Chemicals, biomass furfural

In some cases, the hydrolysis reaction liberates the sugars from the biomass and converts them directly into derivatives such as furfural, hydroxymethyl furfural and/or levulinic acid. These derivatives can be further converted into various chemical intermediates. We will not discuss these further conversions as they are extensively reported in the literature, e.g., for furfural [15, 44], hydroxymethyl furfural [15, 44, 50] and levulinic acid [15, 44-47]. 

In order to gain some information about the fundamentals of the hydrothermal carbonization process, the hydrothermal carbonization of different carbohydrates and carbohydrate products was examined [12, 13]. For instance, hydrothermal carbons synthesized from diverse biomass (glucose, xylose, maltose, sucrose, amylopectin, starch) and biomass derivatives (HMF and furfural) were treated under hydrothermal conditions at 180 °C and were analyzed with respect to their chemical and morphological structures by SEM,13 C solid-state NMR and elemental analysis. This was combined with GC-MS experiments on residual liquor solutions to analyze side products... 

Fig. 15. Furfural, phenols, and ethanol production from wood in a multiproduct process biomass chemical plant (52). Wood (qv) is ca 50% cellulose (qv),...

Furfural - [BUTADIENE] (Vol 4) - [cross-reference entry] (Vol 12) - [EXTRACTION - LIQUm-LIQUID] (Vol 10) -from biomass [FUELS FROMBIOMASS] (Vol 12) -as chemical feedstock [FURANDERIVATIVES] (Supplement) -use of cast copper alloys with [COPPER ALLOYS - CAST COPPER ALLOYS] (V ol 7)... 

When the structure of biomass components has to be quite drastically rearranged compared to the building blocks needed, synthesis gas or different sugars can serve as platform chemicals. The latter can be converted, for example, to sugar-derived building blocks (Figure 2.2.3) - that is, to glycerol, sorbitol, levulinic acid, and furfural. 

The production of multiple products is generally seen as necessary to increase the economic viability of biomass conversion. This is encapsulated in the concept of a biorefmery , which according to the National Renewable Energy Laboratory (NREL) is a facility that integrates conversion processes and equipment to produce fuels, power and chemicals from biomass [23], Examples of chemicals that can be produced from biomass include ethanol, methanol, furfural, paper, lignin, vanillin, lactic acid, dimethylsulfoxide and xylitol. In many cases, using biomass as a feedstock for chemical production requires an initial step to separate or fractionate the three main components into usable fractions [20, 22], This also maximises the usage of the different biomass components. 

Furfural is easily produced from pentoses rich biomass by cyclodehydration. Various acidic reaction conditions have been applied [110, 111]. The precise order of the different dehydration steps is not known for certain. A plausible mechanism is depicted in Scheme 20 [112]. The worldwide production is currently about 300,000 tons per year. Thus, furfural is a low cost, polyfunctional substrate for the production of numerous bulk and fine chemicals. 

Among the various products that can be synthesized from biomass, methanol was selected because of its versatile applicability to the electricity, transportation, and chemical sectors. Conversion of methanol from biomass is achieved via oxygen-steam gasification followed by shift conversion and methanol synthesis. Three feedstocks were selected for conversion to methanol—wood residue, corn stover, and furfural residue. Availability of... 

It has been shown that synthetic zeolites such as ZSM-5 can be used to convert oxygenated compounds derived from biomass materials into hydrocarbons which can be used as fuels or chemicals feedstocks (1,2,3,4). However, the pyrolysis oils obtained from biomass materials by different thermal and thermochemical processes (5,6) showed poor hydrocarbon yields and high tar content when contacted over ZSM-5 zeolite catalysts at high temperatures (7,8). Since the pyrolysis oils are composed of a wide variety of oxygenated compounds such as cyclopentanone, cyclopentenone, furfural, phenol, carbohydrate and carboxylic acid derivatives (9,10) it is difficult to point out exactly which family of compounds is contributing more to the observed tar and to the rapid deactivation of the catalysts. Catalytic studies on model compounds which are usually found in the biomass pyrolysis oils are therefore primordial in order to determine the best catalytic system for the up-grading of pyrolysis oils to useful hydrocarbon products. The reactions of some phenolic, carbonyl and carboxylic acid derivatives over ZSM-5 catalysts are already... 

