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CO2 REMOVAL

TYPES OF CO2REMOVAL
PROCESS

1.Chemical WASHING
2.PHYSICAL WASHING
3.SOLID ADSORPTION:
PRESSURE SWING ADSORPTION
CO2 REMOVAL

DIFF.PROCESSES
1.Chemical-potassium carbonate system :
Benfield,
Giammarco-vetrocoke(GV)
Catacarb
- Alkanolamine systems: MDEA
2.Non chemical- Selexol
Fluor solvent
BASF Sepasolv
Rectisol
CO2 REMOVAL:potassium
carbonate systems

Chemical principle :Reversible


conversion of potassium carbonate to
potassium bicarbonate
K2CO3 + CO2 + H2O = 2KHCO3
+
PROMOTERS + PASSIVATOR
CO2 REMOVAL:Activator

Activator: (DEA + Glycine)


• a. Increase mass transfer rates.

• b. Reduce column sizes.

•c. Reduce heat requirements.


CO2 REMOVAL:Activator

 Liquid-film controlling reaction

 Hydrolysis of CO2 : Alkaline PH

 Amine ‘shuttle” mechanism

 - Activator removes CO2 from interface.


 - Activator is regenerated in bulk solution.
 - Activator returns to interface.
CO2 REMOVAL:Activator

 Absorption reaction in presence of activator

 R2NH + CO 2 = R2NCOOH ( at interface)


 R2NCOOH + K2CO3 + H2O = R 2 NH + 2KHCO3 (in bulk of solution)

 With DEA
 2(CH 3CH2OH)2 NH + CO 2 = (CH3 CH2 OH)2NCOO + (CH3CH2OH) NH2
 DEA Carbamate ion Ammonian ion

 (CH3 CH2 OH)2NCOO + H2O = (CH 3CH2OH)2 NH + H2CO3


 Carbamate ion DEA Carbonic acid

 (CH3CH2OH) NH2 + CO2 + H2O = (CH 3CH2OH)2 NH + 2 H2CO3


 Ammonian ion DEA Carbonic acid
 So the absorption reaction is :
 K2CO3 + H2CO3 = 2KHCO3 OR
 K2CO3 + H2O + CO 2 = 2KHC03
GV process

External reboil duty 67MJ/kmol


DMW
1080c CO2
1160c CW
Semilean
PROCESS Treated gas
regenerator
GAS
Lean CW 700 c
Regenerator 266 t/h
710 c
1580c absorber
1060c 1411 t/h
Reboiler 27 kg/cm2
DIRECT
STEAM 1090c
DMW 0c

1270c LS
LS 1160c

Cond. 1220c
Activator: Glycin e with DEA
Benfield Process
Activator : Diethanolamine(DEA)

CO2 400C Acid gas


4-stage flash tank
1.0KG/CM2
and ejectors
Lean soln.
regenerator cooler 0
70 C

Feed Gas absorber

Hydraulic
carbonate turbine
reboiler
condensate
reboiler 930C
28.3KG/CM2
LP
condensate 1300C 1220C 1120C
reboiler
BFW lean soln. Semilean soln.
heater pump pump

External reboil duty 79MJ/kmol


CO2 REMOVAL

Typical Benfield solution: Typical G V solution:


K2CO3 : 24-28%
K2CO3 : 20-22%
KHCO3: 4-8%
KHCO3: 10-12 %
DEA : 0.3-0.4 %
DEA : 2.7-2.8 %
GLYCIN E : 0.3-0.4 %
V + 4 : 0 .2 - 0.4 %
V + 4 : 0 .2 - 0.4 %
V + 5 : 0.4- 0.7 %
V + 5 : 0.3- 0.5 %

DEA IS VERY EFFECTIVE PROMOTER ,BUT IT DOES TEND TO DEGRADE


OVER A PERIOD TO FORM VARIETY OF SALTS,WHICH IMPAIR THE EFF
ECTIVENESS OF THE SOLUTION AS A CO2 ABSORBENT
Benfield Process

Acid gas

Lean soln.
Feed Gas regenerator cooler

absorber
condensate
reboiler Hydraulic
turbine

carbonate
reboiler 4-stage flash tank Benfield
and ejectors soln. pump
BFW
heater
Catacarb process
Activator : Amine borate

