TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI LUẬN VĂN THẠC SĨ Nghiên cứu xúc tác tẩm chất lỏng ion (SILP) và xúc tác nano vàng cho phản ứng chuyển hóa Etylen Vũ Tùng Lâm Lam.vn Ngành Hóa Học Giảng viên hướng dẫn: GS. Lê Minh Thắng Chữ ký của GVHD Bộ môn: Công nghệ Hữu cơ – Hóa dầu Viện: Kỹ thuật hóa học HÀ NỘI, 07/2022 CỘNG HÒA XÃ HỘI CHỦ NGHĨA VIỆT NAM Độc lập – Tự do – Hạnh phúc BẢN XÁC NHẬN CHỈNH SỬA LUẬN VĂN THẠC SĨ Họ và tên tác giả luận văn: Vũ Tùng Lâm Đề tài luận văn: Nghiên cứu xúc tác tẩm chất lỏng ion (SILP) và xúc tác nano vàng cho phản ứng chuyển hóa Etylen. Chuyên ngành: Hóa học Mã số SV: 20211199M Tác giả, Người hướng dẫn khoa học và Hội đồng chấm luận văn xác nhận tác giả đã sửa chữa, bổ sung luận văn theo biên bản họp Hội đồng ngày 13/07/2022 với các nội dung sau: − Chỉnh sửa lại bố cục còn 3 chương cho gọn và khoa học hơn. − Chỉnh sửa các lỗi về trình bày, tiếng Anh và danh pháp.
− Đã bổ sung phần kết quả nghiên cứu trong công bố khoa học vào luận văn. − Chỉnh sửa định dạng của một số tài liệu tham khảo. Ngày tháng năm Giáo viên hướng dẫn Tác giả luận văn CHỦ TỊCH HỘI ĐỒNG ii HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY THESIS Supported ionic liquid phase catalyst and nanogold catalyst for the conversion of Ethylene Vu Tung Lam Lam.vn Major: Chemistry Thesis advisor : Prof. Le Minh Thang Department : Department of Chemistry Institute : Hanoi University of Science and Technology Hanoi, 7-2022 iii Acknowledgment “Now this is not the end.
It is not even the beginning of the end. But it is, perhaps, the end of the beginning.” Winston Churchill My master’s thesis was the continuation from my engineer’s degree thesis, investigating the application of supported ionic liquid phase catalyst and gold catalyst in ethylene hydroformylation. Following with the previous thesis, the application of a relatively new support in hydroformylation catalyst has been the upgrade from old catalysts on metal oxide support. With high surface area and promising pore characteristics, the behavior and influence of these catalysts system in the hydroformylation are the primary discussion in this thesis.
Aside from that, this thesis concludes my 3 years research at Hanoi University of Science and Technology, from an undergraduate to a master student. I’d like to give my gratitude to Prof. Le Minh Thang for all her hard work and dedication to me. There are no words that can express my appreciation for everything that you have done for me.
I’m also extremely grateful to Dr. Nguyen Van Chuc for everything he has taught me in the past year. You played a decisive role in changing my way of thinking when it comes around science. I would like to extend my sincere thanks to Dr.
Nguyen Ngoc Mai, who patiently helps me with editing and originlab’s tips. Thank should also go to my lab mates Ta Dinh Quang, Khong Manh Hung and Tran Thi Thu Hien, who inspired me to push through the limits and be a better person. Lastly, it is impossible to not mention my family, especially my parents, my sister, my brother-in-law and my nephews, who gave me the encouragement and emotional support along the way. iv CONTENTS Abstract .2 Commercial application and statistics .2 Alternatives development for the current catalyst .1 Implementation of Ionic Liquid as an organic phase .2 Application of different supports .3 Nano gold catalyst in Hydroformylation .3 The goal of this thesis .1 Ordered mesoporous carbon synthesis.1 SBA-15 template synthesis .2 Fabrication of OMCs .2 Supported Ionic Liquid Phase Catalyst .3 Gold catalyst on Ordered mesoporous carbon .1 Fourier-Transform Infrared Spectroscopy .2 Nitrogen adsorption-de adsorption Isotherm method .3 Electron paramagnetic resonance .4 Scanning electron microscopy/energy-dispersive X-ray spectroscopy .5 UV-Vis spectroscopy .6 Catalyst’s activity testing system.
