Catalyst Design and Preparation

Dr. King Lun Yeung Department of Chemical Engineering Hong Kong University of Science and Technology

CENG 511 Lecture 3

Design of Catalyst
(1) Stoichiometric analysis of target reaction (2) Thermodynamic analysis (3) Molecular mechanism (4) Surface mechanism (5) Reaction pathway (6) Catalyst properties (7) Catalytic materials (8) Propose a catalyst

Case Study
Methane Partial Oxidation to Formaldehyde CH4 + O2 CH2O + H2O H = -76.8 kcal/mol G = -70.9 kcal/mol

Current Technology CH4 + H2O CO + 3H2 CO + 2H2 CH3OH CH2O + H2O Poor efficiency high energy and material cost

CH3OH + 0.5 O2

Stoichiometric Analysis-1
(1) List all possible stoichiometric chemical equations (2) Calculate the H and G of reaction (3) Chemical bond changes Primary Reactants CH4 O2 Reactant Self-interactions 2CH4 C2H6 + H2 2CH4 C2H4 + 2H2 2CH4 C2H2 + 3H2 O2 = none G = 8.5 kcal/mol G = 12.8 kcal/mol G = 22.2 kcal/mol

DH DH DH

Stoichiometric Analysis-2
Reactant Cross-interactions CH4 + 0.5 O2 CH3OH CH2O + H2 CO + 2H2 CH4 + O2 CH2O + H2O HCOOH + H2 CO + H2 + H2O CO2 + 2H2 OI OI, DH OI, DH OI, DH, O OI, DH, O OI, DH, O OI, DH, O OI, DH, O OI, DH, O OI, DH, O OI, DH, O G = -20.6 kcal/mol G = -20.0 kcal/mol G = -43.1 kcal/mol G = -70.9 kcal/mol G = -67.0 kcal/mol G = -87.3 kcal/mol G = -90.5 kcal/mol G = -31.0 kcal/mol G = -119.8 kcal/mol G = -136.5 kcal/mol G = -139.8 kcal/mol

CH4 + 1.5O2 CH2O + H2O2 HCOOH + H2O CO + 2H2O CO2 + H2 + H2O

Stoichiometric Analysis-3
Reactant Cross-interactions OI, DH, O CH4 + 2O2 HCOOH + H2O2 CO + H2O2 + H2O OI, DH, O OI, DH, O CO2 + 2H2O Reactant-Product interactions CH4 + C2H6 C3H8 + H2 CH4 + C2H4 C3H8 CH4 + CH3OH C2H5OH + H2 etc. DH, A A DH, A G = -98.6 kcal/mol G = -118.7 kcal/mol G = -189.5 kcal/mol G = 16.6 kcal/mol G = 4.5 kcal/mol G = 10.5 kcal/mol

Thermodynamic Analysis
(1) Assess thermodynamic feasibility (rank by G) (2) Rank and group reactions with common trend CH4 + 2O2 CO2 + 2H2O CH4 + O2 CH2O + H2O HCOOH + H2 CH4 + O2 CH4 + 0.5 O2 CH2O + H2 CH4 + 0.5 O2 CH3OH CH2O CO + H2 CH3OH CH2O + H2 OI, DH, O OI, DH, O OI, DH OI, DH OI DH DH G = -189.5 kcal/mol G = -70.9 kcal/mol G = -67.0 kcal/mol G = -20.0 kcal/mol G = -20.6 kcal/mol G = -17.0 kcal/mol G = 2.0 kcal/mol

Reaction Mechanism
(1) Visualize molecular events leading to formation of desired product(s) (2) Eliminate non-plausible pathways CH4 + 0.5 O2 CH2O + H2

Surface Mechanism
(1) Guess the most plausible surface mechanism that lead to the desired product(s) (2) Research know adsorption, molecular configurations of reactants and products CH4 CH3-S CH2-S CH3OH CH2O, H2 O2 2O-S

