Ionic liquid pre-treatment and fractionation of sugarcane bagasse for the production of bioethanol

Pretretament is an essential and expensive processing step for the manufacturing of ethanol from lignocellulosic raw materials. Ionic liquids are a new class of solvents that have the potential to be used as pretreatment agents. The attractive characteristics of ionic liquid pretreatment of lignocellulosics such as thermal stability, dissolution properties, fractionation potential, cellulose decrystallisation capacity and saccharification impact are investigated in this thesis. Dissolution of bagasse with 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) at high temperatures (110 �‹C to 160 �‹C) is investigated as a pretreatment process. Material balances are reported and used along with enzymatic saccharification data to identify optimum pretreatment conditions (150 �‹C for 90 min). At these conditions, the dissolved and reprecipitated material is enriched in cellulose, has a low crystallinity and the cellulose component is efficiently hydrolysed (93 %, 3 h, 15 FPU). At pretreatment temperatures < 150 �‹C, the undissolved material has only slightly lower crystallinity than the starting. At pretreatment temperatures . 150 �‹C, the undissolved material has low crystallinity and when combined with the dissolved material has a saccharification rate and extent similar to completely dissolved material (100 %, 3h, 15 FPU). Complete dissolution is not necessary to maximize saccharification efficiency at temperatures . 150 �‹C. Fermentation of [C4mim]Cl-pretreated, enzyme-saccharified bagasse to ethanol is successfully conducted (85 % molar glucose-to-ethanol conversion efficiency). As compared to standard dilute acid pretreatment, the optimised [C4mim]Cl pretreatment achieves substantially higher ethanol yields (79 % cf. 52 %) in less than half the processing time (pretreatment, saccharification, fermentation). Fractionation of bagasse partially dissolved in [C4mim]Cl to a polysaccharide rich and a lignin rich fraction is attempted using aqueous biphasic systems (ABSs) and single phase systems with preferential precipitation. ABSs of ILs and concentrated aqueous inorganic salt solutions are achievable (e.g. [C4mim]Cl with 200 g L-1 NaOH), albeit they exhibit a number of technical problems including phase convergence (which increases with increasing biomass loading) and deprotonation of imidazolium ILs (5 % - 8 % mol). Single phase fractionation systems comprising lignin solvents / cellulose antisolvents, viz. NaOH (2M) and acetone in water (1:1, volume basis), afford solids with, respectively, 40 % mass and 29 % mass less lignin than water precipitated solids. However, this delignification imparts little increase in saccharification rates and extents of these solids. An alternative single phase fractionation system is achieved simply by using water as an antisolvent. Regulating the water : IL ratio results in a solution that precipitates cellulose and maintains lignin in solution (0.5 water : IL mass ratio) in both [C4mim]Cl and 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc)). This water based fractionation is applied in three IL pretreatments on bagasse ([C4mim]Cl, 1-ethyl-3-methyl imidazolium chloride ([C2mim]Cl) and [C2mim]OAc). Lignin removal of 10 %, 50 % and 60 % mass respectively is achieved although only 0.3 %, 1.5 % and 11.7 % is recoverable even after ample water addition (3.5 water : IL mass ratio) and acidification (pH . 1). In addition the recovered lignin fraction contains 70 % mass hemicelluloses. The delignified, cellulose-rich bagasse recovered from these three ILs is exposed to enzyme saccharification. The saccharification (24 h, 15 FPU) of the cellulose mass in starting bagasse, achieved by these pretreatments rank as: [C2mim]OAc (83 %)>>[C2mim]Cl (53 %)=[C4mim]Cl(53%). Mass balance determinations accounted for 97 % of starting bagasse mass for the [C4mim]Cl pretreatment , 81 % for [C2mim]Cl and 79 %for [C2mim]OAc. For all three IL treatments, the remaining bagasse mass (not accounted for by mass balance determinations) is mainly (more than half) lignin that is not recoverable from the liquid fraction. After pretreatment, 100 % mass of both ions of all three ILs were recovered in the liquid fraction. Compositional characteristics of [C2mim]OAc treated solids such as low lignin, low acetyl group content and preservation of arabinosyl groups are opposite to those of chloride IL treated solids. The former biomass characteristics resemble those imparted by aqueous alkali pretreatment while the latter resemble those of aqueous acid pretreatments. The 100 % mass recovery of cellulose in [C2mim]OAc as opposed to 53 % mass recovery in [C2mim]Cl further demonstrates this since the cellulose glycosidic bonds are protected under alkali conditions. The alkyl chain length decrease in the imidazolium cation of these ILs imparts higher rates of dissolution and losses, and increases the severity of the treatment without changing the chemistry involved.

