coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases MINISTRY OF EDUCATION AND TRAINING HANOI UNIVERSITY OF TECHNOLOGY NGUYEN THE TIEN: SYNTHESIS AND CATALYTIC P
Trang 1coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
MINISTRY OF EDUCATION AND TRAINING
HANOI UNIVERSITY OF TECHNOLOGY
NGUYEN THE TIEN:
SYNTHESIS AND CATALYTIC PROPERTIES OF CATALYST SYSTEM
BASED ON CeO,-Zr0, FOR TIE COMPLETE OXIDATION OF ITYDROCARBON TO TREAT MOTORCYCLE’S EXHAUST GASES
SPECIALITY: ORGANIC AND PETROCIIEMICAL TECIINOGLOGY
SCTENCE MASTER THESIS
ORGANIC AND PETROCHEMICAL TECHNOLOGY
Trang 2CONTENTS
Page
1.12 Air pollution problem in the world and in Vietnam 21
13 International and Vietnam researches on catalyst for exhaust gas 33
1.3.3 The imperative task, the aim and the research directian of the 39 thesis,
1.4 The catalysts based on Cerium and Zirconium oxide 41
1.421 Role of CcO; in the three-way catalyst 4L
a Oxygen storage capacity (OSC) of CeO,-ZrO, mixed oxides 45
Technology
Trang 3coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
b, Thermal stabllity of CeO,-Zr0, mixed oxtdes 45
1 5.Completed hydrocarbon oxidatian af hydrocarbon 47
IL1.2 Synthesis of several single oxides, CeO0,-Zr0, and CeO,-Co,0, $2
catalysts by sol-gel method
11.1.4 Synthesis af Co,0./CeQ,-Z.r0, catalysts by impregnation %4 1L2 Methods to đetcrmine pollutant conccntration 55
11.3.3 BET method for the determination of surface area a
TIT.1 Composilion of motorcycle exhausts gases 68
TIT.1.2 02 volume concentration in the exhaust gas “ I11.1.3 Hydrocarbon concentrations im the exhaust gas analyzed by T0 GC-MS and GC- FID
H.2 Characterization of several single metallic oxides for the 73
hydrocarbon completed oxidation
Technology
Trang 4TABLES IN THE THESIS
1 Anthropogenic Emissions of Selected Air Pollutants in USA 22
2 Annual Combustion-Gener ated Emissians of Selected Pollutants | 23
by Stationary Source Category in USA
3 Percents of pollutants in Buro in 1994 24
3 Emission Reduction from Different NO, Control Technologies | 27
6 Classification of the phases in tha CeO,-ZrO, binary system 43
7 Chemicals used in the thesis 52
8 Characteristic of BCE R40 and IIMDC driving cycles 56
9 Measurement conditions using a GC-Thermo Electron with FID 38
10 Retention time of some organic compound detected by GC Thermo | 58
Electron with FID detector and the condition mentioned in table 9
11 Measurement conditions using the GC-MS $9
12 Pollutant concentration of some molorcycle types 68
13 Pollutant concentrations analysed by BCE 1140 and TIMDC 69
14 Oxygen concentrations at different operating condition ø9
l5 Camposttion 0ƒ exhatst gas ín địƒorenf operating condiions 70
16 Hydrocarbon concentrations analyzed oy GC-MS 70
17 Composition of Organic compounds in the motoreyele’s exhaust | 7
gases with measurement tima up to 40 minutes
18 BET surface area of some metal oxides 72
19 CO; selectivity of investigated metal oxides at different reaction | 76
temperatures
20 Specific surface area of Ce-Zr oxides 81
21 BET surface area of some Ce-Zr oxides depend on temperature | RA
22 CO; selectivity of CeOz-Co;0, catalysts at different reaction 89
Trang 5coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
PROTESTATION IN THE THESIS
T assure that my scienlific resulls arc righteous They haven’! been published in
any scientific document I have responsibilitios for my protestation and mry roscarch,
results in the thesis
Technology
Trang 6ACKNOWLEDGEMENTS
This Master thesis has been carried oul al the Depariment of Organic and Petrochemical Technology and Laboratory of Petrachomistry and Calalysis Matcrial Faculty of Chemical Technology, Hanoi University of Technology during the petiod February 2010 to Angust 2010 The work has been completed under
supervision of Associate Prof Dr Le Minh Thang
Firstly, I would like to thank Associate Prof Dr Le Minh Thang She helped me a
lot in the scientific work with her thorough guidance her encouragement and kind help
T want to thank all teachers of Department of Organic and Petrochemical Technology and the technicians of Laboratory of Petrochemistry and Catalysis Matetial, Faculty of Chemical Technology for their guidanee, and their helps in my work
1 acknowledge to all members in my research group for their friendly attitude and their assistances
