Synthesis and modification of zr SBA 16 as catalyst for alkylation reaction

VIETNAM NATIONAL UNIVERSITY HOCHIMINH CITY HOCHIMINH CITY UNIVERSITY OF TECHNOLOGY  TRAN BA LUAN SYNTHESIS AND MODIFICATION OF Zr-SBA-16 AS CATALYST FOR ALKYLATION REACTION ( TỔNG HỢP VÀ BIẾN TÍNH Zr-SBA-16 LÀM XÚC TÁC PHẢN ỨNG ALKYL HÓA ) Major : Code : Chemical Engineering 605275 MASTER’S THESIS HO CHI MINH CITY JULY 2013 CƠNG TRÌNH ĐƯỢC HỒN THÀNH TẠI TRƯỜNG ĐẠI HỌC BÁCH KHOA –ĐHQG -HCM Cán hướng dẫn khoa học : P.Giáo sư – Tiến Sĩ Nguyễn Ngọc Hạnh Cán chấm nhận xét : Tiến sĩ Nguyễn Quang Long Cán chấm nhận xét : Tiến sĩ Lý Cẩm Hùng Luận văn thạc sĩ bảo vệ Trường Đại học Bách Khoa, ĐHQG Tp HCM ngày 06 tháng 09 năm 2013 Thành phần Hội đồng đánh giá luận văn thạc sĩ gồm: Tiến sĩ Huỳnh Kỳ Phương Hạ P.GS TS Nguyễn Ngọc Hạnh Tiến sĩ Nguyễn Quang Long Tiến sĩ Lý Cẩm Hùng Tiến sĩ Hồ Quốc Phong Xác nhận Chủ tịch Hội đồng đánh giá LV Trưởng Khoa quản lý chuyên ngành sau luận văn sửa chữa (nếu có) CHỦ TỊCH HỘI ĐỒNG TRƯỞNG KHOA VIETNAM NATIONAL UNIVERSITY HOCHIMINH CITY HOCHIMINH CITY UNIVERSITY OF TECHNOLOGY SOCIALIST REPUBLIC OF VIETNAM Independence -Freedom - Happiness MISSION MASTER’S THESIS Full name: Tran Ba Luan Student number: 11880184 Date of birth : 07/08/1978 Place of birth: Vinh Long Major : Code : 605275 Chemical Engineering I TITLE NAME Synthesis and modification of Zr-SBA-16 as catalyst for alkylation reaction (Tổng hợp biến tính Zr-SBA-16 làm xúc tác phản ứng alkyl hóa) II MISSION AND CONTENT: - Literature reviews - Synthesis of Zr-SBA-16 - Modification of Zr-SBA-16 by chloride compound - Characterization of as-prepared materials - Study of their catalytic activity on the Friedel-Crafts alkylation of toluene III START DATE : 21/01/2013 IV COMPLETION DATE: 21/06/2013 V SUPERVISOR : Prof.Dr Nguyen Ngoc Hanh Ho Chi Minh City- 31st, July, 2013 SUPERVISOR HEAD OF TRAINNING DEPARTMENT DEAN OF FACULTY ACKNOWLEDMENT First and foremost I offer my sincerest gratithude to my supervisor, Prof Nguyen Ngoc Hanh, who has supported me thoughout my thesis with her patience, motivation, enthusiasm and immense knowledge Her guidance helped me in all the time of research and writing of this thesis Besides my advisor, I would like to thank teachers in Faculty of Chemical Engineering, HoChiminh City University of Technology for helping me in encouragement, insightful comments Last but not the least; I would like to thank my family supporting me spiritual throughtout my life Tran Ba Luan ABSTRACT Chloride-promoted zirconium was supported on mesoporous pure silica SBA16 (abbreviated Cl-Zr/SBA-16) It was prepared by direct wet impregnation and reflux methods, followed by thermal decomposition The as-prepared materials were characterised by TDP-NH3, XRD, FT-IR spectroscopy, TEM and SEM images, ICP analysis and nitrogen adsorption-desorption measurements The results showed that the 3D cubic arrangement of mesopores corresponding