using an inner filter effects model to form a corrected spectrum of the si urn- catalyst mixture; and determining a calculated ratio of an amount of the first activated catalyst and an amount of the second activated catalyst in the multi-component catalyst from the corrected spectrum of the slurry catalyst mixture by fitting the spectrum of the slurry catalyst mixture to a single component spectrum of the first activated catalyst and a single component spectrum of the second activated catalyst, using spectral deconvolution.

[0143] Statement 2. The method of statement 1. wherein the slurry catalyst mixture further comprises a third activated catalyst and/or a fourth activated catalyst, and wherein the method further comprises fitting the corrected spectrum of the slurry catalyst mixture to a single component spectrum of the third activated catalyst and/or a single component spectrum of the fourth activated catalyst, using spectral deconvolution.

[0144] Statement 3. The method of any of statements 1-2 wherein the slurry catalyst mixture is illuminated with a light source that outputs light from 200 - 900 nm, and wherein spectrum is the UV-Vis spectrum.

[0145] Statement 4. The method of any of statements 1-3 wherein the slurry catalyst mixture is illuminated with a light source comprising a laser, and wherein the spectrum is the emission spectrum.

[0146] Statement 5. The method of any of statements 1-4 wherein the slurry catalyst mixture is illuminated with a light source comprising a pulsed light source or intensity modulated light source, and wherein the spectrum comprises a time-resolved response of fluorescence and/or phosphorescence lifetimes of the catalyst slurry mixture.

[0147] Statement 6. The method of any of statements 1 -5 further comprising one or more of subtracting background contribution from the corrected spectrum, subtracting scattering contribution from the corrected spectrum, or normalizing the corrected spectrum, to form a modified corrected spectrum wherein the modified corrected spectrum is used in the spectral deconvolution.

[0148] Statement 7. The method of any of statements 1-6 wherein the slurry catalyst mixture comprises a contact product of a first catalyst, a second catalyst, a support, an activator, and the carrier fluid, wherein the support comprises silica, wherein the activator comprises an aluminoxane, wherein the carrier fluid comprises mineral oil or mixture of mineral oils, and wherein the activator activates at least a portion of the first catalyst to produce the first activated catalyst and wherein the activator activates at least a portion of the second catalyst to produce the second activated catalyst. [0149] Statement 8. The method of statement 7 wherein the first catalyst comprises a bridged bis-cyclopentadienyl hafnocene, and wherein the second catalyst comprises an unbridged indenyl- cyclopentadienyl zirconocene.

[0150] Statement 9. The method of any of statements 1-8 wherein the inner filter effects model reconstructs the true emission spectrum from the as-measured emission spectrum by accounting for primary and secondary inner filter effects.

[0151] Statement 10. The method of statement 9, wherein the inner filter effects model ’s output is an emission spectrum expressed as a function of either normalized or raw emission intensity against emission wavelengths.

[0152] Statement 11. The method of statement 10, wherein the inner filter effects model has the form of: E₀ ems ) is true emission spectrum profile, F(Xems) is detected wavelength dependent emission spectrum, n is number of layers, Io is initial intensity of excitation light, Ae is the total absorbance at excitation wavelength, A (Terns) is wavelength dependency of absorption, where n is equal or greater than 2.

[0153] Statement 12. The method of any of statements 1-11 wherein the sample chamber is a component of an optical probe, the optical probe comprising: light source; a UV-vis detector; a fluorescence detector; the sample chamber, wherein the sample chamber comprises an optical path, a first collimating lens positioned at a first end of the sample chamber and a second collimating lens positioned at a second end of the sample chamber such that the first collimating lens and the second collimating lens are in the optical path; an excitation arm configured to transport light from the light source through the first collimating lens to the optical path; an emission arm configured to transport emission light from the optical path through the first collimating lens to the fluorescence detector; and an optical cable configured to transport light from the optical path though the second collimating lens to the UV-vis detector.

