page 1

Comparison of CO2 Removal Systems

and
Conversion Options
by
Norbert Tenbrink
Uhde GmbH, Dortmund, Germany
Prepared for Presentation at the
Uhde Nitrogen Technologies Users Group Meeting 2004
Munich, Germany
24 to 25 March 2004

page 2

Content

Comparison of different Processes

Conversion to more effective Systems

PRA-011 03/01

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Content

Comparison of different Processes

Conversion to more effective Systems

PRA-011 03/01

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Base Scheme
Synthesis Gas
CO2 - Product

Absorption

Desorption

Press.: high

Press.: low

temp.: low

temp.: high

Feedgas

Heat

Rich Solution
Lean solution

PRA-011 03/01

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CO2 Removal History

Wateras
asscrubbing
scrubbingagent
agent
Water

aquqeousMonoethanole
MonoethanoleSolution
Solution(MEA)
(MEA)
aquqeous

DEA,DIPA,
DIPA,
DEA,

HotPotassium
PotassiumCarbonate
CarbonateSolution
Solution
Hot

SELEXOL,RECTISOL
RECTISOL
SELEXOL,

MDEASystems
Systems
MDEA

PRA-033 03/01

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Process Flow Sheet of the first Ammonia Plant

( Herne, Germany )

PRA-002 03/01

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Water as Scrubbing Agent

Advantages
Advantages
cheapestscrubbing
scrubbingagent
agent
cheapest
nontoxic
toxic
non
noregeneration
regenerationheat
heat
no

Disadvantages
Disadvantages
lowCO2
CO2pick-up,
pick-up,high
highsolution
solutioncirculation
circulation
low
highpump
pumpenergy
energy
high
highpressure
pressurerequired
required
high
highlosses
lossesof
ofhydrogen
hydrogen
high

PRA-033 03/01

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Aquaeous MEA Systems

Advantages
Advantages
lowCO2
CO2slip
slip
low
everywhereavailable
available
everywhere

Disadvantages
Disadvantages
lowMEA
MEAconcentrations
concentrationsbecause
becauseof
ofcorrosion
corrosion
low
highregeneration
regenerationheat
heatrequirements
requirements
high
solutiondegradation
degradation
solution
formingof
ofHSS,
HSS,reclaiming
reclaimingrequired
required
forming

PRA-033 03/01

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Hot Potassium Carbonate Processes

Benfield Process

Benfield LoHeat

Giammarco Vetrocoke Process

Catacarb Process

PRA-033 03/01

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CO2 Removal with HPC Processes

CO2 + K2CO3 + H2O

2KHCO3 + Heat

CO2 absorbtion is slow, therefore activator is needed

DEA (Diethanolamine)

CH2CH2OH
HN
CH2CH2OH

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HPC Processes

Advantages
Advantages
cheapscrubbing
scrubbingsolution,
solution,worldwide
worldwideavailable
available
cheap
moderateregeneration
regenerationheat
heatrequired
required
moderate
moderatesolution
solutioncirculation
circulation
moderate
Novapor
vaporPressure
Pressureof
ofKK2CO
CO3
No
2
3

Disadvantages
Disadvantages
corrosioninhibitor
inhibitorrequired
required
corrosion
becomesmore
moreand
andmore
moreenvironmentally
environmentallycritical
critical
becomes
passivationof
ofCS
CSbefore
beforefeed-gas
feed-gasin
in
passivation
potentialfreezing
freezingof
ofthe
thesolution
solution
potential

PRA-033 03/01

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PRA-168 03/01

UOP Benfield CO2 Removal System ( Multiflash )

CO2

Process
gas

Absorber
Absorber
Stripper
Stripper

C.W.
C.W.

Pure
gas

C.W.

Process condensate

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Multistage Flashdrum Principle

Motive
steam
To
desorber

From
desorber

P1
t1

P2
t2

P3
t3

P4

t4

P1
P1>>P2
P2>>P3
P3>>P4
P4
t1t1>>t2t2>>t3t3>>t4t4
To solution
pump

LC

PRA-165 03/01

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Physical Solvents

Advantages
Advantages
no//small
smallregeneration
regenerationheat
heat
no
caneasily
easilyremove
removeCOS,
COS,HH2S,
S,HCN
HCN
can
2
lowcorrosion
corrosionrates
rates
low

Disadvantages
Disadvantages
highvapor
vaporpressure
pressure(RECTISOL)
(RECTISOL)
high
highsolvent
solventcost
cost(SELEXOL)
(SELEXOL)
high
Refrigerationrequired
required
Refrigeration
highcapital
capitalinvestment
investment
high

PRA-033 03/01

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MDEA based Processes

aMDEA

by BASF

Amine Guard FS

by UOP

and OPTIMAL

PRA-033 03/01

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MDEA ( Formula )
Methyldiethanolamine
Methyldiethanolamine
[[ 2.2
2.2 -- (( Methylimino
Methylimino )) bisethanole
bisethanole ]]
H
H33C-N
C-N

CH
CH22CH
CH22OH
OH
CH
CH22CH
CH22OH
OH

++ Activator
Activator (proprietary)
(proprietary)

