Department of Applied Chemistry, School of Engineering, Tohoku University, Aoba 6-6-07, Aramaki, Aoba-ku, Sendai, 980-8579 (Japan).
ChemSusChem. 2015 Feb;8(4):628-35. doi: 10.1002/cssc.201403010. Epub 2014 Nov 3.
Hexanols were produced in high yield by conversion of cellulose over Ir-ReOx /SiO2 (molar ratio Re/Ir=2) catalyst in biphasic reaction system (n-decane+H2 O). The cellulose was depolymerized by mechanocatalysis with the aid of H2 SO4 . The influence of solvent amount, reaction temperature and hydrogen pressure was systematically investigated and the highest yield of hexanols reached 60 % under the conditions of n-decane/water ∼2 (v/v), 413 K, 10 MPa H2 for 24 h. Mechanocatalytic depolymerization of cellulose with the aid of H2 SO4 or HCl and the use of sufficient n-decane were very crucial for the production of hexanols. H2 SO4 not only catalyzed cellulose to water-soluble oligosaccharides but also promoted the hydrogenolysis activity of Ir-ReOx /SiO2 catalyst. The role of n-decane was to extract hexanols and to suppress over-hydrogenolysis of hexanols to n-hexane.
正己醇在 Ir-ReOx/SiO2(摩尔比 Re/Ir=2)催化剂存在下于两相反应体系(正己烷+H2O)中可高收率转化纤维素得到。纤维素在 H2SO4 的助催化下通过机械力化学法解聚。系统考察了溶剂用量、反应温度和氢气压力的影响,在正己烷/水体积比约为 2(v/v)、413 K、10 MPa H2 条件下反应 24 h,正己醇的最高收率达到 60%。纤维素在 H2SO4 或 HCl 助催化和使用足够量的正己烷的机械力化学解聚对正己醇的生成非常关键。H2SO4 不仅催化纤维素生成水溶性寡糖,而且还促进 Ir-ReOx/SiO2 催化剂的氢解活性。正己烷的作用是提取正己醇并抑制正己醇过度氢解为正己烷。