[0154] Statement 13. A method comprising: contacting a base catalyst mixture and a trim catalyst solution to form a contact product comprising a post-trim multi-component catalyst, wherein the base catalyst mixture comprises a first catalyst, a second catalyst, a support, an activator, and a carrier, wherein the trim catalyst solution comprises additional second catalyst, and a solvent, and wherein the post-trim multi-component catalyst comprises a first active catalyst corresponding to the first catalyst and a second active catalyst corresponding to the second catalyst; generating a spectrum of the post-trim multi-component catalyst; correcting the spectrum of the post-trim multi-component catalyst using an inner filter effects model to form a corrected spectrum the post-trim multi-component catalyst; determining a calculated ratio of an amount of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst from the corrected spectrum the post-trim multi-component catalyst by fitting the spectrum of the post-trim multi-component catalyst to a single component spectrum of the first active catalyst and a single component spectrum of the second active catalyst using spectral deconvolution; comparing the calculated ratio to a target ratio of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst and adjusting a flow rate of the trim catalyst solution such that the calculated ratio of amount of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst is closer to the target ratio; introducing the posttrim multi-component catalyst and one or more olefins into a polymerization reactor; and polymerizing the one or more olefins in the presence of the post-trim multi-component catalyst to produce a polymer product.

[0155] Statement 14. The method of statement 13 wherein the support comprises silica, wherein the activator comprises an aluminoxane, and wherein the first catalyst and the second catalyst each comprise a metallocene catalyst.

[0156] Statement 15. The method of any of statements 13-14 wherein the spectrum comprises a UV-Vis spectrum, and wherein generating the spectrum comprises illuminating the post-trim multi-component catalyst with a light source which outputs light from 200 - 900 nm.

[0157] Statement 16. The method of any of statements 13-15 wherein the spectrum comprises an emission spectrum, and wherein generating the spectrum comprises illuminating the post-trim multi-component catalyst with a laser.

[0158] Statement 17. The method of any of statements 13-16 wherein the laser comprises a pulsed laser light source or intensity modulated laser light source, and wherein the spectral deconvolution comprises calculating a time-resolved response and/or a time-gated response of fluorescence and/or phosphorescence lifetimes of the post-trim multi-component catalyst.

[0159] Statement 18. The method of statement 17 wherein the calculated ratio of the amount of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst is determined from the time-resolved and/or the time-gated response of the post-trim multicomponent catalyst by fitting emission spectrum lifetimes and/or time-resolved spectra of the post-trim multi-component catalyst to a single component spectrum response of the first active catalyst and a single component spectrum response of the second active catalyst.

[0160] Statement 19. The method of any of statements 13-18 wherein the first catalyst comprises a bridged bis-cyclopentadienyl hafnocene, and wherein the second catalyst comprises an unbridged indenyl-cyclopentadienyl zirconocene. [0161] Statement 20. The method of any of statements 13-19 further comprising one or more of subtracting background contribution from the spectrum, subtracting scattering contribution from the spectrum, or normalizing the spectrum, to form a modified spectrum wherein the modified spectrum is used in the spectral deconvolution.

[0162] Statement 21. The method of any of statements 13-120 wherein the contacting the base catalyst mixture and the trim catalyst solution occurs in a process feedline downstream from a tie- in point of the base catalyst mixture and the trim catalyst solution, to produce the post-trim multicomponent catalyst on a continuous basis, and wherein the spectrum of the post-trim multicomponent catalyst is generated from the continuously flowing post-trim multi-component catalyst.

[0163] Statement 22. The method of any of statements 13-21 wherein the contacting the base catalyst mixture and the trim catalyst solution takes place in a mixer fluidi cally coupled to a trim pot comprising the trim catalyst solution and a base catalyst mixture pot comprising the base catalyst mixture, and wherein the mixer is configured to mix the base catalyst mixture and the trim catalyst solution to produce the post-trim multi-component catalyst.

[0164] Statement 23. The method of any of statements 13-22 wherein the inner filter effects model has the form of: E_o ( ems ) ems ) is true emission spectrum profile, F(Xems) is detected wavelength dependent emission spectrum, n is number of layers, lo is initial intensity of excitation light. Ae is the total absorbance at excitation wavelength, A (Terns) is wavelength dependency of absorption, where n is equal or greater than 2.