Finally, 1 want to thank my family for their love and encouragement during the whole period
Nguyen The Tien August 2010
Technology
Trang 7coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
TABLES IN THE THESIS
1 Anthropogenic Emissions of Selected Air Pollutants in USA 22
2 Annual Combustion-Gener ated Emissians of Selected Pollutants | 23
by Stationary Source Category in USA
3 Percents of pollutants in Buro in 1994 24
3 Emission Reduction from Different NO, Control Technologies | 27
6 Classification of the phases in tha CeO,-ZrO, binary system 43
7 Chemicals used in the thesis 52
8 Characteristic of BCE R40 and IIMDC driving cycles 56
9 Measurement conditions using a GC-Thermo Electron with FID 38
10 Retention time of some organic compound detected by GC Thermo | 58
Electron with FID detector and the condition mentioned in table 9
11 Measurement conditions using the GC-MS $9
12 Pollutant concentration of some molorcycle types 68
13 Pollutant concentrations analysed by BCE 1140 and TIMDC 69
14 Oxygen concentrations at different operating condition ø9
l5 Camposttion 0ƒ exhatst gas ín địƒorenf operating condiions 70
16 Hydrocarbon concentrations analyzed oy GC-MS 70
17 Composition of Organic compounds in the motoreyele’s exhaust | 7
gases with measurement tima up to 40 minutes
18 BET surface area of some metal oxides 72
19 CO; selectivity of investigated metal oxides at different reaction | 76
temperatures
20 Specific surface area of Ce-Zr oxides 81
21 BET surface area of some Ce-Zr oxides depend on temperature | RA
22 CO; selectivity of CeOz-Co;0, catalysts at different reaction 89
Trang 8TABLES IN THE THESIS
1 Anthropogenic Emissions of Selected Air Pollutants in USA 22
2 Annual Combustion-Gener ated Emissians of Selected Pollutants | 23
by Stationary Source Category in USA
3 Percents of pollutants in Buro in 1994 24
3 Emission Reduction from Different NO, Control Technologies | 27
6 Classification of the phases in tha CeO,-ZrO, binary system 43
7 Chemicals used in the thesis 52
8 Characteristic of BCE R40 and IIMDC driving cycles 56
9 Measurement conditions using a GC-Thermo Electron with FID 38
10 Retention time of some organic compound detected by GC Thermo | 58
Electron with FID detector and the condition mentioned in table 9
11 Measurement conditions using the GC-MS $9
12 Pollutant concentration of some molorcycle types 68
13 Pollutant concentrations analysed by BCE 1140 and TIMDC 69
14 Oxygen concentrations at different operating condition ø9
l5 Camposttion 0ƒ exhatst gas ín địƒorenf operating condiions 70
16 Hydrocarbon concentrations analyzed oy GC-MS 70
17 Composition of Organic compounds in the motoreyele’s exhaust | 7
gases with measurement tima up to 40 minutes
18 BET surface area of some metal oxides 72
19 CO; selectivity of investigated metal oxides at different reaction | 76
temperatures
20 Specific surface area of Ce-Zr oxides 81
21 BET surface area of some Ce-Zr oxides depend on temperature | RA
22 CO; selectivity of CeOz-Co;0, catalysts at different reaction 89
Trang 9coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
FIGURES IN THE THESIS
1 Tages of air pollution in the world 15
Zz Schematic drawing, causes and effects of air pollution: (1) 21
greenhouse effect, (2) particulate contamination, (3) increased LV
radiation, (4) acid rain, (5) increased ozone concentration, (6)
increased levels of nitrogen oxides
4 Diagram of a modern TWC/engine‘axygen sensor control loop for 29
engine exhaust control
3 Three way catalyst performance determined by engine air to fuel 30
6 Wash-coals on automotive catalyst can have different surface 31
structures as shown with SEM micrographs
7 Umprovemens wend of catalytic converter 32
8 Phase diagram of the CeO-ZrOz system 4
9 Scheme of catalytic hydrocarbon oxidation; 1I-Laydrocarbon, C- 50
catalyst, R, io R-tabile intermediate, probably of the peroxide type
10 Scheme of CeO;ZrO; synthesis by sol-gel method 33
1 Seherne gƒ the sunthesis gƒ Co;O//CeO;-ZrO; cafalysts ñp %5
15 Tiustrates how diffraction of ray by erystal planes allows one 60
to derive lanice by using Bragg relation
16 The interaction between the primary electron beam and the sample in 61
an electron microscope leads to a number of detectable signal
17 Constitution and operating principle of SEM instrument 61
18 The BET plot 63
