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Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases MINISTRY OF EDUCATION AND TRAINING HANOI UNIVERSITY OF TECHNOLOGY - NGUYEN THE TIEN SYNTHESIS AND CATALYTIC PROPERTIES OF CATALYST SYSTEM BASED ON CeO2-ZrO2 FOR THE COMPLETE OXIDATION OF HYDROCARBON TO TREAT MOTORCYCLE’S EXHAUST GASES SPECIALITY: ORGANIC AND PETROCHEMICAL TECHNOLOGY SCIENCE MASTER THESIS ORGANIC AND PETROCHEMICAL TECHNOLOGY SUPERVISOR: Associate Professor, Doctor LE MINH THANG HANOI, 2010 Nguyen The Tien Organic and Petrochemical Technology Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases CONTENTS Assistant cover page Acknowledgements Protestation in the thesis Symbols in the thesis Tables in the thesis Figures in the thesis Abstract Introduction, aims and outline of the thesis Chapter I: Literature review I.1 Air pollution problem I.1.1 Air pollutants I.1.2 Air pollution problem in the world and in Vietnam I.2 Air pollution treatments I.2.1 Original pollutant treatments a CO treatments b VOC treatments c NOx treatments I.2.2 Treatments of simultaneous three pollutants – three-way catalysts a Method b Method I.2.3 Three-way catalyst characteristic I.3 International and Vietnam researches on catalyst for exhaust gas treatment I.3.1 International researches a Noble metallic catalysts b Perovskite catalysts c Base metallic catalysts d Metallic oxide catalysts e Other catalysts I.3.2 Researches in Vietnam I.3.3 The imperative task, the aim and the research direction of the thesis I.4 The catalysts based on Cerium and Zirconium oxide I.4.1 Role of CeO2 in the three-way catalyst I.4.2 Phase diagram of CeO2-ZrO2 mixed oxide I.4.3 Synthesis of CeO2-ZrO2 mixed oxide I.4.4 Characteristic of CeO2-ZrO2 mixed oxide a Oxygen storage capacity (OSC) of CeO2–ZrO2 mixed oxides Nguyen The Tien Page 10 12 13 15 15 15 21 24 24 24 25 27 28 28 28 29 33 33 33 36 37 37 38 38 39 41 41 42 44 45 45 Organic and Petrochemical Technology Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases b Thermal stability of CeO2–ZrO2 mixed oxides I 5.Completed hydrocarbon oxidation of hydrocarbon I.5.1 Hydrocarbon oxidation mechanism I.5.2 Kinetic of hydrocarbon oxidation 45 47 47 51 CHAPTER II: EXPERIMENTAL II.1 Chemicals and synthesizes method 52 52 II.1.1 Chemicals II.1.2 Synthesis of several single oxides, CeO2-ZrO2 and CeO2-Co3O4 52 52 catalysts by sol-gel method a Introduction b Application in the thesis II.1.3 Mechanical mixtures of oxides II.1.4 Synthesis of Co3O4/CeO2-ZrO2 catalysts by impregnation II.2 Methods to determine pollutant concentration II.2.1 Driving cycle methods II.2.2 GC methods II.3.Physico-Chemical Experimental Techniques II.3.1 X-ray diffraction a Principles b Application in the thesis II.3.2 Scanning electron microscopy (SEM) a Principles b Application in the thesis II.3.3 BET method for the determination of surface area a Principles b Application in the thesis II.4.Catalytic test II.4.1 Equipment description II.4.2 The loading of the catalyst II.4.3 The analysis of the results 52 52 54 54 55 55 58 59 59 59 61 61 61 62 62 62 64 64 64 66 66 CHAPTER III: RESULTS AND DISCUSSIONS III.1 Composition of motorcycle exhausts gases III.1.1 Pollutant concentrations 68 68 68 III.1.2 O2 volume concentration in the exhaust gas 69 III.1.3 Hydrocarbon concentrations in the exhaust gas analyzed by 70 GC-MS and GC- FID III.2 Characterization of several single metallic oxides for the hydrocarbon completed oxidation Nguyen The Tien 73 Organic and Petrochemical Technology Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases III.2.1 Surface properties of the investigated oxides 73 III.2.2 Phase composition of investigated oxides 73 III.2.3 Catalytic activity of investigated oxides 74 III.3 Characterization of CeO2-SnO2 mechanical mixtures 76 III.3.1 Catalytic activity of CeO2-SnO2 mechanical mixtures for 77 complete oxidation reaction of propylene III.3.2 Phase composition and surface properties of CeO2-SnO2 78 mechanical mixtures III.4 Characterization of CeO2-ZrO2 mixtures 80 III.4.1 Phase composition and surface properties of CeO2-ZrO2 81 III.4.2 Catalytic