Catalysis: Problems & Applications

Chemphobia

Chemical Waste in Industry

How much waste does a chemical process generate (vs. usable product? (reaction efficiency) E-factor (Roger Sheldon, 1994) kgwaste/kgproduct= E-factor
Industrial Sector Petrochemicals Bulk Chemicals Fine Chemicals Specialties/pharmaceuticals Production (ton/yr) 106-108 104-106 102- 104 10- 103 E-factor <0.1 1- 5 5- 520- 100

Does not specific how bad the waste is, could be CO2, H2O, inorganic salts (NaCl, Na2SO4, etc.), heavy metal salts Fine reactions chemicals generate more waste because they require high specificity, involve multistep synthesis, and/or require stoichiometric reagents

Waste is not all created equal

Compound Q-Value

N2
CO2 H2O

zero
low low

NaCl
non-metal salts acids bases heavy-metal salts CFC gases persistent materials

low
medium medium medium high high high

Q-value attributes how hazardous the waste is Environmental Quotient (EQ) is the Q-value of the waste multiplied by the E-factor Typically used to evaluate the waste of a production stream

Catalyst Cost Considerations

Catalytic converter in California: $300-500 Catalysts: Pt, Pd, Rh, Au Reduction of nitrogen oxides 2NOx xO2 + N2 Oxidation of carbon monoxide 2CO + O2 2CO2 Oxidation of unburnt hydrocarbons CxH2x+2 + [(3x+1)/2]O2 xCO2 + (x+1)H2O Catalyst easily poisoned by lead (always use unleaded fuels!)

Metal Abundance

Catalyst Cost Considerations

Catalytic converter in California: $300-500 Catalysts, Costs per ounce Pt ($1381) Fe($0.12) Pd($708) Al($0.04) Rh($1130) Zn($0.06) Au($1268) Cu($0.20) Reduction of nitrogen oxides 2NOx xO2 + N2 Oxidation of carbon monoxide 2CO + O2 2CO2 Oxidation of unburnt hydrocarbons CxH2x+2 + [(3x+1)/2]O2 xCO2 + (x+1)H2O

Cheap Metals for Noble Tasks

Significant area of research is finding non-noble metal catalysts for industrially important reactions Hydroformylation: largest scale industrial reaction that uses a homogeneous catalyst, 6.6 megatons/yr

Cost (metal per oz) Pressure Temperature

HCo(CO)3 Co($1.24) 300 atm 150-170 C

vs.

HRh(CO)(PPh3)2 Rh($1130) 18 atm 95-100 C

Not completely a fair comparison because of different selectivity, but Rh still used because of milder reaction conditions because its recyclable

Compare to:
Electrolyzers use an electrochemical potential to split H2O into H2 and O2 (if you use renewable energy source, its clean H2 fuel, 95% currently made from CH4)

Pt($1381) is the best catalyst; it is almost 100% efficient. Ni($0.40) is currently used (alkaline electrolyzer), its ~70% efficient

Heterogeneous Catalysis- Surface Characterization

Traditionally there are fewer tools to study heterogeneous catalysts, makes it more difficult to come up with or improve activity

Scanning Electron Microscope (first commerical model 1965): Use electron beam to characterize surface, 5-10 nm resolution

Pollen grain

1981, Scanning Tunneling Microscopy: 3-D imaging of surfaces, 0.1 nm lateral, 0.01 nm depth resolution

Chain of Cs atoms on a GaAs surface (NIST)

1986, Atomic Force Microscopy: 3-D imaging of surfaces, first commercially available 1989

Graphite

Nitrogen Fixation: Haber Bosch

Fixed nitrogen is essential to life but used to be limited by natural processes

Habor Bosch catalyst most important invention of the 20th century

500 million tons of artificial fertilizer per year 1% of the world's energy supply is used for it

Sustains roughly 40% of the population

Half of the nitrogen in your body was fixed in this process

How does the catalyst work?

Heterogeneous and Homogeneous methods

Non-noble hydrogen production

Best catalysts for proton reduction to make hydrogen are noble medals

Scanning Tunneling Microscopy Images of MoS2 nanocrystals on gold at increasing resolutions

Catalytic activity corresponds with amount of edge sites. Indicates the active catalyst is probably those sites.