19 Schematic diagram of the micro-reactor setup 65
20 X-ray pattern of several single oxides synthesized using sol-gel 73
method
21 ‘Reaction rate of propylene conversion (r,w, CsH3 conv) of several T5
oxides at different reaction temperatures
Technology
Trang 1011.2.1 Surface properties of the investigated oxtdes Tã IIL2.2 Phase composition of investigated oxides T3 IL2.3 Catal
IIL.3 Characterization of CeO.-8nO, mechanical mixtures 16 11.3.1 Catalytic activity of CcO,-SnO; mechanical mixtures for 77 complete oxidation reaction of propylene
11.3.2 Phase composition and surface propertics of CeO;§nO, 78 mechantcal mixtures
IIL41 Phase composition and surface properties of CeO,-7.rO, 81 mixtures
11.4.2 Catalytic activity of CcO,-ZrO, for complete oxidation 82 reaction of propylene
ILLS Catalytic activity of CoO,-Co,0, catalysts 87
Technology
Trang 11coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
FIGURES IN THE THESIS
1 Tages of air pollution in the world 15
Zz Schematic drawing, causes and effects of air pollution: (1) 21
greenhouse effect, (2) particulate contamination, (3) increased LV
radiation, (4) acid rain, (5) increased ozone concentration, (6)
increased levels of nitrogen oxides
4 Diagram of a modern TWC/engine‘axygen sensor control loop for 29
engine exhaust control
3 Three way catalyst performance determined by engine air to fuel 30
6 Wash-coals on automotive catalyst can have different surface 31
structures as shown with SEM micrographs
7 Umprovemens wend of catalytic converter 32
8 Phase diagram of the CeO-ZrOz system 4
9 Scheme of catalytic hydrocarbon oxidation; 1I-Laydrocarbon, C- 50
catalyst, R, io R-tabile intermediate, probably of the peroxide type
10 Scheme of CeO;ZrO; synthesis by sol-gel method 33
1 Seherne gƒ the sunthesis gƒ Co;O//CeO;-ZrO; cafalysts ñp %5
15 Tiustrates how diffraction of ray by erystal planes allows one 60
to derive lanice by using Bragg relation
16 The interaction between the primary electron beam and the sample in 61
an electron microscope leads to a number of detectable signal
17 Constitution and operating principle of SEM instrument 61
18 The BET plot 63
19 Schematic diagram of the micro-reactor setup 65
20 X-ray pattern of several single oxides synthesized using sol-gel 73
method
21 ‘Reaction rate of propylene conversion (r,w, CsH3 conv) of several T5
oxides at different reaction temperatures
Technology
Trang 1211.2.1 Surface properties of the investigated oxtdes Tã IIL2.2 Phase composition of investigated oxides T3 IL2.3 Catal
IIL.3 Characterization of CeO.-8nO, mechanical mixtures 16 11.3.1 Catalytic activity of CcO,-SnO; mechanical mixtures for 77 complete oxidation reaction of propylene
11.3.2 Phase composition and surface propertics of CeO;§nO, 78 mechantcal mixtures
IIL41 Phase composition and surface properties of CeO,-7.rO, 81 mixtures
11.4.2 Catalytic activity of CcO,-ZrO, for complete oxidation 82 reaction of propylene
ILLS Catalytic activity of CoO,-Co,0, catalysts 87
Technology
Trang 13coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
SYMBOLS IN TIE TITESIS
TUT: Hanoi University of Technology
PMLO: particulate malicr less than 10 nm in diameter
NO,; oxides of nitrogen
YOCs; volatile organic compounds
PAHs: polycyclic aromatic hydrocarbons
ILAPs: hazardous air pollutants
CFCs: chloroflucrocarbons
TIC: hydrocarbon
SO, suifur oxides
COVNM: compound organic volatile not counting methane
PCBs; polychlorinated biphenyls
PCDDs: polychloinated dibenzodioxins
USA: United States of America
HCMC: Ho Chi Minh City
LEA: Low excess air
OFA: Overfire air
FRG: Flue gas recirculation
LNR: Low NO, burner
SNCR: Selective noncatalytic reduction
SCR: Selective catalytic reduction
AVF, ait/fuel ratio
TW: three-way catalyst
Cpsi: call per square inch
SULEY: super ultra low level vehicle
ULRV: nilira low level vehicle
CZ; mixtures of Cerium oxide and Zirconium oxide
CZS: mixtures of Cerium oxide, Zirconium oxide, Strontium oxide
4; the theoretical stoichiometric value
Technology
Trang 1411.2.1 Surface properties of the investigated oxtdes Tã IIL2.2 Phase composition of investigated oxides T3 IL2.3 Catal
IIL.3 Characterization of CeO.-8nO, mechanical mixtures 16 11.3.1 Catalytic activity of CcO,-SnO; mechanical mixtures for 77 complete oxidation reaction of propylene
