Fuel gas and Polymerization

Technology
Syngas Production and Processing
X G L

Coal
Fischer- Syncrude Fuel
Biomass Gasification Syngas Tropsch Refining & &
Natural Gas Processing Synthesis Upgrading Chemicals
 Natural Gas Gasification
 Steam Reforming
• CH4 + H2O → CO + 3H2 (Ni Catalyst)
• H2/CO = 3
• Endothermic
• Favored for small scale operations

 Partial Oxidation
• CH4 + ½O2 → CO + 2H2
• H2/CO ≈ 1.70
• Exothermic
• Favored for large scale applications

 Autothermal Reforming
• A combination of Steam Reforming and Partial Oxidation
 Coal Gasification
2(-CH-) + O2 → 2CO + H2

 H/C Ratio
• Produces Leaner Syngas (Lower H2:CO Ratio)

 Ash
• Non-flammable material in coal complicates Gasifier design

 Impurities (Sulfur)
• Necessitates greater syngas cleanup
 Biomass Gasification
2(-CH-) + O2 → 2CO + H2

 H/C Ratio
• Similar issues to coal
 Ash
• Biomass aggressively forms ash
 Impurities (Sulfur, Nitrogen)
• Necessitates greater syngas cleanup
 Moisture
• High moisture levels lower energy efficiency
 Size Reduction
• The fibrous nature of biomass makes size reduction difficult
 Syngas Processing

 Water Gas Shift Reaction

• CO + H2O ↔ CO2 + H2

 Purification
• Particulates
• Sulfur (<1 ppm) - ZnO Sorbent
• Nitrogenates (comparable to Sulfur compounds)
• BTX (Below dew point)
Syngas Processing
Syngas Processing
Fischer Tropsch Synthesis
CO + 2H2 → (CH2) + H2O
Standard LTFT product distribution
 Fischer-Tropsch Products
Hydrocarbons Types
 Olefins
• High chemical value
• Can be oligomerized to heavier fuels
 Paraffins
• High cetane index
• Crack cleanly
 Oxgenates
 Branched compound (primarily mono-methyl
branching)
 Aromatics (HTFT)
 Fischer-Tropsch Catalysts

 Fused Iron Catalysts – HTFT

• Alkali promotion needed
• Products are high olefinic
• Cheapest
• Reactor: Fluidized bed

Iron oxide
1500 °C Molten Magnetite Cooled rapidly
K2O Crushed in a ball mill Fused Iron
Air (Fe3O4)

MgO or
Al2O3
 Fischer-Tropsch Catalysts

 Supported cobalt catalysts - LTFT

• Incipient wetness impregnation method
• Oxide support: silica, alumina, titania or zinc oxide
• Products: predominantly paraffins
• Low resistance towards contaminants

Co(NO3)2

Supported
Support Drying Calcination
Co Cat.
Comparison of Co and Fe LTFTS
Catalyst
FTS Reactors
 LTFT Reactors
CO + H2 → (CH2) + H2O + 145 kJ/mol
1800 oC Adiabatic Temperature Rise

• Fixed Bed (Gas Phase Reaction Media) – Shell SMDS

– Excellent reactant transport
– Simple design
– Poor product extraction, heat dissipation
– Limited scale-up
– Potential for thermal runaway
• Slurry Bed (Liquid Phase Reaction Media) – Sasol SPR
– Thermal uniformity
– Excellent product extraction
– Excellent economies of scale
– Requires separation of wax (media) from catalyst
– High development cost
 FTS Mechanisms - ASF Plot

• Propagation is exclusively by the addition of one monomer

• αi + bi = 1 (by definition)
• Propagation probability is independent of carbon number
 Polymers

Films Candy Wrappers

 Polymers
 Natural Rubber
• Latex from rubber trees
• Polymers of isoprene
Polymers applications and demand
 Polymerization reactions

 Step growth Polymerization

• Reaction between functional groups (OH-,COOH-
, ..etc) of any two molecules
• Example
 Polymerization reactions
 Chain growth polymerization
• Reaction occurs by successive addition of
monomer molecules to the reactive end.
• An initiator or catalyst required to start the chain
growth reaction
• Example - vinyl monomers like ethene, propene..
etc

• Two types of chain growth polymerization

• Radical polymerization
• Coordination polymerization
 Polymerization reactions

 Radical polymerization
 Polymerization reactions

 Coordination Polymerization
Polyethenes
Autoclave for LDPE
Tubular reactor for LDPE
HDPE Production
Tetra Pack
Thank you