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New Synthetic Routes to Biomass-based Alcohols and Polyols

Alcohols and polyols are important biomass-based chemicals. Starting from simple biomass-based building blocks, such as ethanol, butanol, acetone, 5-hydroxyfurfural or glycerol, a series of new synthetic routes to different biomass-based alcohols and polyols have been developed by the Green ChemoCatalysis Group led by Prof. MU Xindong, at Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences

  

Figure 1. General schemes of direct α-alkylation of ketones with alcohols in water (Figure 1a), direct conversion of biomass-derived 5-hydroxymethylfurfural to 1,2,6-hexanetriol (Figure 1b), formation of propanol from 1,2-propanediol via dehydration and consecutive hydrogen transfer (Figure 1c). (Image by Professor MU’s group)

The direct α-alkylation of ketones with alcohols has emerged as a new green protocol to construct C-C bonds with H2O as the sole byproduct. A very simple and convenient Pd/C catalytic system for the direct α-alkylation of ketones with primary alcohols in pure water has been developed. This method can be applied not only in synthetic chemistry but also in biomass transformation. For example, aqueous mixtures of dilute acetone, 1-butanol, and ethanol (mimicking ABE fermentation products) can be directly transformed into C5--C11 or longer-chain ketones and alcohols, to further produce fuels and chemicals (ChemSusChem, 2013, http://onlinelibrary.wiley.com/doi/10.1002/cssc.201300815/abstract, Figure 1a).

5-Hydroxymethylfural (HMF) has long been regarded as an important platform chemical. They have transformed HMF directly into 1,2,6-hexanetriol, which is an important chemical used as a humectant and a viscosity-controlling agent, through a mild catalytic ring-opening process using Ni-Co-Al mixed oxides as the catalyst. They also identified the major reaction pathways of this process and proved the process is a novel route for direct conversion of bio-based renewable feedstocks into 1,2,6-hexanetriol  (ACS Sustainable Chemistry & Engineering,2013, http://pubs.acs.org/doi/abs/10.1021/sc4003714, Figure 1b)

With the increase production of biodiesel, it is highly desirable to convert low-cost glycerol by-product into value-added chemicals or materials. 1-propanol is one of value-added chemicals, which can be produced from glycerol or glycerol-derived propanediol transforming. Recently, the research group has developed a proposed reaction system using low-cost non-noble metal catalyst and without hydrogen, and for the first time found that supported Nb catalyst exhibited more selective toward propanol than propanal for the dehydration of 1,2-propanediol. (Journal of Industry and Engineering Chemistry, 2013, http://www.sciencedirect.com/science/article/pii/S1226086X13006047, Figure 1c)

The above research works were supported by National Natural Science Foundation of China, Natural Science Foundation of Shandong Province and Qingdao Major Research Program. Prof. MU was also awarded the “En-ze Min Energy Chemical Engineering Prize”. And the results have been published on ChemSusChem, ACS Sustainable Chemistry & Engineering, etc.

 

Contact:

Professor MU Xindong
Email: muxd (AT) qibebt.ac.cn

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