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Hydroformylation of C3 and C8 Olefins in Hydrocarbon Gas-Expanded Solvents

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Hydroformylation of C3 and C8 Olefins in Hydrocarbon Gas-Expanded Solvents HYDROFORMYLATION OF C3 AND C8 OLEFINS IN HYDROCARBON GAS-EXPANDED SOLVENTS By Dupeng Liu Submitted to the graduate degree program in Chemical & Petroleum Engineering and the Graduate Faculty of the University of Kansas in partial fulfillment of the requirements for the degree of Doctor of Philosophy. Chairperson: Bala Subramaniam Raghunath V. Chaudhari Jon Tunge Aaron Scurto Kevin Leonard Date Defended: April 30th, 2018 The dissertation committee for Dupeng Liu certifies that this is the approved version of the following dissertation: HYDROFORMYLATION OF C3 AND C8 OLEFINS IN HYDROCARBON GAS-EXPANDED SOLVENTS Chairperson: Bala Subramaniam Date Approved: May 8th, 2018 ii Abstract Hydroformylation involves the addition of syngas to the double bond of an alkene yielding aldehydes used to produce basic building blocks for myriad consumer goods. Resource-efficient technologies that conserve feedstock and energy continue to be of interest to industry. It has been shown previously by our group that the use of CO2-expanded liquids significantly enhances the Rh-catalyzed 1-octene hydroformylation rate and selectivity. This dissertation extends this concept by employing light alkanes such as propane and n-butane as compressed solvents in propylene and 1-octene hydroformylation, respectively. Phase behavior measurements demonstrate that at identical H2 or CO fugacities in the vapor phase, the H2 and CO solubilities in either propane- or propylene-expanded solvents (PXLs) are greater than those in the corresponding neat solvents by as high as 76% at 70 °C and 1.5 MPa. The H2/CO ratio in PXLs is enhanced by simply increasing the propane partial pressure. In contrast, the H2/CO in the neat solvent at a given temperature is constant at all syngas partial pressures. For Rh/triphenylphosphine catalyzed propylene hydroformylation between 70 to 90°C and pressures up to 2.0 MPa, the n/i aldehyde ratio in PXL media is increased by up to 45% compared to conventional media. However, with Rh/BiPhePhos catalyst complexes, the n/i ratio and turnover frequency (TOF) in PXL media are comparable with those observed in conventional processes in neat solvent. Thus, refinery-grade propane/propylene mixtures, rather than polymer-grade propylene, can be used in industrial propylene hydroformylation obviating purification by distillation. Technoeconomic analyses show ~ 30% lower capital costs and ~ 20% lower utilities costs for the PXL process compared to the conventional process. The reduced material and energy consumption in the PXL process also lowers adverse environmental impacts (greenhouse gas emission, air pollutants emission, and toxic release) associated with the PXL process. For Co- iii catalyzed 1-octene hydroformylation at 180°C, the use of n-butane expanded liquids (BXLs) as reaction media was demonstrated. The results show that the TOF for alcohol formation was enhanced by more than 20% in BXL system with a 20% reduction in organic solvent usage. These results pave the way for the rational application of gas-expanded solvents in hydroformylations. iv Acknowledgments First of all, I would like to express my heartfelt thanks to my supervisor Prof. Bala Subramaniam, director of Center for Environmentally Beneficial Catalysis (CEBC), for introducing me to the world of gas-expanded solvents, and his tremendous help and constructive suggestions during my Ph.D. program. I appreciate his constant encouragement, precious guidance and unwavering support. His optimistic, enthusiastic and meticulous style influences me profoundly in the way of pursuing research and being professional. The knowledge he imparted to me will be a great asset throughout my career. I would like to acknowledge Prof. Raghunath Vitthal Chaudhari, my project collaborator and committee member, for his valuable suggestions and critical review for my research work. I am also grateful to the rest of my committee members Prof. Jon Tunge, Prof. Aaron Scurto and Prof. Kevin Leonard for their precious time, critical evaluations, valuable inputs during my comprehensive examination to help me learn and improve. I would like to express my special thanks to Dr. Zhuanzhuan Xie for her patient guidance when I started my research work and insightful advice in the development of analytical methods. I would like to sincerely acknowledge Dr. Kirk Snavely for his kind help and support in experiment setup design and instrument training and maintenance. I would like to thank Ed Atchison, and Dr. Fenghui Niu for their constant assistance with the experiment setup and instrumentation. I would like to thank Dr. Claudia Bode and Nancy Crisp for their assistance and arrangements with courses and meetings, particularly on the preparation