17 research outputs found
Visualizing the Structure, Composition and Activity of Single Catalyst Particles for Olefin Polymerization and Polyolefin Decomposition
The structural and morphological characterization of individual catalyst particles for olefin polymerization, as well as for the reverse process of polyolefin decomposition, can provide an improved understanding for how these catalyst materials operate under relevant reaction conditions. In this review, we discuss an emerging analytical toolbox of 2D and 3D chemical imaging techniques that is suitable for investigating the chemistry and reactivity of related catalyst systems. While synchrotron-based X-ray microscopy still provides unparalleled spatial resolutions in 2D and 3D, a number of laboratory-based techniques, most notably focused ion beam-scanning electron microscopy, confocal fluorescence microscopy, infrared photoinduced force microscopy and laboratory-based X-ray nano-computed tomography, have helped to significantly expand the arsenal of analytical tools available to scientists in heterogeneous catalysis and polymer science. In terms of future research, the review outlines the role and impact of in situ and operando (spectro−)microscopy experiments, involving sophisticated reactors as well as online reactant and product analysis, to obtain real-time information on the formation, decomposition, and mobility of polymer phases within single catalyst particles. Furthermore, the potential of fluorescence microscopy, X-ray microscopy and optical microscopy is highlighted for the high-throughput characterization of olefin polymerization and polyolefin decomposition catalysts. By combining these chemical imaging techniques with, for example, chemical staining methodologies, selective probe molecules as well as particle sorting approaches, representative structure–activity relationships can be derived at the level of single catalyst particles
Transport Limitations in Polyolefin Cracking at the Single Catalyst Particle Level
Catalytic cracking is a promising approach to chemically recycle polyolefins by converting them into smaller hydrocarbons like naphtha, and important precursors of various platform chemicals, such as aromatics. Cracking catalysts, commonly used in the modern refinery and petrochemical industry, are tailored to process gaseous or liquid feedstock. Polyolefins, however, are very large macromolecules that form highly viscous melts at the temperatures required to break their backbone C-C bonds. Therefore, mass transport is expected to limit the performance of traditional cracking catalysts when applied to the conversion of polymers. In this work, we study these effects during the cracking of polypropylene (PP) over catalysts utilized in the fluid catalytic cracking (FCC) process. Thermogravimetric experiments using PP of varying molecular weight (Mw) and catalysts of varying accessibility showed that low Mw model polymers can be cracked below 275 °C, while PP of higher Mw required a 150 °C higher temperature. We propose that this difference is linked to different degrees of mass transport limitations and investigated this at length scales ranging from milli- to nanometers, utilizing in situ optical microscopy and electron microscopy to inspect cut open catalyst-polymer composites. We identified the main cause of transport limitations as the significantly higher melt viscosity of high Mw polymers, which prohibits efficient catalyst-polymer contact. Additionally, the high Mw polymer does not enter the inner pore system of the catalyst particles, severely limiting utilization of the active sites located there. Our results demonstrate that utilizing low Mw polymers can lead to a significant overestimation of catalyst activity, and suggest that polyolefins might need to undergo a viscosity reducing pre-treatment in order to be cracked efficiently
Advancing the Compositional Analysis of Olefin Polymerization Catalysts with High-Throughput Fluorescence Microscopy