to the Im3hm space group of SBA-16 was retained with the presence of zirconium extra framework about 2% and a change in pore size distribution as well as pore thickness It could be assumed of restructuration of active sites on internal surface for a potential strong acid catalyst For application, liquid - phase alkylation of toluene and benzyl chloride to form 1methyl –4 (phenylmethyl) benzene and 1-methyl –2 (phenylmethyl) benzene using Zr-SBA-16 and Cl-Zr-SBA-16 as catalyst were investigated The influence of reaction parameters such as reactant ratio, temperature, time was studied In this work, the optimum conditions for the alkylation reaction were found to be 0.2g catalyst and volume ratio of toluene and benzyl chloride of 1:1 at 110 oC After hrs, this reaction reached approximately 71% of conversion with a selectivity of 54 % of the main product This catalyst could be reused for several cycles with minimal loss of catalyst activity DECLARATION OF ORGINALITY I hereby declare that this is my own research study The research results and conclusions in this dissertation are true, and are not copied from any other resources The literature references have been quoted with clear citation as requested Dissertation Author Tran Ba Luan TABLE OF CONTENTS LIST OF FIGURES LIST OF TABLES LIST OF ABBREVIATIONS LIST OF PUBLICATIONS CHAPTER - LITERATURE REVIEWS 01 1.1 01 Introduction of SBA materials 1.1.1 SBA materials 1.1.2 Synthetic mechanism of SBA-16 1.2 Modification of SBA materials 1.2.1 Zirconium and its oxide 1.2.2 Modification of SBA by Zr 1.3 Introduction of Friedel-Craft alkylation 1.3.1 Friedel-Craft alkylation 1.3.2 Friedel-Craft alkylation using solid acids 1.4 Aim and objective 01 05 09 09 11 19 19 21 25 CHAPTER – EXPERIMENTAL 27 2.1 Materials and instrumentation 27 2.2 Catalytic synthesis 33 2.2.1 Synthesis of SBA-16 2.2.2 Synthesis of Zr-SBA-16, Cl-Zr-SBA-16 2.3 Catalytic studies – The Friedel-Craft alkylation reaction 33 34 36 CHAPTER - RESULTS AND DISCUSSION 39 3.1 39 Catalytic characterization 3.1.1 XRD patterns and Zr content 3.1.2 FT-IR spectra 3.1.3 Nitrogen adsorption/ desorption 39 44 47 3.1.4 Scanning electron microcopy (SEM) and transmission electron microcopy (TEM): 3.1.5 NH3-TPD 3.2 Catalytic activity of Zr-SBA-16 and their derivatives on alkylation 3.2.1 3.2.2 3.2.3 3.2.4 3.2.5 3.2.6 Effect of ratio Zr/Si on reaction conversion Effect of temperature on reaction conversion Effect of catalytic contents on reaction conversion Leaching test Catalytic recycling studies Selectivity of products 50 51 55 55 59 61 63 67 70 CHAPTER – CONCLUSIONS 80 REFERENCES 83-86 INDEXES LIST OF FIGURES Figure 1.1 Structures of SBA-15 and SBA-16 01 Figure 1.2 Powder X-Ray diffraction of as- synthesized SBA-16 prepared from Na2SiO3.9H2O with surfactants 04 Figure 1.3 Schematic representation synthetic method of SBA-16 06 Figure 1.4 Typical IR spectra of SBA-16 08 Figure 1.5 Typical HRTEM image