Catalytic CO2 refining
Johannes Schedler
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April 18, 2013
Content
Overview CTP
CO2 sources/impurities
Advantages of catalytic approach
Catalyst selection and properties
Selected references and applications
Links
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OUR MISSION
The development of
Individual Solutions
for the removal of
Organic and Inorganic
Compounds from waste gases
while pursuing
Operational Excellence.
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WORLDWIDE NETWORK
> 500 installed systems worldwide
CTP Korea
• Sales
• Customer Service
• Manufacturing
CTP-Dumag Austria
Industrial burner systems
Cooperation with Messer A:
Oxygen burners
CTP Sinto America Inc.
Subsidiary
•Full service
•Manufacturing capabilities
(Roberts Sinto)
Subsidiary
•Detailed engineering
•24 hrs service
•Manufacturing capabilities
(TUKSU)
CTP, AUSTRIA
Headquarters
•Full service
•Manufacturing capabilities
CTP France
Subsidiary
•Full service for the
French market
F.P. Engineering, ZA
Partner
•Full service
•Manufacturing
Aerison, Australia
Licensee
•Full service
•Manufacturing
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SINTOKOGIO, Japan
Licensee
•Detailed engineering
•Full service
•Manufacturing
SYSTEMS
Regenerative thermal
oxidation (RTO)
VOXcube
AutoTherm
EcoTherm007®
CompacTherm
Catalytic oxidation
(CO)
RecuKAT (CO)
AutoKAT (RCO)
Direct thermal
oxidation (TO)
MultiTherm
Selective catalytic
reduction (SCR)
RecuNOx
NOxTherm
AutoNOx
Fixed Bed Adsorption
VOXsorbTherm
Selective non-catalytic
reduction (SNCR)
VOCNOxTherm
Rotary Adsorbers
RotosorbTherm
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Rich CO2 Sources
Chemical industry
Natural gas processing
Fermentation processes
Geothermal
Contaminations:
•Low boiling organic components
(Ethylene, Propane, Butane, BTX)
•Methane
•Traces of Sulfur, Si, salts
Problem of thermal combustion:
Introduction of excess Oxygen!
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Bioethanol production (A)
Principal solution Catalytic Oxidation
Why catalytic cleaning?
• High degree of purification (>99,99%)
• Extremely low excess Oxygen (<0,2%)
• Clean process (electrical heater, stainless)
• Methane injection into raw gas (no el. Heating)
• High pressure design possible
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Catalyst selection
Platinum catalyst
Palladium catalyst
High efficiency for Ethylene, EO…
High efficiency for Methane
Low light-off temperature (<200°C)
High light-off temperature (>250°C)
Not sensitive to sulfur deactivation
Sensitive to sulfur deactivation
No influence of water content
High influence of water content
Variable dotation of Pt
Variable dotation of Pd
Combination of both types for increased performance!
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Reference CO Messer Belgium
Performance data
Emission source: EO production
Flow: 25.000 kg/h CO2
Contaminants:
Ethylene 1.200 ppm
Methane 1.000-2.000 ppm
Traces of Propane, Butane….
Purified gas:
Methane < 50 ppm
Ethylene < 5 ppm
Oxygen < 0,2 %
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Reference CO Messer Belgium
Flow Sheet
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Oxygen and Methane premixing
• Perfect mixing is essential!
• Solution: Uniform injection and primary mixing
• Secondary mixing in main fan
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Tube/shell heat exchanger
• 3.000 tubes at 7 m length
• 990 m² exchange area
• highest efficiency (up to 84%)
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CTP Catalyst Performance
Conversion of Ethylen 1000 vpm
conversion
%
100,000
SV 8000 1/h (Pd+Pt)
conversion at 325°C inlet
conversion at 300°C inlet
conversion at 275°C inlet
99,995
99,990
99,985
99,980
Limit
99,975
99,970
99,965
99,960
99,955
99,950
0,00
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0,10
0,20
0,30
0,40
Oxygen content downstream of catalyst in Vol.-%
0,50
0,60
CTP Catalyst Performance
Conversion of Methane 2000 vpm
conversion
%
100,0
SV 8000 1/h (Pt+Pd)
conversion at 400°C inlet
conversion at 375°C inlet
conversion at 350°C inlet
conversion at 325°C inlet
99,5
99,0
98,5
98,0
Limit
97,5
97,0
96,5
96,0
95,5
95,0
94,5
94,0
0,00
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0,10
0,20
0,30
0,40
Oxygen content downstream of catalyst in Vol.-%
0,50
0,60
Palladium catalyst
Influence of humidity and system pressure
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Catalyst Performance
TOC after cat
Methane conversion
21 Vol.-% O2 for 30 s
Deactivation at Lack of O2 and Reactivation
O2 after cat
100
95
85
80
0,70
75
0,60
65
0,50
60
55
50
45
40
35
0,40
0,30
30
25
0,20
20
15
0,10
10
5
0
0,00
0
16
10
20
30
40
50
60
70
80
time in min
90
100
110
120
130
140
O2 after cat in Vol.-%
70
0 Vol.-% O2 for 30 s
TOC in mg/Nm³
Methane conversion in %
90
0,80
Reference CO from EO production
(Germany)
Performance data
Capacity: 15.000 kg/h CO2
CO2 production: 110.000 to/year
Contaminants from EO production:
Ethylene
4.000 ppm
Ethylene Oxide 4.500 ppm
Methane
3.500 ppm
Limits purified gas:
Ethylene
< 1 ppm
Ethylene Oxide < 0,5 ppm
Methane
< 50 ppm
Oxygen
< 0,2 %
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Reference CO from EO production
(Germany)
Scope for revamping 2010
• Heat exchanger in steel frame
• Piping
• Additional catalyst
• Injection and mixing devices
• Blower
• Valves
• Insulation
• Erection
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Customer specific solutions (Asia)
Catalytic Oxidation
Unit
CTP scope
Typical scheme of a CATOX unit used to
purify weakly contaminated CO2 coming
from an Ethylene Oxide Production plant
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High pressure Catalytic Oxidizer
Application: Geothermal energy from water + CO2
Emission source: CO2 recovery
Contaminants: Methane (CH4)
Low hydrocarbons
H2S, COS
CTP system: CO 5.000 kg/h – 25 bar (g)
Auxiliary systems: Sulfur adsorption device
Start up: 2012
Location: Turkey (TR)
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High pressure Catalytic Oxidizer
Design
El.Heater
Aftercooler
Control
panel
Adsorber
Catalyst
Recuperator
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Chemical Industry
Catalytic
Oxidation Unit
CTP scope
Customer specific approach
for optimum solution!
Typical scheme of a CATOX unit used to
purify highly contaminated CO2 coming
from an Ethylene Oxide Production plant
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Links
http://ctp-airpollutioncontrol.com
http://us.ctp-airpollutioncontrol.com
http://ctp-dumag.com
http://www.messergroup.com
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