Depositing catalytically active particles onto flat, thin and oxidic support forms an attractive way to make supported catalyst suitable for surface science characterization. Here we show how this approach has been applied to the Phillips (CrOx/SiO2) ethylene polymerization catalyst. The model catalyst shows a respectable polymerization activity after thermal activation in dry air (calcination). Combining the molecular information from X‐ray Photoelectron Spectroscopy (XPS) and Secondary Ion Mass Spectrometry (SIMS) we can draw a molecular level of the activated catalyst that features exclusively monochromate species, which are anchored to the silica support via ester bonds with the surface silanol groups. These surface chromates form the active polymerization site upon contact with ethylene. Upon increasing calcination temperature we observe a decrease in chromium coverage as some of the surface chromate desorbs from the silica surface. Nevertheless, we also find an increasing polymerization activity of the model catalyst. We attribute this increase in catalytic activity to the isolation of the supported chromium, which prevents dimerization of the coordinatively unsaturated active site. Diluting the amount of chromium to 200 Cr‐atoms/nm2 of silica surface enables the visualisation of polyethylene produced by a single active site. 相似文献
Studies on Catalytically Active Surface Compounds. XI. Influence of the Topology of Silanol Groups on the Formation of Vanadium Oxide Clusters on SiO2 Surfaces Interaction of VOCl3 dissolved in CCl4 with silanol groups of Aerosil gives rise to reaction products, the Cl/V-ratio of which depends on thermal pretreatment of Aerosil and the amount of the vanadium fixed on the surface. Geometrically different arrangements of the silanol groups (centers) show kinetically differing behaviour, thus giving the possibility to establish a mathematic model for the interpretation of experimental data. Quantitative estimation of the population with silanol groups depending on the annealing temperature is achieved and correlated with the existence of two vanadium oxide surface species which differ with respect to their catalytic activity. 相似文献
The effect of the vanadium content on the catalytic characteristics of samples of V2O5/SiO2, prepared by molecular layering, was investigated. It was shown that in the region of relatively small vanadium contents in the catalyst its surface concentration does not affect the selectivity of the process. The obtained relation between the initial selectivity and the relative reactivity of formaldehyde and the surface density of oxide-vanadium groups in the deposited catalyst is discussed. 相似文献
The homopolymerization of vinyl chloride and its copolymerization with ethylene over dibutyl ether–modified SiO2-supported Ziegler–Natta catalysts based on titanium and vanadium chlorides have been studied. The supported metal complexes are sufficiently active in the polymerization of vinyl chloride. Their activity depends on the catalyst composition and conditions of formation of the catalyst on the surface of the support. The chain structure of the resulting polyvinyl chloride (PVC) has been studied by NMR spectroscopy. The thermal properties of the synthesized PVC have been investigated by differential scanning calorimetry. The PVC obtained possesses enhanced thermal stability owing to the specific features of its chain structure. Vinyl chloride polymerization over the supported metalorganic catalyst proceeds mainly via a free-radical mechanism. Process conditions have been found for conducting the copolymerization of vinyl chloride with ethylene over supported metal complexes resulting in the formation of true statistical copolymers, which is confirmed by IR and NMR spectroscopy. 相似文献
A novel vanadium‐modified (SiO2/MgO/MgCl2)·TiClx Ziegler–Natta ethylene polymerization catalyst with much better catalytic performance is successfully developed. The catalyst is prepared by co‐impregnation of aqueous solution of water‐soluble magnesium and vanadium compounds on SiO2, and a supported thin layer of magnesium and vanadium oxides is formed over the surface of SiO2 after high temperature calcination in dry air, followed by further reaction with titanium tetrachloride to synthesize the magnesium dichloride carrier in situ and to support the titanium species simultaneously. By characterization of the catalysts and the polymers and investigation of the polymerization behaviors, it is found that compared with the original (SiO2/MgO/MgCl2)·TiClx ZN catalyst, the introduction of vanadium species induce improved catalytic performance with 27% higher activity, 48% higher hydrogen response, and 60% higher 1‐hexene incorporation ability with better short chain branch distribution.