[0165] Statement 24. A system comprising: an optical probe comprising: a light source; a UV- vis detector; a fluorescence detector; a sample chamber comprising an optical path, a first collimating lens positioned at a first end of the sample chamber and a second collimating lens positioned at a second end of the sample chamber such that the first collimating lens and the second collimating lens are in the optical path; an excitation arm configured to transport light from the light source through the first collimating lens to the optical path; an emission arm configured to transport emission light from the optical path through the first collimating lens to the fluorescence detector; and an optical cable configured to transport light from the optical path though the second collimating lens to the UV-vis detector; wherein the sample chamber is configured to hold a post-trim multi-component catalyst mixture, and wherein the optical probe is configured to illuminate the post-trim multi-component catalyst mixture in the sample chamber and generate a spectrum of the post-trim multi-component catalyst mixture; and a control system configured to: receive the spectrum of the post-trim multi-component catalyst mixture; correct the spectrum of the post-trim multi-component catalyst mixture using an inner filter effects model to form a corrected spectrum of the post-trim multi-component catalyst mixture determine a calculated ratio of an amount of the first activated catalyst and the second activated catalyst in the post-trim multi-component catalyst mixture from the corrected spectrum of the post-trim multicomponent catalyst mixture by fitting the spectrum of the post-trim multi-component catalyst mixture to a single component spectrum of the first activated catalyst and a single component spectrum of the second activated catalyst using spectral deconvolution; compare the calculated ratio of the amount of the first activated catalyst and the second activated catalyst in the multimodal catalyst to a set point ratio of the amount of the first activated catalyst and the second activated catalyst in the multimodal catalyst: and adjust a flow rate of a trim catalyst solution such that the calculated ratio of amount of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst is closer to the set point ratio.

[0166] Statement 25. The system of statement 24 wherein the control system is further configured to perform one or more of subtracting background contribution from the spectrum, subtracting scattering contribution from the spectrum, or normalizing the spectrum, to form a modified spectrum wherein the modified is used in the spectral deconvolution.

[0167] Statement 26. The system of any of statements 24-25 wherein the inner filter effects model has the form of: E₀ Aems ~) = j_s true emission spectrum profile, F(Xems) is detected wavelength dependent emission spectrum, n is number of layers, Io is initial intensity' of excitation light, Ae is the total absorbance at excitation wavelength, and Af (Terns) is wavelength dependency of absorption.

[0168] Statement 27. The system of any of statements 24-26 wherein the post-trim multicomponent catalyst mixture comprises a first activated catalyst and a second activated catalyst, wherein the post-trim multi-component catalyst mixture is produced by contacting a base catalyst mixture and a trim catalyst solution to form a contact product comprising a post-trim multicomponent catalyst, wherein the base catalyst mixture comprises a first catalyst, a second catalyst, a support, an activator, and a carrier, wherein the trim catalyst solution comprises additional second catalyst, and a solvent, and wherein the post-trim multi-component catalyst comprises a first active catalyst corresponding to the first catalyst and a second active catalyst corresponding to the second catalyst. To facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are given. In no way should the following examples be read to limit, or define, the entire scope of the disclosure. EXAMPLE 1

[0169] In this example, an optical probe as described above was characterized. The experimental setup was optic probe as described in FIG. 3 A and used the sample chamber configuration of FIG. 3C which included a light source, bifurcated optical fiber, sample chamber with two collimating lenses, an optical fiber, a UV-vis detector, a removable long-pass filter, and a fluorescence detector. The sample chamber had a distance between the collimating lenses of 1 mm.

[0170] The diameter of both arms of the bifurcated optical fiber was 0.6 mm. and the two arms were separated by 0.34 mm. The light source for the UV-vis measurement was an ocean optic portable lamp supplying light in the 450 nm - 900 nm range. The detector used for the UV-vis measurement was an ocean optic detector.

[0171] The light source for the fluorescence emission measurement was an ISS Xenon lamp supplying sufficient and stable intensity for the excitation light. The detector for the emission measurement was an ocean optic detector. Depending on the wavelength of the excitation light, an appropriate long-pass filter was placed in front of the detector to reject scattered excitation light. The focal distance of the collimating light was estimated to be 5 - 7 mm. Since the fiber diameter is much smaller than the focal distance of the collimating lens (i.e., 0.6 vs 10+ mm), the displacement between the excitation arm and the emission arm in the bifurcated optical fiber can be approximated as 0 for the simplicity⁷ of calculation.

[0172] A series of UV-vis tests were performed on supported multi-component catalyst slurries with the described experimental setup. It was observed that for samples with absorbance up to 1.5, the UV-vis spectra obtained from the optical probe is shown to be equivalent to the UV-vis spectra obtained on a commercial spectrometer with the same sample at the same sample thickness. For samples with absorbance above 1.5, the intensity of the transmitted light w as observed to be too low for the ocean optic detector, causing non-linear response likely due to insufficient sensitivity⁷ of the Ocean Optic detector.

