open proposal project #2
TRANSCRIPT
Microsoft PowerPoint - GCRC 2013 Presentation_(#02).pptxOpen
Proposal Project #2
- Design and reliability of porous ceramics and functional materials
: Ceramic Filter, SCR Catalysts, Dielectrics for MLCC, Cathode Materials for SOFC, Hard Coating, etc.
Lab. Introduction - Members
Pusan National University
- Ph. D Candidates : 4 (9)
- Master Candidates : 3 (1)
Efficiency Test
Durability Test
(NRL program, MOST)
(G-7 project, ME)
1. Research background
Contents
Research background
- Global warming - Human body
Smog Acid rain
1 / 23Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Current and Future Emission Limits for NOx (IMO Regulation)
0 With the aim of reducing ship emissions of NOx world-wide by 30%,
the IMO decided in 1997 on a first ruling.
- Modern marine diesel engines are capable of keeping to these limits or below. (Tier I and II)
→ This is achieved with engine measures: the design of optimal combustion chambers,
injection and charging systems.
Research background
n ≥
2000
Valid
since/from
g/kWh
9.8
g/kWh
7.7
g/kWh
2.0
Source : International Maritime Organization (IMO)
(n : crankshaft rotation per minute) Table . Current and Future Emission Limits for NOx
Source: H+H Umwelt- und Industrietechnik GmbH
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II) 2 / 23
Different ways and technologies for NOx reduction
Research background
0 NOx reduction can be achieved in different ways.
- Basic internal engine modification
- Humid air motor (HAM) – (Tier II level)
→ The SCR technology can reduce the NOx emissions to Tier III level.
Table . Different ways and technologies for NOx reduction
Technology Efficiency [% below IMO]
Direct water injection ~ 50 %
Humid air motor (HAM) ~ 70 %
Selective catalytic reduction (SCR) ~ 95 %
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II) 3 / 23
Research background
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
SCR: selective catalytic reduction
Undesirable Parallel Reactions
0 Stationary & mobile sources
4 / 23
High Temperature
Working Temperature
SCR system
0 Downstream
0 Upstream
dustSOx
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
BOILER / Engine
NH3NOxNOxNOx
Research background
Contents
(MnO2-TiO2, CeO2-TiO2)
0 Synthesis of de-NOx SCR catalyst with different transition metal
(MnO2-CeO2/TiO2, CeO2-WO3/TiO2)
0 Durability test and failure analysis
0 Accelerated testing for de-NOx SCR catalyst of marine
Characterization and
durability test
0 Durability test and failure analysis for marine applications
- Design of durability test with SO2/SO3 and ammonium bisulfate/sulfate
Research purpose & contents
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II) 6 / 23
Roadmap – Design and reliability of de-NOx SCR catalysts for marine
Research purpose & contents
0 Durability test - Stress factor : temperature, SO2 gas, ammonium bisulfate, humidity, etc. - Stress mode : constant, etc.
0 Failure analysis
Characterization
CeO2-MnOx/TiO2, CeO2-WO3/TiO2
0 Powder characteristics
0 Physico-chemical properties
: types of engine for marine
0 Failure analysis
Topic 1 Topic 2
: As-is , : To-be
- Impregnation, sol-gel,
0 Accelerated stress leveling 0 Accelerated test & modeling → Lifetime prediction
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II) 7 / 23
Roadmap – Design and reliability of de-NOx SCR catalysts for marine
Research purpose & contents
0 Simultaneous removal
0 Failure analysis
: As-is , : To-be
- Impregnation, sol-gel,
0 Reliability test - Accelerated test & modeling - Technical support for assessment
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
SAMSUNG HEAVY INDUSTRIES
8 / 23
Contents
1μm 1μm
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
0 Preparation method : sol-gel method
- Solvent content: amorphous / crystallinity
- Acidity control: active site
(Brønsted & Lewis acid sites)
: specific surface area, crystallinity,
Catalytic activity (performance)
- NOx conversion efficiency
Topic 1 : Design of low-temperature de-NOx SCR catalysts
Fig . XRD patterns of TiO2 and CeO2-TiO2
with different CeO2 content.. Fig . SEM images of the CeO2-TiO2 powders with different
CeO2 content: (a) 0 wt.% CeO2-TiO2 (b) 30 wt.% CeO2-TiO2.
