Green synthesis from biomass
© Donate 2014
Received: 25 March 2014
Accepted: 16 June 2014
Published: 27 August 2014
This review describes how to apply green chemistry principles to transform biomass into several types of molecules. On the basis of selected papers published over the last three to four years, it includes the main reactions used to convert renewable feedstocks into chemical products that are potentially applicable as raw materials or synthetic intermediates in fine chemical industries with emphasis on preparative organic synthesis.
The humankind relies on a wide variety of feedstocks that can be used to produce an array of chemicals. Biomass constitutes an inexpensive renewable resource that is available on a global scale and which can sequester carbon. Several industrial areas have switched to biomass as feedstock, to increase their sustainability and reduce the overall environmental impact. The conversion of biomass into a great variety of valuable chemicals is the key concept of a biorefinery –.
The main components of wood biomass are cellulose (35% to 50%), hemicelluloses (20% to 35%), lignin (5% to 30%), and other extracted compounds (1% to 10%) ,. Although cellulose, hemicelluloses, and lignin transformation has been extensively studied –, less attention has been given to other extracted compounds, which also constitute important feedstocks for commodities and fine chemicals . For example, parts of trees that are normally considered waste contain extracted compounds consisting mainly of resin acids, terpenes, sterols, phenolic substances, lignans, and sugars, among others, which are ultimately valuable for chemical synthesis ,. Secondary plant metabolites include essential oils, which have found wide application in the flavor and fragrance industries. Many plant-derived chemicals also constitute secondary metabolites with application in the pharmaceutical field or as non-prescription health supplements .
Ideally, biomass conversion should reduce the use of toxic chemicals and improve the profitability of biorefineries while respecting the environment. Several methods to transform biomass into useful products have been reviewed in recent years ,–.
Lignin represents over 20% of the total mass of the Earth's biosphere. Using it to obtain chemical feedstocks represents a real challenge in terms of sustainability and environmental protection. The different chemical composition of lignin requires that it be processed separately to obtain phenol derivatives. Alternatively, it could be used as an energy source. According to a survey in the 2007 US Department of Energy, lignin could function as a precursor of valuable chemicals in several ways, mainly to replace oil .
Recent articles on the use of lignin have reviewed the different methods that chemists have used to convert this material into chemical compounds with added value. Authors have pointed out the major difficulties encountered while handling lignin; they have also discussed the recent use of ionic liquids  as solvents, aiming to provide some new opportunities to efficiently convert lignin into aromatic chemicals with added value –.
Cellulose and hemicelluloses conversion
Cellulose and hemicelluloses represent the largest part of wood biomass (55% to 80%) . A recently published paper has reviewed the application of ionic liquids to deconstruct and fractionate lignocellulosic biomass . The article focuses on the major advantage of using ionic liquids in the dissolution process as compared with other pretreatment options. Ionic liquids can decrystallize the cellulose portion of lignocellulosic biomass and simultaneously disrupt the lignin and hemicellulose network. This paper  also discusses the possibility of removing lignin with the ionic liquid and recovering a separate and possibly more valuable lignin fraction.
Cellulose and hemicelluloses hydrolysis generates monomeric sugar units. These unit and their derivatives can be transformed into a wide range of value-added chemicals. An overview of the chemical transformation of low-molecular weight carbohydrates into products with versatile industrial application profiles has been published . Another article has discussed the chemical catalytic transformations of biomass-derived oxygenated feedstocks (primarily sugars and sugar alcohols) into value-added chemicals and fuels. The key reactions involved in biomass processing are hydrolysis, dehydration, isomerization, aldol condensation, reforming, hydrogenation, and oxidation .
Catalytic lignocellulose hydrolysis converts cellulose and hemicellulose into small oligomers and sugars; lignin separates from the mixture. Selective catalytic hydrodeoxygenation (HDO) transforms part of the small oligomers into biofuels or chemicals. Sugar fermentation via the known routes gives ethanol or other several higher-chain alcohols. Part of the sugars can also be converted to hydrocarbons following the aqueous phase reforming, or adapted to produce the biohydrogen that is necessary in many steps of furfural upgrading. Because furfurals show higher chemical functionality and reactivity, it is easier to catalytically upgrade them to a variety of value-added products. For example, catalytic hydrogenation/hydrogenolysis of furfural and 5-hydroxymethyl-2-furfural (HMF) produces 2-methylfuran and 2,5-dimethylfuran, respectively, both of which display high octane number and good miscibility with gasoline .