of research posters and presentation. v I would also like to thank my KU friends and colleagues from the CEBC family, Dr. Swarup K. Maiti, Dr. Anand Ramanathan, Dr. Hyun-Jin Lee, Dr. Xiaobin Zuo, Dr. Jianfeng Wu, Dr. Simin Yu. Ziwei Song, Xuhui Chen, Pallavi Bobba and Kakasaheb Nandiwale. We have a great time collaborating and contributing together. Special thanks should go to Dr. Xin Jin, Dr. Wenjuan Yan, Dr. Hongda Zhu, Dr. Yuson So, Dr. Rich Lorenzo and Kunjie Guo. Your assistance, friendship and company always warm my heart and make my life in Lawrence colorful and memorable. I would like to acknowledge CEBC for providing the financial support under the US Department of Agriculture and the National Institute of Food and Agriculture through Grant No. 2011-10006-30362 and the joint National Science Foundation and Environmental Protection Agency program Networks for Sustainable Material Synthesis and Design (NSF-EPA 1339661). Last but certainly not the least, I would like to thank my parents back in China for their unconditional love, enduring support and financial aid for my oversea study. Thanks to my wife Honghong Shi, without her love, understanding, scarifies and encouragement, I would have never been able to finish my degree. Thanks to Grace’s entry in my life, her birth gets a fresh start of my life. vi DEDICATED TO My wife Honghong Shi and my daughter Grace Shiyi Liu vii Table of Contents 1. Chapter 1: Introduction ........................................................................................................ 1 1.1 Hydroformylation reaction and industrial applications .................................................. 2 1.2 Novel developments and research areas in hydroformylation ........................................ 5 1.2.1 Alternative metals for homogeneous catalyzed hydroformylation reactions ............ 6 1.2.2 Heterogeneously catalyzed hydroformylation reaction ........................................... 8 1.2.3 Hydroformylation using ionic liquid and supported ionic liquid phase (SILP) catalysts ............................................................................................................................ 10 1.2.4 Hydroformylation in supercritical CO2 ................................................................. 14 1.3 Gas-expanded liquids and its application for hydroformylation reaction ...................... 16 1.3.1 Introduction of gas-expanded liquids ................................................................... 16 1.3.2 Hydroformylation in CO2-expanded liquids ......................................................... 18 1.4 Objective and overview of this work ........................................................................... 20 2. Chapter 2: Enhanced Solubility of Hydrogen and Carbon Monoxide in Propane- and Propylene-Expanded Liquids .................................................................................................... 23 2.1 Introduction ................................................................................................................ 23 2.2 Experimental............................................................................................................... 25 2.3 Vapor-liquid-equilibrium (VLE) modeling .................................................................. 27 2.4 Results and discussion ................................................................................................ 31 2.4.1 Propane/Toluene and Propylene/Toluene Systems. .............................................. 32 2.4.2 Propane/NX-795 and Propylene/NX-795 Systems. .............................................. 34 2.4.3 Propane/H2/Toluene and Propane/H2/NX-795 Systems. ....................................... 35 2.4.4 Propane/CO/Toluene and Propane/CO/NX-795 Systems. ..................................... 37 2.4.5 Propylene/H2/Toluene and Propylene/H2/NX-795 Systems. ................................. 40 viii 2.4.6 Propylene/CO/Toluene and Propylene/CO/NX-795 Systems................................ 41 2.4.7 VLE Simulations ................................................................................................. 43 2.5 Conclusion .................................................................................................................. 46 2.6 Notation ...................................................................................................................... 47 3. Chapter 3 Homogeneous catalytic hydroformylation of propylene in propane-expanded solvent media ............................................................................................................................ 48 3.1 Introduction ................................................................................................................ 48 3.2 Experimental..............................................................................................................
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