A supported magnesium-vanadium-aluminium catalyst was prepared by depositing –with the use of a milling technique–VOCl3 on the MgCl2(THF)2 support and subsequent activation with diethylaluminium chloride. Catalytic activity of the obtained system for ethylene polymerization was evaluated as a function of Mg/V and Al/V ratios as well as catalyst ageing time and polymerization temperature. High concentrations of THF in the catalytic system and considerable excess of an organoaluminium co-catalyst were found to have no deactivating action on vanadium active sites. The catalyst obtained is stable and its activity for ethylene polymerization is high. It yields polyethylene with higher molecular weight and higher melting point than offered by the materials produced with the use of a corresponding unsupported vanadium catalyst or a titanium-based system on the same magnesium support. Kinetic investigations confirmed stability of this catalyst irrespective of its concentration in the polymerization medium or of monomer concentration. Moreover, analysis of the kinetic findings revealed that over 80% of vanadium employed forms active polymerization sites. 相似文献
Summary: We previously discovered that structurally well-defined polymer/inorganic composite particles, i.e., poly(methyl methacrylate) (PMMA)/CaCO3/SiO2 three-component composite particles, can be achieved via reverse atom transfer radical polymerization (ATRP), using 2,2′-azo-bis-isobutyronitrile as initiator and CuII bromide as catalyst. In the present study, the influence of the mass ratio of CaCO3/SiO2 two-component composite particles to methyl methacrylate (MMA) on the rate and behavior of the polymerization was studied in detail. The results illustrate that increasing the mass ratio of CaCO3/SiO2 two-component composite particles will decrease the overall rate of polymerization of MMA under standard reverse ATRP conditions. Thermal properties of the obtained well-defined particles were characterized and determined by thermogravimetric analysis (TGA). The results indicate that well-defined PMMA chains grafted on the surface of CaCO3/SiO2 particles were only degraded by random chain scission of C C linkages within the PMMA chain, which is different from the degradation of PMMA chains prepared via traditional radical polymerization. This difference is reasonably ascribed to the difference between the end groups of PMMA prepared via reverse ATRP and that via traditional radical polymerization, which has been confirmed by end group analysis measured by 1H–NMR spectroscopy. 相似文献
Crystalline titanium dichloride, in the absence of organometallic cocatalyst, is a very poor catalyst for the polymerization of ethylene. It is transformed into a very active catalyst through mechanical activation (ball-milling). This catalyst is active in the absence not only of organometallic cocatalysts, but also metals and compounds (such as aluminium and AlCl3) capable of forming organometallic compounds in situ (i.e., with ethylene, before polymerization starts). Ball-milling causes not only the expected increase in surface area but also disproportionation of Ti++ to Ti+++ and metallic titanium, as well as a crystal phase change to a structure not previously identified with those of TiCl2 or TiCl3. Catalyst activity (polymerization rate) is shown to be proportional to surface area and a direct function of Ti++ content of the catalyst; an empirical equation relates catalyst activity to surface area and to Ti++ lost through disproportionation. Titanium trichloride was found to be inactive in the absence of organometallic cocatalyst, even after ball-milling. The difference in structure of the catalytically active species in the conventional Ziegler (organometallic cocatalyst) and in the titanium dichloride catalyst are discussed. The mechanism of polymerization is compared with that of the supported (CrO3 on SiO2/Al2O3 and MoO3 on Al2O3) catalyst systems. 相似文献
In spite of great commercial importance of the Phillips CrOx/SiO2 catalyst and long term research efforts, the precise physicochemical nature of active sites and polymerization mechanisms
still remains unclear. The difficulties in a clear mechanistic understanding of this catalyst mainly come from the complexity
of the surface chemistry of the amorphous silica gel support. In this work, novel silsesquioxane-supported Phillips Cr catalysts
are utilized as realistic models of the industrial catalyst for theoretical investigation using the density functional theory
(DFT) method in order to elucidate the effects of surface chemistry of silica gel in terms of supporting of chromium compounds
and fluorination of the silica surface on the catalytic properties of the Phillips catalyst. Both qualitative and quantitative
aspects with respect to various electronic properties and thermodynamic characteristics of the model catalysts were achieved.
The future prospects of a state-of-the-art catalyst design and mechanistic approaches for the heterogeneous SiO2-supported Phillips catalyst has been demonstrated.