RESULTS AND DICUSSIONS.1 Synthesis and characterization of ordered mesoporous carbon .1 Ordered mesoporous carbon on SiO2 template.2 Ordered mesoporous carbon on SBA-15 template.3 Ordered mesoporous carbon on γ-Al2O3 template .2 Supported Ionic liquid phase catalysts.1 Investigating ionic liquid impregnation in SILP catalyst .2 Surface area and pore distribution of SILP catalysts .3 SILP catalysts activity at different temperatures.4 SILP catalysts activity at 120°C .5 SILP catalysts activity at 140°C .7 Catalyst characteristics after the reaction .3 Nanogold catalysts on ordered mesoporous carbon .1 Gold catalysts electron paramagnetic resonance’s spectrum .2 Gold catalysts surface area and pore distribution.3 Gold catalysts UV-Vis spectra.4 Gold catalysts elemental mapping and EDX results .5 Gold catalyst activity .4 Au/OMC activity and others catalysts activity comparison.70 vi LIST OF FIGURES Fig.1: Fischer - Tropsch Proces.2: Disused Zollverein Coal Mine Industrial Coking plant.3: Roelen's accidental discovery of hydroformylation .4: First and second generations of hydroformyl catalyst .5: Otto Roelen, in front of the Ruhrchemie’s plant based on his research.6: Aldehydes product’s variation .7: Verbund site in Nanjing, China: A joint industrial plant operated by BASF and SINOPEC, which houses the Butylene oxo s ynthesis plant .8: Cobalt tetracarbonyl hydride - First generation of hydroformylation catalyst .9: Cobalt catalyst salt formation.10: Cobalt Phosphine-modified catalyst. The second catalyst generation .11: Low-pressure oxo process plant in Ponce, Puerto Rico (1971) .12: Aqueous biphasic catalyst system .13: Rhodium/TPPTS biphasic catalyst used in Ruhrchemie Oxo process.14: Ionic liquid cations and anions.15: Supported ionic liquid phase catalyst [22].17: Two methods to synthesize ordered mesoporous carbon .18: hydroformylation and Hydrogenation under the influence of Gold catalyst .1: Ordered mesoporous carbon hard-template method.2: Ligand synthesis using Schlenk line.3: The 3-steps ligand separation.4: SILP catalyst synthesis.5: Stretching and bending vibrations formation [41] .6: Nicolet iS50 FT-IR .7: Pre-treatment degassed system for sample .8: Gemini VII, Micromeritics. Surface Area and Porosity .9: Bruker EMX-Micro EPR spectrometer.10: JCM-7000 NeoScope T M Benchtop SEM .11: Principle of UV-Vis spectroscopy.12: Avaspec 2048L, UV-Vis spectroscopy .13: Hydroformylation Catalyst’s activity testing system.14: Trace GC Ultra instrument to analyze products.1: FT-IR spectra of OMC-SiO2.2: Pore distribution of OMC-SiO2 .3: FT-IR spectra of OMC-SBA-15 .4: Pore distribution of OMC-SBA-15.5: FT-IR spectra of OMC-γ-Al2O3 .6: Al-O formation in OMC-γ-Al2O3-4g.7: FT-IR spectra of OMC-γ-Al2O3 , excluding OMC-γ-Al2 O3-4g.8: Pore distribution of OMC-γ-Al2 O3 .9: FT-IR spectra of Cat-SILP samples.10: FT-IR spectra of different ionic liquid loading in SILP c atalysts.11: Pore distribution of Cat-SILP-2 at different temperatures.12: Pore distribution of Cat-SILP-2 and Cat-SILP-3.13: Pore size distribution of OMC-SiO2-3g and OMC-γ-Al2 O3-4g and SILP catalysts.14: Ethylene Conversion with time-on-stream over 0.15g powder Cat- SILP-2, gas flow rate 60mL/min, at 7 bar.15: Propanal, propan-1-ol, propan-2-ol selectivity with time-on-stream over 0.15g powder Cat-SILP-2, gas flow rate 60mL/min, at 7 bar.16: Propanal, propan-1-ol, propan-2-ol’s TOF with time-on-stream over 0.15g powder Cat-SILP-2, gas flow rate 60mL/min, at 7 bar.17: Ethylene Conversion with time-on-stream over 0.15g powder Cat- SILP, gas flow rate 60mL/min, at 7 bar and 120°C.18: Propanal, propan-1-ol, propan-2-ol selectivity with time-on-stream over 0.15g powder Cat-SILP, gas flow rate 60mL/min, at 7 bar and 120°C.19: Propanal, propan-1-ol, propan-2-ol TOF with time-on-stream over 0.15g powder Cat-SILP, gas flow rate 60mL/min, at 7 bar and 120°C.20: Ethylene Conversion with time-on-stream over 0.15g powder Cat- SILP, gas flow rate 60mL/min, at 7 bar and 140°C.21: Propanal, propan-1-ol, propan-2-ol selectivity with time-on-stream over 0.15g powder Cat-SILP, gas flow rate 60mL/min, at 7 bar and 140°C.22: Propanal, propan-1-ol, propan-2-ol TOF with time-on-stream over 0.15g powder Cat-SILP, gas flow rate 60mL/min, at 7 bar and 140°C.23: FT-IR spectrum of SILP-2 and SILP-3 catalyst before and after the reaction.24: Pore distribution of Cat-SILP-2 before and after the reaction .25: Pore distribution of Cat-SILP before and after the reaction.26: Gold catalysts EPR's spectrum.27: The pore distribution of Au catalysts and respective support .28: Pore size distribution of Cat-Au-2 pre-reaction and after the reaction 57 Fig.29: Pore distribution of Cat-Au-3 pre-reaction and after the reaction.30: