Xúc tác Pt/SBA-15 Al-B: Tổng hợp, đặc tính và ứng dụng hydroisomerization

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 luan an 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: 1. Pham Thanh Huyen 2. Graziella Liana Turdean Ha Noi – 2020 luan an 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: 1. Pham Thanh Huyen 2. Graziella Liana Turdean i luan an ACKNOWLEDGEMENT First of all, I would like to thank my advisors Assoc. Dr Pham Thanh Huyen and Prof.

Graziella Liana Turdean for all support and encouragement which really helped me and motivated me during my research. I would like to thank Prof. 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 luan an CONTENTS STATUTORY DECLARATION ------------------------------------------------------------ i ACKNOWLEDGEMENT ------------------------------------------------------------------- ii CONTENTS ----------------------------------------------------------------------------------- iii LIST OF ABBREVIATIONS ------------------------------------------------------------- vii LIST OF FIGURES -------------------------------------------------------------------------- ix LIST OF TABLES --------------------------------------------------------------------------xiii INTRODUCTION ----------------------------------------------------------------------------- 1 THE NEW CONTRIBUTION OF THE DESSERTATION-------------------------- 4 CHAPTER 1. Mesoporous material and ordered mesoporous silica SBA-15 ------------------- 5 1. The modified SBA-15 materials and applications --------------------------------- 6 1.

The hydroisomerization of n-alkane over bifunctional catalysts ----------------10 1. Metal function of bifunctional catalysts --------------------------------------11 1. Acid function of bifunctional catalysts ---------------------------------------12 1. Hydrogenation of polynuclear aromatic hydrocarbon (PAHs) ------------------17 1.

Hydrogenation of polynuclear aromatic hydrocarbon (PAHs) ------------17 1. Catalysts for PAHs hydrogenation --------------------------------------------20 1. Overview of paracetamol detection. Introduction of paracetamol ----------------------------------------------------24 1.

Electroanalytical methods based on using chemically modified electrodes (CMEs) for paracetamol detection. Chemically modified electrodes (CMEs) for PA detection ----------------30 1. Preparation of catalysts ---------------------------------------------------------------37 2. Direct synthesis procedure of M-SBA-15 (where M=Al and/or B) -------37 iii luan an 2.

Indirect synthesis of B/SBA-15 ------------------------------------------------38 2. Synthesis of Pt/M-SBA-15 (where M=Al-, B- and Al-B-) catalysts------38 2. Preparation of Pt/M-SBA-15-GPE electrodes -------------------------------38 2. Preparation of supporting electrolyte and standard solution of paracetamol -------------------------------------------------------------------------------39 2.

Catalyst characterization techniques ------------------------------------------------40 2. Transmision electron microscopy (TEM) ------------------------------------41 2. Fourier Transformed Infrared Spectroscopy (FT-IR) -----------------------41 2. Temperature Programmed Desorption (NH3-TPD) -------------------------42 2.

Nitrogen adsorption-desorption ------------------------------------------------42 2.7 Inductively coupled plasma optical emission spectrometry (ICP - OES) 44 2. Energy Dispersive X-Ray Spectroscopy (EDS or EDX) -------------------44 2. 11B MAS NMR spectrocopy -------------------------------------------------45 2. Hydroisomerization activity test-----------------------------------------------------45 2.

Hydrogenation activity test-----------------------------------------------------------45 2. Electrochemical measurements ------------------------------------------------------46 CHAPTER 3. RESULTS AND DISCUSSION -----------------------------------------49 3. Effect of preparation methods of support.

Characterizations of modified SBA-15 supports ----------------------------------53 3. Nitrogen physisorption isotherms. Transition electron microscopy (TEM) ---------------------------------------56 3. Fourier-transform infrared spectroscopy (FTIR) ---------------------------57 iv luan an 3.

11B MAS-NMR spectroscopy -------------------------------------------------60 3. Ammonia Temperature- Programmed Desorption (NH3-TPD) -----------60 3. FTIR spectra of chemisorbed pyridine ----------------------------------------63 3. Characterizations of Pt/modified SBA-15 catalysts ------------------------------63 3.

Nitrogen physisorption isotherms----------------------------------------------63 3. Transition electron microscopy (TEM) ---------------------------------------65 3. NH3-TPD profiles ---------------------------------------------------------------65 3. Performance of platinum supported on modified SBA-15 catalysts for hydro- isomerization of n-heptane ----------------------------------------------------------------68 3.

Effect of the acidic supports on hydroisomerization activity of catalysts 68 3. Effect of temperature and reaction time in the hydroisomerization of n- heptane ------------------------------------------------------------------------------------70 3. Cracked product yield and coke formation -----------------------------------72 3. Performance of platinum supported on modified SBA-15 catalysts for hydrogenation of tetralin -------------------------------------------------------------------75 3.