activity of CeO2-ZrO2 for complete oxidation 82 mixtures reaction of propylene III.5 Catalytic activity of CeO2-Co3O4 catalysts 87 III.6 Catalytic activities of Co3O4/CeO2-ZrO2 89 CONCLUSIONS 92 REFERENCES 94 Nguyen The Tien Organic and Petrochemical Technology Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases ACKNOWLEDGEMENTS This Master thesis has been carried out at the Department of Organic and Petrochemical Technology and Laboratory of Petrochemistry and Catalysis Material, Faculty of Chemical Technology, Hanoi University of Technology during the period February 2010 to August 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 I want to thank all teachers of Department of Organic and Petrochemical Technology and the technicians of Laboratory of Petrochemistry and Catalysis Material, Faculty of Chemical Technology for their guidance, and their helps in my work I acknowledge to all members in my research group for their friendly attitude and their assistances Finally, I want to thank my family for their love and encouragement during the whole period Nguyen The Tien August 2010 Nguyen The Tien Organic and Petrochemical Technology Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases PROTESTATION IN THE THESIS I assure that my scientific results are righteous They haven’t been published in any scientific document I have responsibilities for my protestation and my research results in the thesis Nguyen The Tien Organic and Petrochemical Technology Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases SYMBOLS IN THE THESIS HUT: Hanoi University of Technology PM10: particulate matter less than 10 nm in diameter NOx: oxides of nitrogen VOCs: volatile organic compounds PAHs: polycyclic aromatic hydrocarbons HAPs: hazardous air pollutants CFCs: chlorofluorocarbons HC: hydrocarbon SOx: sulfur oxides COVNM: compound organic volatile not counting methane PCBs: polychlorinated biphenyls PCDDs: polychlorinated dibenzodioxins USA: United States of America HCMC: Ho Chi Minh City LEA: Low excess air OFA: Overfire air FRG: Flue gas recirculation LNB: Low NOx burner SNCR: Selective noncatalytic reduction SCR: Selective catalytic reduction A/F: air/fuel ratio TWC: three-way catalyst Cpsi: cell per square inch SULEV: super ultra low level vehicle ULEV: ultra low level vehicle CZ: mixtures of Cerium oxide and Zirconium oxide CZS: mixtures of Cerium oxide, Zirconium oxide, Strontium oxide λ: the theoretical stoichiometric value Nguyen The Tien Organic and Petrochemical Technology Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases T50: temperature for 50% conversion in.: inch OSC: oxygen storage capacity CZALa: mixtures of Cerium oxide, Zirconium oxide, Aluminum oxide, Lanthanum oxide NGVs: Natural Gas Vehicles LPG: Liquefied Petroleum Gas ECE R40: Economic Commission for Euro Regulation 40- Emission of gaseous pollutants of motorcycles) HMDC: Hanoi Motorcycle Driving Cycle GC-MS: Gas Chromatography – Mass Spectroscopy GC-FID: Gas Chromatography- Flame Ionization Detector XRD: X-ray diffraction SEM: Scanning Electron Microscopy BET equation: Brunauer- Emmett-Teller r,w, C3H6 cons: Reaction rate of propylene consumption Nguyen The Tien Organic and Petrochemical Technology Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases TABLES IN THE THESIS Number Table Name Anthropogenic Emissions of Selected Air Pollutants in USA Annual Combustion-Generated Emissions of Selected Pollutants by Stationary Source Category in USA Page 22 23 10 Percents of pollutants in Euro in 1994 EU emission standard for passenger car Emission Reduction from Different NOx Control Technologies Classification of the phases in the CeO2-ZrO2 binary system Chemicals used in the thesis Characteristic of ECE R40 and HMDC driving cycles Measurement conditions using a GC-Thermo Electron with FID Retention time of some organic compound detected by GC Thermo Electron with FID detector and the condition mentioned in table 24 24 27 43 52 56 58 58 11 12 13 14 15 16 17 Measurement conditions using the GC-MS Pollutant concentration of some motorcycle types Pollutant concentrations analyzed by ECE R40 and HMDC