FLASHCARDS - Heterogeneous Catalysis

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FLASHCARDS - Heterogeneous Catalysis
Sulivan González
Fichas por Sulivan González, actualizado hace más de 1 año
Sulivan González
Creado por Sulivan González hace más de 8 años
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Benefits of Heterogeneous Catalysts (3 P) - Easier recovery (filtration) -- Easier to use in continuous (flow) reactors - Easier to handle (eg. strong acids) - Nearly all are porous: v. important property
Surface area formula r = radius n = no. of pores l = length of cube
IUPAC definition... size for: 1) Micropores 2) Mesopores 3) Macropores 1) <2.0 nm 2) 2 - 50 nm 3) >50 nm
Variable surface chemistry
2D Materials: - Clays
Clays - neutral, no catalyst activity --> Isomorphous substitution: inserts charge into system: more active catalyst
Clays: - Effect of isomorphous substituion - Bronsted acid: Charge polarises OH - No direct \(H^{+}\) exchange as it will dissolve the material
Clays: - Effect of isomorphous substituion 2 - Hydrated interlayer gaps reduce catalyst activity --> DRY - BUT, drying makes interlayers come closer together, so slower catalysis --> COMPROMISE
Catalyst activation
Pillaring cations Layer collpase - problem especially w/ high charge density cations Replace a (eg) \(Na^{+}\) w/ this: Gap maintained even when heated (dried)
Reactions of clays
Other layered materials
3D Catalysts - Microporous systems
Catalytic sites within zeolites
Acidic Zeolites
Pore size and diffusion Aperture diameter used to define narrowest entry point - Ring size defined by no. of O atoms present (= no. of Si + heteroatoms) - Apreture dimensions between 0.4-0.75 nm
Pore size and diffusion 2: (3 P) - Molecular: pores >> molecule - Knudsen: pores > molecule - Configurational: pores \(\simeq\) molecule
Diffusion in porous materials depend on: (3 P) 1) Pore diameter 2) Connectivity (move & connect between pores: more degrees of freedom --> better catalytic activity) 3) Tortuosity
5 stages involved in a liquid phase reaction using a porous solid catalyst - NOTE: for gas phase reactions, thickness of hydrodynamic layer = 0, so 1) and 5) can be omitted 1) Diffusion of reactants through hydrodynamic layer 2) Diffusion of reactants through pore system 3) Reaction 4) Diffusion of products through pore system 5) Diffusion of products through hydrodynamic layer - For 1) & 2), parameters influencing the rate are: Thickness of hydrodynamic layer & pore size/geometry respectively
5 stages involved in a liquid phase reaction using a porous solid catalyst 2 - Optimizing performance: - 1) & 5) --> Heating: viscosity drops, rate increases. Stirring: hydrodynamic layer decreases, rate increases - 3) If high \(E_a\) --> heating increases rate - Low \(E_a\) suggests process is diffusion controlled - To distinguish between each: If RDS is 1), 5), 2) & 4), stirring will increase rate for 1) and 5), NOT for 2) and 4) NOTE: Increasing temperature does NOT increase rate of 2) and 4)
Test for diffusion control - Diffusion dependent on pore size & pore size is not temperature dependent.
How is pore size measured (2 P): - X-ray diffractions (work for crystalline systems) - Porosimetry: Gives pore size of porous solids. Adsrobtion of gas (eg N2) onto a solid over a range of partial pressures at the b.p of the gas Stage 1: low partial pressure - monolayer of gas on surface (surface area calc.) Stage 2: higher partial pressure - pores fill with liquid N2 to stabilise the meniscus (pore size calc.)
How is pore size measured - Porosimetry
Measuring acidity of zeolites - Desorption of ammonia: Higher temp of desorp. higher the acidity - Acidic strength \(\propto\) 1/Al content - Concentration of sites \(\propto\) Al content
Shape selectivity - Key property of zeolites (eg H-ZSM5) Selectivity based on shape/size rather than electronic properties
Reactant selectivity
Other uses of zeolites AS a host for catalytic species (reactants can enter the supercage)
Titanium silicates (TS-1): Oxidation catalyst
Titanium silicates (TS-1): Oxidation catalyst 2
Titanium silicates (TS-1) w/ 2 Ti: Oxidation catalyst
Mesoporous systems - Larger templates give unstable materials. Solution... Micelle Templated Silicas (MTS)
Addition of Heteroatoms to MTS
ALMA industrial process Catalyst = \((VO)_2P_2O_7\)
What is meant by isomorphous substitution in context of porous solids
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