430c 1. 38 bara
CO2
CW
Semilean
DISCHARGES Treated gas
regenerator
PROCESS 840 c
Lean
GAS 310 t/h
Regenerator 850 c
1960c absorber
reboiler 2050 t/h
SC 1200c
29 . 5 bara
1250c
3 . 5 barg 1260c
610c
Reboiler steam

1000c

External reboil duty : 93 MJ/kmol


Catacarb process
Rich Reflux Reboiler
430c 1. 38 bara
CO2
CW
Semilean
DISCHARGES Treated gas
regenerator 1160c
840 c
PROCESS
Lean 288 t/h
GAS 6 bara
Regenerator 850 c
1960c Ri ch- absorber
reflux 2061 t/h
reboiler 1180c
1220c 29 . 5 bara
1250c
1280c
610c
Reboiler

1000c

External reboil duty reduced from 93 to 78 MJ/kmol


BASF’s a MDEA
PROCESS
Methyl-di-ethanol amine
Co2slip :50ppm purity of CO2 >99.9% Off gas
Flash gas
Treated
gas
500C 720C
water

740C stripper
Feed gas

700C
830C 1120C
absorber hp flash
lean/semi-lean exchanger
aMDEA: 40% MDEA and 6.5% Piprazine.
Density: 80 % of K2CO3
External reboil duty : 40 MJ/kmol
BASF’s a MDEA
PROCESS

Advantages
 Non-corrosive solvent
 No toxic corrosion inhivitors
 No passivation procedure
 Lower thermal energy consumption
 No solid precipitation
 No special heat tracing
 High thermal and chemical stability of the
solvent,therefore no degradation.
 Low vapor pressure, therefore low solvent loss.
 It is environment friendly and biodegradable
chemical.
BASF’s a MDEA
PROCESS
Process Description of Two stage a-MDEA.
The solvent is an Amine solution, Methyl-di-ethanol amine
(MDEA) being the active component. In addition, the scrubbing
solution contains an activator (Piprazine) to enhance the CO2
absorption rate.
The feed gas enters the absorber at the bottom, and CO2 is
removed from the gas by counter-current absorption in two
stages. In the bottom portion of the absorber,flash regenerated
solution is used for bulk CO2 removal. In the top portion of the
absorber, stripped solvent is used for purification to
specification. The treated gas with a CO2 conc. Of less than 50
ppm, leaves the absorber.
BASF’s a MDEA
PROCESS

The rich solution from the bottom of the absorber is


depressurized through a hydraulic turbine which is used for
driving the semi-lean pumps. The flash regeneration of the rich
solution is performed in two stages. In the high pressure flash
column a large part of the dissolved inert components is
expelled. The liquid is then flashed in the low pressure flash
column, where CO2 is removed from the solution to a large
extent.. The CO2 released in the low pressure flash vessel is
saturated with water vapour. It is cooled in condenser. The
condensate is then separated and recycled to the regenerator
system.. The CO2 leaves the system with a purity of 99.6
percent.
BASF’s a MDEA
PROCESS
The flashed solution from the bottom of low pressure flash
column is split into two streams. The major part of the solution
is pumped back to the bottom portion of the absorber as semi-
lean solution. Only a minor part of the flashed solution is fed to
the stripper via a lean/semi-lean exchanger. The solution is
stripped completely with the help of steam, generated in the
stripped gas reboiler. The stripper off gas is passed through low
pressure flash vessel to assist flashing in the low pressure
column. Thus the heat of the stripper reboiler is recovered
within the process to a large. The lean solu. From bottom of
stripper is cooled in lean/semi-lean exchanger and lean solution
cooler
BASF’s a MDEA
PROCESS

Most of the ammonia plants are attempting to uprate the plant


capacity, one of the bottleneck identified is CO2 removal section as
use of naphtha along with NG, the CO2 production can be increased.
The use of a-MDEA process has advantage than others because.
 It can be retrofitted in same equipments and lower circulation rate.
 Low inert make up in Syn gas due to low CO2 slip which is good for
ammonia synthesis catalyst, also less hydrogen consumption in
methanator and reduction of purge gas.
The purity of CO2 is more (99.9%), the Hydrogen concentration in
CO2 is less. H2 makes explosive mixture in Urea plant and influence
corrosion.

However the foaming is observed as a concern in this process.


