Biofuels and Co-Products Out of Hemicellulos es

Ariadna Fuente-Hernandez, Pierre-Olivier Corcos, Romain Beauchet and Jean-Michel Lavoie

Additional information is available at the end of the chapter http://dx. doi. org/10.5772/52645

1. Introduction

Second generation biofuels are based on the utilisation of non-edible feedstock for the production either of ethanol to be inserted in the gasoline pool or of biodiesel to be insert­ed in the diesel pool. Ethanol is usually produced out of fermentation of C6 sugars (al­though other approaches does exist, see [1]) and the latter came, in first generation ethanol, from starch. In second-generation ethanol, the source of carbohydrate considered is usually cellulose, which, in turns, is obtained from lignocellulosic biomass. Recent work by Lavoieet al. [2] have depicted an overview of many types of lignocellulosic biomass and in most cases, cellulose, although a major component, is not the only one and is ac­companied by lignin, hemicelluloses, extractives and, in case of agricultural biomass, pro­teins. High grade biomass (as wood chips, sugar cane or even corn) are usually very expensive (more than 100 USD/tonne) because, in most part, of the important demand re­lated to those feedstock in industries and this is why cellulosic ethanol is more than often related to residual biomass. The latter includes but is not limited to residual forest and ag­ricultural biomass as well as energy crops. In all cases, although the feedstock is rather in­expensive (60-80 USD/tonne), it is composed of many different tissues (leaves, bark, wood, stems, etc.) making its transformation rather complex [3]. Industrialisation of second-gen­eration biofuel requires specific pre-treatment that should be as versatile as efficient in or­der to cope with the economy of scale that has to be implemented in order to make such conversion economical.

The whole economics of cellulosic ethanol relies first on ethanol, which has a commodity beneficiates from a quasi-infinite market as long as prices are competitive. Assuming aver­age cellulose content of 45-55 % (wt) in the lignocellulosic biomass, the ethanol potential of lignocellulosic biomass would range between 313-390 L per tonne of biomass converted.

With an actual market price of 0.48 USD per liter the value of this ethanol would range be­tween 150-187 USD per tonne of biomass processed. Since the latter is more expensive to process (first isolation of cellulose then hydrolysis of cellulose) and considering the fact that the feedstock is itself expensive, there is a necessity to get an added value out of the remain­ing 55-45 % (wt) content. This residual carbon source is composed mostly of hemicelluloses and of lignin. The latter is a very energetic aromatic-based macromolecule, that has a high calorific value explaining why many processes converting such biomass (as some pulp and paper processes) relies on the combustion of lignin to provide part of the energy for the in­dustry. It could also serve as a feedstock for the production of added-value compounds and although the subject is very pertinent to the field, it is out of the scope of this review, which focuses mostly on C5 sugars derived from hemicelluloses.

Conversion of the carbohydrates is of course an important part of the process although; iso­lation of hemicellulose for the lignocellulosic matrix is also crucial for such an approach and in consequence should also be briefly assessed. For years now, the pulp and paper industry have worked with lignocellulosic substrates and they have over the year developed many techniques allowing isolation of hemicelluloses. Chemical processes as soda pulping and kraft pulping allows isolation of both lignin and hemicellulose whilst protecting the cellulo — sic fibres in order to produce the largest amount of pulp possible per ton of biomass. Never­theless, in both chemical processes previously mentioned, the hemicellulose are rather difficult to reach since they are mixed with a variety of organic and inorganic compounds including lignin as well as the chemicals that were used for the pulping process. During the last decades, the pulp and paper industry have started to look toward other processes that could allow a preliminary removal of hemicelluloses in order to avoid a complicated and ex­pensive isolation after a chemical pulping process.

Amongst the techniques used for prehydrolysis, treatments with hot water catalyzed or not have been investigated in details in literature. As an example, Schildet al. [4] performed a preliminary extraction with water (via auto-hydrolysis) or with alkaline water prior to soda pulping in order to recuperate the hemicellulose prior to pulping. Similar testing was also performed on northern spruce with pressurised hot water in the presence of sodium bicar­bonate [5]. Hot water extractions were also performed at temperature around 170 °C at dif­ferent pH (the latter were adjusted with a phthalate buffer) and these experiments showed that control of pH was crucial in order to extract more of the hemicelluloses (up to 8 % wt on original biomass) [6]. Hot water extractions at similar temperature range have also been per­formed on maple [7] as well as on sugarcane bagasse [8]. Overall the hot water pretreatment may be a very promising approach for isolation of hemicelluloses although reported rates did not go far over 10 % because of the necessity to preserve the cellulosic fibres in order to avoid losses for papermaking. Acid catalyst has also been used as pretreatment to remove hemicellulose prior to pulping as reported by Liuet al. [9]. Utilisation of sulphuric acid, al­though very efficient to remove hemicellulose may also have an impact on cellulose thus re­ducing the pulp production rates.