of SBA-16 09 Figure 1.6 Eight-coordinated structure of SiO2-ZrO2 11 Figure 1.7 Mechanism of MPV reduction and B–V oxidation of carbonyl compounds over supported metal species 12 Figure 1.8 Zr-SBA-15 as an acid catalyst for produring biodiesel 13 Fig 1.9 Effect of reaction temperature (X4) and catalyst loading (X5) on the yield to FAME (Y) for the methanolysis of crude palm oil 14 Figure 1.10 Structure of WO3/Zr-SBA-15 16 2-/ Figure 1.11 Brønsted and Lewis acid site of SO4 ZrO2 16 Figure 1.12 Mechanism of the Friedel-Crafts alkylation reaction 20 Figure 2.1 Architecture of XRD diffractometer 28 Figure 2.2 IUPAC classification of sorption isotherms 30 Figure 2.3 Synthetic scheme of Zr-SBA-16 35 Figure 3.1 Low-angle (a) and large-angle (b) XRD of SBA-16 39 Figure 3.2 Low-angle (a) and large-angle (b) XRD of Zr-SBA-16 40 Figure 3.3 Low-angle (a) and large-angle (b) of XRD of Cl-Zr-SBA-16 40 Figure 3.4 Content of Zr 42 Figure 3.5 IR spectra of SBA-16 44 Figure 3.6 IR spectra of Zr-SBA-16 44 Figure 3.7 IR spectra of Cl-Zr-SBA-16 45 Figure 3.8 Pore size distribution curve of Cl-Zr-SBA-16 46 Figure 3.9 Pore size distribution curve of Zr-SBA-16 47 Figure 3.10 Isotherm profiles of Zr-SBA-16 48 Figure 3.11 Isotherm profiles of Cl-Zr-SBA-16 48 Figure 3.12 Scanning electron microcopy (SEM) of Zr-SBA-16 49 Figure 3.13 Transmission electron microcopy (TEM) of Zr-SBA-16 51 Figure 3.14 NH3-TPD curve of Cl-Zr-10 53 Figure 3.15 NH3-TPD curve of Zr-10 54 Figure 3.16 Reaction conversion on difference of ratio Zr/Si 56 Figure 3.17 Reaction conversion on difference of ratio Zr/Si (impregnated chloride) 58 Figure 3.18 Reaction conversion of Zr-X and Cl-Zr-X 59 Figure 3.19 Reaction conversion of various temperatures 61 Figure 3.20 Reaction conversion on difference of catalytic contents 62 Figure 3.21 Leaching test result of Zr-20 65 Figure 3.22 Reaction conversion on different of reactants and catalyst 66 Figure 3.23 Reaction conversion of normal recycling test 68 Figure 3.24 Reaction conversion of recycling test (impregnated chloride) 69 Figure 3.25 Reaction conversion in comparison of recycling test 70 Figure 3.26 The schematic substitute for toluene 72 Figure 3.27 GC-MS of reaction (using Zr-10) 75 Figure 3.28 GC-MS of reaction (using Cl-Zr-10 ) 77 Figure 3.29 GC-MS of reaction (using Zr-20) 79 Hanoi University of Technology ASAP 2010 V5.02 H Sample: Operator: Submitter: File Name: Unit Serial # 3021 Page 12 ZrO NHH Mr Luan HCMC D:\ \VILAS\001-429.SMP Started: 5/23/2013 9:53:02AM Analysis Adsorptive: N2 Completed: 5/23/2013 5:05:09PM Analysis Bath: 77.61 K Report Time: 5/23/2013 6:40:35PM Thermal Correction: No Sample Weight: 0.0846 g Smoothed Pressures: No Warm Freespace: 8.4467 cm³ ENTERED Cold Freespace: 19.9684 cm³ Equil Interval: 10 secs Low Pressure Dose: None BJH Desorption Cumulative Pore Volume 0.70 0.65 0.60 0.55 Pore Volume (cm³/g) 0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 1e+02 