Benfield-a MDEA
revamping
Condenser 2
and knock-out drum Condenser 1
and knock-out drum
CO2 PRODUCT

Co2 absorber

Co2 slip
CO2
Semi-lean
1000 PPM
STRIPPER
Cooler Lean/rich
500 PPM
New LEAN
exchanger(New)
Reboiler
RICH
54MW

29MW
External reboil duty reduced from 120 MJ/ kmol to 65 MJ/kmol
CO2 REMOVAL:Corrosion
Inhibitor

 Permit mostly carbon steel material.

 Extend equipment life.

 Reduce maintenance .
CO2 REMOVAL:Corrosion
Inhibitor

 Reaction for corrosion protection :


v+5 + Fe+2 v+4 + Fe+3
 As v+5 is yellow in colour and v+4 is blue in colour , the
colour of solution would be yellowish green or bluish green
depending upon the majority of v+5 or v+4
 Factor of conversion:
Fc=1-{K2CO3 / (K2CO3 + 0.69 KHCO3 ) }
 Less amount of KHCO3 than K2CO3 is advantageous due to
the vast difference in the solubilities of KHCO3 (60
gms/100cc in boiling water) and K2CO3(331 gms/100 cc in
boiling water) .This will always keep the bicarbonate in
soln. Which would otherwise precipitate and start fouling
.The precipitated bicarbonate not only peels off the
passivating layer but also the iron and vanadium in the
solution “ Co-precipitate ” forming a slurry.
CO2 REMOVAL:Corrosion
Inhibitor

 Iron on surfaces is oxidised to Fe2O3 (Fe+2 to Fe+3)


 V+5 provides potential required for Fe,Fe3O4 to Fe2O3
 Vanadium (V2O5) is reduced from V+5 to V+4
 V2O5 in solution as KVO3 (actual composition of vanadium in
soln.)

 Fe2O3 produces tight, adherent film, so there should be no


reaction unless film is disturbed. Once system is passivated,
there is no corrosion, means no consumption of V2O5 and need
minimum concentration to maintain Fe2O3 film.
 The passivation film may shrink or crack on drying out or
exposure to oxygen.

CO2 REMOVAL:Foaming

 A.Types of antifoam
 - Polyglycols ( UCON, NIXOLEN SL 150 etc.)
 - Silicones
 -High M.W. Alcohol
 B. Causes of foaming Due to Contamination
 -Particulate
 dirt, rust, sooth, catalyst dust, etc.
 -Hydrocarbons
 oils & greases
 -Plasticizers
 DEA degradation compounds
CO2 REMOVAL:Foaming

Indications of foaming:

Any one or all the mentioned.


 Rapid increase in pressure drop across the columns.
 Solution carryover to downstream separators.
 By routine foam test.
 Widely fluctuating solution levels of towers.
 Fluctuating CO2 levels in absorber exit gas.
CO2 REMOVAL:Aeration

A small stream of GV solution made in contact with air to convert


V+4 V+5 To lean soln.
Pump suction

GV soln.from filtration AERATION


TANK

s
Lean soln. Oxid.soln.
from To soln.
lean soln. Storage
pump tank
CW Instrument air
CO2 REMOVAL:Filtration

 Mechanical Filters
5 micron filter elements to catch suspended particles, rust, catalyst dust,
refractory etc.
 Carbon Filter
Activated carbon to filter out foaming impurities.

To & from
aeration system

From LP Reg. To Lean pump


From HP Reg. suction From
From Storage tank To HP Reg. soln.prep
From soln.prep.tank .tank
CO2 REMOVAL:Physical
Absorption
Advantage:Very low energy requirement

Disadvantage:
•Volatility is a prime concern in choice of solvent

•Physical solvents have slow absorption, so larger vessels required and circulation
of solvent is high.

•They operate cold absorber, so need cooling / reheating.

•In process gas CO2 slip is high for ammonia plant requirement.

.
CO2 REMOVAL

Physical absorption.
Selexol process -Here solvent used is a
homologue of diethylether of polyethylene-
glycols.
Rectisol process - The method uses
various organic liquids as solvent, but for
ammonia syn. Gas, methanol is choice.The
process is quite flexible in regard to
operating pressure and composition of
feed gas.
CO2 REMOVAL:Solid
Adsorption

CO2 is selectively adsorbed by a porous solid


and then desorbed by depressurizing-
Pressure swing adsorption
PGR & B-510
DMW
1080c CO2
1160c CW
Semilean
Treated gas
regenerator CW
700 c
Lean 266 t/h
Regenerator 710 c
absorber
1060c 1411 t/h
27 kg/cm2
1090c
DMW

1160c