Another process that could lead to isolation of hemicellulose is the organosolv process, which is to a certain extent comparable to classical chemical pulping in that sense that the

technique allows simultaneous removal both for lignin and hemicelluloses. However, in­stead of using only an aqueous mixture of ions, the process relies on the utilisation of a com­bination of ions (usually alkaline) in a 50/50 mixture of aqueous organic solvent. In most cases, the solvent is methanol for obvious economic reasons although other solvents as buta­nol and certain organic acids have also been investigated to the same purposes. Recent work by Wanget al. [10]have shown that in an organosolv process using different solvent as well as different catalyst with poplar, sodium hydroxide was shown to be the best catalyst for hemicellulose removal from the pulp. Recent work by Brosse et al. [11] also showed that for Miscanthus Gigantheus, an ethanol organosolv process combined with an acid catalyst (sul­phuric) lead to removal of most of the hemicelluloses and lignin from the original biomass.

Finally, another approach that could lead to isolation of hemicellulose from a lignocellulosic matrix is steam processes. This technique relies on impregnation of the feedstock with water (either catalyzed or not) then treatment under pressure at temperature ranging from 180-230 °C for a certain period of time after which pressure is relieved suddenly thus creating an "explosion" of the feedstock. Such process could lead, depending on the operating condi­tion, to the isolation of either hemicellulose or lignin in two steps or in a single step. Our team has demonstrated the feasibility of both processes for different substrates [1214].

Independently of the substrate or the technique used for the isolation of the hemicelluloses, conversion of lignocellulosic biomass, either for the production of paper or for the produc­tion of biofuels requires a complete utilization of the carbon compound found in biomass. Once the hemicelluloses are isolated from the original feedstock, they can undergo different types of transformation leading to different added value compounds that could lead to in­crease the margin of profit for the industries in the field.

Hemicelluloses account for 15-35 % of lignocellulosic biomass dry weight [2] and they are usually composed of different carbohydrates as well as small organic acids as acetic and for­mic acid. Glucose and xylose are often the most abundant sugars in hemicelluloses hydroly­sis although mannose, arabinose and galactose might also be present in lower concentrations. The carbohydrate compositions of some lignocellullosic biomass are shown in Table 1. Whilst the C6 sugars could easily be fermented to ethanol following detoxifica­tion of the mixture, C5 sugars remains hard to convert to ethanol, mostly because classical yeasts don’t metabolise them and the genetically modified organism that ferment C5 sugars are usually slower than classical organisms used in the production of etanol from C6 sugars. Nevertheless, even if ethanol production may remain a challenge, other alternatives could be considered, both on the chemical and on the microbiological point of view, to allow con­version of C5 sugar into added value products.

Carbohydrates tend to react in acidic, basic, oxidative or reductive mediums and therefore, numerous do arise for the conversion of C5 sugars. Although many options are available, this review will focus solely on 4 different pathways: acid, base, oxidative, and reductive. Each of these pathways could be inserted in an integrated biorefinery process where each of the fractions could be isolated and upgraded to high value compounds (see Figure 1).



Energy crops

Agricol residues








Wheat Straw [15]


Stover [17]



Loblolly Pine [19]






























Table 1. Carbohydrate composition of some lignocellulosic biomass.


Figure 1. Potential utilization of hemicelluloses in an optimized conversion process for residual lignocellulosic biomass where C6 sugars are converted to ethanol, lignin and extractives to other added value products.

In this review, emphasis will be made on the recent work made for each of these conversion pathways both on the chemical and on the biochemical pathways. The review will focus on these 4 approaches also for their generally simple nature that would make them adaptable to an industrial context. These results will be compared to classical fermentation processes to produce ethanol with different types of organisms that can metabolise C5 sugars.

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