1μm 1μm 1μm
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
10 20 30 40 50 60 70 80 90
C : Cubic CeO 2
2
TiO2 10 wt.% CeO2 -TiO2 20 wt.% CeO2 -TiO2 30 wt.% CeO2 -TiO2
A
0 Crystal structure : anatase structure without rutile or brookite structure
0 Particle size : CeO2-TiO2 (80 ~ 100 nm), CeO2-MnOx-TiO2 (10 ~ 20 nm, 200 ~ 300 nm)
√ Commercial powder (150 ~ 500 nm)
0 Specific surface area: CeO2-TiO2 (80 ~ 90 m2/g), CeO2-MnOx-TiO2 (110 ~ 120 m2/g)
√ Commercial powder ( > 60 m2/g)
Fig . De-NOx efficiency
100 150 200 250 300 350 400 450 500 10
20
30
40
50
60
70
80
90
100
100 150 200 250 300 350 400 450 500 10
20
30
40
50
60
70
80
90
100
MnOx/TiO2
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
100 150 200 250 300 350 400 10
20
30
40
50
60
70
80
90
100
V2O5-based catalyst
MnOx-based catalyst
CeO2-based catalyst
0 Ternary system (CeO2-doped MnOx-TiO2) - superior both de-NOx efficiency and SO2-resistance
- De-NOx efficiency : poor
NOx conversion and physical characteristics – CeO2-MnOx-TiO2
Fig. . The catalytic activities of CeO2-doped MnOx-TiO2 catalysts as a function of ceria contents for the NOx conversion efficiency with NH3.
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
100 150 200 250 300 0
20
40
60
80
100
0 wt.% CeO2 - MnOx(20 wt.%) -TiO2
10 wt.% CeO2 - MnOx(20 wt.%) -TiO2
20 wt.% CeO2 - MnOx(20 wt.%) -TiO2
30 wt.% CeO2 - MnOx(20 wt.%) -TiO2
- The de-NOx efficiency with NH3 of MnOx-TiO2 was increased by the addition of CeO2.
- The addition of ceria induces the enhancement of specific surface area and pore volume.
Table. Physical characteristics of the CeO2-doped MnOx-TiO2 catalysts.
Samples BET surface
12 / 23
The morphology of CeO2-MnOx-TiO2 catalyst with ceria content
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Fig. TEM images of CeO2-doped MnOx-TiO2 catalyst
MnOx-TiO2 10 wt.% CeO2-MnOx-TiO2
Topic 1 : Design of low-temperature de-NOx SCR catalysts
- The grain growth of CeO2-doped catalysts was well-suppressed by the addition of CeO2.
It is originated from the hygroscopic property of CeO2 during sol-gel method.
13 / 23
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Chemical characteristics (catalytic acid sites)
- NH4 + species : Brønsted acid sites
- Amid (-NH2) species : Lewis acid sites
→ The Lewis and Brønsted acid sites increased
with increasing NH3 adsorption.
after-treated in flowing NH3 at room temperature
2000 1800 1600 1400 1200 1000
15411623 1399
A b
so rb
an ce
Wavenumber (cm-1)
3600 3400 3200 3000
0 wt.% CeO2-MnOx-TiO2 10 wt.% CeO2-MnOx-TiO2 20 wt.% CeO2-MnOx-TiO2 30 wt.% CeO2-MnOx-TiO2
Wavenumber (cm-1)
A b
so rb
an ce
NH3 adsorption
14 / 23
S O
(unreacted) (200 ~ 250 )
Sulfate
N
H
H
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Topic 2 : Durability and failure analysis
SO3 + MnO2 / Mn2O3 Mn(SO4)2 / Mn2(SO4)3
Mn sulfate Poisoning
15 / 23
0 SO2 resistance
Fig. The SO2 effect of (a) MnOx-TiO2 and (b) 30 wt. % CeO2-doped MnOx-TiO2 catalysts on catalytic activity with and without SO2 gas.