Oxygen concentrations at different operating condition Composition of exhaust gas in different operating conditions Hydrocarbon concentrations analyzed by GC-MS Composition of Organic compounds in the motorcycle’s exhaust gases with measurement time up to 40 minutes 59 68 69 69 70 70 71 18 19 BET surface area of some metal oxides CO2 selectivity of investigated metal oxides at different reaction temperatures 72 76 20 21 22 Specific surface area of Ce-Zr oxides BET surface area of some Ce-Zr oxides depend on temperature CO2 selectivity of CeO2-Co3O4 catalysts at different reaction 81 82 89 temperatures 23 CO2 selectivity of CeO2-ZrO2 supports, Co3O4 active phase, 91 Co3O4/CeO2-ZrO2 samples Nguyen The Tien Organic and Petrochemical Technology Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases Number FIGURES IN THE THESIS Figure name Images of air pollution in the world Schematic drawing, causes and effects of air pollution: (1) greenhouse effect, (2) particulate contamination, (3) increased UV radiation, (4) acid rain, (5) increased ozone concentration, (6) increased levels of nitrogen oxides Page 15 21 Scheme of successive two converter model Diagram of a modern TWC/engine/oxygen sensor control loop for engine exhaust control 28 29 Three way catalyst performance determined by engine air to fuel Wash-coats on automotive catalyst can have different surface structures as shown with SEM micrographs 30 31 Improvement trend of catalytic converter Phase diagram of the CeO2-ZrO2 system Scheme of catalytic hydrocarbon oxidation; H-hydrocarbon, Ccatalyst, R1 to R5-labile intermediate, probably of the peroxide type 32 43 50 10 11 Scheme of CeO2-ZrO2 synthesis by sol-gel method Scheme of the synthesis of Co3O4/CeO2-ZrO2 catalysts by impregnation method Velocity profile of ECE R40 driving cycle Velocity profile of HMDC Scheme of CVS (constant volume sampling) system to determine pollutant concentrations 53 55 12 13 14 56 56 57 15 Illustrates how diffraction of X-ray by crystal planes allows one to derive lattice by using Bragg relation 60 16 The interaction between the primary electron beam and the sample in an electron microscope leads to a number of detectable signal 61 17 18 19 20 Constitution and operating principle of SEM instrument The BET plot Schematic diagram of the micro-reactor setup X-ray pattern of several single oxides synthesized using sol-gel method 61 63 65 73 21 Reaction rate of propylene conversion (r,w, C3H6 conv) of several oxides at different reaction temperatures 75 Nguyen The Tien Organic and Petrochemical Technology 10 Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases Figure 31 showed the X-ray pattern of sol-gel sample of Ce-Zr oxide with CeO2/ZrO2 molar ratio is 8/2 before and after reaction and initial mechanical mixture corresponding with this ratio It can be seen that, in mechanical sample there are only strongest XRD reflection of CeO2 and ZrO2 The reflection of ZrO2 in the mechanical mixture decreases than that of pure ZrO2 In XRD pattern of sol-gel sample before reaction, no peak belonged to ZrO2 could be found It can be concluded that ZrO2 enter to the structure of CeO2 in the sol-gel mixture to form a solid solution ZrO2 peaks with low intensity were detected in XRD pattern of solgel sample after reaction The reason may be the separation of solid solution at high temperature during the catalytic test Figure 32 showed the change of CeO2/ZrO2=8/2 sol-gel sample before and after reaction Before reaction sample has many pores After reaction, almost pores of sample were encapsulated The reason may be the harsh reaction condition, exothermicity of complete oxidation of C3H6 and the formation of coke Before reaction After reaction Fig 32 SEM images of CeO2/ZrO2=8/2 sol-gel sample before and after reaction III.5 Catalytic activity of CeO2-Co3O4 catalysts As results were mentioned in section III.2.3 of this chapter, Co3O4 has high reaction rate of propylene consumption but low selectivity whereas, CeO2 has quite high r,w, C3H6 cons and high CO2 selectivity Therefore, catalytic activity for complete oxidation of C3H6 of CeO2-Co3O4 mixture oxides