Pore Diameter (A) 1e+03 Hanoi University of Technology ASAP 2010 V5.02 H Sample: Operator: Submitter: File Name: Unit Serial # 3021 Page 13 ZrO NHH Mr Luan HCMC D:\ \VILAS\001-429.SMP Started: 5/23/2013 9:53:02AM Analysis Adsorptive: N2 Completed: 5/23/2013 5:05:09PM Analysis Bath: 77.61 K Report Time: 5/23/2013 6:40:35PM Thermal Correction: No Sample Weight: 0.0846 g Smoothed Pressures: No Warm Freespace: 8.4467 cm³ ENTERED Cold Freespace: 19.9684 cm³ Equil Interval: 10 secs Low Pressure Dose: None BJH Desorption dV/dD Pore Volume 0.014 0.013 0.012 0.011 Pore Volume (cm³/g-A) 0.010 0.009 0.008 0.007 0.006 0.005 0.004 0.003 0.002 0.001 0.000 1e+02 Pore Diameter (A) 1e+03 Hanoi University of Technology ASAP 2010 V5.02 H Sample: Operator: Submitter: File Name: Unit Serial # 3021 ZrO NHH Mr Luan HCMC D:\ \VILAS\001-429.SMP Started: 5/23/2013 9:53:02AM Analysis Adsorptive: N2 Completed: 5/23/2013 5:05:09PM Analysis Bath: 77.61 K Report Time: 5/23/2013 6:40:35PM Thermal Correction: No Sample Weight: 0.0846 g Smoothed Pressures: No Warm Freespace: 8.4467 cm³ ENTERED Cold Freespace: 19.9684 cm³ Equil Interval: 10 secs Low Pressure Dose: None Options Report Adsorptive Properties Adsorptive: Maximum manifold pressure: Non-ideality factor: Density conversion factor: Therm tran hard-sphere diameter: Molecular cross-sectional area: Nitrogen @ 77.35 K 925.00 mmHg 0.000062 0.0015468 3.860 A 0.162 nm² Analysis Conditions Analysis preparation options: Fast evacuation: Yes Evacuation time: 1.00 hours Leak test: No Free Space Free space group: Entered Warm free space: 16.0000 cm³ Cold free space: 45.0000 cm³ Equilibration options: Equilibration interval: 10 secs Min equil delay at P/Po >= 0.995: 600 secs Sample backfill options: Backfill at start of analysis:Yes Backfill at end of analysis:Yes Backfill Gas:Analysis gas Target pressure options: Page 14 Hanoi University of Technology ASAP 2010 V5.02 H Sample: Operator: Submitter: File Name: Unit Serial # 3021 ZrO NHH Mr Luan HCMC D:\ \VILAS\001-429.SMP Started: 5/23/2013 9:53:02AM Analysis Adsorptive: N2 Completed: 5/23/2013 5:05:09PM Analysis Bath: 77.61 K Report Time: 5/23/2013 6:40:35PM Thermal Correction: No Sample Weight: 0.0846 g Smoothed Pressures: No Warm Freespace: 8.4467 cm³ ENTERED Cold Freespace: 19.9684 cm³ Equil Interval: 10 secs Low Pressure Dose: None Options Report Use first pressure fixed dose:No Use maximum volume increment: No Target tolerance: 5.0 % Low pressure dosing: No or 5.0 mmHg Po and Temperature options: Po type: Measured Temperature type: Calculated from measured Psat Measurement interval: 120 minutes Inside diameter of sample tube: 9.530 mm Page 15 Hanoi University of Technology ASAP 2010 V5.02 H Sample: Operator: Submitter: File Name: Unit Serial # 3021 Page 16 ZrO NHH Mr Luan HCMC D:\ \VILAS\001-429.SMP Started: 5/23/2013 9:53:02AM Analysis Adsorptive: N2 Completed: 5/23/2013 5:05:09PM Analysis Bath: 77.61 K Report Time: 