Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, WI 53706, USA.
Faraday Discuss. 2017 Sep 21;202:247-267. doi: 10.1039/c7fd00036g.
Catalytic strategies for the synthesis of 1,5-pentanediol (PDO) with 69% yield from hemicellulose and the synthesis of 1,6-hexanediol (HDO) with 28% yield from cellulose are presented. Fractionation of lignocellulosic biomass (white birch wood chips) in gamma-valerolactone (GVL)/HO generates a pure cellulose solid and a liquid stream containing hemicellulose and lignin, which is further dehydrated to furfural with 85% yield. Furfural is converted to PDO with sequential dehydration, hydration, ring-opening tautomerization, and hydrogenation reactions. Acid-catalyzed cellulose dehydration in tetrahydrofuran (THF)/HO produces a mixture of levoglucosenone (LGO) and 5-hydroxymethylfurfural (HMF), which are converted with hydrogen to tetrahydrofuran-dimethanol (THFDM). HDO is then obtained from hydrogenolysis of THFDM. Techno-economic analysis demonstrates that this approach can produce HDO and PDO at a minimum selling price of $4090 per ton.
本文提出了一种从半纤维素中以 69%的收率合成 1,5-戊二醇（PDO）、从纤维素中以 28%的收率合成 1,6-己二醇（HDO）的催化策略。木质纤维素生物质（白桦木片）在γ-戊内酯（GVL）/HO 中的分级分离生成了一种纯纤维素固体和一种含有半纤维素和木质素的液体流，该液体流进一步脱水生成 85%收率的糠醛。糠醛通过顺序脱水、水合、开环互变异构和加氢反应转化为 PDO。在四氢呋喃（THF）/HO 中酸催化纤维素脱水生成了左旋葡聚糖酮（LGO）和 5-羟甲基糠醛（HMF）的混合物，它们在氢气作用下转化为四氢呋喃二甲醇（THFDM）。然后通过 THFDM 的氢解得到 HDO。技术经济分析表明，这种方法可以以每吨 4090 美元的最低销售价格生产 HDO 和 PDO。
