Elsevier

Catalysis Today

Volume 319, 1 January 2019, Pages 14-24
Catalysis Today

The production of furfural directly from hemicellulose in lignocellulosic biomass: A review

https://doi.org/10.1016/j.cattod.2018.06.042Get rights and content

Highlights

  • The production of furfural directly from raw biomass is reviewed.

  • The effective utilization of raw biomass materials to its fullest is discussed.

  • Selective dissolution of hemicellulose keeping cellulose and lignin intact.

  • Effective conversion of hemicellulose to furfural with high yield and selectivity.

  • The important roles of solvents and catalysts in hemicellulose upgrading process.

Abstract

As one main component of lignocellulosic biomass, hemicellulose is a promising alternative for the replacement of limited fossil resources to produce furfural, thus preserving a high atom efficiency. However, the complex structure of hemicellulose and the interaction between the other two components in lignocellulosic biomass (cellulose and lignin) make the effective utilization of naturally formed structure of hemicellulose challenging. This review presents an overview of the production of furfural directly from hemicellulose in lignocellulosic biomass with special emphasis on achieving the effective utilization of hemicellulose, which includes the selective dissolution of hemicellulose from lignocellulosic biomass and the selective formation of furfural from hemicellulose derivatives. Whereas the cellulose and lignin structures are retained, which can be utilized separately. Solvents and catalysts are considered as two main factors in this valorization process of hemicellulose.

Graphical abstract

Solvents and catalysts played important roles on the selective dissolution and conversion of hemicellulose in actual biomass to produce furfural with high yield and selectivity.

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Introduction

The challenges faced by the over-dependence of petroleum-based resources are increasing due to diminishing fossil fuel reserves and environmental concerns [[1], [2], [3], [4], [5]]. Lignocellulosic biomass is viewed as a sustainable feedstock because of its renewability, abundance and wide distribution in nature, which is mainly composed of the three components, hemicellulose, cellulose, and lignin [2,[6], [7], [8], [9]]. This composition holds significant challenges for the effective utilization of biomass due to the rigid structure of polymeric composite and complicated interactions connecting the three main components [10,11]. Successfully replacing petroleum based fuels and chemicals by lignocellulosic biomass-based products will require high-yield, low-cost and energetically efficient targeted upgrading processes [1]. Therefore, the development of green and sustainable technologies is required for the conversion of lignocellulosic biomass to value-added chemicals and biofuels.

Hemicellulose is the second most abundant polysaccharide after cellulose in plant cell walls, accounting for 15–30% of lignocellulosic biomass by weight [8]. In general, the amounts of hemicellulose in wood and woody biomass are greater than those in herbaceous and agricultural biomass [12]. Among the three main components in biomass, hemicellulose is a promising material to produce value-added chemicals. Unlike cellulose, hemicellulose consists of short, highly branched polymer of five- and six-carbon polysaccharide units, such as xylan, mannan, β-glucans and xyloglucans [2,13,14]. The highly branched and amorphous nature of hemicellulose enables it to be easily converted. Noteworthy is that hemicellulose has a much lower degree of polymerization (100–200 U) compared with that of cellulose and lignin. Hemicellulose is more unstable than cellulose and therefore, degrades more easily when subjected to heat treatment [15]. Hemicellulose shows many excellent properties, including biodegradability, biocompatibility, bioactivity, and so on, which enable it be applied in a variety of areas such as food, medicine, energy, chemical industry and polymeric materials [[16], [17], [18], [19], [20], [21]]. At present, there are many researches about the conversion of cellulose and lignin, however, the reports about hemicellulose conversion are limited.

The effective utilization of hemicellulose in lignocellulosic biomass includes the selective dissolution of hemicellulose from raw biomass and the selective formation of target products from hemicellulose derivatives. In the plant cell walls, hemicellulose is thought to adhere to cellulose through hydrogen bonds and Van der Waal’s interactions, which enable hemicellulose to form highly resistant networks with cellulose [22,23]. Ferulic acid forms covalent feruloyl ester-ether bridges between hemicellulose and lignin, resulting in the formation of hemicellulose-lignin linkages. The extraction of hemicellulose is restricted by the physical and /or covalent interactions with other cell-wall components. So, the development of effective methods toward the selective conversion of hemicellulose to target products with high yield and selectivity is crucial in facilitating the effective utilization of hemicellulose, avoiding significant decomposition of cellulose and lignin [[24], [25], [26]].

Furfural, identified by the US Department of Energy (DOE) as one of the top 12 value-added products, is a valuable product with a word market of around 300.000 tons per year [27,28]. Furfural is a typical product which could be obtained from hemicellulose in raw biomass and is also a key platform chemical produced in lignocellulosic biorefineries that could further be transformed to fuels and useful chemicals, which is widely used in oil refining, plastics, pharmaceutical and agrochemical industries (Fig. 1) [29]. With the aim to obtain furfural with high yield and selectivity from the selective dissolution and conversion of hemicellulose, solvent and catalyst were considered as two main crucial factors. In this paper, different techniques investigated in the selective dissolution of hemicellulose from raw biomass using solvents or catalysts have been reviewed. Additionally, a potential bio-refinery aim is to produce furfural with high yield and selectivity via the further depolymerization and conversion of dissolved hemicellulose derivatives obtained directly from raw biomass materials (Fig. 2).

Section snippets

Solvent-thermal conversion of hemicellulose in biomass

Lignocellulosic biomass has proved to be difficult to degrade, with its complex composition and interactions among the three main components, requiring additional energy inputs for their dissolution [11,30]. The conversion of biomass involves multi-scale complexity from molecular to macro raw biomass level (Fig. 3), which limits the conversion of biomass into valuable products [[30], [31], [32]]. Among the three main components in biomass, hemicellulose is a promising resource to produce

The role of catalyst in hemicellulose conversion to furfural

Breaking down the complex lignocellulose to dissolve and convert hemicellulose selectively requires pre-treatment under harsh conditions such as high temperature, high pressure and long reaction time [[44], [45], [46], [47], [48]]. These processes of achieving the selective dissolution and conversion of hemicellulose were complex, and chemically-energy intensive. Therefore, it required additional upgrading and separation steps, leaving a distinct negative environmental footprint. Holm et al.

Conversion of xylose and pure hemicellulose to furfural

As an abundant and non-edible component of biomass, hemicellulose possessed the potential to serve as a sustainable feedstock for bio-based energy and value-added chemical products [[52], [53], [54], [55]]. Furfural can be derived from hemicellulose in raw biomass, generally from C5 sugars, mainly xylose, the monomer unit contained in hemicellulose of lignocellulosic materials [27,56]. Much attention has been paid to use xylose as model compound to produce furfural (Table 1). Solvent-thermal

Conclusions and future perspectives

Today, there is a need to rapidly develop new technologies that allow us to convert biomass to value-added chemicals. In the domain of value-added chemicals, furfural possesses significant advantages using biomass as a starting material, which could alleviate the utilization of petroleum-derived chemicals. However, the production of furfural with high yield and selectivity from raw biomass is challenging. A large volume of work has investigated the conversion of hemicellulose to furfural.

Acknowledgements

This work is financially supported by the National Natural Science Foundation of China (No. 21536007), 111 Project (No. B17030) and Sichuan Science and Technology Program (No.2018JY0207).

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