Catalysis Lecture 7

Heterogeneous Catalysis: Catalytic Purification of exhaust gases, Fischer-Tropsch Process

Scope of the lecture

Catalytic purification of Exhaust gases in internel compustion engines

Fischer Tropsch synthesis

Exhaust Gases
Overview
Average exhaust gas composition of engine

Exhaut gas limits in EU for HD commercial vehicles in g/kWh

Catalytic Exhauts Purification

Brief history
-1927, Kettering proposed the carbon monoxide catalyst, since automotive exhausts were considered as noisy, dangerous and smelly. -1959 General motors tested the very first catalysts -1964 First emission standards were introduced in California and in the seventies the catalyst development accelerated even more, which led to that Volvo as the very first car manufacturer could introduce the threeway catalytic converter. -1996 Petrol engine vehicles equipped with catalytic converters and registered after 1 August 1995 became subject to the new cat emissions test. The new test procedure includes tests on the emission levels of CO and HC. -1997 Legislation will also require the majority of diesel cars to be equipped with converters.

Purification of Exhaust Gases

Some examples

Purification of Exhaust Gases

Some examples
Typical examples of exhaust air streams that can be treated by a catalytic process are: Residual gases from pharmaceutical plants Off-gases with dust-like or sticky components, e.g. from paint shops Off-gases from tank aeration Process gases with odor load Exhaust-air with solvent load Linde installation

Construction requirements for exhaust purification catalysts

The material of the substrate and the construction of the catalyst are subjected to great mechanical, thermal and chemical strain. The construction should meet the stringent requirements such as: Large effective area Light weight Small size Good thermal conductivity High mechanical strength Low back pressure

Main types of exhaust purification catalysts

Catalyst Support Ceramic-based monolith Alumina or cordierite (magnesium aluminosilicate) Metal-based monolith ferritic chromium strip steel : C max. 0.02%; Cr 20%; Al 5%; Rare earth elements+ Fe 0.002% Better thermal conductivity Shorter light off time Less risk of overheating Larger effective area Greater catalytic capacity Smaller and more flexible design Higher mechanical strength Better resistance to thermal shock High price

Advantages

Lower price

Disadvantages

Fragile structure Risk of overheating, thermal shock

Catalytic purification of exhaust gases

Three-way catalyst (TWC)
Three main reaction to be catalyzed: a HC + b O2 c CO2 + d H2O 2CO + O2 2 CO2 2 NO + 2 CO N2 + 2 CO2 ------------------------------------Reactions of less importance: H2O + CO H2 + CO2 2 H2 + O2 2 H2O HC + NO N2 + CO2 + H2O

(Pt) (Pt) (Rh)

Catalytic purification of exhaust gases

Three-way catalyst (TWC) Impact of oxygen

a HC + b O2 c CO2 + d H2O 2CO + O2 2 CO2 2 NO + 2 CO N2 + 2 CO2

Efficiency of an exhaust gas catalyst as a function of air/fuel ratio

Temperature: > 250oC active, optimal conditions: 400- 600oC Rh/Pt for catalyst: 1/5 to 1/10; natural ration: 1/16.5

Catalytic purification of exhaust gases

Mechanism of CO oxidation
Kinetic scheme: CO + * CO-* O2 + 2 * 2 O-* CO-* + O-* CO2 + 2 *
O C
O C O

Pt Pt Pt Pt Pt Pt Pt

Pt Pt Pt Pt Pt Pt Pt

Pt Pt Pt
Pt Pt Pt

Pt Pt Pt
Pt Pt Pt

Pt Pt Pt

Pt Pt Pt

Catalytic purification of exhaust gases

Mechanism of NOx reduction
NO + CO N2 + CO2 NO + 2 * N-* + O-* fast CO + O-* CO2 + * N-* + N-* N2-* + * slow N2-* N2 + * Other possible steps: N-* + NO-* N2 + O-* + * CO + * CO-* followed by: CO-* + O-* CO2 + 2*

Exhaust Gases Catalyst

FinnKat B Model

Diesel and LPG Engine Emissions Filters

Selectivity of process depends on the catalyst

Products of Fischer-Tropsch process depending on the catalyst

CO + H2

CH4 CH3OH C2H5OH CH3(CH2)nCH2OH CH3(CH2)nCH3 CH3 H3C C (CH2)nCH3 CH3 CH2 CH2 OH OH

Ni CuO/ZnO/Cr2O3 Rh + promotores Co/Ru Fe + promotores ThO2 Rh/MgO

Fischer-Tropsch Synthesis
Mechanism

Fischer-Tropsch Synthesis
Mechanism Initiation Step
COgas C S O S +H2 CH3OH +H2 H C S OH C S +H2 CH2 S +H2 CH4

O S

+H2

H2O

Fischer-Tropsch Synthesis
Mechanism Chain growth (insertion)
R CH2 CH3 CH S CH2 CH S

CH2 S

R CH S

CO

R CH C S O S

+H2

Fischer-Tropsch Synthesis
Mechanism - termination
R CH2 CH S +H2 +2 H2 O S + H2O RCH2COOH RCH=CH2 + H2 RCH2CH3

R CH C S

RCH2CHO RCH2CH2OH

Fischer-Tropsch Synthesis
Present and future

Fischer-Tropsch Synthesis - Catalysts

Fischer-Tropsch Synthesis
Role of catalyst components

Fischer-Tropsch Active Metals (Co, Fe, Ru) Reduction Promotores (Pt, Ru, Pd, Re, Cu) Activity/ Selectivity Promotores (K, Zr, etc.) Support and/or structural promotores (Al2O3, SiO2, TiO2)

Fischer-Tropsch Synthesis
Patented Catalyst

Fischer-Tropsch Synthesis Palnt