11.3.2 Phase composition and surface propertics of CeO;§nO, 78 mechantcal mixtures
IIL41 Phase composition and surface properties of CeO,-7.rO, 81 mixtures
11.4.2 Catalytic activity of CcO,-ZrO, for complete oxidation 82 reaction of propylene
ILLS Catalytic activity of CoO,-Co,0, catalysts 87
Technology
Trang 15coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
TABLES IN THE THESIS
1 Anthropogenic Emissions of Selected Air Pollutants in USA 22
2 Annual Combustion-Gener ated Emissians of Selected Pollutants | 23
by Stationary Source Category in USA
3 Percents of pollutants in Buro in 1994 24
3 Emission Reduction from Different NO, Control Technologies | 27
6 Classification of the phases in tha CeO,-ZrO, binary system 43
7 Chemicals used in the thesis 52
8 Characteristic of BCE R40 and IIMDC driving cycles 56
9 Measurement conditions using a GC-Thermo Electron with FID 38
10 Retention time of some organic compound detected by GC Thermo | 58
Electron with FID detector and the condition mentioned in table 9
11 Measurement conditions using the GC-MS $9
12 Pollutant concentration of some molorcycle types 68
13 Pollutant concentrations analysed by BCE 1140 and TIMDC 69
14 Oxygen concentrations at different operating condition ø9
l5 Camposttion 0ƒ exhatst gas ín địƒorenf operating condiions 70
16 Hydrocarbon concentrations analyzed oy GC-MS 70
17 Composition of Organic compounds in the motoreyele’s exhaust | 7
gases with measurement tima up to 40 minutes
18 BET surface area of some metal oxides 72
19 CO; selectivity of investigated metal oxides at different reaction | 76
temperatures
20 Specific surface area of Ce-Zr oxides 81
21 BET surface area of some Ce-Zr oxides depend on temperature | RA
22 CO; selectivity of CeOz-Co;0, catalysts at different reaction 89
Trang 16SYMBOLS IN TIE TITESIS
TUT: Hanoi University of Technology
PMLO: particulate malicr less than 10 nm in diameter
NO,; oxides of nitrogen
YOCs; volatile organic compounds
PAHs: polycyclic aromatic hydrocarbons
ILAPs: hazardous air pollutants
CFCs: chloroflucrocarbons
TIC: hydrocarbon
SO, suifur oxides
COVNM: compound organic volatile not counting methane
PCBs; polychlorinated biphenyls
PCDDs: polychloinated dibenzodioxins
USA: United States of America
HCMC: Ho Chi Minh City
LEA: Low excess air
OFA: Overfire air
FRG: Flue gas recirculation
LNR: Low NO, burner
SNCR: Selective noncatalytic reduction
SCR: Selective catalytic reduction
AVF, ait/fuel ratio
TW: three-way catalyst
Cpsi: call per square inch
SULEY: super ultra low level vehicle
ULRV: nilira low level vehicle
CZ; mixtures of Cerium oxide and Zirconium oxide
CZS: mixtures of Cerium oxide, Zirconium oxide, Strontium oxide
4; the theoretical stoichiometric value
Technology
Trang 17coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
FIGURES IN THE THESIS
1 Tages of air pollution in the world 15
Zz Schematic drawing, causes and effects of air pollution: (1) 21
greenhouse effect, (2) particulate contamination, (3) increased LV
radiation, (4) acid rain, (5) increased ozone concentration, (6)
increased levels of nitrogen oxides
4 Diagram of a modern TWC/engine‘axygen sensor control loop for 29
engine exhaust control
3 Three way catalyst performance determined by engine air to fuel 30
6 Wash-coals on automotive catalyst can have different surface 31
structures as shown with SEM micrographs
7 Umprovemens wend of catalytic converter 32
8 Phase diagram of the CeO-ZrOz system 4
9 Scheme of catalytic hydrocarbon oxidation; 1I-Laydrocarbon, C- 50
catalyst, R, io R-tabile intermediate, probably of the peroxide type
10 Scheme of CeO;ZrO; synthesis by sol-gel method 33
1 Seherne gƒ the sunthesis gƒ Co;O//CeO;-ZrO; cafalysts ñp %5
15 Tiustrates how diffraction of ray by erystal planes allows one 60
to derive lanice by using Bragg relation
16 The interaction between the primary electron beam and the sample in 61
an electron microscope leads to a number of detectable signal
17 Constitution and operating principle of SEM instrument 61
18 The BET plot 63
19 Schematic diagram of the micro-reactor setup 65
20 X-ray pattern of several single oxides synthesized using sol-gel 73
method
21 ‘Reaction rate of propylene conversion (r,w, CsH3 conv) of several T5
oxides at different reaction temperatures
Technology
Trang 1811.2.1 Surface properties of the investigated oxtdes Tã IIL2.2 Phase composition of investigated oxides T3 IL2.3 Catal
