Adipic Acid Production via Metal-Free Selective Hydrogenolysis of Biomass-Derived Tetrahydrofuran-2,5-Dicarboxylic Acid [electronic resource]

• Ngôn ngữ: eng
• Ký hiệu phân loại: 641.38 Honey
• Thông tin xuất bản: Washington, D.C. : Oak Ridge, Tenn. : United States. Dept. of Energy. Office of Science ; Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy, 2017
• Mô tả vật lý: Size: p. 6619-6634 : , digital, PDF file.
• Bộ sưu tập: Metadata
• ID: 263162
• Chủ đề: 1. 09 biomass fuels; 2. 37 inorganic, organic, physical, and analytical chemistry; 3. Biofuels (including algae and biomass); 4. Catalysis (heterogeneous); 5. Catalysis (homogeneous)

Tóm tắt

 Biomass-derived furans offer sustainable routes to adipic acid (AA), a key chemical in Nylon-6,6 synthesis. In this work, we show that tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) is a viable precursor for AA production, achieving up to 89% yield in a metal-free system containing HI and molecular H<
 sub>
 2<
 /sub>
  in a propionic acid solvent at 160 �C. Reactivity studies demonstrate that the interplay between HI, H<
 sub>
 2<
 /sub>
 , and the solvent is essential for effective THFDCA ring opening. By measuring the reaction orders of HI and molecular H<
 sub>
 2<
 /sub>
  and calculating an acid?base equilibrium constant in a nonaqueous solvent, we show that HI plays a multifaceted role in the reaction by acting both as a proton source and an iodide source to selectively cleave C?O bonds without overhydrogenation of carboxylic acid groups. Using reactivity studies, kinetic measurements, and first-principles computational insights, we demonstrate that metal-free activation of molecular H<
 sub>
 2<
 /sub>
  plays a key role in the reaction, following HI-mediated cleavage of the etheric C?O bond in THFDCA.