was studied Nguyen The Tien Organic and Petrochemical Technology 87 Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases Compared with single oxides (CeO2, Co3O4) and CeO2-ZrO2 sol-gel samples (Ce/Zr=9/1, 8/2), CeO2-Co3O4 catalysts have high activity at low temperature and high CO2 selectivity at reaction temperature (CO2 selectivity = 1) The r,w, C3H6 cons of these catalysts with the content of CeO2 more than 4% at 2000C is as high as that of at 4000C, except sample contain 20% mol CeO2, which has very high r,w, C3H6 cons at 4000C This is also the optimal Ce/Co ratio, which results in the highest activity However, the thermal resistant of this catalyst is low It was broken-up at temperature higher than 4000C Therefore, Co-Ce catalyst should be Reaction Rate of propylene consumption, mol/g.s supported on higher thermal resistant CeO2-ZrO2 supports Co3O4 3.7%CeO2-96.3%Co3O4 5%CeO2-95%Co3O4 10 CeO2-90%Co3O4 20%CeO2-80%Co3O4 CeO2 1.60E-007 1.40E-007 1.20E-007 1.00E-007 8.00E-008 6.00E-008 4.00E-008 2.00E-008 0.00E+000 200 250 300 350 400 450 500 Reaction Temperature, C Fig 33 Reaction rate of propylene consumption of CeO2-Co3O4 catalysts at different reaction temperatures Nguyen The Tien Organic and Petrochemical Technology 88 Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases Table 22 CO2 selectivity of CeO2-Co3O4 catalysts at different reaction temperatures Reaction temperature, 0C 200 250 300 350 400 450 500 Co3O4 - 100 100 100 90 60 51 3.7%CeO2-96.3%Co3O4 100 100 100 100 100 + + 5%CeO2- 95% Co3O4 100 100 100 100 100 + + 10%CeO2- 90% Co3O4 100 100 100 100 100 + + 20%CeO2- 80% Co3O4 100 100 100 100 100 + + CeO2 - - - 91 93 94 93 +: catalyst was broken- up -: CO and CO2 peaks weren’t detected III.6 Catalytic activities of Co3O4/CeO2-ZrO2 As mentioned at section III.2.3, Co3O4 exhibited high reaction rate of propylene consumption and therefore, in this thesis, cobalt oxide was impregnated on Ce-Zr supports The result was showed in Figure 34 and 35 100% Ce0.9Zr0.1O 100% Co3O4 %wt Co3O 4/Ce0.9Zr0.1O2 10 %w tCo3O 4/Ce0.9Zr0.1O 20% wt Co3O 4/Ce0.9Zr0.1O -9 r, w, C3H6 cons, mol/g.s 140x10 120 100 80 60 40 20 200 250 300 350 400 reaction temperature, oC 450 500 Fig 34 Reaction rate of propylene consumption of CeO2-ZrO2 support, Co3O4 active phase, Co3O4 supported on Ce0.9Zr0.1O2 samples At temperatures below 3500C, the order of the reaction rate of propylene consumption is Co3O4>10% wt Co3O4/Ce0.9Zr0.1O2>5%wt Co3O4/Ce0.9Zr0.1O2> Ce0.9Zr0.1O2 > 20%wt Co3O4/Ce0.9Zr0.1O2 At temperatures from 4000C to 4500C, Nguyen The Tien Organic and Petrochemical Technology 89 Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases Ce0.9Zr0.1O2 has highest r,w, C3H6 cons whereas at temperature above 4500C, Co3O4 has highest reaction rate of propylene consumption Three impregnation samples maintained constant catalytic activity from 2500C to 5000C although their activities are lower than those of Co3O4 and Ce0.9Zr0.1O2 The reaction rate of propylene consumption of 10%wt Co3O4/Ce0.9Zr0.1O2 is higher than those of 5%wt Co3O4 and 20%wt Co3O4 samples Thus, the impregnation limit should be 10% 100 % Ce0.9Zr0.1O 100 % Ce0.8Zr0.2O 100%Co3O % wt Co3O 4/Ce0.8Zr0.2O 10%w tCo3O 4/Ce0.8Zr0.2O -9 r, w, C3H6 cons, mol/g.s 140x10 120 100 80 60 40 20 200 250 300 350 400 reaction temperature, oC 450 500 Fig 35 Reaction rate of propylene consumption of CeO2-ZrO2 supports, Co3O4 active phase, Co3O4 supported on Ce0.8Zr0.2O2 sample From figure 35, it can be seen that 5%wt Co3O4 and 10%wt Co3O4 /Ce0.8Zr0.2O2 sample reached to the highest reaction rate of propylene consumption from 2500C to 5000C which is similarly to three supported on Ce0.9Zr0.1O2 At temperature below 3500C, Co3O4 and 5%wt Co3O4/Ce0.8Zr0.2O2 exhibited the highest activity Meanwhile at higher temperatures, Co3O4 and Ce0.9Zr0.1O2 has higher activity than those of other samples From table 23, it can be seen that CO2 selectivity of these samples is very high except for Co3O4 sample at temperatures above 4000C It reaches approximately 100% for samples supported on Ce0.9Zr0.1O2 and Ce0.8Zr0.2O2 The reason may be the interaction between