The text was submitted by the authors in English. 相似文献
The magnetic shielding tensor and quadrupole interaction parameters, as well as the mutual orientation of tensors for the (SiO)VOCl2complex obtained by the immobilization of VOCl3on the SiO2surface are determined. The state of VOCl3on the surfaces of MgCl2and modified SiO2with all surface OH groups replaced by Cl atoms is studied. To prepare the modified SiO2, CCl4and SiCl4are used as chlorinating agents. The formation of structurally similar pentavalent vanadium complexes on the surface of these supports is shown. A model for the coordination environment of vanadium on the chlorine-containing supports is proposed. The vanadium atom exists in the distorted pentahedral environment and is bound to the support through either two chlorine atoms or chlorine and oxygen atoms. A correlation between the coordination of VOCl3and catalytic properties of VOCl3/MgCl2is assumed. 相似文献
The surface acidity of SiO2, γ-Al2O3 and TiO2 supported vanadia catalysts has been studied by the microcalorimetry and infrared spectroscopy using ammonia as the probe molecule. The acidity in terms of nature, number and strength was correlated with surface structures of vanadia species in the catalysts, characterized by X-ray diffraction and UV-Vis spectroscopy. It was found that the dispersion and surface structure of vanadia species depend on the nature of supports and loading and affect strongly the surface acidity. On SiO2, vanadium species is usually in the form of polycrystalline V2O5 even for the catalyst with low loading (3%) and these V2O5 crystallites exhibit similar amount of Brönsted and Lewis acid sites. The 25%V2O5/SiO2 catalyst possesses substantial amount of V2O5 crystallites on the surface with the initial heat of 105 kJ mol-1 and coverage of about 600 mmol g-1 for ammonia adsorption. Vanadia can be well dispersed on g-Al2O3and TiO2 to form isolated tetrahedral species and polymeric two-dimensional network. Addition of vanadia on γ-Al2O3 results in the change of acidity from that associated with g-Al2O3 (mainly Lewis sites) to that associated with vanadia (mainly Brönsted sites) and leads to the decreased acid strength. The 3%V2O5/TiO2 catalyst may have the vanadia structure of incomplete polymeric two-dimensional network that possesses the Ti-O-V-OH groups at edges showing strong Brönsted acidity with the initial heat of about 140 kJ mol-1 for ammonia adsorption. On the other hand, the 10%V2O5/TiO2 catalyst may have well defined polymeric two-dimensional vanadia network, possessing V-O-V-OH groups that exhibit rather weak Brönsted acidity with the heat of 90 kJ mol-1 for NH3 adsorption. V2O5 crystallites are formed on the 25%V2O5/TiO2 catalyst, which exhibit the acid properties similar to those for 25%V2O5 on SiO2 and γ-Al2O3. 相似文献
The surface composition of TiCl3-based Ziegler—Natta catalysts prepared by various methods was analyzed by ESCA to correlate the total amount of surface titanium with the catalyst activity in propylene polymerization. The ESCA peak ratio (Ti 2P3/2/Cl 2P) of the catalysts was measured to estimate the surface composition. The titanium index defined as the product of the (Ti/Cl peak ratio and surface area) was closely correlated with the catalyst activity in polymerization. This indicates that surface titanium concentration and surface area determine the catalyst activity. It was also found that removal of surface aluminum and chlorine at the catalyst preparation stage results in concentration of titanium at the surface and an increase in surface area. 相似文献
The vanadium trapping effect of Mg and La containing additives in cracking catalyst contaminated with 2300 ppm Ni and 4700 ppm V has been analyzed by microactivity test (MAT) and imaging secondary ion mass spectrometry (SIMS). The results of SIMS imaging are consistent with cracking activity data and show that the La/spinel is a superior vanadium trap for the fluid catalytic cracking of hydrocarbons (FCC) operation. La/spinel serves as a dual function additive for both vanadium trap and SOx removal. The optimum amount of La/spinel added to the cracking catalyst is about 15% by weight. This results in an increased catalytic activity, an increase in gasoline yield, and a decrease in coke and gas factors. The MgAl2O4 phase of Mg/Al2O3 additive is found capable of trapping vanadium while its MgO of Mg/Al2O3 phase can migrate to zeolite particles (the active component of the FCC catalyst) that, in turn, causes a decline in the activity of that catalyst. 相似文献
The Cr/SiO2 Phillips catalyst has taken a central role in ethylene polymerization since its invention in 1953. The uniqueness of this catalyst is related to its ability to produce broad molecular weight distribution (MWD) PE materials as well as that no co-catalysts are required to attain activity. Nonetheless, co-catalysts in the form of metal-alkyls can be added for scavenging poisons, enhancing catalyst activity, reducing the induction period, and tailoring polymer characteristics. The activation mechanism and related polymerization mechanism remain elusive, despite extensive industrial and academic research. Here, we show that by varying the type and amount of metal-alkyl co-catalyst, we can tailor polymer properties around a single Cr/SiO2 Phillips catalyst formulation. Furthermore, we show that these different polymer properties exist in the early stages of polymerization. We have used conventional polymer characterization techniques, such as size exclusion chromatography (SEC) and 13C NMR, for studying the metal-alkyl co-catalyst effect on short-chain branching (SCB), long-chain branching (LCB) and molecular weight distribution (MWD) at the bulk scale. In addition, scanning transmission X-ray microscopy (STXM) was used as a synchrotron technique to study the PE formation in the early stages: allowing us to investigate the produced type of early-stage PE within one particle cross-section with high energy resolution and nanometer scale spatial resolution. 相似文献