EXAMPLE 2

[0173] As discussed above with regards to FIG. 5, emission measurement using the bifurcated fiber and a collimating lens should result in the observed emission intensity staying constant up to the distance equal to the lens’ focal distance f. then slowly decrease as the distance between the emitting point and the lens increases. To experimentally verily the distance of constant emission, the experimental setup included a 100-pm thick PVA film doped yvith Rhodamine 6G (R6G) as a source of fluorophores. The PVA film was placed in a petri dish underneath the fiber optic head mounted on a precise positioner capable of moving up and down to position the fiber optic head at arbitrary positions above the PVA film. The fiber optic head includes a collimated lens at the end which provides a point for excitation light to exit the excitation arm and illuminate the PVA film and a point for the emission arm to collect emitted light. The Experimental setup is illustrated in FIG. 6 where PVA film 600 is positioned below movable fiber optic head 602 capable of being precisely moved height “X” above PVA film. Laser light source 604 provides excitation energy to PVA film 600 via bifurcated optical cable 606 which returns the emitted light from fluorophores in PVA film 600 to fluorescence detector 610 through long-pass filter 608. FIG. 7 is a graph the experimentally detected emission intensity as a function of the distance X from the collimating lens. It was observed that the emission intensity stays relatively constant for up to 10 mm distance from the lens the experimentally detected emission intensity as a function of the distance x from the collimating lens. Effectively, for a distance of over 10 mm the signal does not depend on the separation. Within this distance an increase in distance is compensated by the increase in lens surface area utilized for collection that effectively focuses the light into the fiber. Since the lens is mounted in a metal cast, the zero distance (contact point) is about 2 mm from the lens, making the effective distance for a constant signal for over 12 mm. After the next 50 turns or 25 mm, the signal decreased 50%. This indicates that the signal drop does not obey a quadratic dependence and the drop due to the distance increase is partially compensated by the increase of the apparent utilized surface of the lens which is the surface of the lens that can effectively focus light into the fiber tip.

EXAMPLE 3

[0174] In this example, the inner filter effect model derived above was used to predict spectral shifts in simulated Rhodamine B solutions. A series of Rhodamine B solutions in ethanol with varying optical density was utilized for the simulation. Rhodamine B was selected for this simulation because its absorption and emission spectra overlap significantly, rendering the emission measurement highly susceptible to spectral distortion by the inner filter effect in high optical density samples. FIG. 8A is a normalized absorption (dotted line) and true emission (solid line) spectra of Rhodamine B in the absence of inner filter effects in ethanol. It can be observed that the absorption and emission are significantly overlapping.

[0175] Five Rhodamine B solutions a-e were utilized in the simulation with each having a different concentration of Rhodamine B such that each solution had a differing optical density. The concentration of Rhodamine B was increased from a baseline concentration in solution a to solution e which had 40 times the baseline concentration. The inner filter effect model above was utilized with the 5 Rhodamine B solutions with a path length set at 10 mm. [0176] FIG. 8B is a spectrogram result of the spectral absorption of each of the solutions a-e. Optical density- comparison of solutions a - e shows that the absorbance is proportional to the concentration of Rhodamine B in solution.

[0177] The inner filter effect model was again utilized with the 5 Rhodamine B solutions and the path length was adjusted to 20 mm for simulation. FIG. 8C is a spectrogram of the model output normalized mission intensity of the 5 Rhodamine B solutions when using an excitation wavelength of 490 nm and 20 mm path length. As shown in FIG. 8C, the model predicted that the peak emission redshifts about 13 nm as the optical density of the sample increased from sample a to sample e.

[0178] The inner filter effect model was again utilized with a path length set to 1 mm for simulation. FIG. 8D is a spectrogram of the model output normalized mission intensity of the 5 Rhodamine B solutions when using an excitation wavelength of 490 nm and 1 mm path length. As shown in FIG. 8C, the model predicted negligible emission peak redshifts as the optical density of the sample increased from sample a to sample e.

EXAMPLE 4

[0179] In this example, the inner filter effect model was used to correct the as-measured emission spectra of a series of Rhodamine B solutions with varying optical density. The inner filter effect model was used to calculate the true emission spectra without the inner filter effects based on the as-measured emission spectra and its corresponding UV-vis absorption spectra. Three Rhodamine B in ethanol solutions f, g. and h were prepared with low, medium, and high concentration of Rhodamine B. FIG. 9A is a spectrogram of the results of the UV-vis absorption test for each sample. It was observed that in the 1 mm path-length cuvette, the maximum absorbance of the three solutions were 0.06 (low in concentration and optical density). 1.4 (medium in concentration and optical density), and 3. 1 (high in concentration and optical density) respectively.