The results of GC-MS analysis of hydrogenation of tetralin---------------75 3. Effect of reaction temperature and pressure on catalytic activity ---------76 3. Effect of the acidity of modified supports on catalytic activity. The mesoporous catalysts of Pt loaded on modified SBA-15 material for the paracetamol detection ----------------------------------------------------------------------82 3.

Characterization of 1%Pt/Al-SBA-15 catalyst ------------------------------83 3. Electrochemical characterization of Pt/Al-SBA-15-GPE electrode material -----------------------------------------------------------------------------------85 3. Electrochemical impedance spectroscopy measurements at Pt/Al-SBA- 15-GPE electrode ------------------------------------------------------------------------88 v luan an 3. Analytical characterization of Pt/Al-SBA-15-GPE electrode material ---89 3.

Real sample analysis-------------------------------------------------------------92 CONCLUSIONS ------------------------------------------------------------------------------94 PUBLICATIONS OF THE DISSERTATION -----------------------------------------96 REFERENCES --------------------------------------------------------------------------------97 vi luan an 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 luan an SBA-15 Santa Barbara Amorphous No 15 SWV Square wave voltammetry TEM Transmision electron microscopy TEOS Tetraethyl orthosilicate TGA Thermogra vimetric analysis TMOS Tetramethyl orthosilicate UA Uric acid WE Working electrode XRD X-ray diffraction viii luan an LIST OF FIGURES Fig 1. Formation mechanism of MCM-41 suggested by Beck et al. Co-condensation approach for the functionalization of mesoporous materials. Functionalization of SBA-15 through post-grafting.

Formation of Bronsted acidic site in mesoporous materials. Two different tetrahedral structures of boron in B-SBA-15 framework. Scheme of n-alkane hydroisomerization over bifunctional catalysts. Stepwise hydrogenation of an adsorbed tetralin molecule to cis- and trans- decalin.

Reaction network of tetralin hydrocracking. Reaction scheme for the selective hydrocracking of tetralin into BTX. Chemical structure of PA. Electrochemical oxidation of PA.

Cyclic potential sweep (a) and resulting cyclic voltammogram (b). Cyclic voltammogram of a reversible reaction system (a), quasi-reversible system (b) and irreversible reaction system (c). (a) Scheme of application of potentials of square wave voltammetry method. (b) The response contains a forward (anodic, I(1)), backward (cathodic, I(2)) and net current ΔI.

The relation of a real part (Z’) and an imaginary part (Z”) in the complex plane. The Randles equivalent circuit- frequently used to represent an electrochemical cell. Where: Cdl: capacitance of the double layer charging; Rsol: the solution resistance; Zf: the impedance of the faradic process. Direct-synthesis of M-SBA-15 (M = Al and/or B).

Synthetic procedure of Pt supported on modified supports (Al-SBA-15; Al- B-SBA-15; B-SBA-15). 39 ix luan an Fig 2. Schematic illustration of diffraction according to Bragg’s law. (a) The high pressure autoclave batch reactor and (b) schematic batch reaction system used for the n-heptane hydroisomerization and the tetralin hydrogenation.

Cyclic voltammogram for a reversible system. Low angle XRD patterns of SBA-15, B/SBA-15 and B-SBA-15. TEM images of SBA-15 (A), B-SBA-15 (B) and B/SBA-15(C). Nitrogen adsorption–desorption isotherm (A) and BJH pore size distribution (B) of SBA-15, B-SBA-15 and B/SBA-15.

NH3-TPD curves of SBA-15; B-SBA-15 and B/SBA-15. Low angle XRD patterns of SBA-15; M-SBA-15 (M=Al and/or B) samples. Nitrogen adsorption isotherms and (A) Pore size distribution of SBA-15; Al-SBA-15, Al-B-SBA-15; B-SBA-15 (B). TEM images of SBA-15 (A); Al-SBA-15 (B); Al-B-SBA-15 (C) and B- SBA-15 (D).

FTIR spectra of SBA-15 and modified SBA-15 samples. EDX spectras of Al-SBA-15 (A); Al-B-SBA-15 (B); B-SBA-15 (C). 11B MAS-NMR for B-SBA-15 sample. NH3-TPD curves of Al-SBA-15; Al-B-SBA-15; B-SBA-15 samples.

The Py-FTIR spectras of Al-SBA-15 (A), Al-B-SBA-15 (B), B-SBA-15 (C). Nitrogen adsorption-desorption isotherms and pore size distribution of catalysts. Low angle XRD patterns 0.5%Pt/Al-SBA-15 (A); 0.5%Pt/Al-B-SBA-15 (B) and 0.5%Pt/B-SBA-15 (C) catalysts. TEM images of 0.5%Pt/Al-SBA-15; 0.5%Pt/Al-B-SBA-15 and 0.