Chemical degradation of de-NOx SCR catalysts in flue gas containing SO2
100 150 200 250 300
40
50
60
70
80
90
100
40
50
60
70
80
90
% )
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Topic 2 : Durability and failure analysis
- MnOx-TiO2 catalyst, NOx conversion efficiency decreased in flue gas containing SO2.
- CeO2-doped catalyst, its efficiency was improved as about 15-19 %.
(a)
16 / 23
0 The increase of Mn sulfate and S=O double bonding
: Mn sulfate affects the poisoning on SCR reaction
Fig. FT-IR (fourier transform infrared) spectra of CeO2-doped MnOx-TiO2
after-treated in flowing NH3 at room temperature
Chemical degradation of de-NOx SCR catalysts with SOx
1500 1400 1300 1200 1100 1000 900 800
964
20 wt. % CeO2-MnOx-TiO2
30 wt. % CeO2-MnOx-TiO2
10 wt. % CeO2-MnOx-TiO2
Asymmetric vibration mode of O=S=O (SO2)
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Topic 2 : Durability and failure analysis
NH3 adsorption
Reaction mechanism of Ce oxides over CeO2-MnOx-TiO2 catalyst with SOx
* Redox cycling: Ce4+ ↔ Ce3+
H
Ce3+
O
O
O
Ce3+
O
O
O
O OO or
H
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Topic 2 : Durability and failure analysis
18 / 23
Characterization and durability test for marine applications
0 Characterization of ceramic filter/SCR catalyst
- Powder characteristics and physico-chemical properties
- NOx conversion efficiency
- SO2/SO3 resistance
Fig. Catalytic activity of ceramic filter/catalyst with and without ammonium bisulfate/sulfate.
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Ammonium Bisulfate
20
30
40
50
60
Temperature(oC)
5. 61 %
Catalyst (V2O5-based)
- Technical meeting
Korea testing laboratory, Pusan national university
6 March, 28 May, 29 August, 2 October, 4 November.
- Open Lecture (at Samsung heavy industries)
“Design and reliability of hybrid materials–Porous materials”
June 7, 2013
December 27, 2013
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Punched Plate
Air pulse
Ammonia gas(NH3)
Fly ash
Design of low-temperature de-NOx SCR catalysts
: MnOx-TiO2, CeO2-TiO2, CeO2-MnOx-TiO2, CeO2-WO3-TiO2
CeO2-MnOx-TiO2 (10 ~ 20 nm, 200 ~ 300 nm)
- Specific surface area : CeO2-TiO2 (80 ~ 90 m2/g),
CeO2-MnOx-TiO2 (110 ~ 120 m2/g)
0 NOx conversion efficiency
0 Catalytic acid sites
- FT-IR spectroscopy: Lewis & Brønsted acid sites increased by the addition of CeO2
→ It caused by the enhancement of NH3 adsorption.
Summary of research results
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II) 21 / 23
Summary of research results
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Durability and failure analysis – CeO2-MnOx-TiO2
0 Improvement and modification
- Decrease of the formation of Mn sulfate (FT-IR)
→ maintained the SCR efficiency of NOx
- Increase of the NH3 adsorption
0 Future plan
Stress level: SO2 concentration & reaction time, H2O, etc.
- Improvement and modification by feedback research
· De-NOx efficiency and durability (of multi-stress)
- Technical support for reliability assessment
Characterization
- Journal of Alloys and Compounds, April 2013
- Journal of the Korean Institute of Metals and Materials, October 2013
- Journal of of Solid State Electrochemistry, October 2013
0 Domestic Journal - 1
0 Conference Presentation - 2
Research outcomes
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Industry-University Liaison
- Characterization and durability test of ceramic filter/SCR catalyst for marine applications
0 Open Lecture
- Design and reliability of hybrid materials – Porous materials, 7 June 2013 at SHI.
(December 27, 2013)
23 / 23
Many thanks for your kind attention ! [Acknowledgement] This study is financially supported by GCRC-SOP.