PRA-181 03/01

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MDEA based Processes

Advantages
Advantages
lowCO2
CO2slip
slip
low
goodCO2
CO2solubility
solubility
good
smallsolubility
solubilityof
ofproduct
productgases
gases
small
nosolid
solidprecipitation
precipitationsolution
solution//no
noheat
heattracing
tracing
no
lowcorrosion
corrosiontendency
tendency//no
noinhibitor
inhibitorrequired
required//no
no
low
passivation
passivation
lowregeneration
regenerationheat
heatrequirement
requirement
low
notoxic
toxicsolution
solutioneasy
easybiological
biologicaldegradable
degradable
no
chemicaland
andthermal
thermalstability
stability
chemical
lowvapor
vaporpressure
pressure
low

Disadvantages
Disadvantages
solutioncomposition
compositionis
issecret
secret
solution

PRA-033 03/01

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aMDEA CO2 Removal System

CO2 ( high pure )

Absorber
Absorber

CO2 ( fuel )

Stripper
Stripper

C.W.

Process
gas

C.W.

Pure
gas

Flash
Flashvessel
vessel

Process condensate

PRA-166 03/01

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CO2 - Solubility
3

CO2-Partialpressure [bar]

HPC
2,5

Water

MEA

1,5

Methanol
0,5

10

15

20

25

30

Nm3 CO2 / m3 Solution

35

40

45

50

PRA-011 03/01

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Specific Heat Consumption

kJ/Nm BTU/lb
BTU/lb mole
mole
kJ/Nm
aMDEA
aMDEA

1650
1650

15900
15900

Amine Guard
Guard FS
FS
Amine

1650
1650

15900
15900

Benfield LoHeat
LoHeat
Benfield

3200
3200

30800
30800

Benfield (convent.)
(convent.)
Benfield

5200
5200

50100
50100

MEA
MEA

6000
6000

58000
58000

PRA-033 03/01

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Spec. Heat Consumption depending on

Battery Limit CO2 Pressure
Pressure
Pressure

MDEA //
MDEA
AG-FS
AG-FS

Benfield
Benfield

bar(a)
bar(a)

kJ/Nm
kJ/Nm

kJ/Nm
kJ/Nm

1.15
1.15

1350
1350

3033
3033

1.30
1.30

1472
1472

3086
3086

1.50
1.50

1648
1648

3190
3190

1.80
1.80

1914
1914

n.a.
n.a.

PRA-033 03/01

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Column Packings
Selected based on performance, price, reliability
Main suppliers
Raschig
Koch Glitsch
Norton
Sulzer
etc.

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Content

Comparison of different Processes

Conversion to more effective Systems

PRA-011 03/01

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Revamp Options
MEA
Usually the solution can be changed to aMDEA or
Amine Guard FS without major modifications of the
system.

PRA-011 03/01

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Revamp of MEA Units

Advantages:
Eliminating the corrosion problems
Eliminating solution degradation
Easier operation, no reclaimer required

PRA-011 03/01

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Revamp Options

Benfield
Installation of a multistage flash for energy
reduction
Change of Activator
Change to aMDEA or Amine Guard FS

PRA-011 03/01

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Multistage Flash

Reduces the regeneration heat from approx.

1200 to 800 kcal/Nm CO2
Can be installed in Split-stream and in two
stage units

PRA-011 03/01

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Change of Activator

ACT-1
developed by UOP
LRS-10
developed by British Gas

PRA-011 03/01

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Change of Activator

Reduction of CO2 slip from 1000 to 700 ppm

Reduced solvent flow: 90 to 95%
Reduced regeneration heat: 90 to 95%
Stable solution, less degradation
Can be installed, while DEA is still present

PRA-011 03/01

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Change of Activator

Foaming can be a Problem if DEA and ACT-1

is used in the solution

PRA-011 03/01

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Change of Solvent I

HPC can be changed to aMDEA or Amine

Guard FS
But not as easy as for MEA Units
Heat Integration
HPC units are running with high Absorber
temperature; no lean/rich heat exchanger

PRA-011 03/01

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Change of Solvent II

CO2 loading capacity of solution

The pump capacity has to be checked
carefully; Density of Amine solution is lower
than for HPC-Systems
Vessel and Column Sizes
Carefully cleaning of the system is required

PRA-011 03/01

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Conversion to aMDEA

Different solvent characteristic and physical

properties

Different operational temperatures

Main equipment is similar, can be re-used

without changes

PRA-011 03/01

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Additional equipment and Modifications

Solvent/solvent heat exchanger

Lean solvent cooler (size)

Solution Pumps
Column Internals

PRA-011 03/01

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Typical Process Temperatures

Hot-pot process
C

Feed gas

aMDEA-process
C

105

70

70

50

semi-lean solution

110

74

absorber bottom

115

83

98

72

115

112

lean solution

regenerator top
regenerator bottom

PRA-011 03/01

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Heat Recovery with Lean / Rich Heat Exchanger

treated-gas

off-gas
water

absorber
regenerator

feed-gas

lean / rich
heat exchanger

PRA-011 03/01

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Possible Modifications

Pumps

Larger Impeller
Installation of a booster pump
Columns
Distributors, Flashing Feed Gallery
Packing Material, use high efficient or
structured Packing

PRA-011 03/01

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Achievable Improvements

Avoiding corrosion inhibitors

Decreased CO2 slippage
Energy savings upto 30%
Capacity increase upto 20%

PRA-011 03/01