Formic acid and acetic acid production from corn cob by catalytic oxidation using O2
Formic acid and acetic acid production from corn cob by catalytic oxidation using O2
复制标题
O-2 催化氧化玉米芯生产甲酸和乙酸
DOI：
10.1016/j.fuproc.2017.11.010
复制
发表时间：
2018-03-01
影响因子：
7.5
通讯作者：
Wang, Yupeng
中科院分区：
文献类型：
--
作者：
Lu, Ting;Hou, Yucui;Wang, Yupeng
将生物质原料直接转化为精细化学品具有重要的概念和实际意义。到目前为止，生物质原料直接转化为精细化工品仍然是一个很大的挑战。生物质氧化制甲酸（FA）和乙酸（AA）是一种很有前途的工业化生产工艺。在本工作中，我们报道了Keggin型杂多酸H5 PV 2 Mo 10 O 40 + H2SO 4的二元催化剂体系是有效的，直接转化玉米芯，一个高度丰富的可再生农业废物，使用O-2作为氧化剂，在水溶液中的FA和AA。考察了催化剂用量、H2SO 4浓度、反应温度、反应时间和初始O2压力对玉米芯转化率的影响。在优化的反应条件下，在170 ℃下反应30 min后，转化玉米芯，FA产率为42.5%，AA产率为9.1%（基于碳）。在氧化过程中，水溶液的pH值起着关键作用。探讨了pH值对玉米芯各组分的固体降解、反应途径和氧化的影响。半纤维素被迅速氧化，随后木质素被部分氧化，纤维素是最难转化的部分。产物FA和AA主要来自多糖（半纤维素和纤维素），pH对纤维素有主要影响。催化剂体系的循环使用证明，并显示出良好的可重复使用性。
Direct conversion of raw biomass to fine chemicals is of significant conceptual and practical interest. Up to now, the direct conversion of raw biomass to fine chemicals is still a big challenge. The oxidation of biomass to formic acid (FA) and acetic acid (AA) is a promising industrial process in the future. In this work, we reported that a binary catalyst system of Keggin-type heteropoly acid H5PV2Mo10O40 + H2SO4 was efficient to directly convert corn cob, a highly abundant renewable agricultural waste, to FA and AA using O-2 as the oxidant in aqueous solutions. The effects of catalyst amount, H2SO4 concentration, reaction temperature, reaction time and initial O-2 pressure on the conversions of corn cob were investigated. Under optimized reaction conditions, corn cob was transformed with a FA yield of 42.5% and an AA yield of 9.1% (based on carbon) after 30 min of reaction at 170 degrees C. In the oxidation, the pH of the aqueous solution plays a key role. The influences of pH on solid degradation, reaction pathway and oxidation of the components of corn cob were discussed. Hemicellulose is oxidized rapidly followed by partly oxidation of lignin, and cellulose is the most difficult converted part. Products FA and AA mainly come from polysaccharides (hemicellulose and cellulose) and pH has a major influence on cellulose. The recycling of the catalyst system is demonstrated and shows good reusability.