Microalgal biomass as a fermentation feedstock for bioethanol production

BACKGROUND The increasing cost of fossil fuels as well as the escalating social and industrial awareness of the environmental impacts associated with the use of fossil fuels has created the need for more sustainable fuel options. Bioethanol, produced from renewable biomass such as sugar and starch materials, is believed to be one of these options, and it is currently being harnessed extensively. However, the utilization of sugar and starch materials as feedstocks for bioethanol production creates a major competition with the food market in terms of land for cultivation, and this makes bioethanol from these sources economically less attractive. RESULT This study explores the suitability of microalgae (Chlorococum sp.) as a substrate for bioethanol production via yeast (Saccharomycesbayanus)under different fermentation conditions. Results show a maximum ethanol concentration of 3.83 g L -1 obtained from 10 g L-1 of lipid-extracted microalgae debris. CONCLUSION This productivity level (∼38% w/w), which is in keeping with that of current production systems endorses microalgae as a promising substrate for bioethanol production.

The environmental and economic sustainability of potential bioethanol from willow in the UK.

Life cycle assessment has been used to investigate the environmental and economic sustainability of a potential operation in the UK in which bioethanol is produced from the hydrolysis and subsequent fermentation of coppice willow. If the willow were grown on idle arable land in the UK, or, indeed, in Eastern Europe and imported as wood chips into the UK, it was found that savings of greenhouse gas emissions of 70-90%, when compared to fossil-derived gasoline on an energy basis, would be possible. The process would be energetically self-sufficient, as the co-products, e.g. lignin and unfermented sugars, could be used to produce the process heat and electricity, with surplus electricity being exported to the National Grid. Despite the environmental benefits, the economic viability is doubtful at present. However, the cost of production could be reduced significantly if the willow were altered by breeding to improve its suitability for hydrolysis and fermentation.

Potential CO2 Emission Reduction by Development of Non-Grain-Based Bioethanol in China

Assessment of the potential CO2 emission reduction by development of non-grain-based ethanol in China is valuable for both setting up countermeasures against climate change and formulating bioethanol policies. Based on the land occupation property, feedstock classification and selection are conducted, identifying sweet sorghum, cassava, and sweet potato as plantation feedstocks cultivated from low-quality arable marginal land resources and molasses and agricultural straws as nonplantation feedstocks derived from agricultural by-products. The feedstock utilization degree, CO2 reduction coefficient of bioethanol, and assessment model of CO2 emission reduction potential of bioethanol are proposed and established to assess the potential CO2 emission reduction by development of non-grain-based bioethanol. The results show that China can obtain emission reduction potentials of 10.947 and 49.027 Mt CO2 with non-grain-based bioethanol in 2015 and 2030, which are much higher than the present capacity, calculated as 1.95 Mt. It is found that nonplantation feedstock can produce more bioethanol so as to obtain a higher potential than plantation feedstock in both 2015 and 2030. Another finding is that developing non-grain-based bioethanol can make only a limited contribution to China's greenhouse gas emission reduction. Moreover, this study reveals that the regions with low and very low potentials for emission reduction will dominate the spatial distribution in 2015, and regions with high and very high potentials will be the majority in 2030.

Utilisation of whole sorghum crop residues for bioethanol production

Sorghum is the fifth most important cereal worldwide and is a major source of agricultural residues in tropical regions. Bioconversion of whole sorghum crop residues comprising stalks, leaves, peduncles and panicles to ethanol has great potential for improving ethanol yield per sorghum crop cultivated, and for sustainable biofuel production. Effective pretreatment of sorghum lignocellulosic biomass is central to the efficiency of subsequent fermentation to ethanol. Previous studies have focused on bioconversion of sorghum stalks and/or leaves only to bioethanol, but the current study is the first report dealing with whole crop residues. We specifically focused on the impact of Nigerian sorghum cultivation location and cultivar type on the potential ethanol yield from whole sorghum crop residues. Efficient bioconversion of whole sorghum residues to ethanol provides a sustainable route for utilisation of crop residues thereby providing a non-food feedstock for industrial scale bioethanol production.