To optimize the performance of supported olefin polymerization catalysts, novel methodologies are required to evaluate the composition, structure, and morphology of both pristine and prepolymerized samples in a resource-efficient, high-throughput manner. Here, we report on a unique combination of laboratory-based confocal fluorescence microscopy and advanced image processing that allowed us to quantitatively assess support fragmentation in a large number of autofluorescent metallocene-based catalyst particles. Using this approach, significant inter- and intraparticle heterogeneities were detected and quantified in a representative number of prepolymerized catalyst particles (2D: ≥135, 3D: 40). The heterogeneity that was observed over several stages of slurry-phase ethylene polymerization (10 bar) is primarily attributed to the catalyst particles' diverse support structures and to the inhomogeneities in the metallocene distribution. From a mechanistic point of view, the 2D and 3D analyses revealed extensive contributions from a layer-by-layer fragmentation mechanism in synergy with a less pronounced sectioning mechanism. A significant number of catalyst particles were also found to display limited support fragmentation at the onset of the reaction (i.e., at lower polymer yields). This delay in activity or "dormancy" is believed to contribute to a broadening of the particle size distribution during the early stages of polymerization. 2D and 3D catalyst screening via confocal fluorescence microscopy represents an accessible and fast approach to characterize the structure of heterogeneous catalysts and assess the distribution of their fluorescent components and reaction products. The automation of both image segmentation and postprocessing with machine learning can yield a powerful diagnostic tool for future research as well as quality control on industrial catalysts
Fluorescent-Probe Characterization for Pore-Space Mapping with Single-Particle Tracking
Porous solids often contain complex pore networks with pores of various sizes. Tracking individual fluorescent probes as they diffuse through porous materials can be used to characterize pore networks at tens of nanometers resolution. However, understanding the motion behavior of fluorescent probes in confinement is crucial to reliably derive pore network properties. Here, we introduce well-defined lithography-made model pores developed to study probe behavior in confinement. We investigated the influence of probe-host interactions on diffusion and trapping of confined single-emitter quantum-dot probes. Using the pH-responsiveness of the probes, we were able to largely suppress trapping at the pore walls. This enabled us to define experimental conditions for mapping of the accessible pore space of a one-dimensional pore array as well as a real-life polymerization-catalyst-support particle
Elucidating the Sectioning Fragmentation Mechanism in Silica-Supported Olefin Polymerization Catalysts with Laboratory-Based X-Ray and Electron Microscopy
Strict morphological control over growing polymer particles is an indispensable requirement in many catalytic olefin polymerization processes. In catalysts with mechanically stronger supports, e. g., polymerization-grade silicas, the emergence of extensive cracks via the sectioning fragmentation mechanism requires severe stress build-up in the polymerizing catalyst particle. Here, we report on three factors that influence the degree of sectioning in silica-supported olefin polymerization catalysts. Laboratory-based X-ray nano-computed tomography (nanoCT) and focused ion beam-scanning electron microscopy (FIB-SEM) were employed to study catalyst particle morphology and crack propagation in two showcase catalyst systems, i.e., a zirconocene-based catalyst (i.e., Zr/MAO/SiO2, with Zr=2,2’-biphenylene-bis-2-indenyl zirconium dichloride and MAO=methylaluminoxane) and a Ziegler-Natta catalyst (i.e., TiCl4/MgCl2/SiO2), during slurry-phase ethylene polymerization. The absence of extensive macropores in some of the catalysts’ larger constituent silica granulates, a sufficient accessibility of the catalyst particle interior at reaction onset, and a high initial polymerization rate were found to favor the occurrence of the sectioning pathway at different length scales. While sectioning is beneficial for reducing diffusion limitations, its appearance in mechanically stronger catalyst supports can indicate a suboptimal support structure or unfavourable reaction conditions
Correlating the Morphological Evolution of Individual Catalyst Particles to the Kinetic Behavior of Metallocene-Based Ethylene Polymerization Catalysts
Kinetics-based differences in the early stage fragmentation of two structurally analogous silica-supported hafnocene- and zirconocene-based catalysts were observed during gas-phase ethylene polymerization at low pressures. A combination of focused ion beam-scanning electron microscopy (FIB-SEM) and nanoscale infrared photoinduced force microscopy (IR PiFM) revealed notable differences in the distribution of the support, polymer, and composite phases between the two catalyst materials. By means of time-resolved probe molecule infrared spectroscopy, correlations between this divergence in morphology and the kinetic behavior of the catalysts' active sites were established. The rate of polymer formation, a property that is inherently related to a catalyst's kinetics and the applied reaction conditions, ultimately governs mass transfer and thus the degree of homogeneity achieved during support fragmentation. In the absence of strong mass transfer limitations, a layer-by-layer mechanism dominates at the level of the individual catalyst support domains under the given experimental conditions