IIL.3 Characterization of CeO.-8nO, mechanical mixtures 16 11.3.1 Catalytic activity of CcO,-SnO; mechanical mixtures for 77 complete oxidation reaction of propylene
11.3.2 Phase composition and surface propertics of CeO;§nO, 78 mechantcal mixtures
IIL41 Phase composition and surface properties of CeO,-7.rO, 81 mixtures
11.4.2 Catalytic activity of CcO,-ZrO, for complete oxidation 82 reaction of propylene
ILLS Catalytic activity of CoO,-Co,0, catalysts 87
Technology
Trang 19coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
PROTESTATION IN THE THESIS
T assure that my scienlific resulls arc righteous They haven’! been published in
any scientific document I have responsibilitios for my protestation and mry roscarch,
results in the thesis
Technology
Trang 20FIGURES IN THE THESIS
1 Tages of air pollution in the world 15
Zz Schematic drawing, causes and effects of air pollution: (1) 21
greenhouse effect, (2) particulate contamination, (3) increased LV
radiation, (4) acid rain, (5) increased ozone concentration, (6)
increased levels of nitrogen oxides
4 Diagram of a modern TWC/engine‘axygen sensor control loop for 29
engine exhaust control
3 Three way catalyst performance determined by engine air to fuel 30
6 Wash-coals on automotive catalyst can have different surface 31
structures as shown with SEM micrographs
7 Umprovemens wend of catalytic converter 32
8 Phase diagram of the CeO-ZrOz system 4
9 Scheme of catalytic hydrocarbon oxidation; 1I-Laydrocarbon, C- 50
catalyst, R, io R-tabile intermediate, probably of the peroxide type
10 Scheme of CeO;ZrO; synthesis by sol-gel method 33
1 Seherne gƒ the sunthesis gƒ Co;O//CeO;-ZrO; cafalysts ñp %5
15 Tiustrates how diffraction of ray by erystal planes allows one 60
to derive lanice by using Bragg relation
16 The interaction between the primary electron beam and the sample in 61
an electron microscope leads to a number of detectable signal
17 Constitution and operating principle of SEM instrument 61
18 The BET plot 63
19 Schematic diagram of the micro-reactor setup 65
20 X-ray pattern of several single oxides synthesized using sol-gel 73
method
21 ‘Reaction rate of propylene conversion (r,w, CsH3 conv) of several T5
oxides at different reaction temperatures
Technology
Trang 21coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
ACKNOWLEDGEMENTS
This Master thesis has been carried oul al the Depariment of Organic and Petrochemical Technology and Laboratory of Petrachomistry and Calalysis Matcrial Faculty of Chemical Technology, Hanoi University of Technology during the petiod February 2010 to Angust 2010 The work has been completed under
supervision of Associate Prof Dr Le Minh Thang
Firstly, I would like to thank Associate Prof Dr Le Minh Thang She helped me a
lot in the scientific work with her thorough guidance her encouragement and kind help
T want to thank all teachers of Department of Organic and Petrochemical Technology and the technicians of Laboratory of Petrochemistry and Catalysis Matetial, Faculty of Chemical Technology for their guidanee, and their helps in my work
1 acknowledge to all members in my research group for their friendly attitude and their assistances
Finally, 1 want to thank my family for their love and encouragement during the whole period
Nguyen The Tien August 2010
Technology
Trang 22FIGURES IN THE THESIS
1 Tages of air pollution in the world 15
Zz Schematic drawing, causes and effects of air pollution: (1) 21
greenhouse effect, (2) particulate contamination, (3) increased LV
radiation, (4) acid rain, (5) increased ozone concentration, (6)
increased levels of nitrogen oxides
4 Diagram of a modern TWC/engine‘axygen sensor control loop for 29
engine exhaust control
3 Three way catalyst performance determined by engine air to fuel 30
6 Wash-coals on automotive catalyst can have different surface 31
structures as shown with SEM micrographs
7 Umprovemens wend of catalytic converter 32
8 Phase diagram of the CeO-ZrOz system 4
9 Scheme of catalytic hydrocarbon oxidation; 1I-Laydrocarbon, C- 50
catalyst, R, io R-tabile intermediate, probably of the peroxide type
10 Scheme of CeO;ZrO; synthesis by sol-gel method 33
1 Seherne gƒ the sunthesis gƒ Co;O//CeO;-ZrO; cafalysts ñp %5
15 Tiustrates how diffraction of ray by erystal planes allows one 60