Thank Dr. MC Shin and Dr. JS Cha in Korea Testing Laboratory.
+82-51-510-2388
To make the SKY more beautiful ..!
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Fig. Schematic diagram of SCR micro reactor Fig. Photographs of SCR micro reactor
SCR catalytic activity
: NOx conversion efficiency
- Bulk : 4 cm diameter (Square 1 inch X 1 inch)
- Powder : 2 cm diameter
0 [SO2] = 300 ppm, [H2O] = 5%, 10%
0 Temp. range : 100 ~500, SV = about 30,000 h-1
Q & A
a
b
- Bulk density, porosimetry
- Thermal analysis (TG-DTA, DSC)
0 Catalytic performance
- Catalyst Activity Testing
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Q & A
0 Types of engine for ships
- 4-stroke diesel engine
· Exhaust gas temp after T/C : 200 – 290
*T/C : turbo charger
- 2-stroke diesel engine
: Main engine, 100rpm.
· Gas temp after *T/C : 200 – 290
· High/low pressure
Q & A
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Preparation and characteristics of SCR catalysts
Fig . XRD patterns of TiO2 and CeO2-TiO2 with different CeO2 content..
Fig . SEM images of the CeO2-TiO2 powders with different CeO2 content: (a) 0 wt.% CeO2-TiO2 (b) 30 wt.% CeO2-TiO2.
1μm 1μm 1μm
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
10 20 30 40 50 60 70 80 90
C : Cubic CeO 2
20 wt.% CeO2 -TiO2 30 wt.% CeO2 -TiO2
A
0 Crystal structure : anatase structure without rutile or brookite structure
0 Particle size : MnOx-TiO2 (100 ~ 150 nm), MnOx-WO3/TiO2 (80 ~ 100 nm),
CeO2-TiO2 (80 ~ 100 nm), CeO2-MnOx-TiO2 (10 ~ 20 nm, 200 ~ 300 nm)
0 Specific surface area: MnOx-TiO2 (80 ~ 90 m2/g) → (150 ~ 170 m2/g),
CeO2-TiO2 (80 ~ 90 m2/g), CeO2-MnOx-TiO2 (110 ~ 120 m2/g)
Q & A
Crystallinity – CeO2-doped MnOx-TiO2
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
- The characteristic diffraction lines of CeO2 and MnOx were not detected in all catalysts
- The amorphous states of anatase (TiO2) are decreased by CeO2 loadings
Fig. XRD spectra of CeO2-MnOx-TiO2 as a function of CeO2 contents.
10 20 30 40 50 60 70 80 90
a : anatase a
2
2
2
2
CeO 2CeO2
Q & A
The dispersion of CeO2-MnOx-TiO2 catalyst with ceria content
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
20 wt.% CeO2
MnOx-TiO2
Q & A
NH3 desorption in the temperature range 100 – 850 °C with/without SOx
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Fig. NH3-TPD profiles of 30 wt. % CeO2-MnOx-TiO2
100 200 300 400 500 600 700 800 900
Temperature (C)
T C
D s
ig n
Weakly adsorb NH3
Chemisorbed NH3 by sulfate
3600 3400 3200 3000
30 wt.% CeO2-MnOx-TiO2
with and without SO2 gas at room temperature.
- NH3 adsorption increased with SO2
Q & A
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Q & A
0
0 Hazard of ammonia - Ammonia gas makes pH of our body decrease by transferring NH3 to NH4+.-
- When ammonia exists in the air,
→ can make fine dust by reacting with other acid pollutant.
→ can make ammonium nitrate by reacting with NOx or ozone.
0 removal method of ammonia gas
- Direct Combustion method
- Adsorption method
→ is not appropriate for long-term use such as automobile.
- Catalytic oxidation method
→ is appropriate for low ammonia concentration.