5/23/2013 6:40:35PM Thermal Correction: No Sample Weight: 0.0846 g Smoothed Pressures: No Warm Freespace: 8.4467 cm³ ENTERED Cold Freespace: 19.9684 cm³ Equil Interval: 10 secs Low Pressure Dose: None Summary Report Area Single Point Surface Area at P/Po 0.20683762 : 481.2231 m²/g BET Surface Area: 501.0823 m²/g Langmuir Surface Area: 709.9336 m²/g BJH Adsorption Cumulative Surface Area of pores between 17.000000 and 3000.000000 A Diameter: 512.0388 m²/g BJH Desorption Cumulative Surface Area of pores between 17.000000 and 3000.000000 A Diameter: 565.1390 m²/g Volume Single Point Adsorption Total Pore Volume of pores less than 712.7425 A Diameter at P/Po 0.97208005: 0.590354 cm³/g BJH Adsorption Cumulative Pore Volume of pores between 17.000000 and 3000.000000 A Diameter: 0.679392 cm³/g BJH Desorption Cumulative Pore Volume of pores between 17.000000 and 3000.000000 A Diameter: 0.702229 cm³/g Pore Size Adsorption Average Pore Diameter (4V/A by BET): 47.1263 A BJH Adsorption Average Pore Diameter (4V/A): 53.0735 A BJH Desorption Average Pore Diameter (4V/A): 49.7031 A Micromeritics Instrument Corporation AutoChem II 2920 AutoChem II 2920 V4.01 Sample: Operator: Submitter: File: Unit Serial # 120 NH3 TPD Zr-SBA- 16 Zr/Si =10% impac Clo N.H.Hanh 2013 D:\KETQUA~1\2013\004-085.SMP Started: 1/30/2013 11:17:12AM Completed: 1/30/2013 5:13:44PM Sample Mass: 0.0938 g Report Time: 2/1/2013 11:18:15AM Comments: Heat of Desorption experiment using ammonia; Zr-SBA 16- Zr/Si=10% Summary Report Experiment 1: 10 C/min Analysis Type: Temperature Programmed Desorption Calibration: (292_0003) 10.13 NH3/He 25 ml/min Measured Flow Rate: 25.55 cm³ STP/min Signal Offset: -0.70641 Signal Inverted: Yes Peak Number Temperature at Quantity (cm³/g Maximum (°C) STP) 230.7 482.5 537.8 1.06890 0.67566 0.30438 Peak Concentration (%) -0.37 -0.38 -0.38 Page Micromeritics Instrument Corporation AutoChem II 2920 AutoChem II 2920 V4.01 Sample: Operator: Submitter: File: Unit Serial # 120 NH3 TPD Zr-SBA- 16 Zr/Si =10% impac Clo N.H.Hanh 2013 D:\KETQUA~1\2013\004-085.SMP Started: 1/30/2013 11:17:12AM Completed: 1/30/2013 5:13:44PM Sample Mass: 0.0938 g Report Time: 2/1/2013 11:18:15AM Comments: Heat of Desorption experiment using ammonia; Zr-SBA 16- Zr/Si=10% First Order Kinetics Report Experiment 1: 10 C/min Analysis Type: Temperature Programmed Desorption Calibration: (292_0003) 10.13 NH3/He 25 ml/min Measured Flow Rate: 25.55 cm³ STP/min Signal Offset: -0.70641 Signal Inverted: Yes Peak Number Temperature Start Stop Ramp Rate at Maximum Temperature Temperature (°C/min) (°C) (°C) (°C) 230.7 482.5 537.8 E: Slope: Y-Intercept: Correlation Coefficient: 119.9 119.9 119.9 549.4 549.4 549.4 k = ko exp( -E / RT ) -10.4 ± 0.3 kJ/mol -1251.2 ± 34.7 13.4 ± 0.1 -1.000 4.6 4.6 4.6 Page Micromeritics Instrument Corporation AutoChem II 2920 AutoChem II 2920 V4.01 Sample: Operator: Submitter: File: Unit Serial # 120 Page NH3 TPD Zr-SBA- 