to derive lanice by using Bragg relation
16 The interaction between the primary electron beam and the sample in 61
an electron microscope leads to a number of detectable signal
17 Constitution and operating principle of SEM instrument 61
18 The BET plot 63
19 Schematic diagram of the micro-reactor setup 65
20 X-ray pattern of several single oxides synthesized using sol-gel 73
method
21 ‘Reaction rate of propylene conversion (r,w, CsH3 conv) of several T5
oxides at different reaction temperatures
Technology
Trang 23coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
ACKNOWLEDGEMENTS
This Master thesis has been carried oul al the Depariment of Organic and Petrochemical Technology and Laboratory of Petrachomistry and Calalysis Matcrial Faculty of Chemical Technology, Hanoi University of Technology during the petiod February 2010 to Angust 2010 The work has been completed under
supervision of Associate Prof Dr Le Minh Thang
Firstly, I would like to thank Associate Prof Dr Le Minh Thang She helped me a
lot in the scientific work with her thorough guidance her encouragement and kind help
T want to thank all teachers of Department of Organic and Petrochemical Technology and the technicians of Laboratory of Petrochemistry and Catalysis Matetial, Faculty of Chemical Technology for their guidanee, and their helps in my work
1 acknowledge to all members in my research group for their friendly attitude and their assistances
Finally, 1 want to thank my family for their love and encouragement during the whole period
Nguyen The Tien August 2010
Technology
Trang 24FIGURES IN THE THESIS
1 Tages of air pollution in the world 15
Zz Schematic drawing, causes and effects of air pollution: (1) 21
greenhouse effect, (2) particulate contamination, (3) increased LV
radiation, (4) acid rain, (5) increased ozone concentration, (6)
increased levels of nitrogen oxides
4 Diagram of a modern TWC/engine‘axygen sensor control loop for 29
engine exhaust control
3 Three way catalyst performance determined by engine air to fuel 30
6 Wash-coals on automotive catalyst can have different surface 31
structures as shown with SEM micrographs
7 Umprovemens wend of catalytic converter 32
8 Phase diagram of the CeO-ZrOz system 4
9 Scheme of catalytic hydrocarbon oxidation; 1I-Laydrocarbon, C- 50
catalyst, R, io R-tabile intermediate, probably of the peroxide type
10 Scheme of CeO;ZrO; synthesis by sol-gel method 33
1 Seherne gƒ the sunthesis gƒ Co;O//CeO;-ZrO; cafalysts ñp %5
15 Tiustrates how diffraction of ray by erystal planes allows one 60
to derive lanice by using Bragg relation
16 The interaction between the primary electron beam and the sample in 61
an electron microscope leads to a number of detectable signal
17 Constitution and operating principle of SEM instrument 61
18 The BET plot 63
19 Schematic diagram of the micro-reactor setup 65
20 X-ray pattern of several single oxides synthesized using sol-gel 73
method
21 ‘Reaction rate of propylene conversion (r,w, CsH3 conv) of several T5
oxides at different reaction temperatures
Technology
Trang 25coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
Tee! temperature for 50% conversion
in: inch
OSC: oxygen slorage capacity
CZALa: mixtures of Cerium oxide, Zirconium oxide, Alumitum oxide, Lanthanum oxide
NGVs: Natural Gas Velucles
LPG: Liquefied Petroleum Gas
ECE R40: Economic Commission for Euro Regulation 40- Emission of gaseous pollutants of motorcycles)
HMDC: Hanoi Motoroycle Driving Cycle
GC-MS: Gas Chromatography — Mass Spectroscopy
GC-FID: Gas Chromatography- Flame Ionization Detector
XRD: Xuay diffraction
SEM: Scanning Electron Microscopy
BET equation: Branauer- Emmett-Teller
Trang 26ACKNOWLEDGEMENTS
This Master thesis has been carried oul al the Depariment of Organic and Petrochemical Technology and Laboratory of Petrachomistry and Calalysis Matcrial Faculty of Chemical Technology, Hanoi University of Technology during the petiod February 2010 to Angust 2010 The work has been completed under
supervision of Associate Prof Dr Le Minh Thang
Firstly, I would like to thank Associate Prof Dr Le Minh Thang She helped me a
lot in the scientific work with her thorough guidance her encouragement and kind help