→ is the best method for ammonia removal
→This method common called as “Selective Catalytic oxidation”
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Q & A
- Use Platinum Group Metal(PGM)
pollutant
0 N2(nitrogen) Selectivity
pollutant
spotlighted
NH3 slip monolith
- Design and reliability of porous ceramics and functional materials
: Ceramic Filter, SCR Catalysts, Dielectrics for MLCC, Cathode Materials for SOFC, Hard Coating, etc.
Lab. Introduction - Members
Pusan National University
- Ph. D Candidates : 4 (9)
- Master Candidates : 3 (1)
Efficiency Test
Durability Test
(NRL program, MOST)
(G-7 project, ME)
1. Research background
Contents
Research background
- Global warming - Human body
Smog Acid rain
1 / 23Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Current and Future Emission Limits for NOx (IMO Regulation)
0 With the aim of reducing ship emissions of NOx world-wide by 30%,
the IMO decided in 1997 on a first ruling.
- Modern marine diesel engines are capable of keeping to these limits or below. (Tier I and II)
→ This is achieved with engine measures: the design of optimal combustion chambers,
injection and charging systems.
Research background
n ≥
2000
Valid
since/from
g/kWh
9.8
g/kWh
7.7
g/kWh
2.0
Source : International Maritime Organization (IMO)
(n : crankshaft rotation per minute) Table . Current and Future Emission Limits for NOx
Source: H+H Umwelt- und Industrietechnik GmbH
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II) 2 / 23
Different ways and technologies for NOx reduction
Research background
0 NOx reduction can be achieved in different ways.
- Basic internal engine modification
- Humid air motor (HAM) – (Tier II level)
→ The SCR technology can reduce the NOx emissions to Tier III level.
Table . Different ways and technologies for NOx reduction
Technology Efficiency [% below IMO]
Direct water injection ~ 50 %
Humid air motor (HAM) ~ 70 %
Selective catalytic reduction (SCR) ~ 95 %
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II) 3 / 23
Research background
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
SCR: selective catalytic reduction
Undesirable Parallel Reactions
0 Stationary & mobile sources
4 / 23
High Temperature
Working Temperature
SCR system
0 Downstream
0 Upstream
dustSOx
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
BOILER / Engine
NH3NOxNOxNOx
Research background
Contents
(MnO2-TiO2, CeO2-TiO2)
0 Synthesis of de-NOx SCR catalyst with different transition metal
(MnO2-CeO2/TiO2, CeO2-WO3/TiO2)
0 Durability test and failure analysis
0 Accelerated testing for de-NOx SCR catalyst of marine
Characterization and
durability test
0 Durability test and failure analysis for marine applications
- Design of durability test with SO2/SO3 and ammonium bisulfate/sulfate
Research purpose & contents
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II) 6 / 23
Roadmap – Design and reliability of de-NOx SCR catalysts for marine
Research purpose & contents
0 Durability test - Stress factor : temperature, SO2 gas, ammonium bisulfate, humidity, etc. - Stress mode : constant, etc.
0 Failure analysis
Characterization
CeO2-MnOx/TiO2, CeO2-WO3/TiO2
0 Powder characteristics
0 Physico-chemical properties
: types of engine for marine
0 Failure analysis
Topic 1 Topic 2
: As-is , : To-be
- Impregnation, sol-gel,
0 Accelerated stress leveling 0 Accelerated test & modeling → Lifetime prediction
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II) 7 / 23
Roadmap – Design and reliability of de-NOx SCR catalysts for marine
Research purpose & contents
0 Simultaneous removal
0 Failure analysis
: As-is , : To-be
- Impregnation, sol-gel,
0 Reliability test - Accelerated test & modeling - Technical support for assessment
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
SAMSUNG HEAVY INDUSTRIES
8 / 23
Contents
1μm 1μm
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
0 Preparation method : sol-gel method
- Solvent content: amorphous / crystallinity
- Acidity control: active site
(Brønsted & Lewis acid sites)
: specific surface area, crystallinity,
Catalytic activity (performance)
- NOx conversion efficiency
Topic 1 : Design of low-temperature de-NOx SCR catalysts
Fig . XRD patterns of TiO2 and CeO2-TiO2
with different CeO2 content.. Fig . SEM images of the CeO2-TiO2 powders with different
CeO2 content: (a) 0 wt.% CeO2-TiO2 (b) 30 wt.% CeO2-TiO2.