Reaction Pathways
(1) Based on the analysis of surface mechanism establish the desired reaction pathways for the reaction CH4 + 0.5 O2 CH2O + H2 G = -20.0 kcal/mol
O2 CH3 O O

OI, DH
CH4 H

(1) Must promote oxygen insertion (OI) (2) Must be a mild dehydrogenation (DH) (3) Must prevent strong dehydrogenation (4) Must prevent oxidation

CH2O H

CH3 O

Catalyst Properties
(1) Identify the desired catalyst properties based on surface mechanism/reaction pathway (1) Oxygen adsorption site leading to dissociated and immobile oxygen species (2) Mild dehydrogenation to produce CH3 (3) Adjacent sites to facilitate final dehydrogenation
CH4 H CH3 O O O2

CH2O H

CH3 O

Catalyst Selection
(1) Based on knowledge of catalyst materials (1) Mild dehydrogenating catalysts Usually oxide catalysts, metals are strong DH catalyst Cu2+, Ni2+, Fe3+, Mn2+, V3+, V5+, Ti4+ (2) Mild oxidation catalysts Sc3+, Ti4+, V3+, Cr3+, Fe2+, Zn2+, Zr3+, Nb3+, Mo6+ (3) Low mobility Co3O4 > MnO2 > NiO > CuO > Fe2O3 > Cr2O3 > V2O5 > MoO3 (4) Hard to reduce CoAl2O4, NiAl2O4, ZnTiO4

Bond G.C. Catalysis by Metals, Academic Press (1962) Krylov O.V. Catalysis by Non-metals, Academic Press (1970)

Propose a Catalyst
Mild DH Fe3+ V3+ V5+ Ti4+ Mild OI Sc3+ V3+ Ti4+ Fe2+ Zn2+ Zr3+ Nb3+ Mo6+ Possible Catalysts Single TiO2, V2O3 Mixed TiO2 + MoO3 V2O3 + ZnO Complex Fe2O3 Zn TiO3

Catalyst Preparation
(1) Unsupported Catalyst are typically usually very active catalyst that do not require high surface area e.g., Iron catalyst for ammonia production are usually used for high temperature applications e.g., refractory aluminates for catalytic combustion intrinsically have a large surface area e.g., gamma alumina catalyst for isomerization clay catalyst for hydrogenation (2) Supported Catalyst requires a high surface area support to disperse the primary catalyst, the support may also act as a co-catalyst or secondary catalyst for the reaction

Unsupported Catalyst
Typical preparation methods

Unsupported Catalyst
Required preparation steps

Unsupported Catalyst
Typical preparation methods (1) Fusion Method

Unsupported Catalyst
Typical preparation methods (2) Precipitation and Co-precipitation Methods

Unsupported Catalyst
(2) Precipitation and Co-precipitation Methods

Unsupported Catalyst
(2) Precipitation and Co-precipitation Methods
Preparation of aluminum oxide

Unsupported Catalyst
Typical preparation methods (3) Sol-gel synthesis

Unsupported Catalyst
Typical preparation methods (3) Sol-gel synthesis

Silica-alumina acid catalyst

Unsupported Catalyst
Typical preparation methods (4) Frame Pyrolysis
Fumed silica
(a) vaporizer (b) mixing chamber (c) burner (d) cooling section (e) separation (f) deacidification (g) hopper (h) compactor

Frame Pyrolysis (Fumed Silica)

(a) 380 m2g-1 (b) 300 (c) 200 (d) 90

Supported Catalyst
Maintains large catalyst surface area and prevents sintering during high temperature operation

Supported Catalyst
Typical support materials

Support Materials

Metal Ion Distribution in Support Pellet

Supported Catalyst
Weak Interaction Interaction

Catalyst-Support Interactions

Supported phase-support interaction (transition layer attachment)

Monolayer formation

Bilayer formation

Catalyst-Support Interactions

Formation of solid solution

Formation of new compounds

Grafted catalyst

Supported Catalyst
Typical preparation methods (1) Precipitation method

Precipitation Method