CO2 Removal - Process Technology

for Ammonia Plants

By:
Gerard B. Hawkins
Managing Director, CEO
 Why Remove CO2 ?

 Poisons Synthesis catalyst

 Can be used downstream in Urea production
 If allowed into the loop would
 Also act as inert in loop
 Increase the compression costs
 Used as a product in its own right
 Carbonated drinks
 Refrigeration units
 Can be exported to methanol plant
 Systems for Removing CO2

 Started with Monoethanolamine

 Chemical absorption
 Highly corrosive
 High energy consumption (14% of total
plant)
 Modern plants use MDEA
 Other options include physical solvents
 Selexol (UOP)
 Benefield (hot potassium carbonate)
 Vetrocoke
 MDEA

 Uses diethanolamine with an amine

activator
 No corrosion inhibitors required
 No solvent degradation is observed
 Acts as a combination of physical and
chemical solvent
 CO2 can be recovered by flashing only
 Typical System for MDEA
Treated CO2
Gas

Feed
Gas
 Advantages of MDEA

 Some stated above

 Can use MDEA to retrofit plants using MEA
 Can tailor balance between physical and
chemical
 Allows for versatility especially in retrofit
cases
 Benfield System
Treated
Gas Lean 75°C
CO2 and H2O

Semi
Lean 120°C
Regenerator
Feed
Gas

Reboilers

Absorber
 CO2 Removal issues
 Benfield Problems
• Dirty solution
• Foaming due to contaminants or
degradation products
• DEA degradation products
• Difficulty of oxidizing V4+ to V5+
 Results
• Low DEA concentration
• Poor corrosion protection
• Reduced CO2 removal capability
 Vanadation

 Method of protecting stable magnetite layer

from corrosion
 Must reduce V5+ and deposition on surface
 Steady state is reached when V5+ : V2O5 is
0.4
 If ratio less than 0.3 - rapid break down and
corrosion
 High levels can lead to degradation of DEA
 Most plants have a slow reduction of V5+ to
V4+
 Can counter by addition of KNO2
 Benefield - Water Balance

 Large volumes of solution being circulated

 Must keep water balance right to ensure
strength of solution is between 27 and 30%
 >30% - crystallisation and vessel
corrosion
 <27% - poor scrubbing
 Benfield Water Balance

Absorber Inlet Catchpot

34 te/hr
52 te/hr
Process Gas PG Exit Absorber
2 te/hr

Benfield
System
Inlet Absorber
CO2 Catchpot Drain
21 te/hr
6 te/hr CO2 Export Main
Pump Gland Seals 1 te/hr
Purges to levels
 Common Problems - Benfield

 High DP on Absorber
• High level in base - flooding inlet gas line
• Foaming due to contaminants
• Fouled packing causing restriction to flow
• High gas flow causing solution to be held up
• High circulation rates leading to flooding
• Temperature variations
 Common Problems - Benfield

 Consequences
• Solution help up creating low levels in regen
tower
• Make gas supply to syn gas machine
reduced
• Vibrations/Surging of machine
• Benfield solution carried forward from
absorber and deposited on methanator
catalyst
 Common Problems - Benfield

 High PD in Regenerator
• High vapour rates leading to hold up of
solution from low level in base of regen
column
• High make gas temperatures or excessive
steam usage in reboilers
• Foaming
• Fouled/Choked packing
• Mechanical failure of trays or distributors
 Common Problems - Benfield

 Consequences
• Levels fall in base of regen column
• Reduction in suction head available to
pumps - cavitation
• Reduced flows to absorber - high CO2 in exit
gas
• Trips methanator on high temperature
• Carry over of benfield solution into CO2
condensate recovery system
• Excess boiling of solution - changes in
concentration and potential for corrosion
 Amine Promotion Mechanism
Promotion mechanism of organic Amine on CO2 Absorption
into Potassium Carbonate solution

Gas phase interface Liquid phase

Slow reaction
CO2 of CO2 and HCO3-
hydroxylation

Carbamate diffusion

Fast reaction Hydrolysis of

CO2 of CO2 and amine carbamate to amine HCO3-

Free amine diffusion

 Benfield CO2 Removal Improvements

 LRS 10 Benfield Promoter

• British Gas Technology
• New amine mixture
• Completely compatible with DEA
• Replaces DEA in hot potash solutions
• Improves absorption and desorption of
CO2
• Reduces CO2 removal energy
 Effect of 3% LRS 10 to Benfield
CO2 concentration in absorber overheads

%CO
Conc

Time (hours)
 Benefits of LRS 10 Promotion

 Retrofit easy, just add 3% LRS solution

 CO2 slip reduces immediately, giving scope

to:-
• Increase plant throughput, or
• reduce steam/carbon ratio, or
• reduce methane to synloop, and
• plant becomes more controllable
UOP Lo-Heat Process Schematic