Development of novel deNPAC catalysts for treatment of diesel engine exhaust

DEVELOPMENT OF NOVEL deNPAC CATALYSTS FOR TREATMENT OF DIESEL ENGINE EXHAUST ZENG HOUXU (M ENG, RIPP) A THESIS SUBMITTED FOR THE DEGREE OF MASTER OF ENGINEERING DEPARTMENT OF CHEMICAL & BIOMOLECULAR ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2005 Acknowledgements Acknowledgement First of all, I would like to express my sincerest thanks to my supervisors, Prof Sibudjing Kawi and Dr Yu Liya, for their unselfish help throughout all my master candidate period I appreciate their constant encouragement and invaluable guidance Their profound understanding of catalysis and environment helped me a lot whenever I met problems during my research Besides, I would like to express my thanks to Prof Hidajat, who gave me many constructive suggestions I also want to take this chance to thank all our group members who share the laboratories and gave me a lot of help, Dr Shen Shoucang, Yong Siekting, Zhang Sheng, Tang Yunpeng, Luan Deyan, Li Peng, Song Shiwei, Yang Jun, Sun Gebiao They are all my best friends and teachers From them, I learned not only technical knowledge but also personality The time I spent with them will give me indelible good memory Special mentions should go to Mdm Chiang Hock Joo, Mdm Siew Woon Chee and Mr Ng Kim Poi for all the help they have offered throughout my research My thanks also should give to Mdm Fam Hwee Koong, Dr Yuan Zeliang, Mr Chia Phai Ann and Mr Shang Zhenhua The last, I also wish to thank National University of Singapore for providing me excellent environment and abundant resources of research This thesis is dedicated to my family for their encouragement and support i Table of Contents Table of Contents Acknowledgement i Table of Contents ii Summary v Nomenclature vii List of Figures ix List of Tables and Scheme xii Chapter Introduction 1.1 Background 1.2 Nitrogen-containing polycyclic aromatic compounds (NPACs) 1.2.1 NPACs in the atmosphere 1.2.2 NPACs in diesel exhaust 1.3 Research objectives 1.4 Organization of thesis Chapter Literature Review 2.1 Introduction to catalytic combustion of NPACs 2.1.1 Oxidation of ammonia 2.1.2 Oxidation of hydrogen cyanide 2.1.3 Oxidation of organic nitrogen-containing compounds 11 2.2 Introduction to the catalytic oxidation of pyridine 12 2.2.1 Pyridine oxidation over metal oxide catalysts 12 2.2.2 Catalytic supercritical water oxidation of pyridine (SCWO) 15 2.2.3 Kinetics of catalytic oxidation of pyridine 17 2.2.4 Intermediates and mechanism of pyridine oxidation 18 2.3 Ordered mesoporous SBA-15 material 19 ii Table of Contents 2.3.1 Synthesis and formation mechanism of SBA-15 21 2.3.2 Modification of SBA-15 24 2.3.3 Highly dispersed nanoparticles on SBA-15 26 Chapter Synthesis, Characterization and Application of SBA-15 Modified with nano Cu Particles 28 3.1 Preface 28 3.2 Introduction 28 3.3 Experimental techniques 30 3.3.1 Chemicals 30 3.3.2 Synthesis of pure SBA-15 and modified SBA-15 30 3.3.3 Characterization 31 3.3.4 Catalytic activity 32 3.4 Results and discussion 33 3.5 Conclusions 45 Chapter Design Cu-containing Catalysts for deNPAC 46 4.1 Preface 46 4.2 Introduction 46 4.3 Experimental techniques 48 4.3.1 Synthesis of CuO/SBA-15, CuAl/SBA-15 and CuOAl/SBA-15 48 4.3.2 Characterization 49 4.3.3 Catalytic activity test 50 4.4 Results and discussion 51 4.5 Conclusions 64 Chapter Synthesis, Characterization and Application of Cu-Zn-Al Spinel-Structured Catalysts for deNPAC Reaction 65 iii Table of Contents 5.1 Preface 65 5.2 Introduction 65 5.3 Experimental techniques 67 5.3.1 Catalyst preparation 67 5.3.2 Characterization 68 5.3.3 Catalytic activity test 69 5.4 Results and discussion 70 5.4.1 Effects of catalysts preparation methods 70 5.4.2 Effects of molar ratio 73 5.4.3 Effects of hydrothermal treatment temperature 77 5.5 Conclusions 88 Chapter SBA-15 Embedded with Spinel: Synthesis and Application 89 6.1 Preface 89 6.2 Introduction 89 6.3 Experimental techniques 91 6.3.1 Chemicals 91 6.3.2 Synthesis of modified SBA-15 91 6.3.3 Characterization 92 6.3.4 Catalytic activity test 93 6.4 Results and discussion 93 6.5 Conclusions 103 Chapter Conclusions and Future Work 104 7.1 Conclusions 104 7.2 Future Work 106 References 108 iv Summary Summary This thesis reports the study of catalytic oxidation of pyridine in the presence of excess oxygen Four catalysts: SBA-15 modified with nano Cu (Cu/SBA-15), SBA-15 modified with Cu and Al (CuAl/SBA-15), Cu-Zn-Al spinel and SBA-15 modified with Cu-Zn-Al spinel (SBA/SP-x), have been synthesized It has been found that compared with SBA-15 impregnated with CuO particles, Cu/SBA-15 has improved the catalytic activity of pyridine