[0180] The three solutions were subjected to fluorescence spectroscopy using a 490 nm excitation light. FIG. 9B is a spectrogram of the as-measured emission spectra for each solution. FIG. 9C is a normalized spectrogram of the as-measured emission spectra for each solution. FIG. 9C also includes the expected spectrum for Rhodamine B without inner filter effects. The inner filter effects are evident from the red shifting in the measured emission spectra for the medium and high concentration solutions.

[0181] The inner filter effect model was applied to the as-measured emission spectra in FIG. 9B. Then the corrected emission spectra were normalized so that the maximum intensity equals 1, resulting in the normalized and corrected spectrogram in FIG. 9D. After the correction for inner filter effects, the spectrum for the medium concentration sample is nearly identical to the true spectrum. For the high concentration sample, a small deviation from the true spectrum was observed. This deviation is subtle, but consistently present for higher concentration samples and as such is attributable to the nonlinear responses of ocean optic detectors in measurements of high optical density samples.

[0182] While the disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the disclosure as disclosed herein. Although individual embodiments are discussed, the present disclosure covers all combinations of all those embodiments.

[0183] While compositions, methods, and processes are described herein in terms of “comprising,’’ “containing,” “having,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. The phrases, unless otherwise specified, “consists essentially of’ and “consisting essentially of’ do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[0184] All numerical values within the detailed description are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[0185] Many alterations, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description without departing from the spirit or scope of the present disclosure and that when numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.

Claims

CLAIMS;

1. A method comprising: introducing a slurry catalyst mixture into a sample chamber, where the slurry catalyst mixture comprises a multi-component catalyst and a carrier fluid, wherein the multi-component catalyst comprises a first activated catalyst and a second activated catalyst; illuminating the slurry catalyst mixture in the sample chamber; capturing a spectrum of the slurry catalyst mixture, wherein the spectrum comprises at least one spectrum selected from the group consisting of UV-Vis spectrum, emission spectrum, and combinations thereof; correcting the spectrum using an inner filter effects model to form a corrected spectrum of the slurry catalyst mixture; and determining a calculated ratio of an amount of the first activated catalyst and an amount of the second activated catalyst in the multi-component catalyst from the corrected spectrum of the si urn ■ catalyst mixture by fitting the spectrum of the slurry catalyst mixture to a single component spectrum of the first activated catalyst and a single component spectrum of the second activated catalyst, using spectral deconvolution.

2. The method of claim 1, wherein the slurry⁷ catalyst mixture further comprises a third activated catalyst and/or a fourth activated catalyst, and wherein the method further comprises fitting the corrected spectrum of the slurry catalyst mixture to a single component spectrum of the third activated catalyst and/or a single component spectrum of the fourth activated catalyst, using spectral deconvolution.

3. The method of any of claims 1-2 wherein the slurry catalyst mixture is illuminated with a light source that outputs light from 200 - 900 nm, and wherein spectrum is the UV-Vis spectrum.

4. The method of any of claims 1 -3 wherein the slurry⁷ catalyst mixture is illuminated with a light source comprising a laser, and wherein the spectrum is the emission spectrum.

5. The method of any of claims 1-4 wherein the slurry catalyst mixture is illuminated with a light source comprising a pulsed light source or intensity⁷ modulated light source, and wherein the spectrum comprises a time-resolved response of fluorescence and/or phosphorescence lifetimes of the catalyst slurry mixture.

6. The method of any of claims 1-5 further comprising one or more of subtracting background contribution from the corrected spectrum, subtracting scattering contribution from the corrected spectrum, or normalizing the corrected spectrum, to form a modified corrected spectrum wherein the modified corrected spectrum is used in the spectral deconvolution.

7. The method of any of claims 1-6 wherein the slurry catalyst mixture comprises a contact product of a first catalyst, a second catalyst, a support, an activator, and the carrier fluid, wherein the support comprises silica, wherein the activator comprises an aluminoxane, wherein the carrier fluid comprises mineral oil or mixture of mineral oils, and wherein the activator activates at least a portion of the first catalyst to produce the first activated catalyst and wherein the activator activates at least a portion of the second catalyst to produce the second activated catalyst.