T want to thank all teachers of Department of Organic and Petrochemical Technology and the technicians of Laboratory of Petrochemistry and Catalysis Matetial, Faculty of Chemical Technology for their guidanee, and their helps in my work
1 acknowledge to all members in my research group for their friendly attitude and their assistances
Finally, 1 want to thank my family for their love and encouragement during the whole period
Nguyen The Tien August 2010
Technology
Trang 27coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
ACKNOWLEDGEMENTS
This Master thesis has been carried oul al the Depariment of Organic and Petrochemical Technology and Laboratory of Petrachomistry and Calalysis Matcrial Faculty of Chemical Technology, Hanoi University of Technology during the petiod February 2010 to Angust 2010 The work has been completed under
supervision of Associate Prof Dr Le Minh Thang
Firstly, I would like to thank Associate Prof Dr Le Minh Thang She helped me a
lot in the scientific work with her thorough guidance her encouragement and kind help
T want to thank all teachers of Department of Organic and Petrochemical Technology and the technicians of Laboratory of Petrochemistry and Catalysis Matetial, Faculty of Chemical Technology for their guidanee, and their helps in my work
1 acknowledge to all members in my research group for their friendly attitude and their assistances
Finally, 1 want to thank my family for their love and encouragement during the whole period
Nguyen The Tien August 2010
Technology
Trang 2811.2.1 Surface properties of the investigated oxtdes Tã IIL2.2 Phase composition of investigated oxides T3 IL2.3 Catal
IIL.3 Characterization of CeO.-8nO, mechanical mixtures 16 11.3.1 Catalytic activity of CcO,-SnO; mechanical mixtures for 77 complete oxidation reaction of propylene
11.3.2 Phase composition and surface propertics of CeO;§nO, 78 mechantcal mixtures
IIL41 Phase composition and surface properties of CeO,-7.rO, 81 mixtures
11.4.2 Catalytic activity of CcO,-ZrO, for complete oxidation 82 reaction of propylene
ILLS Catalytic activity of CoO,-Co,0, catalysts 87
Technology
Trang 29coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
11.2.1 Surface properties of the investigated oxtdes Tã IIL2.2 Phase composition of investigated oxides T3 IL2.3 Catal
IIL.3 Characterization of CeO.-8nO, mechanical mixtures 16 11.3.1 Catalytic activity of CcO,-SnO; mechanical mixtures for 77 complete oxidation reaction of propylene
11.3.2 Phase composition and surface propertics of CeO;§nO, 78 mechantcal mixtures
IIL41 Phase composition and surface properties of CeO,-7.rO, 81 mixtures
11.4.2 Catalytic activity of CcO,-ZrO, for complete oxidation 82 reaction of propylene
ILLS Catalytic activity of CoO,-Co,0, catalysts 87
Technology
Trang 30PROTESTATION IN THE THESIS
T assure that my scienlific resulls arc righteous They haven’! been published in
any scientific document I have responsibilitios for my protestation and mry roscarch,
results in the thesis
Technology
Trang 31coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
SYMBOLS IN TIE TITESIS
TUT: Hanoi University of Technology
PMLO: particulate malicr less than 10 nm in diameter
NO,; oxides of nitrogen
YOCs; volatile organic compounds
PAHs: polycyclic aromatic hydrocarbons
ILAPs: hazardous air pollutants
CFCs: chloroflucrocarbons
TIC: hydrocarbon
SO, suifur oxides
COVNM: compound organic volatile not counting methane
PCBs; polychlorinated biphenyls
PCDDs: polychloinated dibenzodioxins
USA: United States of America
HCMC: Ho Chi Minh City
LEA: Low excess air
OFA: Overfire air
FRG: Flue gas recirculation
LNR: Low NO, burner
SNCR: Selective noncatalytic reduction
SCR: Selective catalytic reduction
AVF, ait/fuel ratio
TW: three-way catalyst
Cpsi: call per square inch
SULEY: super ultra low level vehicle
ULRV: nilira low level vehicle
CZ; mixtures of Cerium oxide and Zirconium oxide
CZS: mixtures of Cerium oxide, Zirconium oxide, Strontium oxide
4; the theoretical stoichiometric value
Technology
Trang 32FIGURES IN THE THESIS
1 Tages of air pollution in the world 15
Zz Schematic drawing, causes and effects of air pollution: (1) 21
greenhouse effect, (2) particulate contamination, (3) increased LV
radiation, (4) acid rain, (5) increased ozone concentration, (6)
increased levels of nitrogen oxides
4 Diagram of a modern TWC/engine‘axygen sensor control loop for 29
engine exhaust control