oxidation with a lower NOx yield, which may be due to nano Cu particles on Cu/SBA-15 have a smaller particle size and a better distribution, yet the performance of Cu/SBA-15 catalyst at high temperatures still needs to be improved In order to investigate the influence of acidic property and active component on the catalytic activity and NOx yield, CuAl/SBA-15 catalyst has been designed For the pyridine oxidation reaction, Al provides acidic sites to adsorb the reactant and Cu is the source of active component to control the yield of NOx By improving the acidic properties of the catalyst, the pyridine adsorption ability of catalyst can be enhanced The NOx yield is controlled by Cu ion loaded by an ion-exchange method Compared with CuO/SBA-15 and CuOAl/SBA-15, CuAl/SBA-15 has a better catalytic activity of pyridine oxidation and a lower NOx yield In addition, CuAl/SBA-15 is more easily prepared than Cu/SBA-15 But its NOx control ability at high temperatures is still not good enough v Summary Cu-Zn-Al spinel has been chosen in this experiment because of its excellent thermal and hydrothermal stability The influence of preparation method, molar ratio of precursors and hydrothermal treatment temperature on the morphology of spinel has been investigated Spinel prepared by hydrothermal method at pH=8 with a molar ratio of Cu:Zn:Al=1:1:4 has the optimal catalytic activity and a lower NOx yield Calcination is a necessary step for Cu-Zn-Al spinel prepared by the hydrothermal method, but too high a calcination temperature will decompose the spinel Spinel prepared at 180°С has the best reactivity Finally, a novel catalyst combining the advantages of SBA-15 and spinel has been prepared successfully Spinel was embedded into SBA-15 by a precipitation method Two diameter Cu-Zn-Al spinel particles have been observed: one at 15 nm, the other below nm The best modified catalyst with the lowest NOx yield even at high temperatures is SBA/SP-5, which achieves 100% pyridine conversion at 450°C with zero NOx formation Keywords: Cu/SBA-15, CuAl/SBA-15, Cu-Zn-Al spinel, SABA/SP, pyridine oxidation, NOx yield vi Nomenclature Nomenclature °C Degree Centigrade Å angstrom BET Brunauer Emmett Teller method DTA differential thermal analysis EDX Energy Dispersive X-ray FESEM Field Emission Scanning Electron Microscopy FETEM Field Emission Transmission Electron Microscopy FTIR Fourier Transform Infrared Spectroscopy GC Gas Chromatography ppm part per million SEM Scanning Electron Microscopy TEM Transmission Electron Microscopy vol Volume wt Weight XPS X-ray Photoelectron Spectroscopy XRD X-Ray Diffraction Si/Al atom ratio of Si and Al Cu/SBA-15 SBA-15 material modified with nano Cu particles CuO/SBA-15 SBA-15 material modified with CuO particle Al/SBA-15 SBA-15 material incorporated with Al CuAl/SBA-15 AlSBA-15 material ion-exchanged with Cu vii Nomenclature CuOAl/SBA-15 AlSBA-15 material modified with CuO Cu-Zn-Al spinel CuO, ZnO and Al2O3 oxide complex SBA/SP-x SBA-15 modified with Cu-Zn-Al spinel, here x is the weight ratio of CuO in spinel to SBA-15 viii List of Figures List of Figures Fig 3.1 Small angle XRD patterns of SBA-15,CuO/SBA-15 and Cu/SBA15 34 Fig 3.2 Large angle XRD patterns of CuO,CuO/SBA-15 and Cu/SBA-15 35 Fig 3.3 in-situ XRD patterns of Cu/SBA-15 at different temperatures 36 Fig 3.4 N2 adsorption-desorption isotherms of SBA-15, Cu/SBA-15 and CuO/SBA-15 37 Fig 3.5 Pore size distribution of SBA-15, Cu/SBA-15 and CuO/SBA-15 38 Fig 3.6 TEM images of (a) SBA-15; (b) Cu/SBA-15; (c) CuO/SBA-15 40 Fig 3.7 IR spectra of :(A) SBA-15, treated with ethanol; (B) Cu/SBA-15, before reduction 42 Fig 3.8 XPS spectrum of Cu 2p for Cu/SBA-15 43 Fig 3.9 Pyridine conversion on SBA-15, Cu/SBA-15 and CuO/SBA-15 44 Fig 3.10 NOx yield on SBA-15, Cu/SBA-15 and CuO/SBA-15 45 Fig 4.1 Low angle XRD patterns of SBA-15, CuO/SBA-15, CuOAl/SBA15 and CuAl/SBA-15 52 Fig 4.2 Large angle XRD patterns of CuO, CuO/SBA-15, CuOAl/SBA-15 and CuAl/SBA-15 53 Fig 4.3 TEM images of SBA-15,CuAl/SBA-15 and CuO/SBA-15 55 Fig 4.4 N2 adsorption-desorption isotherms of SBA-15, CuO/SBA-15, CuOAl/SBA-15 and CuAl/SBA-15 56 Fig 4.5 Pore size distribution curves of SBA-15, CuO/SBA-15, CuOAl/SBA-15 and CuAl/SBA-15 57 Fig 4.6 XPS spectra of Cu for CuO/SBA-15, CuOAl/SBA-15 60 Fig 4.7 FTIR spectra of pyridine adsorption on CuO/SBA-15, CuOAl/SBA-15 and CuAl/SBA-15 61 ix Chapter Conclusions and Future Work makes CuAl/SBA-15 and CuOAl/SBA-15 to possess better pyridine oxidation than CuO/SBA-15 Meanwhile, CuAl/SBA-15 has improved the NOx control ability as compared to CuOAl/SBA-15, because the Cu ions play a key role in controlling NOx emissions Besides these two factors, a higher