A recent review article has reported on the synthesis and use of sugar derivatives originating from cellulose and hemicellulose using various methodologies . Another critical review has recently discussed the various strategies for the valorization of waste biomass to platform chemicals, and the developments in chemical and biological catalysis .
5-Hydroxymethyl-2-furfural production and transformation
Among the several building blocks derived from renewable resources, HMF has been identified as a very promising building block. ,,,. HMF possesses two functionalities attached to a furan ring. These functionalities aid HMF conversion into several value-added compounds that are useful in a wide variety of chemical manufacturing applications and industrial products –. HMF can also be transformed into many specific molecules , such as the natural herbicide δ-aminolevulinic acid  and the active pharmaceutical ingredient ranitidine (Zantac) .
The most desirable route to produce HMF involves widely available biorenewable resources like cellulose ,. However, achieving efficient direct transformation of cellulose into HMF seems less feasible ,. Most frequently, the synthetic route used to obtain HMF relies on a multistep approach comprising cellulose hydrolysis to glucose, glucose isomerization to fructose, and fructose dehydration to HMF. A broader range of efficient catalysts has been reported to promote fructose dehydration to HMF ,. The transformation can also take place in the absence of a catalyst, using specific solvents, such as ionic liquids, to promote the reaction .
The specific properties of HMF, such as its high solubility in aqueous media and polar solvents as well as its thermal and chemical instability, make its isolation from the reaction mixture a very important issue. These factors complicate large-scale HMF isolation by solvent extraction or distillation. In fact, the majority of literature papers have reported HMF conversion and/or yields on the basis of HPLC analysis of the reaction mixture rather than isolated yields .
Furan conversion into ketones and n-alkanes
The furan aldehydes derived from hexoses and pentoses offer pathways for the desired chain extensions via aldol condensation ,. Coupling these aldehydes with other biomass-derived carbon units using aldol condensation chemistry constitutes an attractive route toward fuel precursors of sufficient energy density.
Applying the green chemistry principles to synthesis from biomass
Producing green chemicals from renewable resources is a very broad topic ,–. Several reviews have focused on developments achieved over the last years with respect to (1) renewable biomass as a source of chemicals, (2) possible conversion pathways, and (3) obtained products –.
The literature survey indicates that the benefits for green chemistry depend upon feedstocks, processes, and products. Processes requiring too many conversion and separation steps affect the overall atom economy, energy demand, and waste emissions . Due to the heterogeneous composition of renewables, clean and energy-efficient separation and purification technologies are very important . Biomass conversion processes that involve one or few steps and do not call for separation of the intermediates are certainly more efficient in terms of biomass utilization and waste minimization as compared with the traditional approach .
The literature also brings reports on a variety of more complex molecular architectures . A critical review focusing on the preparation of bio-based surfactants in which the carbon atoms are derived from renewable feedstocks has been recently published .
The use of microwave heating to conduct chemical transformations has increased over the last years . Microwave energy is attractive in the area of chemistry because it elicits highly efficient energy transfer and selectivity, which reduces reaction time significantly ,.
A very recent paper  has described an unprecedented catalyst and a solvent-free protocol for the microwave-assisted acetalization of glycerol and carbonyl compounds. High yields of cyclic acetals or ketals have been achieved, including commercially valuable hyacinth fragrance and fuel additive precursors. This methodology does not require excessive amount of solvents or precious catalysts, and it provides a clean and green approach towards glycerol valorization.
Ultrasound is another important alternative energy with application in chemical processes. Sonochemistry, the chemical effects and applications of ultrasonic waves, aims to reduce energy consumption. This process increases product selectivity. Ultrasound has been applied in a number of fields , which is conveniently discussed in the book recently edited by Xie and Gathergood .
Many research groups have contributed to increasing the application of green chemistry principles to biomass handling over the last few years. Chemists and chemical companies have been actively searching for greener alternatives that can replace their current manufacturing practices. Significant progress has been made in several key research areas, such as the use of new multifunctional catalysts, environmentally benign solvents, ionic liquids prepared from renewable biomaterials, and alternative energy, especially microwave radiation. All these initiatives should help to develop a new chemical industry based on renewable feedstocks.
However, some technical challenges remain. Designing technologies that enable analysis of the chemical processes developed in the laboratory is mandatory. It is also necessary to improve separation methods and to optimize process and energy efficiency.
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