3 Three way catalyst performance determined by engine air to fuel 30
6 Wash-coals on automotive catalyst can have different surface 31
structures as shown with SEM micrographs
7 Umprovemens wend of catalytic converter 32
8 Phase diagram of the CeO-ZrOz system 4
9 Scheme of catalytic hydrocarbon oxidation; 1I-Laydrocarbon, C- 50
catalyst, R, io R-tabile intermediate, probably of the peroxide type
10 Scheme of CeO;ZrO; synthesis by sol-gel method 33
1 Seherne gƒ the sunthesis gƒ Co;O//CeO;-ZrO; cafalysts ñp %5
15 Tiustrates how diffraction of ray by erystal planes allows one 60
to derive lanice by using Bragg relation
16 The interaction between the primary electron beam and the sample in 61
an electron microscope leads to a number of detectable signal
17 Constitution and operating principle of SEM instrument 61
18 The BET plot 63
19 Schematic diagram of the micro-reactor setup 65
20 X-ray pattern of several single oxides synthesized using sol-gel 73
method
21 ‘Reaction rate of propylene conversion (r,w, CsH3 conv) of several T5
oxides at different reaction temperatures
Technology
Trang 33coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
Tee! temperature for 50% conversion
in: inch
OSC: oxygen slorage capacity
CZALa: mixtures of Cerium oxide, Zirconium oxide, Alumitum oxide, Lanthanum oxide
NGVs: Natural Gas Velucles
LPG: Liquefied Petroleum Gas
ECE R40: Economic Commission for Euro Regulation 40- Emission of gaseous pollutants of motorcycles)
HMDC: Hanoi Motoroycle Driving Cycle
GC-MS: Gas Chromatography — Mass Spectroscopy
GC-FID: Gas Chromatography- Flame Ionization Detector
XRD: Xuay diffraction
SEM: Scanning Electron Microscopy
BET equation: Branauer- Emmett-Teller
Trang 3411.2.1 Surface properties of the investigated oxtdes Tã IIL2.2 Phase composition of investigated oxides T3 IL2.3 Catal
IIL.3 Characterization of CeO.-8nO, mechanical mixtures 16 11.3.1 Catalytic activity of CcO,-SnO; mechanical mixtures for 77 complete oxidation reaction of propylene
11.3.2 Phase composition and surface propertics of CeO;§nO, 78 mechantcal mixtures
IIL41 Phase composition and surface properties of CeO,-7.rO, 81 mixtures
11.4.2 Catalytic activity of CcO,-ZrO, for complete oxidation 82 reaction of propylene
ILLS Catalytic activity of CoO,-Co,0, catalysts 87
Technology
Trang 35coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
PROTESTATION IN THE THESIS
T assure that my scienlific resulls arc righteous They haven’! been published in
any scientific document I have responsibilitios for my protestation and mry roscarch,
results in the thesis
Technology
Trang 36PROTESTATION IN THE THESIS
T assure that my scienlific resulls arc righteous They haven’! been published in
any scientific document I have responsibilitios for my protestation and mry roscarch,
results in the thesis
Technology
Trang 37coniplete oxidation of hydrocarbon fo treat motoreyele x exhaust gases
TABLES IN THE THESIS
1 Anthropogenic Emissions of Selected Air Pollutants in USA 22
2 Annual Combustion-Gener ated Emissians of Selected Pollutants | 23
by Stationary Source Category in USA
3 Percents of pollutants in Buro in 1994 24
3 Emission Reduction from Different NO, Control Technologies | 27
6 Classification of the phases in tha CeO,-ZrO, binary system 43
7 Chemicals used in the thesis 52
8 Characteristic of BCE R40 and IIMDC driving cycles 56
9 Measurement conditions using a GC-Thermo Electron with FID 38
10 Retention time of some organic compound detected by GC Thermo | 58
Electron with FID detector and the condition mentioned in table 9
11 Measurement conditions using the GC-MS $9
12 Pollutant concentration of some molorcycle types 68
13 Pollutant concentrations analysed by BCE 1140 and TIMDC 69
14 Oxygen concentrations at different operating condition ø9
l5 Camposttion 0ƒ exhatst gas ín địƒorenf operating condiions 70
16 Hydrocarbon concentrations analyzed oy GC-MS 70
17 Composition of Organic compounds in the motoreyele’s exhaust | 7
gases with measurement tima up to 40 minutes
18 BET surface area of some metal oxides 72
19 CO; selectivity of investigated metal oxides at different reaction | 76
temperatures
20 Specific surface area of Ce-Zr oxides 81
21 BET surface area of some Ce-Zr oxides depend on temperature | RA
22 CO; selectivity of CeOz-Co;0, catalysts at different reaction 89