Luận án Tiến sĩ Synthesis of catalysts based on PtSBA15 modified with Al andor B and their applicability on nheptane hydroisomerization, tetralin hydrogenation and paracetamol detection

MINISTRY OF EDUCATION AND TRANING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY NGO THI THANH HIEN Synthesis of catalysts based on Pt/SBA-15 modified with Al and/or B and their applicability on n-heptane hydroisomerization, tetralin hydrogenation and paracetamol detection CHEMICAL ENGINEERING DOCTORAL DISSERTATION Ha Noi – 2020 MINISTRY OF EDUCATION AND TRANING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY NGO THI THANH HIEN Synthesis of catalysts based on Pt/SBA-15 modified with Al and/or B and their applicability on n-heptane hydroisomerization, tetralin hydrogenation and paracetamol detection Major: Chemical Engineering Code No: 9520301 CHEMICAL ENGINEERING DOCTORAL DISSERTATION ADVISORS: Assoc Prof Pham Thanh Huyen Prof Graziella Liana Turdean Ha Noi – 2020 STATUTORY DECLARATION I hereby declare that I myself have written this thesis book The data and results presented in the dissertation are true and have not been published by other authors Ha Noi, 25th September 2020 PhD Student Ngo Thi Thanh Hien ADVISORS: Assoc.Prof Pham Thanh Huyen Prof Graziella Liana Turdean i ACKNOWLEDGEMENT First of all, I would like to thank my advisors Assoc Prof Dr Pham Thanh Huyen and Prof Dr Graziella Liana Turdean for all support and encouragement which really helped me and motivated me during my research I would like to thank Prof Vasile I Parvulescu at Deparment of Organic Chemistry, Biochemistry and Catalysis, University of Bucharest, Romania for the support in hydroisomerization experiments I would like to thank my friends at HaNoi University of Science and Technology (HUST) and at “Babes- Bolyai” University (UBB) for all assistances and for the enjoyable time, friendly events we shared together I would like to acknowledge the Eramus+ Program with partner countries for the financial support of my stages at “Babes- Bolyai” University, Cluj –Napoca, Romania I want to extend my thanks to Assoc Prof Do Ngoc My – Rector of QuyNhon University (QNU), Dr Nguyen Le Tuan – Former Dean of Faculty of Chemistry, Dean of Faculty of Natural Sciences - QNU and my colleagues at QNU for their support Finally, I would like to express my deep thanks to my family for all their love, encouragement and unconditional support throughout my PhD studying ii CONTENTS STATUTORY DECLARATION i ACKNOWLEDGEMENT - ii CONTENTS - iii LIST OF ABBREVIATIONS - vii LIST OF FIGURES ix LIST OF TABLES xiii INTRODUCTION - THE NEW CONTRIBUTION OF THE DESSERTATION CHAPTER LITERATURE REVIEW - 1.1 Mesoporous material and ordered mesoporous silica SBA-15 - 1.2 The modified SBA-15 materials and applications - 1.3 The hydroisomerization of n-alkane over bifunctional catalysts 10 1.3.1 Metal function of bifunctional catalysts 11 1.3.2 Acid function of bifunctional catalysts -12 1.4 Hydrogenation of polynuclear aromatic hydrocarbon (PAHs) 17 1.4.1 Hydrogenation of polynuclear aromatic hydrocarbon (PAHs) 17 1.4.2 Catalysts for PAHs hydrogenation 20 1.5 Overview of paracetamol detection 24 1.5.1 Introduction of paracetamol 24 1.5.2 Electroanalytical methods based on using chemically modified electrodes (CMEs) for paracetamol detection 25 1.5.3 Chemically modified electrodes (CMEs) for PA detection 30 1.6 Conclusions 35 CHAPTER EXPERIMENTAL -37 2.1 Preparation of catalysts -37 2.1.1 Direct synthesis procedure of M-SBA-15 (where M=Al and/or B) -37 iii 2.1.2 Indirect synthesis of B/SBA-15 38 2.1.3 Synthesis of Pt/M-SBA-15 (where M=Al-, B- and Al-B-) catalysts 38 2.2 Electrochemical procedure -38 2.2.1 Preparation of