Chemical routes for the transformation of biomass into chemicals, particularly, into furfural, N-heterocycles, and epoxides 07CRV2411. 

The first part of this chapter is intended to survey recent literature on new catalytic materials because the development of new types of metal oxides and layered- and carbon-based materials with different morphologies opens up novel acid-base catalysis that enables new type of clean reaction technologies. Mechanistic considerations of acid- and base-catalyzed reactions should result in new clean catalytic processes for Green and Sustainable Chemistry, for example, transformations of biorenewable feedstock into value-added chemicals and fuels [21-35]. The latter part of this chapter, therefore, focuses on biomass conversion using solid acid and base catalysts, which covers recent developments on acid-base, one-pot reaction systems for carbon-carbon bond formations, and biomass conversion including synthesis of furfurals from sugars, biodiesel production, and glycerol utilization. 

Chemical-Catalytic Approaches to the Production of Furfurals and Levulinates from Biomass... 

Abstract The synthesis and chemistry of 5-(hydroxymethyl)furfural (HMF), 5-(chloromethyl)furfural (CMF), and levulinic acid (LA), three carbohydrate-derived platform molecules produced by the chemical-catalytic processing of lignocellulosic biomass, is reviewed. Starting from the historical derivation of these molecules and progressing through modem approaches to their production from biomass feedstocks, this review will then survey their principal derivative chemistries, with particular attention to aspects of commercial relevance, and discuss the relative merits of each molecule in the future of biorefining. 

Keywords 5-(Chloromethyl)furfural 5-(Hydroxymethyl)furfural Biomass Biomass derivatives Biorefinery Catalysis CMF Green chemistry HMF Levulinic acid Platform chemicals Renewable chemistry... 

As discussed in detail in Chapter 1 [1], the chemical-catalytic approach to biomass valorization is poised to come to the fore of biorefinery operations due to its advantages over microbial and thermochemical processing of lignocellulosic feedstocks. Below, we consider three mainstream platform chemicals, collectively referred to as furanics, that are derived from the acid-catalyzed dehydration of carbohydrates. The first, 5-(hydroxymethyl)furfural, or HMF 1, is an icon of the biorefinery movement. With derivatives that branch out over multiple product manifolds, HMF is a recognized commercial opportunity for whoever can manage to produce it economically, and approaches towards the realization of this aim will be discussed. 

Casanova O, Iboira S, Corma A (2010) Chemicals from biomass etherification of 5-hydroxymethyl-2-furfural (HMF) into 5,5 (oxy-bis(methylene))bis-2-fifffural (OBMF) with solid catalysts. J Catal 275 236-242... 

Casanova O, Iborra S, Corma A (2009) Biomass into chemicals one pot-base free oxidative esterification of 5-hydroxymethyl-2-furfural into 2,5-dimethylfuroate with gold on nanoparticulated ceria. J Catal 265 109-116... 

Furfural and HMF are readily prepared from various catalytic biomass conversion processes. Both furfural and HMF can be readily converted to a large variety of monomers for polymerizations by chain-growth and/or condensation mechanisms. As the transformation of furfural and HMF to fine chemicals or monomers for polymers has been well documented by several comprehensive reviews [107-113, 130, 131], this chapter has mainly focused on the bio-based furan polymers with self-healing ability through thermally reversible Diels-Alder reactions, which is a recently exploited prosperous research area. In addition, the furan-based DA reaction has also been used in the thermoreversible nonlinear polymerization and dendrimer chemistry. 

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