Selection of yeast strains for bioethanol production from UK seaweeds

Macroalgae (seaweeds) are a promising feedstock for the production of third generation bioethanol, since they have high carbohydrate contents, contain little or no lignin and are available in abundance. However, seaweeds typically contain a more diverse array of monomeric sugars than are commonly present in feedstocks derived from lignocellulosic material which are currently used for bioethanol production. Hence, identification of a suitable fermentative microorganism that can utilise the principal sugars released from the hydrolysis of macroalgae remains a major objective. The present study used a phenotypic microarray technique to screen 24 different yeast strains for their ability to metabolise individual monosaccharides commonly found in seaweeds, as well as hydrolysates following an acid pre-treatment of five native UK seaweed species (Laminaria digitata, Fucus serratus, Chondrus crispus, Palmaria palmata and Ulva lactuca). Five strains of yeast (three Saccharomyces spp, one Pichia sp and one Candida sp) were selected and subsequently evaluated for bioethanol production during fermentation of the hydrolysates. Four out of the five selected strains converted these monomeric sugars into bioethanol, with the highest ethanol yield (13 g L−1) resulting from a fermentation using C. crispus hydrolysate with Saccharomyces cerevisiae YPS128. This study demonstrated the novel application of a phenotypic microarray technique to screen for yeast capable of metabolising sugars present in seaweed hydrolysates; however, metabolic activity did not always imply fermentative production of ethanol.

Bioethanol production from a sub-product of pulping industry

A vida da sociedade atual é dependente dos recursos fósseis, tanto a nível de energia como de materiais. No entanto, tem-se verificado uma redução das reservas destes recursos, ao mesmo tempo que as necessidades da sociedade continuam a aumentar, tornando cada vez mais necessárias, a produção de biocombustíveis e produtos químicos. Atualmente o etanol é produzido industrialmente a partir da cana-de-açúcar e milho, matérias-primas usadas na alimentação humana e animal. Este fato desencadeou o aumento de preços dos alimentos em todo o mundo e, como consequência, provocou uma série de distúrbios sociais. Os subprodutos industriais, recursos independentes das cadeias alimentares, têm-se posicionado como fonte de matérias-primas potenciais para bioprocessamento. Neste sentido, surgem os subprodutos gerados em grande quantidade pela indústria papeleira. Os licores de cozimento da madeira ao sulfito ácido (SSLs) são uma matériaprima promissora, uma vez que durante este processo os polissacarídeos da madeira são hidrolisados originando açúcares fermentáveis. A composição dos SSLs varia consoante o tipo de madeira usada no processo de cozimento (de árvores resinosas, folhosas ou a mistura de ambas). O bioprocessamento do SSL proveniente de folhosas (HSSL) é uma metodologia ainda pouco explorada. O HSSL contém elevadas concentrações de açúcares (35-45 g.L-1), na sua maioria pentoses. A fermentação destes açúcares a bioetanol é ainda um desafio, uma vez que nem todos os microrganismos são capazes de fermentar as pentoses a etanol. De entre as leveduras capazes de fermentar naturalmente as pentoses, destaca-se a Scheffersomyces stipitis, que apresenta uma elevada eficiência de fermentação. No entanto, o HSSL contém também compostos conhecidos por inibirem o crescimento de microrganismos, dificultando assim o seu bioprocessamento. Neste sentido, o principal objetivo deste trabalho foi a produção de bioetanol pela levedura S. stipitis a partir de HSSL, resultante do cozimento ao sulfito ácido da madeira de Eucalyptus globulus. Para alcançar este objetivo, estudaram-se duas estratégias de operação diferentes. Em primeiro lugar estudou-se a bio-desintoxicação do HSSL com o fungo filamentoso Paecilomyces variotii, conhecido por crescer em resíduos industriais. Estudaram-se duas tecnologias fermentativas diferentes para a biodesintoxicação do HSSL: um reator descontínuo e um reator descontínuo sequencial (SBR). A remoção biológica de inibidores do HSSL foi mais eficaz quando se usou o SBR. P. variotii assimilou alguns inibidores microbianos como o ácido acético, o ácido gálico e o pirogalol, entre outros. Após esta desintoxicação, o HSSL foi submetido à fermentação com S. stipitis, na qual foi atingida a concentração máxima de etanol de 2.36 g.L-1 com um rendimento de 0.17 g.g-1. P. variotti, além de desintoxicar o HSSL, também é útil na produção de proteína microbiana (SCP) para a alimentação animal pois, a sua biomassa é rica em proteína. O estudo da produção de SCP por P. variotii foi efetuado num SBR com HSSL sem suplementos e suplementado com sais. A melhor produção de biomassa foi obtida no HSSL sem adição de sais, tendo-se obtido um teor de proteína elevado (82,8%), com uma baixa concentração de DNA (1,1%). A proteína continha 6 aminoácidos essenciais, mostrando potencial para o uso desta SCP na alimentação animal e, eventualmente, em nutrição humana. Assim, a indústria papeleira poderá integrar a produção de bioetanol após a produção SCP e melhorar a sustentabilidade da indústria de pastas. A segunda estratégia consistiu em adaptar a levedura S. stipitis ao HSSL de modo a que esta levedura conseguisse crescer e fermentar o HSSL sem remoção de inibidores. Operou-se um reator contínuo (CSTR) com concentrações crescentes de HSSL, entre 20 % e 60 % (v/v) durante 382 gerações em HSSL, com uma taxa de diluição de 0.20 h-1. A população adaptada, recolhida no final do CSTR (POP), apresentou uma melhoria na fermentação do HSSL (60 %), quando comparada com a estirpe original (PAR). Após esta adaptação, a concentração máxima de etanol obtida foi de 6.93 g.L-1, com um rendimento de 0.26 g.g-1. POP possuía também a capacidade de metabolizar, possivelmente por ativação de vias oxidativas, compostos derivados da lenhina e taninos dissolvidos no HSSL, conhecidos inibidores microbianos. Por fim, verificou-se também que a pré-cultura da levedura em 60 % de HSSL fez com que a estirpe PAR melhorasse o processo fermentativo em HSSL, em comparação com o ensaio sem pré-cultura em HSSL. No entanto, no caso da estirpe POP, o seu metabolismo foi redirecionado para a metabolização dos inibidores sendo que a produção de etanol decresceu.