Co3O4 and CeO2, which helped the catalysts obtained high conversion of propylene from low temperature (property of Co3O4) and high selectivity of CO2 (property of CeO2) Nguyen The Tien Organic and Petrochemical Technology 90 Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases Table 23 CO2 selectivity of CeO2-ZrO2 supports, Co3O4 active phase, Co3O4/CeO2ZrO2 samples CO2 selectivity, % Sample 2000C 2500C 3000C 3500C 4000C 4500C 5000C Ce0.9Zr0.1O2 - 100 100 97 96.7 96.7 95.5 Ce0.8Zr0.2O2 - - 100 97.4 97.5 97.1 96.1 Co3O4 - 100 100 100 90.2 60.9 51.1 5% wt Co3O4/ Ce0.9Zr0.1O2 10% wt Co3O4/ Ce0.9Zr0.1O2 20% wt Co3O4/ Ce0.9Zr0.1O2 5% wt Co3O4/ Ce0.8Zr0.2O2 10% wtCo3O4/ Ce0.8Zr0.2O2 - - 100 100 100 100 100 - 100 100 100 100 100 100 - 100 100 100 100 99.4 98.5 - 100 100 97 96.7 98.3 100 - 100 100 100 100 100 98.2 -: CO or CO2 were not detected Pure Ce0.8Zr0.2O2 5%wt Co3O4/ Ce0.8Zr0.2O2 Fig 36 SEM images of pure Ce0.8Zr0.2O2 and 5%wt Co3O4/ Ce0.8Zr0.2O2 before reaction In order to observe the dispersion of Co3O4 on Ce0.8Zr0.2O2 support, SEM images of this support and impregnated sample were introduced SEM image of 5%wt Co3O4 / Ce0.8Zr0.2O2 sample showed that Co3O4 was dispersed finely on support The particle size of Co3O4 is only few nm However, the support surface wasn’t impregnated completely Nguyen The Tien Organic and Petrochemical Technology 91 Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases CONCLUSIONS In this thesis, main findings were investigated carefully Some conclusions have been concluded: - Main pollutants of exhaust gas were analyzed in different driving conditions such as ECE R40 and HDMC The result showed that the main composition of the exhaust gases are 0.5÷4.5 vol.% hydrocarbon, 0.5÷ vol.% CO, 4÷12 vol.% CO2, 0.05 to 0.4 vol.% NOx and 1.8÷12 vol.% O2 - The composition of hydrocarbons in exhaust gases was determined C3H6 and C7H8 are the main hydrocarbons in exhaust gas C3H6 was chosen to be studied for the complete oxidation in a lacking oxygen condition - Catalytic activity of metal oxides such as: Co3O4, CeO2, SnO2, TiO2, NiO, ZrO2, V2O5 and Al2O3 for complete oxidation of hydrocarbon (C3H6) were investigated Reaction rate of propylene consumption increases but CO2 selectivity decreases with the increase of temperature Amongst investigated oxides, Co3O4 has highest reaction rate of propylene consumption, high CO2 selectivity (approximately 100%) at low temperature but low CO2 selectivity at high temperature Meanwhile, CeO2 has not only high reaction rate of propylene but also high CO2 selectivity (above 90%) NiO has quite high activity but very low thermal resistant - Catalytic activity of mixtures of CeO2 and SnO2, CeO2 and ZrO2 were investigated CeO2-SnO2 mixtures exhibited rather high activity for the complete oxidation of propylene but CeO2-ZrO2 sample has even higher activity The catalytic activity of CeO2-ZrO2 mixture prepared by mechanical mixing is equivalent to that of CeO2-ZrO2 mixture synthesized by sol-gel method at temperature above 4500C - Some sol-gel samples such as Ce-Zr and Ce-Co sol-gel samples were researched Synergy effect was present in molar ratio Ce/Zr= 9/1, 8/2 resulting in higher activity than pure component samples (CeO2, ZrO2) due to formation of Ce-Zr solid solution by dissolve of Zr into CeO2 lattice Ce-Co sample maintain high activity at reaction temperatures but low thermal resistant Nguyen The Tien Organic and Petrochemical Technology 92 Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases - Catalytic activity of some cobalt oxide supported 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Nonferrous Met.Soc.China 19, pp.1227-1231 Nguyen The Tien Organic and Petrochemical Technology 101 ... 22 Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases thousand tons of NO2 , which excess the. .. Technology 21 Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases modification or reaction of constituents... Technology Synthesis and catalytic properties of catalyst system based on CeO2 – ZrO2 for the complete oxidation of hydrocarbon to treat motorcycle’s exhaust gases III.2.1 Surface properties of the