8. The method of claim 7 wherein the first catalyst comprises a bridged bis-cyclopentadienyl hafnocene, and wherein the second catalyst comprises an unbridged indenyl-cyclopentadienyl zirconocene.

9. The method of any of claims 1-8 wherein the inner filter effects model reconstructs the true emission spectrum from the as-measured emission spectrum by accounting for primary and secondary inner filter effects.

10. The method of claim 9, wherein the inner filter effects model's output is an emission spectrum expressed as a function of either normalized or raw emission intensity against emission wavelengths.

11. The method of claim 10, wherein the inner filter effects model has the form of: where Eo(Xems) is true emission spectrum profile, F(Xems) is detected wavelength dependent emission spectrum, n is number of layers, Io is initial intensity of excitation light. Ae is the total absorbance at excitation wavelength, Af Aems) is wavelength dependency of absorption, where n is equal or greater than 2.

12. The method of any of claims 1-11 wherein the sample chamber is a component of an optical probe, the optical probe comprising: a light source; a UV-vis detector; a fluorescence detector; the sample chamber, wherein the sample chamber comprises an optical path, a first collimating lens positioned at a first end of the sample chamber and a second collimating lens positioned at a second end of the sample chamber such that the first collimating lens and the second collimating lens are in the optical path; an excitation arm configured to transport light from the light source through the first collimating lens to the optical path; an emission arm configured to transport emission light from the optical path through the first collimating lens to the fluorescence detector; and an optical cable configured to transport light from the optical path though the second collimating lens to the UV-vis detector.

13. A method comprising: contacting a base catalyst mixture and a trim catalyst solution to form a contact product comprising a post-trim multi-component catalyst, wherein the base catalyst mixture comprises a first catalyst, a second catalyst, a support, an activator, and a carrier, wherein the trim catalyst solution comprises additional second catalyst, and a solvent, and wherein the post-trim multicomponent catalyst comprises a first active catalyst corresponding to the first catalyst and a second active catalyst corresponding to the second catalyst; generating a spectrum of the post-trim multi-component catalyst; correcting the spectrum of the post-trim multi-component catalyst using an inner filter effects model to form a corrected spectrum the post-trim multi-component catalyst; determining a calculated ratio of an amount of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst from the corrected spectrum the post-trim multi-component catalyst by fitting the spectrum of the post-trim multi-component catalyst to a single component spectrum of the first active catalyst and a single component spectrum of the second active catalyst using spectral deconvolution; comparing the calculated ratio to a target ratio of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst and adjusting a flow rate of the trim catalyst solution such that the calculated ratio of amount of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst is closer to the target ratio; introducing the post-trim multi-component catalyst and one or more olefins into a polymerization reactor; and polymerizing the one or more olefins in the presence of the post-trim multi-component catalyst to produce a polymer product.

14. The method of claim 13 wherein the support comprises silica, wherein the activator comprises an aluminoxane, and wherein the first catalyst and the second catalyst each comprise a metallocene catalyst.

15. The method of any of claims 13-14 wherein the spectrum comprises a UV-Vis spectrum, and wherein generating the spectrum comprises illuminating the post-trim multi-component catalyst with a light source which outputs light from 200 - 900 nm.

16. The method of any of claims 13-15 wherein the spectrum comprises an emission spectrum, and wherein generating the spectrum comprises illuminating the post-trim multi-component catalyst with a laser.

17. The method of any of claims 13-16 wherein the laser comprises a pulsed laser light source or intensity modulated laser light source, and wherein the spectral deconvolution comprises calculating a time-resolved response and/or a time-gated response of fluorescence and/or phosphorescence lifetimes of the post-trim multi-component catalyst.

18. The method of claim 17 wherein the calculated ratio of the amount of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst is determined from the time-resolved and/or the time-gated response of the post-trim multi-component catalyst by fitting emission spectrum lifetimes and/or time-resolved spectra of the post-trim multi-component catalyst to a single component spectrum response of the first active catalyst and a single component spectrum response of the second active catalyst.

19. The method of any of claims 13-18 wherein the first catalyst comprises a bridged bis- cyclopentadienyl hafnocene, and wherein the second catalyst comprises an unbridged indenyl- cyclopentadienyl zirconocene.