16 Zr/Si =10% impac Clo N.H.Hanh 2013 D:\KETQUA~1\2013\004-085.SMP Started: 1/30/2013 11:17:12AM Completed: 1/30/2013 5:13:44PM Sample Mass: 0.0938 g Report Time: 2/1/2013 11:18:15AM Comments: Heat of Desorption experiment using ammonia; Zr-SBA 16- Zr/Si=10% First Order Desorption Kinetics E: -10.4 ± 0.3 kJ/mol NH3 TPD Zr-SBA- 16 Zr/Si =10% impac Clo 11.8 11.7 11.6 ln(Tp²/beta) 11.5 11.4 11.3 11.2 11.1 11.0 10.9 0.0013 0.0014 0.0015 0.0016 1/Tp 0.0017 0.0018 0.0019 0.0020 Micromeritics Instrument Corporation AutoChem II 2920 AutoChem II 2920 V4.01 Sample: Operator: Submitter: File: Unit Serial # 120 Page NH3 TPD Zr-SBA- 16 Zr/Si =10% impac Clo N.H.Hanh 2013 D:\KETQUA~1\2013\004-085.SMP Started: 1/30/2013 11:17:12AM Completed: 1/30/2013 5:13:44PM Sample Mass: 0.0938 g Report Time: 2/1/2013 11:18:15AM Comments: Heat of Desorption experiment using ammonia; Zr-SBA 16- Zr/Si=10% TCD Signal (a.u.) vs Time TCD Signal (a.u.) - 10 C/min Temperature - 10 C/min 0.018 550 0.016 500 0.014 450 400 0.010 350 0.008 300 0.006 250 0.004 200 0.002 150 0.000 10 20 30 40 50 60 Time (minutes) 70 80 90 100 110 Temperature (°C) TCD Signal (a.u.) 0.012 Micromeritics Instrument Corporation AutoChem II 2920 AutoChem II 2920 V4.01 Sample: Operator: Submitter: File: Unit Serial # 120 Page NH3 TPD Zr-SBA- 16 Zr/Si =10% impac Clo N.H.Hanh 2013 D:\KETQUA~1\2013\004-085.SMP Started: 1/30/2013 11:17:12AM Completed: 1/30/2013 5:13:44PM Sample Mass: 0.0938 g Report Time: 2/1/2013 11:18:15AM Comments: Heat of Desorption experiment using ammonia; Zr-SBA 16- Zr/Si=10% TCD Signal (a.u.) vs Temperature TCD Signal (a.u.) - 10 C/min 0.018 0.016 0.014 TCD Signal (a.u.) 0.012 0.010 0.008 0.006 0.004 0.002 0.000 150 200 250 300 350 Temperature (°C) 400 450 500 550 Micromeritics Instrument Corporation AutoChem II 2920 AutoChem II 2920 V4.01 Sample: Operator: Submitter: File: Unit Serial # 120 NH3 TPD Zr-SBA- 16 Zr/Si =10% N.H.Hanh 2013 D:\KETQUA~1\2013\004-086.SMP Started: 1/31/2013 10:26:10AM Completed: 1/31/2013 3:49:19PM Sample Mass: 0.1323 g Report Time: 2/1/2013 11:19:07AM Comments: Heat of Desorption experiment using ammonia; Zr-SBA 16- Zr/Si=10% Summary Report Experiment 1: 10 C/min Analysis Type: Temperature Programmed Desorption Calibration: (292_0003) 10.13 NH3/He 25 ml/min Measured Flow Rate: 25.53 cm³ STP/min Signal Offset: -0.70706 Signal Inverted: Yes Peak Number Temperature at Quantity (cm³/g Maximum (°C) STP) 218.4 425.6 533.6 0.96563 1.04715 0.37760 Peak Concentration (%) -0.37 -0.37 -0.37 Page Micromeritics Instrument Corporation AutoChem II 2920 AutoChem II 2920 V4.01 Sample: Operator: Submitter: File: Unit Serial # 120 NH3 TPD Zr-SBA- 16 Zr/Si =10% N.H.Hanh 2013 D:\KETQUA~1\2013\004-086.SMP Started: 1/31/2013 10:26:10AM Completed: 1/31/2013 3:49:19PM Sample Mass: 0.1323 g Report Time: 2/1/2013 11:19:07AM Comments: Heat of Desorption experiment using ammonia; Zr-SBA 16- Zr/Si=10% First Order Kinetics Report