Biomass derived alcohols

Parvulescu AN, Flausoul PJC, Bruijnincx PCA, Korhonen ST, Teodorescu C, Klein Gebbink RJM, Weckhuysen BM (2011) Telomerization of 1,3-butadiene with biomass-derived alcohols over a heterogeneous Pd/TPPTS catalyst based on layered double hydroxides. ACS Catal 1 526-536... 

Qu YC, Wei XL, Zuo Y, et al. A novel catalyst-free process for producing hydrogen and carboxylate from biomass-derived alcohols. Int J Hydrog Energy. 2014 39 13136-13140. 

The experiments were designed to model the hydrogenation process being developed for use in converting biomass-derived sugars into sugar alcohol products. The levels of the sugar solution contaminant tested were... 

Rhenium-catalyzed deoxygenation reactions, on the other hand, can be divided in two topics deoxydehydration and dehydration. These reactions have mostly been applied on biomass-derived substrates such as sugar alcohols and polyols. This procedure lowers the high 0 C ratio present in biomass and as such is of particular interest for the production of both fuels and chemicals from biomass. 

Where rhenium-catalyzed deoxydehydration has attracted a lot of interest, only two reports concerning dehydration catalyzed by rhenium complexes are noteworthy in view of their application on biomass-derived substrates. The first was published in 1996 by Zhu and Espenson and uses MTO as catalyst for the dehydration reaction of various alcohols, either aliphatic or aromatic, to obtain the corresponding olefins. Using MTO in benzene or in the alcohol itself at room temperature after 3 days gives reasonable turnovers and, in the case of benzylic alcohols, good yields. In the same paper, MTO is used for the amination, etherification, and disproportionation of alcohols, which are all reactions interesting in the viewpoint of biomass transformation [123]. 

The FTS converts synthesis gas into mostly liquid hydrocarbons [12-15]. Depending on the origin of the synthesis gas, the overall process from carbon feedstock to liquid product is called gas-to-liquids (GTL), coal to liquids (CTL), or biomass to liquids (BTL). The product spectrum, however, is broader than liquid hydrocarbons alone and can include methane and alkanes, C H2 +2 (with n from 1 — 100), alkenes or olefins (C H2 n > 2), and to a lesser extent, oxygenated products such as alcohols. Hence the FTS offers the opportunity to convert gas, coal, or biomass-derived syngas into transportation fuels, such as gasoline, jet fuel, and diesel oil, and chemicals, such as olefins, naphtha, and waxes. The reactions need a catalyst, which in commercial applications is either based on cobalt or iron. 

The liquid portion of biomass-derived process samples may also contain carbohydrate degradation products, such as 5-(hydroxymethyl)-2-furaldehyde (HMF), levulinic acid, and furfural, as well as other components of interest, such as organic acids and sugar alcohols. Portfolio methods are available for the quantitative measurement of these degradation products and byproducts of polymer hydrolysis. 

The OECD transport sector produced nearly three times as much carbon dioxide in 1990 as it did in 1960 (lEA, 1993). There is a growing concern that these increasing carbon dioxide emissions will create a greenhouse effect on our planet (Boer et al., 1990). One way of reducing the emissions of CO2 would be to introduce renewable fuels, such as alcohol fuels or biogas. Carbon dioxide, which is produced by combustion of biomass-derived fuels, is naturally recycled and consumed in the photosynthesis. This means that there will be no net increase of COj in the atmosphere when using, for example, ethanol produced from biomass. This is valid if biomass-derived fuels or chemicals are used in all parts of the production chain. 

The oxidative dehydrogenation of alcohols represents key steps in the synthesis of aldehyde, ketone, ester, and acid intermediates employed within the fine chemical, pharmaceutical, and agrochemical sectors, with allylic aldehydes in particular high-value components used in the perfume and fiavoring industries [1]. For example, crotonaldehyde is an important agrochemical and a valuable precursor for the food preservative sorbic acid, while citronellyl acetate and cinnamaldehyde confer rose/fruity and cinnamon flavors and aromas, respectively. There is also considerable interest in the exploitation of biomass-derived feedstocks such as glycerol (a by-product of biodiesel synthesis from plant or... 

Shiramizu M, Toste FD (2012) Deoxygenation of biomass-derived feedstocks oxorhenium-catalyzed deoxydehydration of sugars and sugar alcohols. Angew Chem Int Ed 51 8082-8086... 

Primary and secondary alcohols widely occur in natural products, and they are therefore challenging sources of biomass-derived platform molecules [43]. Olsen and Madsen [44] disclosed that by using a homogeneous iridium catalyst, primary alcohols can be converted into syngas. Exemplarily, 1.0 mmol of 2-naphthylmethanol was treated with a phosphine-modified iridium complex at enhanced temperature (Scheme 3.20). The time-dependent gas formation is shown below. It indicates that 42.4 ml gaseous compounds were formed, which corresponds to about 1.8 mmol. 

Hu, J., Wang, Y., Cao, C, Elliott, D.C., Stevens, D.J., and White, J.F. (2007) Conversion of biomass-derived syngas to alcohols and C2 oxygenates using supported Rh catalysts in a microchannel reactor. Catal Today,... 

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