Pt/M-SBA-15-GPE electrodes -38 2.2.2 Preparation of supporting electrolyte and standard solution of paracetamol -39 2.3 Catalyst characterization techniques 40 2.3.1 X-Ray Diffraction -40 2.3.2 Transmision electron microscopy (TEM) 41 2.3.3 Fourier Transformed Infrared Spectroscopy (FT-IR) -41 2.3.4 Temperature Programmed Desorption (NH3-TPD) -42 2.3.5 Nitrogen adsorption-desorption 42 2.3.6 Thermal analysis -43 2.3.7 Inductively coupled plasma optical emission spectrometry (ICP - OES) 44 2.3.8 Pyridine-FTIR 44 2.3.9 Energy Dispersive X-Ray Spectroscopy (EDS or EDX) -44 2.3.10 11B MAS NMR spectrocopy -45 2.4 Hydroisomerization activity test -45 2.5 Hydrogenation activity test -45 2.6 Electrochemical measurements 46 CHAPTER RESULTS AND DISCUSSION -49 3.1 Effect of preparation methods of support. 49 3.2 Characterizations of modified SBA-15 supports 53 3.2.1 X-ray diffraction (XRD) 54 3.2.2 Nitrogen physisorption isotherms -54 3.2.3 Transition electron microscopy (TEM) -56 3.2.4 Fourier-transform infrared spectroscopy (FTIR) -57 iv 3.2.5 EDX analysis -58 3.2.6 11B MAS-NMR spectroscopy -60 3.2.7 Ammonia Temperature- Programmed Desorption (NH3-TPD) -60 3.2.8 FTIR spectra of chemisorbed pyridine 63 3.3 Characterizations of Pt/modified SBA-15 catalysts 63 3.3.1 Nitrogen physisorption isotherms 63 3.3.2 X-ray diffraction (XRD) 64 3.3.3 Transition electron microscopy (TEM) -65 3.3.4 NH3-TPD profiles -65 3.4 Performance of platinum supported on modified SBA-15 catalysts for hydroisomerization of n-heptane 68 3.4.1 Effect of the acidic supports on hydroisomerization activity of catalysts 68 3.4.2 Effect of temperature and reaction time in the hydroisomerization of nheptane 70 3.4.3 Cracked product yield and coke formation -72 3.5 Performance of platinum supported on modified SBA-15 catalysts for hydrogenation of tetralin -75 3.5.1 The results of GC-MS analysis of hydrogenation of tetralin -75 3.5.2 Effect of reaction temperature and pressure on catalytic activity -76 3.5.3 Effect of the acidity of modified supports on catalytic activity -78 3.5.4 Coke formation -80 3.6 The mesoporous catalysts of Pt loaded on modified SBA-15 material for the paracetamol detection 82 3.6.1 Characterization of 1%Pt/Al-SBA-15 catalyst 83 3.6.2 Electrochemical characterization of Pt/Al-SBA-15-GPE electrode material -85 3.6.3 Electrochemical impedance spectroscopy measurements at Pt/Al-SBA15-GPE electrode 88 v 3.6.4 Analytical characterization of Pt/Al-SBA-15-GPE electrode material -89 3.6.5 Interference study 91 3.6.6 Real sample analysis -92 CONCLUSIONS 94 PUBLICATIONS OF THE DISSERTATION -96 REFERENCES 97 vi LIST OF ABBREVIATIONS AA Ascorbic acid BET Brunauer-Emmet-Teller CE Counter electrode CMEs Chemically modified electrodes CN Cetane Number CV Cyclic voltammetry DTA Differential thermal analysis EIS Electrochemical impedance spectroscopy FCC Fluid catalytic cracking FT-IR Fourier transformed infrared spectroscopy FWHM Full width at half maximum GCE Glassy carbon electrode GPE Graphite paste electrode ICP Inductively coupled plasma method LCO Light cycle oil LOD Limit of detection MSA Amorphous silica-alumina NH3-TPD Ammonia Temperature- Programmed Desorption PA Paracetamol PAHs Polynuclear aromatic hydrocarbons PBS Phosphate buffer solution Py-FTIR FTIR spectra of chemisorbed pyridine RE Reference electrode SAPO-n Silicoaluminophosphate vii SBA-15 Santa Barbara Amorphous No 15 SWV Square wave voltammetry TEM Transmision electron microscopy TEOS 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is to synthesize the effective catalysts based on Pt/SBA-15 modifed with Al and/ or B and their applicability in n-heptane hydroisomerization, tetralin hydrogenation and paracetamol