1μm 1μm 1μm
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
10 20 30 40 50 60 70 80 90
C : Cubic CeO 2
2
TiO2 10 wt.% CeO2 -TiO2 20 wt.% CeO2 -TiO2 30 wt.% CeO2 -TiO2
A
0 Crystal structure : anatase structure without rutile or brookite structure
0 Particle size : CeO2-TiO2 (80 ~ 100 nm), CeO2-MnOx-TiO2 (10 ~ 20 nm, 200 ~ 300 nm)
√ Commercial powder (150 ~ 500 nm)
0 Specific surface area: CeO2-TiO2 (80 ~ 90 m2/g), CeO2-MnOx-TiO2 (110 ~ 120 m2/g)
√ Commercial powder ( > 60 m2/g)
Fig . De-NOx efficiency
100 150 200 250 300 350 400 450 500 10
20
30
40
50
60
70
80
90
100
100 150 200 250 300 350 400 450 500 10
20
30
40
50
60
70
80
90
100
MnOx/TiO2
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
100 150 200 250 300 350 400 10
20
30
40
50
60
70
80
90
100
V2O5-based catalyst
MnOx-based catalyst
CeO2-based catalyst
0 Ternary system (CeO2-doped MnOx-TiO2) - superior both de-NOx efficiency and SO2-resistance
- De-NOx efficiency : poor
NOx conversion and physical characteristics – CeO2-MnOx-TiO2
Fig. . The catalytic activities of CeO2-doped MnOx-TiO2 catalysts as a function of ceria contents for the NOx conversion efficiency with NH3.
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
100 150 200 250 300 0
20
40
60
80
100
0 wt.% CeO2 - MnOx(20 wt.%) -TiO2
10 wt.% CeO2 - MnOx(20 wt.%) -TiO2
20 wt.% CeO2 - MnOx(20 wt.%) -TiO2
30 wt.% CeO2 - MnOx(20 wt.%) -TiO2
- The de-NOx efficiency with NH3 of MnOx-TiO2 was increased by the addition of CeO2.
- The addition of ceria induces the enhancement of specific surface area and pore volume.
Table. Physical characteristics of the CeO2-doped MnOx-TiO2 catalysts.
Samples BET surface
12 / 23
The morphology of CeO2-MnOx-TiO2 catalyst with ceria content
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Fig. TEM images of CeO2-doped MnOx-TiO2 catalyst
MnOx-TiO2 10 wt.% CeO2-MnOx-TiO2
Topic 1 : Design of low-temperature de-NOx SCR catalysts
- The grain growth of CeO2-doped catalysts was well-suppressed by the addition of CeO2.
It is originated from the hygroscopic property of CeO2 during sol-gel method.
13 / 23
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Chemical characteristics (catalytic acid sites)
- NH4 + species : Brønsted acid sites
- Amid (-NH2) species : Lewis acid sites
→ The Lewis and Brønsted acid sites increased
with increasing NH3 adsorption.
after-treated in flowing NH3 at room temperature
2000 1800 1600 1400 1200 1000
15411623 1399
A b
so rb
an ce
Wavenumber (cm-1)
3600 3400 3200 3000
0 wt.% CeO2-MnOx-TiO2 10 wt.% CeO2-MnOx-TiO2 20 wt.% CeO2-MnOx-TiO2 30 wt.% CeO2-MnOx-TiO2
Wavenumber (cm-1)
A b
so rb
an ce
NH3 adsorption
14 / 23
S O
(unreacted) (200 ~ 250 )
Sulfate
N
H
H
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Topic 2 : Durability and failure analysis
SO3 + MnO2 / Mn2O3 Mn(SO4)2 / Mn2(SO4)3
Mn sulfate Poisoning
15 / 23
0 SO2 resistance
Fig. The SO2 effect of (a) MnOx-TiO2 and (b) 30 wt. % CeO2-doped MnOx-TiO2 catalysts on catalytic activity with and without SO2 gas.
