Carbon Dioxide Removal

Introduction
Carbon dioxide is undesirable for synthesis gas.
CO2 can be reduced to ppm range
Commercially available processes are:
1. Mono Ethanolamine Process
2. Benfield Process
3. Catacarb Process
4. Sulphinol Process
5. Tri Ethanolamine Dual Solvent Process
6. Flour Propylene Carbonate Process
7. Activated Methyl Di Ethanol Amine (aMDEA)
Process
 Mono Ethanolamine Process
15 20 % MEA solution used at low temperature
for absorption
Desorption by application of heat
80 140 OF for Absorption and 215 280 OF for
Regeneration

2 (HOCH2 CH2 NH2) + CO2 + H2O (HOCH2 CH2 NH3)2 CO3

HOCH2 CH2 NH2 + CO2 + H2O HOCH2 CH2 NH3 HCO3
2 (HOCH2 CH2 NH2) + CO2 CH2NHCOONH3 CH2
 Advantages
High absorption capacity for CO2 and low capacity for
other components
Highest rate of absorption for CO2
Lean solution with very low CO2 partial pressure can be
obtained
Low circulation rates, small towers and lesser packings
MEA not harmful for Methanation catalyst
Good for lower scrubbing pressures
 Disadvantages

High regeneration heat requirements

Corrosion to CS equipments
 Benfield Process
Hot Potassium carbonate solution
Original process has limitation of 1 2 %
slippage
Promoted benfield process can reduce CO2
contents to 500 ppm
Cheaper process as compared with MEA
 Catacarb Process
Aqueous Potassium carbonate solution with
catalyst and corrosion inhibitor
K2CO3 + CO2 + H2O 2KHCO3
2KHCO3 K2CO3 + CO2 + H2O
Reaction with K2CO3 is slow and is catalyzed to make
it fast
 Reaction Mechanism and Kinetics
CO2 + H2O HCO3- + H+
HCO3- CO2 + OH-
OH ions concentration is greater in K2CO3 than
water
OH = Kw / Kc * CO3/HCO3
Kw = (H+)(OH-)
Kc = (H+)(CO3)/(HCO3)
Borate added in improved process reacts with
water to form OH ions
Borate also provides buffering effect
 Properties of System
1. Catacarb Catalyst:
251-H, 202W, 400
10 12 volume%
Potassium tetra borate and or mixtures of
amines
Alkanol amines are good absorbing media for
CO2

CO2 + R2NH R2NOO + H R2NH + HCO3

 Properties of System
2. Corrosion Inhibitor:
100 H, 922A
Metavandate 13 15% in the solution
Colourless and changes to green colour when reduced to trivalent
form
Active in oxidized form
80 97% in oxidized form Relative Available Inhibitor
Regeneration by air
3. Percent Conversion:
Incomplete conversion to Carbonate form
80% conversion to bicarbonate form in absorber
20% conversion in lean solution
Difference > 19% is necessary to keep up the efficiency of the
system
 Properties of System
4. Total Alkalinity
In Straight Carbonate system pH of
rich soln = 8 - 9,
lean soln = 9 11
In borate-carbonate system, pH of
Lean soln = 10 10.5
Semi lean soln = 9.5 10
Total N = 4.5 5.5
High strength salting out and corrosion
Low alkalinity more CO2 slippage
 Properties of System
5. Borate Normality:
High borate normality salting out
Low normality no operational problem
Limits = 1.3 1.5
6. Formate Normality:
Undesirable reaction
K+ + CO + OH- HCOOK
CO slippage from LTS
Reaction sensitive to temperature (>300OF)
LTS bypassed or old / inactive catalyst
Operating limits 0.1 0.2 N
 Advantages

Low heating and cooling requirements

Low capital investment (20 -30 % less than MEA)
Simple and reliable operation and control
Low corrosion rate
Very low residual CO2
Non fouling solution
Low cost non hazardous solution
Low maintenance
High purity of recovered CO2
 Sulphinol Process
Mixture of sulpholane (tetra hydro thiophine 1,1-
dioxide), an alkanol amine (diaso-propanolamine)
and water is used
Used for syn gas purification removal of carbonyl
sulphide
H2S, mercaptans and other sulphur compounds are
removed
 Flour Solvent Process

Propylene carbonate used

High capital cost but maintenance is less
Pressure 800 2500 psig
High solubility of CO2
Low heat of solution
Non corrosive
 Tri Ethanolamine Dual Solvent Process
Pressure 20 30 atm
TEA is medium reactive solvent
Easier to regenerate
Mixture of MEA and TEA used in dual solvent
process
High CO2 removal
Low heat requirements
 aMDEA Process
Latest Technology
Used in almost all new plants
Low Energy Requirements (14 KBTU/lbmole CO2
removed)
High efficiency
Low circulation rates
Smaller towers and exchangers required
Single Solution System
Double Solution System
 Rich Solution Flasher

Installed in year 2000

To improve urea reactors efficiency
Operating pressure of 65 psig
H2 in CO2 product reduced from 0.8 1.0 % to 0.1 0.2%
Phase I implemented
H2 rich stream sent to MP CO2 compressor
Phase II will be implemented in BMR
 Filtration of Catacarb Solution
One Carbon Filter installed to remove colour
and SS
Two mechanical filters with cotton as filtering
media installed to remove Suspended Solids (SS)
Colour = 225 AH
TSS = 20 ppm
Iron = 45 ppm (Lean)
Iron = 40 ppm (Semi lean)
Service Life of filters
Dye Penetrant Testing
Pinhole
 Problems of Catacarb System
Corrosion
Leakage of carbon from 117-F
Corrosion in Absorber
Corrosion in Absorber
Corrosion in Absorber
Replacement of Damaged Section
Packing Rings after Carbon
leakage from 117-F
Packing Rings
Packing Rings