Fluorescent-Probe Characterization for Pore-Space Mapping with Single-Particle Tracking
Porous solids often contain complex pore networks with pores of various sizes. Tracking individual fluorescent probes as they diffuse through porous materials can be used to characterize pore networks at tens of nanometers resolution. However, understanding the motion behavior of fluorescent probes in confinement is crucial to reliably derive pore network properties. Here, we introduce well-defined lithography-made model pores developed to study probe behavior in confinement. We investigated the influence of probe-host interactions on diffusion and trapping of confined single-emitter quantum-dot probes. Using the pH-responsiveness of the probes, we were able to largely suppress trapping at the pore walls. This enabled us to define experimental conditions for mapping of the accessible pore space of a one-dimensional pore array as well as a real-life polymerization-catalyst-support particle
Silica-magnesium-titanium Ziegler–Natta catalysts. Part II. Properties of the active sites and fragmentation behaviour
In this work, which follows Part I that is dedicated to the precatalyst, we investigate the electronic properties and the accessibility of the Ti active sites in a highly active silica-supported Ziegler–Natta catalyst for industrial polyethylene production, applying a multi-scale, multi-technique approach. Complementary electronic spectroscopies (i.e. Ti K-edge XANES, Ti L2,3-edge NEXAFS and DR UV–Vis-NIR) reveal the coexistence of several titanium phases, whose relative amount depends on the concentration of the alkyl aluminum activator. In addition to β-TiCl3-like clusters and monomeric Ti(IV) sites, which are already present in the precatalyst, isolated Ti(III) sites and α-TiCl3-like clusters are formed in the presence of the activator. Two families of alkylated Ti(III) sites characterized by a different electron density are detected by IR spectroscopy of adsorbed CO, and two types of Ti-acyl species are formed upon CO insertion into the Ti-alkyl bond, characterized by a different extent of η2-coordination. The whole set of data suggests that TiCl3 clusters are preferentially formed at the exterior of the catalyst particles, likely as a consequence of Ti(III) mobility in the presence of strong Lewis acids, in most cases hampering the spectroscopic detection of isolated Ti(III) sites. In contrast, only monomeric Ti(III) sites are formed at the interior of the catalyst particles, characterized by a high electron density evocative of the presence of electron donors in the close proximity (e.g. aluminum alkoxide by-products). These sites are less accessible because of diffusion limitations, and only become visible by surface-sensitive spectroscopic methods (such as Ti L2,3-edge TEY-NEXAFS) upon the fragmentation of the catalyst particles
Regulating thermosalient behaviour in three polymorphs
10.1107/S2052252517005577IUCrJ4202-20
X-ray nanotomography uncovers morphological heterogeneity in a polymerization catalyst at multiple reaction stages
During olefin polymerization on supported catalysts, the controlledmorphological evolution of the catalyst particle is vital for ensuringoptimal product properties and high catalyst activity. We employednon-destructive hard X-ray holotomography to quantitatively assessthe 3D morphology of multiple silica-supported hafnocene-basedcatalyst particles during the early stages of gas-phase ethylene polymerization.Image processing and pore network modeling revealedclear variations in the dimensions and interconnectivity of pristineparticles’ macropore networks. This, together with apparent differencesin the fragmentation behavior of pre-polymerized particles,suggests that the reactivity and morphological evolution of individualparticles are largely dictated by their unique support and porespace architectures. By minimizing the structural heterogeneityamong pristine catalyst particles, more uniform particle morphologiesmay be obtained. Significant polymerization activity,observed in the particles’ interiors, further implies that appropriatepolymerization conditions and catalyst kinetics can guarantee sufficientlyhigh particle accessibilities and thus more homogeneoussupport fragmentation