Chemical degradation of de-NOx SCR catalysts in flue gas containing SO2
100 150 200 250 300
40
50
60
70
80
90
100
40
50
60
70
80
90
% )
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Topic 2 : Durability and failure analysis
- MnOx-TiO2 catalyst, NOx conversion efficiency decreased in flue gas containing SO2.
- CeO2-doped catalyst, its efficiency was improved as about 15-19 %.
(a)
16 / 23
0 The increase of Mn sulfate and S=O double bonding
: Mn sulfate affects the poisoning on SCR reaction
Fig. FT-IR (fourier transform infrared) spectra of CeO2-doped MnOx-TiO2
after-treated in flowing NH3 at room temperature
Chemical degradation of de-NOx SCR catalysts with SOx
1500 1400 1300 1200 1100 1000 900 800
964
20 wt. % CeO2-MnOx-TiO2
30 wt. % CeO2-MnOx-TiO2
10 wt. % CeO2-MnOx-TiO2
Asymmetric vibration mode of O=S=O (SO2)
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Topic 2 : Durability and failure analysis
NH3 adsorption
Reaction mechanism of Ce oxides over CeO2-MnOx-TiO2 catalyst with SOx
* Redox cycling: Ce4+ ↔ Ce3+
H
Ce3+
O
O
O
Ce3+
O
O
O
O OO or
H
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Topic 2 : Durability and failure analysis
18 / 23
Characterization and durability test for marine applications
0 Characterization of ceramic filter/SCR catalyst
- Powder characteristics and physico-chemical properties
- NOx conversion efficiency
- SO2/SO3 resistance
Fig. Catalytic activity of ceramic filter/catalyst with and without ammonium bisulfate/sulfate.
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Ammonium Bisulfate
20
30
40
50
60
Temperature(oC)
5. 61 %
Catalyst (V2O5-based)
- Technical meeting
Korea testing laboratory, Pusan national university
6 March, 28 May, 29 August, 2 October, 4 November.
- Open Lecture (at Samsung heavy industries)
“Design and reliability of hybrid materials–Porous materials”
June 7, 2013
December 27, 2013
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Punched Plate
Air pulse
Ammonia gas(NH3)
Fly ash
Design of low-temperature de-NOx SCR catalysts
: MnOx-TiO2, CeO2-TiO2, CeO2-MnOx-TiO2, CeO2-WO3-TiO2
CeO2-MnOx-TiO2 (10 ~ 20 nm, 200 ~ 300 nm)
- Specific surface area : CeO2-TiO2 (80 ~ 90 m2/g),
CeO2-MnOx-TiO2 (110 ~ 120 m2/g)
0 NOx conversion efficiency
0 Catalytic acid sites
- FT-IR spectroscopy: Lewis & Brønsted acid sites increased by the addition of CeO2
→ It caused by the enhancement of NH3 adsorption.
Summary of research results
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II) 21 / 23
Summary of research results
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Durability and failure analysis – CeO2-MnOx-TiO2
0 Improvement and modification
- Decrease of the formation of Mn sulfate (FT-IR)
→ maintained the SCR efficiency of NOx
- Increase of the NH3 adsorption
0 Future plan
Stress level: SO2 concentration & reaction time, H2O, etc.
- Improvement and modification by feedback research
· De-NOx efficiency and durability (of multi-stress)
- Technical support for reliability assessment
Characterization
- Journal of Alloys and Compounds, April 2013
- Journal of the Korean Institute of Metals and Materials, October 2013
- Journal of of Solid State Electrochemistry, October 2013
0 Domestic Journal - 1
0 Conference Presentation - 2
Research outcomes
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Industry-University Liaison
- Characterization and durability test of ceramic filter/SCR catalyst for marine applications
0 Open Lecture
- Design and reliability of hybrid materials – Porous materials, 7 June 2013 at SHI.
(December 27, 2013)
23 / 23
Many thanks for your kind attention ! [Acknowledgement] This study is financially supported by GCRC-SOP.
Thank Dr. MC Shin and Dr. JS Cha in Korea Testing Laboratory.