NH3-TPD curves of 0.5% Pt/Al-SBA-15; 0.5% Pt/Al-B-SBA-15 and 0.5% Pt/B-SBA-15 catalyst. 66 x luan an Fig 3. Conversion of n-heptane over the three catalysts of 0.5%Pt/Al-SBA-15; 0.5%Pt/Al-SBA-15 and 0. The selectivity of branched heptanes over the investigated catalysts.

The heptane conversion versus reaction time and temperature over the Pt/M-SBA-15 catalysts (M=Al and/or B). The variation of the selectivity to branched heptanes versus reaction time and temperature over the investigated catalysts (Pt/Al-SBA-15 (a), Pt/Al-B-SBA-15 (b), Pt/B-SBA-15 (c). The yield of the cracked product over the investigated catalysts (300 oC, 12 h). DTA/TGA curves of the investigated catalysts after 24hours reaction time.

Effect of reaction temperature on the conversion of tetralin over investigated catalysts((A): Pt/Al-SBA-15; (B): Pt/Al-B-SBA-15; (C): Pt/B-SBA- 15). The reaction condition: liquid phase; reaction time: 3 hours. Effect of hydrogen pressure on the conversion of tetralin over investigated catalysts ( (A): Pt/Al-SBA-15; (B): Pt/Al-B-SBA-15; (C): Pt/B-SBA-15). The reaction condition: liquid phase; reaction time: 3 hours.

The conversion of tetralin and cis/trans ratio over the investigated catalysts. TG curves of Pt/ B-SBA-15 (A) after reaction. TG curves of Pt/ Al-SBA-15 (B) and Pt/Al-B-SBA-15 (C) catalysts after reaction. Square wave voltammograms of 10-5M PA at the 1%Pt/M-SBA-15-GPE (where M=Al and/or B) electrodes in 0.

Low angle XRD pattern of 1%Pt/Al-SBA-15 catalyst. Nitrogen adsorption-desorption isotherms at 77K (A) and pore size distribution (B) applying BJH method in the desorption branch of 1%Pt/Al-SBA-15 catalyst. TEM image of 1% Pt/Al-SBA-15 catalyst. 85 xi luan an Fig.

Cyclic voltammograms at Pt/Al-SBA-15-GPE in absence (dot line) and in presence of 7 x 10-5 M of PA (solid line). Inset: CV at unmodified GPE in presence of 7 M of PA. Cyclic voltamogramms of 7 x 10-5 M PA at Pt/Al-SBA-15-GPE recorded at different scan rate. Inset influence of scan rate on anodic peak currents intensities at Pt/Al-SBA-15-GPE () and GPE () electrodes (A).

Nyquist plots recorded at Pt/Al-SBA-15-GPE modified electrode () and GPE unmodified electrode () (inset) into a solution containing 1 mM K4[Fe(CN)6]/K3[Fe(CN)6] + 0. Square wave voltamogramms for different concentration of PA at Pt/Al- SBA-15-GPE modified graphite paste electrode (A) and calibration curve of Pt/Al- SBA-15-GPE modified graphite paste electrode () and GPE () for PA (B). Square wave voltamogramms recorded at Pt/Al-SBA-15-GPE modified electrode in a presence of a mixture of 7 x 10-6 M paracetamol, 9 x 10-3 M ascorbic acid and 10-6 M uric acid. SWVs (A) and calibration curve (B) for detection of PA from tablets using Pt/Al -SBA-15-GPE modified electrode.

92 xii luan an LIST OF TABLES Table. Physicochemical properties of SBA-15, B-SBA-15 and B/SBA-15 samples. Amonia TPD results of SBA-15; B-SBA-15 and B/SBA-15. Textual characteristic of SBA-15 and the modified SBA-15 samples.

Results of EDX analysis. Acidic properties of Al-SBA-15; Al-B-SBA-15; B-SBA-15 samples according to NH3-TPD. Surface area and pore size of catalysts and the corresponding supports. Results in NH3-TPD of catalysts.

Conversion of n-heptane over the Pt/M-SBA-15 (M=Al and/or B) catalysts. Coke content determined from the thermogravimetry analysis of the investigated catalysts after a 24 hours reaction time. Tetralin conversion and selectivity of products. Surface area and pore size of Al-SBA-15 support and 1%Pt/Al-SBA-15 catalyst.

The electrochemical parameters of the Pt/Al-SBA-15-GPE electrode material. Slope of log I versus log v dependence. EIS fitting parameters for Pt/Al-SBA-15-GPE modified electrodes. Determination of PA from pharmaceutical tablets using Pt/Al-SBA-15- GPE modified electrode.

93 xiii luan an INTRODUCTION During the last two decades, the synthesis of mesoporous materials is one of the most attractive and successful achievements in material science and catalysis.