Bioethanol from lignocelluloses: Status and perspectives in Brazil

The National Alcohol Program - ProAlcool, created by the government of Brazil in 1975 resulted less dependency on fossil fuels. The addition of 25% ethanol to gasoline reduced the import of 550 million barrels oil and also reduced the emission CO(2) by 110 million tons. Today, 44% of the Brazilian energy matrix is renewable and 13.5% is derived from sugarcane. Brazil has a land area of 851 million hectares, of which 54% are preserved, including the Amazon forest (350 million hectares). From the land available for agriculture (340 million hectares), only 0.9% is occupied by sugarcane as energy crop, showing a great expansion potential. Studies have shown that in the coming years, ethanol yield per hectare of sugarcane, which presently is 6000 L/ha, could reach 10,000 L/ha, if 50% of the produced bagasse would be converted to ethanol. This article describes the efforts of different Brazilian institutions and research groups on second generation bioethanol production, especially from sugarcane bagasse. (C) 2009 Elsevier Ltd. All rights reserved.

Thermophysical Properties of Industrial Sugar Cane Juices for the Production of Bioethanol

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Bioethanol - Brazil, 30 years of Proálcool

Brazil, which has always been in the forefront of sugarcane production, also occupies a prominent position as the first country to produce and use biofuel in its automobile fleet. This fact is a consequence of the introduction of a program which has already turned 30 years, the Próalcool (National Alcohol Program). The oil crisis in the seventies encouraged the government to develop an alternative way to replace gasoline. Bioethanol was then born as fuel obtained from fermentation of sugarcane juice, molasses or both. In the eighties, 85% of the cars ran exclusively on alcohol. Ethanol production in that decade exceeded sugarcane production by the mills. The installed units reached in that period the capacity to produce 18 billion liters of bioethanol per season, a volume equivalent to 100 million barrels of gasoline. The fermentation process, which so far had been restricted to manufacturing sugarcane liquor (aguardente) or ethanol as a byproduct of sugarcane, takes over the spotlight in the entrepreneurial scene. As a result, processes comprising engineering concepts came up and most of the biological phenomena involved in fermentation were understood. The knowledge gathered and the units installed have granted Brazil the hold of production technology and use of a clean fuel.