+82-51-510-2388
To make the SKY more beautiful ..!
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Fig. Schematic diagram of SCR micro reactor Fig. Photographs of SCR micro reactor
SCR catalytic activity
: NOx conversion efficiency
- Bulk : 4 cm diameter (Square 1 inch X 1 inch)
- Powder : 2 cm diameter
0 [SO2] = 300 ppm, [H2O] = 5%, 10%
0 Temp. range : 100 ~500, SV = about 30,000 h-1
Q & A
a
b
- Bulk density, porosimetry
- Thermal analysis (TG-DTA, DSC)
0 Catalytic performance
- Catalyst Activity Testing
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Q & A
0 Types of engine for ships
- 4-stroke diesel engine
· Exhaust gas temp after T/C : 200 – 290
*T/C : turbo charger
- 2-stroke diesel engine
: Main engine, 100rpm.
· Gas temp after *T/C : 200 – 290
· High/low pressure
Q & A
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Preparation and characteristics of SCR catalysts
Fig . XRD patterns of TiO2 and CeO2-TiO2 with different CeO2 content..
Fig . SEM images of the CeO2-TiO2 powders with different CeO2 content: (a) 0 wt.% CeO2-TiO2 (b) 30 wt.% CeO2-TiO2.
1μm 1μm 1μm
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
10 20 30 40 50 60 70 80 90
C : Cubic CeO 2
20 wt.% CeO2 -TiO2 30 wt.% CeO2 -TiO2
A
0 Crystal structure : anatase structure without rutile or brookite structure
0 Particle size : MnOx-TiO2 (100 ~ 150 nm), MnOx-WO3/TiO2 (80 ~ 100 nm),
CeO2-TiO2 (80 ~ 100 nm), CeO2-MnOx-TiO2 (10 ~ 20 nm, 200 ~ 300 nm)
0 Specific surface area: MnOx-TiO2 (80 ~ 90 m2/g) → (150 ~ 170 m2/g),
CeO2-TiO2 (80 ~ 90 m2/g), CeO2-MnOx-TiO2 (110 ~ 120 m2/g)
Q & A
Crystallinity – CeO2-doped MnOx-TiO2
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
- The characteristic diffraction lines of CeO2 and MnOx were not detected in all catalysts
- The amorphous states of anatase (TiO2) are decreased by CeO2 loadings
Fig. XRD spectra of CeO2-MnOx-TiO2 as a function of CeO2 contents.
10 20 30 40 50 60 70 80 90
a : anatase a
2
2
2
2
CeO 2CeO2
Q & A
The dispersion of CeO2-MnOx-TiO2 catalyst with ceria content
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
20 wt.% CeO2
MnOx-TiO2
Q & A
NH3 desorption in the temperature range 100 – 850 °C with/without SOx
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Fig. NH3-TPD profiles of 30 wt. % CeO2-MnOx-TiO2
100 200 300 400 500 600 700 800 900
Temperature (C)
T C
D s
ig n
Weakly adsorb NH3
Chemisorbed NH3 by sulfate
3600 3400 3200 3000
30 wt.% CeO2-MnOx-TiO2
with and without SO2 gas at room temperature.
- NH3 adsorption increased with SO2
Q & A
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Q & A
0
0 Hazard of ammonia - Ammonia gas makes pH of our body decrease by transferring NH3 to NH4+.-
- When ammonia exists in the air,
→ can make fine dust by reacting with other acid pollutant.
→ can make ammonium nitrate by reacting with NOx or ozone.
0 removal method of ammonia gas
- Direct Combustion method
- Adsorption method
→ is not appropriate for long-term use such as automobile.
- Catalytic oxidation method
→ is appropriate for low ammonia concentration.
→ is the best method for ammonia removal
→This method common called as “Selective Catalytic oxidation”
Project 2: Design and reliability of De-NOx SCR catalyst at low temperature for marine (II)
Q & A
- Use Platinum Group Metal(PGM)
pollutant
0 N2(nitrogen) Selectivity
pollutant
spotlighted
NH3 slip monolith