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Utilization of CO and CO2 as C1 Sources: Synthesis of Carboxylic Acids, Organic Carbonates and Polyketones
- Alternative Title
- Yu Na Lim
- Author(s)
- 임유나
- Alternative Author(s)
- Yu Na Lim
- Advisor
- 장혜영
- Department
- 일반대학원 에너지시스템학과
- Publisher
- The Graduate School, Ajou University
- Publication Year
- 2017-02
- Language
- eng
- Keyword
- CO; CO2; C1 source; carbonate; carboxylic acid; polyketone
- Alternative Abstract
- Greenhouse gas (GHG) generated in the use of fossil fuels that is not consumed naturally in the atmosphere and caused by the human race has resulted in global warming. GHGs generally include carbon dioxide (CO2), methane (CH4), carbon monoxide (CO), nitrogen dioxide (NO2), hydrofluorocarbons (HFCS), and perfluorocarbons (PFC), etc. The utilization of C1 gas like carbon monoxide, carbon dioxide, and, methane as chemical feedstock can be the solution to global warming. I have presented the chemical conversion of CO and CO2 as a C1 source in this thesis. In Chapter 1, the metal-catalyzed carbonyl/carboxylation of alkene and alkynes reaction have been reviewed overall. Typically, catalysts such as Pd, Ru, and Ni are known as an active catalyst for carbonylation. In particular, Pd catalysts have been successfully used for the synthesis of carboxylic acid and carboxylic acid esters from alkene and alkynes. Thus, in the first section of Chapter 1, I reviewed Pd-catalyzed carbonylation of alkenes and alkynes from CO. On the other hand, in the second section of Chapter 1, I reviewed the metal-catalyzed carboxylation of alkene and alkyne from CO2. The carbonation of CO2 was different from the carbonylation of CO, with the reaction acting according to the metal catalysts acting on the reaction different from each other. The Ni catalyst mainly induces hydrocarbonylation and the Cu or Ag catalyst induces a direct coupling reaction. In Chapter 2, a Pd catalyst was used to polymerize CO and ethylene. The co-polymers of CO and ethylene, called polyketone, can be used for the same industrial materials used in automotive and electronics as polymers with high impact strength, chemical resistance, flame retardancy, and so on. However, polyketones had the problem of having a "reactor fouling" (disturbed formation of some of the polymer particles attached to the reactor wall and the agitator) and a high melting point (over 250 oC). In this study, we have developed polyketones without reactor fouling by using sulfonated HMON, silica, and polystyrene as heterogonous catalysts. Terpolymerization was performed to add a phenyl acetylene derivative to reduce meting point. In Chapter 3, the synthesis of the transition metal-free organic carbonates and carboxylic acid was carried out using a CO2 and CO2 derivative (Cs2CO3). The CO2 required vigorous reaction condition using an organometallic catalyst for activating CO2 due to its high thermo-dynamic and kinetic safety. In this research, we developed an environmentally-friendly CO2 activation process with a mild condition that uses a transition metal free method and uses CO2 as low pressure. We used TBD and DBU for CO2 activation and synthesized various organic carbonates by advancing CO2 direct coupling to alcohol. Also, carboxylic acid was synthesized through direct CO2 coupling to acetylene derivatives using TBD.
- Fulltext
- Appears in Collections:
- Graduate School of Ajou University > Department of Energy Systems > 4. Theses(Ph.D)
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