Instituto de Física de São Carlos, Universidade de São Paulo, Caixa Postal 369, CEP 13560-970, São Carlos, SP, Brazil.
Escola de Engenharia de Lorena, Universidade de São Paulo, CEP 12602-810, Lorena, SP, Brazil.
Biotechnol Biofuels. 2011 Nov 28;4(1):54. doi: 10.1186/1754-6834-4-54.
In recent years, biorefining of lignocellulosic biomass to produce multi-products such as ethanol and other biomaterials has become a dynamic research area. Pretreatment technologies that fractionate sugarcane bagasse are essential for the successful use of this feedstock in ethanol production. In this paper, we investigate modifications in the morphology and chemical composition of sugarcane bagasse submitted to a two-step treatment, using diluted acid followed by a delignification process with increasing sodium hydroxide concentrations. Detailed chemical and morphological characterization of the samples after each pretreatment condition, studied by high performance liquid chromatography, solid-state nuclear magnetic resonance, diffuse reflectance Fourier transformed infrared spectroscopy and scanning electron microscopy, is reported, together with sample crystallinity and enzymatic digestibility.
Chemical composition analysis performed on samples obtained after different pretreatment conditions showed that up to 96% and 85% of hemicellulose and lignin fractions, respectively, were removed by this two-step method when sodium hydroxide concentrations of 1% (m/v) or higher were used. The efficient lignin removal resulted in an enhanced hydrolysis yield reaching values around 100%. Considering the cellulose loss due to the pretreatment (maximum of 30%, depending on the process), the total cellulose conversion increases significantly from 22.0% (value for the untreated bagasse) to 72.4%. The delignification process, with consequent increase in the cellulose to lignin ratio, is also clearly observed by nuclear magnetic resonance and diffuse reflectance Fourier transformed infrared spectroscopy experiments. We also demonstrated that the morphological changes contributing to this remarkable improvement occur as a consequence of lignin removal from the sample. Bagasse unstructuring is favored by the loss of cohesion between neighboring cell walls, as well as by changes in the inner cell wall structure, such as damaging, hole formation and loss of mechanical resistance, facilitating liquid and enzyme access to crystalline cellulose.
The results presented herewith show the efficiency of the proposed method for improving the enzymatic digestibility of sugarcane bagasse and provide understanding of the pretreatment action mechanism. Combining the different techniques applied in this work warranted thorough information about the undergoing morphological and chemical changes and was an efficient approach to understand the morphological effects resulting from sample delignification and its influence on the enhanced hydrolysis results.
近年来,利用木质纤维素生物质生产乙醇和其他生物材料的生物炼制已成为一个充满活力的研究领域。对甘蔗渣进行分馏的预处理技术对于成功将这种原料用于乙醇生产至关重要。在本文中,我们研究了两步处理法(先用稀酸处理,再用氢氧化钠浓度逐渐增加的脱木质素过程)对甘蔗渣形态和化学成分的影响。通过高效液相色谱、固态核磁共振、漫反射傅里叶变换红外光谱和扫描电子显微镜对每种预处理条件下的样品进行了详细的化学和形态特征分析,并报告了样品结晶度和酶解度。
对不同预处理条件下得到的样品进行化学组成分析表明,当氢氧化钠浓度为 1%(m/v)或更高时,两步法可分别去除高达 96%和 85%的半纤维素和木质素。高效的木质素去除导致水解产率提高到 100%左右。考虑到预处理过程中纤维素的损失(取决于处理过程,最高可达 30%),总纤维素转化率从 22.0%(未处理甘蔗渣的数值)显著提高到 72.4%。核磁共振和漫反射傅里叶变换红外光谱实验也清楚地表明,脱木质素过程会导致纤维素与木质素的比例增加。我们还证明,这种显著改善的形态变化是由于样品中木质素的去除而产生的。由于相邻细胞壁之间的凝聚力丧失以及细胞壁内部结构的变化,如破坏、形成孔和失去机械阻力,有利于液体和酶进入结晶纤维素,从而使甘蔗渣解纤。
本文所展示的结果表明,所提出的方法可有效提高甘蔗渣的酶解可及性,并有助于理解预处理的作用机制。结合本文应用的不同技术,保证了对正在发生的形态和化学变化的全面了解,是一种理解样品脱木质素对水解增强结果的形态影响的有效方法。