Experiment 1: 10 C/min Analysis Type: Temperature Programmed Desorption Calibration: (292_0003) 10.13 NH3/He 25 ml/min Measured Flow Rate: 25.53 cm³ STP/min Signal Offset: -0.70706 Signal Inverted: Yes Peak Number Temperature Start Stop Ramp Rate at Maximum Temperature Temperature (°C/min) (°C) (°C) (°C) 218.4 425.6 533.6 E: Slope: Y-Intercept: Correlation Coefficient: 120.9 120.9 120.9 549.5 549.5 549.5 k = ko exp( -E / RT ) -10.2 ± 0.5 kJ/mol -1227.4 ± 64.8 13.3 ± 0.1 -0.999 4.8 4.8 4.8 Page Micromeritics Instrument Corporation AutoChem II 2920 AutoChem II 2920 V4.01 Sample: Operator: Submitter: File: Unit Serial # 120 Page NH3 TPD Zr-SBA- 16 Zr/Si =10% N.H.Hanh 2013 D:\KETQUA~1\2013\004-086.SMP Started: 1/31/2013 10:26:10AM Completed: 1/31/2013 3:49:19PM Sample Mass: 0.1323 g Report Time: 2/1/2013 11:19:07AM Comments: Heat of Desorption experiment using ammonia; Zr-SBA 16- Zr/Si=10% First Order Desorption Kinetics NH3 TPD Zr-SBA- 16 Zr/Si =10% E: -10.2 ± 0.5 kJ/mol 11.8 11.7 11.6 ln(Tp²/beta) 11.5 11.4 11.3 11.2 11.1 11.0 10.9 0.0013 0.0014 0.0015 0.0016 1/Tp 0.0017 0.0018 0.0019 0.0020 Micromeritics Instrument Corporation AutoChem II 2920 AutoChem II 2920 V4.01 Sample: Operator: Submitter: File: Unit Serial # 120 Page NH3 TPD Zr-SBA- 16 Zr/Si =10% N.H.Hanh 2013 D:\KETQUA~1\2013\004-086.SMP Started: 1/31/2013 10:26:10AM Completed: 1/31/2013 3:49:19PM Sample Mass: 0.1323 g Report Time: 2/1/2013 11:19:07AM Comments: Heat of Desorption experiment using ammonia; Zr-SBA 16- Zr/Si=10% TCD Signal (a.u.) vs Time TCD Signal (a.u.) - 10 C/min Temperature - 10 C/min 0.030 550 500 0.025 450 0.020 350 0.015 300 0.010 250 200 0.005 150 0.000 10 20 30 40 50 60 Time (minutes) 70 80 90 100 110 Temperature (°C) TCD Signal (a.u.) 400 Micromeritics Instrument Corporation AutoChem II 2920 AutoChem II 2920 V4.01 Sample: Operator: Submitter: File: Unit Serial # 120 Page NH3 TPD Zr-SBA- 16 Zr/Si =10% N.H.Hanh 2013 D:\KETQUA~1\2013\004-086.SMP Started: 1/31/2013 10:26:10AM Completed: 1/31/2013 3:49:19PM Sample Mass: 0.1323 g Report Time: 2/1/2013 11:19:07AM Comments: Heat of Desorption experiment using ammonia; Zr-SBA 16- Zr/Si=10% TCD Signal (a.u.) vs Temperature 0.030 TCD Signal (a.u.) - 10 C/min 0.025 TCD Signal (a.u.) 0.020 0.015 0.010 0.005 0.000 150 200 250 300 350 Temperature (°C) 400 450 500 550 ... distribution curve of Zr- SBA- 16 47 Figure 3.10 Isotherm profiles of Zr- SBA- 16 48 Figure 3.11 Isotherm profiles of Cl -Zr- SBA- 16 48 Figure 3.12 Scanning electron microcopy (SEM) of Zr- SBA- 16 49 Figure... temperature and catalytic contents on reaction conversion and selectivity 38 Table 2.1 Table of catalytic studies of Zr- SBA- 16 (A) and Cl -Zr- SBA- 16( B) A o Studies of Zr- SBA- 16 Ratio of Zr/ Si T,... Zr- SBA- 16 in reaction and regeneration The study was scoped in alkylation reaction of toluene and benzyl chloride, using ZrSBA-6 and Cl -Zr- SBA- 16 as catalysts in liquid phase This reaction is