distribution of the active component on CuAl/SBA-15 also improves the activity of the catalyst Spinel materials were employed in this experiment due to their excellent thermal and hydrothermal stability The influence of different preparation methods, compositions of different precursors and hydrothermal treatment temperature on the morphology and reaction activities of the resulted catalysts have been investigated Among the three preparation methods of wet-impregnation, co-precipitation and hydrothermal method, the hydrothermal method can synthesize an optimal Cu-Zn-Al spinel for pyridine oxidation The Cu-Zn-Al spinel prepared with the molar ratio of Cu:Zn:Al=1:1:4 showed the best reactivity Calcination is a necessary step for the synthesis of the Cu-Zn-Al spinel with the hydrothermal method The reaction data indicate that the spinel prepared by the hydrothermal method at 180°С is an effective catalyst for pyridine oxidation due to its smaller particle size In order to combine the advantages of SBA-15 and the Cu-Zn-Al spinel, a series of SBA-15 introduced with different amounts of spinel were synthesized The spinel-structural type of Cu-Zn-Al complex oxides was introduced into SBA-15 by a co-precipitation method The catalysts prepared in this novel method are proven to have a very good catalytic activity for pyridine oxidation, as well as control ability for NOx yield in the presence of excess oxygen These catalysts can lower the NOx yield under 20% even at 650°C 105 Chapter Conclusions and Future Work 7.2 Future Work Catalytic exhaust aftertreatment of diesel engines is increasingly employed to the benefit of air quality Unlike NOx and hydrocarbon pollutants in diesel exhaust, little research has been done on the removal of nitrogen-containing polycyclic aromatic compounds due to their low concentration in diesel exhaust NPACs are potent mutagens, as well as possible carcinogens Since the emission regulations are becoming stricter, developing catalysts for deNPAC is necessary and practical This thesis has dealt with some aspects: design catalysts and test their activity for pyridine oxidation However, further investigations need to be performed in order to learn more about deNPAC Therefore, we propose the following studies that can be implemented Firstly, in this experiment, we have prepared different catalysts for pyridine oxidation and obtained some good results All these catalysts have increased the reactivity and lowered the NOx yield Among these catalysts, SBA/SP-x catalysts show very excellent catalytic activity, even at high temperatures Based on the results of pyridine oxidation, they are promising catalysts for industrial application in the removal of nitrogen-containing compounds In this research, there are two reasons to choose pyridine as the model reactant: (i) It is easily handled, since it is the simplest cyclic nitrogen-containing compound; (ii) As one important pollutant, the catalytic oxidation of pyridine has been investigated before, which will provide some useful reference information However, the most abundant NPAC in diesel emission extracts is 1-nitropyrene (Schuetzle et al., 1982; Schuetzle et al., 1983), so it will be more representative as the model reactant for deNPAC Hopefully, further studies can be performed on the catalytic oxidation of 1-nitropyrene 106 Chapter Conclusions and Future Work Secondly, as mentioned in Chapter 2, Pyridine oxidation has been studied before But the reaction mechanisms are still in doubt, because the reaction pathways significantly depend on the type of reactants, catalyst active components and reaction conditions As a result, it is important to systematically study the mechanisms of the pyridine oxidation However, due to time limits, we cannot much research on this area Here we provide a proposal on how to carry out the research as a reference to interested parties The catalytic reactions can be carried out at selected temperatures to collect the intermediates The reaction pathways of pyridine oxidation can be proposed, incorporating the yield of NOx by analyzing both gas-phase intermediates and catalyst adsorbates For the gaseous intermediates, a few bubblers can be placed in a liquid nitrogen bath along the reaction line to instantaneously trap all gas-phase intermediates generated during the reactions After removal from the liquid-nitrogen bath, tetrahydrofuran (THF) will be used to extract the trapped compounds For the adsorbate intermediates on the catalyst surfaces, the reactions will be quenched at selected stages before the catalysts are retrieved from the reactor THF can be used to extract the 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