UV-Vis spectra of Au catalysts and support.31: Cat-Au-2 elemental mapping at 5,000×magnification.32: Cat-Au-2-after SEM images at 5000×magnification.33: Cat-Au-2-after elemental mapping at 5,000×magnification.34: Cat-Au-3 elemental mapping at 5,000×magnification.35: Cat-Au-3-after elemental mapping at 5,000×magnification.36: Ethylene Conversion with time-on-stream over 0.15g powder Cat-Au, gas flow rate 60mL/min, at 7 bar and 300°C.37: Product selectivity with time-on-stream over 0.15g powder Cat-Au, gas flow rate 60mL/min, at 7 bar and 300°C.38: Product TOF with time-on-stream over 0.15g powder Cat-Au, gas flow rate 60mL/min, at 7 bar and 300°C.39: Comparison of Cat-Au-2 at 300°C, Cat-SILP-3 and Cat-SILP-5 at 120°C ethylene conversion.40: Comparison of Cat-Au-2 at 300°C, Cat-SILP-3 and Cat-SILP-5 at 120°C selectivity.41: Comparison of Cat-Au-2 at 300°C, Cat-SILP-3 and Cat-SILP-5 at 120°C products’ TOF.68 ix LIST OF TABLES Table 1.1: Nameplate capacity (* 1000 tons) for productions of aldehydes by hydroformylation in 1998 .2: Aqueous biphasic catalyst specifications for Ruhrchemie oxo process.1: Synthesized OMC supports .2: Supported Ionic liquid phase catalysts component and abbreviations 18 Table 2.3: Gold catalyst synthesized.4: Activity testing system properties.5: GC-FID gas flows and products’ retention time .1: Surface area and porosity of OMC-SiO2.2: Pore characteristics of OMC-SBA-15 and SBA-15 template .3: Surface area and porosity of OMC-γ-Al2O3 .1: Surface area and pore characteristics of Cat-SILP-2 at different degas temperature .2: Surface area and pore characteristics of Cat-SILP-2 and Cat-SILP-3 39 Table 4.3: SILP catalysts on OMC- γ-Al2O3 and OMC-SiO2‘s surface area and pore characteristics.4: Surface area and porosity of SILP catalysts before and after the reaction.1: Surface area and pore characteristics of Au catalysts and support .2: EDS results of Cat-Au-2 before and after the reaction .3: EDS results of Cat-Au-3 .61 x Abbreviations Supported Ionic liquid phase SILP Ordered mesoporous carbon OMC Fourier Transform – Infrared Spectroscopy FT-IR Triphenylphosphine Trisulfonate TPPTS Nano particles NPs Turnover frequency TOF Santa Barbara Amorphous-15 SBA-15 Scanning electron microscopy SEM Energy dispersive X-ray spectroscopy EDS xi Abstract Hydroformylation is currently a homogeneous catalyst process designed to change alkene to aldehyde with syn gas. However, the two main obstacles to the reaction are catalyst leaching to other phases and mass transfer between phases.
Implementing ordered mesoporous carbon into the supported ionic liquid catalysts has been done as a solution for both problems. Synthesized by the hard-template method, ordered mesoporous carbon’s on various templates are characterized by FT-IR and N2 adsorption methods to select the suitable support in each template category. Incorporated to SILP catalysts, N2 adsorption and FT-IR methods are again used to determine the impregnation of ionic liquid into the structure of SILP. The catalysts after the reaction are re-evaluated by surface area changing and pore distribution to estimate the recycling properties of the catalyst.
Heterogeneous gold catalysts on ordered mesoporous carbon are also discussed to see the product formation and selectivity of SILP catalysts. With N 2 adsorption, electron paramagnetic resonance, scanning electron microscopy/energy-dispersive X-ray spectroscopy, and Ultraviolet-visible spectroscopy, catalysts' characteristics are investigated to understand the difference between both catalysts.1 History Hydroformylation reaction is the addition of synthesis gas, consisting of CO and H2, to olefin, enabled by a catalyst to form aldehydes. The name “hydroformyl” comes from the combination of additional hydrogen (hydro) and a formyl group (H-C=O) to the double bond. In theory, the only product is the aldehyde and can only initiate in the presence of a catalyst, along with high temperatures and pressure conditions [1].
Little is known that hydroformylation was discovered accidentally by a former soldier, scientist Otto Roelen (1897-1993). In the aftermath of the First World War, Otto returned to coal research at Kaiser-Wilhelm Institute in Germany. During his research, he initially conducted experiments regarding the Fischer-Tropsch process, converting carbon monoxide, and hydrogen to liquid hydrocarbons. Various short and long-chain hydrocarbons are formed in the process, using several metallic catalysts, including cobalt [2].1: Fischer - Tropsch Proces The Fischer-Tropsch process used a mixture of H2 and CO, which is called synthesis gas.
The name is derived from the reaction of carbon and water at high temperatures, producing the mentioned products.