20. The method of any of claims 13-19 further comprising one or more of subtracting background contribution from the spectrum, subtracting scattering contribution from the spectrum, or normalizing the spectrum, to form a modified spectrum wherein the modified spectrum is used in the spectral deconvolution.

21. The method of any of claims 13-20 wherein the contacting the base catalyst mixture and the trim catalyst solution occurs in a process feedline downstream from a tie-in point of the base catalyst mixture and the trim catalyst solution, to produce the post-trim multi-component catalyst on a continuous basis, and wherein the spectrum of the post-trim multi-component catalyst is generated from the continuously flowing post-trim multi-component catalyst.

22. The method of any of claims 13-21 wherein the contacting the base catalyst mixture and the trim catalyst solution takes place in a mixer fluidically coupled to a trim pot comprising the trim catalyst solution and a base catalyst mixture pot comprising the base catalyst mixture, and wherein the mixer is configured to mix the base catalyst mixture and the trim catalyst solution to produce the post-trim multi-component catalyst.

23. The method of any of claims 13-22 wherein the inner filter effects model has the form of:

F (Terns)

E_o (Terns where Eo(Xems) is true emission spectrum profile, F(X_ems) is detected wavelength dependent emission spectrum, n is number of layers, Io is initial intensity of excitation light, Ae is the total absorbance at excitation wavelength, A (Terns) is wavelength dependency of absorption, where n is equal or greater than 2.

24. A system comprising: an optical probe comprising: a light source; a UV-vis detector; a fluorescence detector; a sample chamber comprising an optical path, a first collimating lens positioned at a first end of the sample chamber and a second collimating lens positioned at a second end of the sample chamber such that the first collimating lens and the second collimating lens are in the optical path; an excitation arm configured to transport light from the light source through the first collimating lens to the optical path; an emission arm configured to transport emission light from the optical path through the first collimating lens to the fluorescence detector; and an optical cable configured to transport light from the optical path though the second collimating lens to the UV-vis detector; wherein the sample chamber is configured to hold a post-trim multi-component catalyst mixture, and wherein the optical probe is configured to illuminate the post-trim multi-component catalyst mixture in the sample chamber and generate a spectrum of the post-trim multi-component catalyst mixture; and a control system configured to: receive the spectrum of the post-trim multi-component catalyst mixture; correct the spectrum of the post-trim multi-component catalyst mixture using an inner filter effects model to form a corrected spectrum of the post-trim multi-component catalyst mixture determine a calculated ratio of an amount of the first activated catalyst and the second activated catalyst in the post-trim multi-component catalyst mixture from the corrected spectrum of the post-trim multi-component catalyst mixture by fitting the spectrum of the posttrim multi-component catalyst mixture to a single component spectrum of the first activated catalyst and a single component spectrum of the second activated catalyst using spectral deconvolution; compare the calculated ratio of the amount of the first activated catalyst and the second activated catalyst in the multimodal catalyst to a set point ratio of the amount of the first activated catalyst and the second activated catalyst in the multimodal catalyst; and adjust a flow rate of a trim catalyst solution such that the calculated ratio of amount of the first active catalyst and the second active catalyst in the post-trim multi-component catalyst is closer to the set point ratio.

25. The system of claim 24 wherein the control system is further configured to perform one or more of subtracting background contribution from the spectrum, subtracting scattering contribution from the spectrum, or normalizing the spectrum, to form a modified spectrum wherein the modified is used in the spectral deconvolution.

26. The system of any of claims 24-25 wherein the inner filter effects model has the form of: where Eo(Xems) is true emission spectrum profile, F(Xems) is detected wavelength dependent emission spectrum, n is number of layers, Io is initial intensity of excitation light. Ae is the total absorbance at excitation wavelength, and A (hems) is wavelength dependency of absorption.

27. The system of any of claims 24-26 wherein the post-trim multi-component catalyst mixture comprises a first activated catalyst and a second activated catalyst, wherein the post-trim multicomponent catalyst mixture is produced by contacting a base catalyst mixture and a trim catalyst solution to form a contact product comprising a post-trim multi-component catalyst, wherein the base catalyst mixture comprises a first catalyst, a second catalyst, a support, an activator, and a carrier, wherein the trim catalyst solution comprises additional second catalyst, and a solvent, and wherein the post-trim multi-component catalyst comprises a first active catalyst corresponding to the first catalyst and a second active catalyst corresponding to the second catalyst.