Pretreatment of Miscanthus for hydrogen production by Thermotoga elfii

Pretreatment methods for the production of fermentable substrates from Miscanthus, a lignocellulosic biomass, were investigated. Results demonstrated an inverse relationship between lignin content and the efficiency of enzymatic hydrolysis of polysaccharides. High delignification values were obtained by the combination of mechanical, i.e. extrusion or milling, and chemical pretreatment (sodium hydroxide). An optimized process consisted of a one-step extrusion-NaOH pretreatment at moderate temperature (70°C). A mass balance of this process in combination with enzymatic hydrolysis showed the following: pretreatment resulted in 77% delignification, a cellulose yield of more than 95% and 44% hydrolysis of hemicellulose. After enzymatic hydrolysis 69% and 38% of the initial cellulose and hemicellulose fraction, respectively, was converted into glucose, xylose and arabinose. Of the initial biomass, 33% was converted into monosaccharides. Normal growth of Thermotoga elfii on hydrolysate was observed and high amounts of hydrogen were produced.     

Gasification efficiencies of cellulose,hemicellulose and lignin fractions of biomass in aqueous media by using Pt on activated carbon catalyst

The diversity in the chemical composition of lignocellulosic feedstocks can affect the conversion technologies employed for biofuel production. Aqueous-phase reforming (APR) activities of cellulose, hemicellulose and lignin components of lignocellulosic biomass materials were evaluated for production of hydrogen content gas mixture using platinum catalyst on activated carbon support. Wheat straw, an abundant by-product from wheat production and kenaf (Hibiscus cannabinus L.), an annual herbaceous plant growing very fast with low lodging susceptibility were used as lignocellulosics in the present study. The hydrolysates of cellulose fractions of biomass materials showed the best performance for gasification. The results indicated that hemicellulose isolated from kenaf was more sensitive to degradation and therefore, produced more gaseous products than that of wheat straw. The hemicellulose isolated from kenaf biomass left the lowest amount of ungasified solid residue in APR among other cellulose and hemicellulose materials studied. Lignin fractions of both biomass materials were not reactive in APR to produce hydrogen rich gas mixture.Gasification efficiencies of kenaf and wheat straw's hemicelluloses were also compared with xylans from beechwood and oat spelts which were commercially available as hemicellulosic fractions.Oat spelts xylan showed better reforming activity over the beechwood xylan.     

Pretreatment and fractionation of barley straw using steam explosion at low severity factor

Agricultural residues represent an abundant, readily available, and inexpensive source of renewable lignocellulosic biomass. However, biomass has complex structural formation that binds cellulose and hemicellulose. This necessitates the initial breakdown of the lignocellulosic matrix. Steam explosion pretreatment was performed on barley straw grind to assist in the deconstruction and disaggregation of the matrix, so as to have access to the cellulose and hemicellulose. The following process and material variables were used: temperature (140–180 °C), corresponding saturated pressure (500–1100 kPa), retention time (5–10 min), and mass fraction of water 8–50%. The effect of the pretreatment was assessed through chemical composition analysis. The severity factor R_o, which combines the temperature and time of the hydrolytic process into a single reaction ordinate was determined. To further provide detailed chemical composition of the steam exploded and non-treated biomass, ultimate analysis was performed to quantify the elemental components. Data show that steam explosion resulted in the breakdown of biomass matrix with increase in acid soluble lignin. However, there was a considerable thermal degradation of cellulose and hemicellulose with increase in acid insoluble lignin content. The high degradation of the hemicellulose can be accounted for by its amorphous nature which is easily disrupted by external influences unlike the well-arranged crystalline cellulose. The carbon content of the solid steam exploded product increased at higher temperature and longer residence time, while the hydrogen and oxygen content decreased, and the higher heating value (HHV) increased.     

Thermogravimetric analysis as a new method to determine the lignocellulosic composition of biomass

Biomass energy uses organic matter such as wood or plants - lignocellulosic biomass - for creating heat, generating electricity and producing green oil for cars. Modern biomass energy recycles organic leftovers from forestry and agriculture, like corn stovers, rice husks, wood waste and pressed sugar cane, or uses special, fast-growing “energy crops” like willow and switchgrass, as fuel. Biomass is composed of three major components: cellulose, hemicelluloses, and lignin. Their differences in chemical structures lead to different chemical reactivities, making the relative composition in cellulose, hemicelluloses and lignin in the biomass a crucial factor for process design. In this paper thermogravimetric analysis is investigated as a new method to obtain lignin, hemicellulose and ??-cellulose contents in biomass. It is shown that this alternative method lead to comparable results than common methods used for the determination of the ??-cellulose content, with an enhancement of the accuracy in the determination of the hemicellulose content. Unfortunately, this method cannot be adopted for the determination of the lignin amount.     

油棕废弃物及生物质三组分的热解动力学研究

主要利用热重分析仪(TG)对油棕废弃物和生物质的三组分(半纤维素,纤维素和木质素)的热解特性进行了系统研究,对比分析了热解特性,计算了其热解动力学参数,并研究了升温速率对生物质热解特性的影响。研究发现半纤维素和纤维素易于热降解而木质素难于热解;油棕废弃物的热解可以化分为:干燥、半纤维素热解、纤维素热解和木质素热解4个阶段;生物质的热解反应主要是一级反应,油棕废弃物的活化能很低,约为60kJ/kg;升温速率对生物质影响很大,随升温速率加快,生物质热解温度升高,热解速率降低。     

Optimization and modeling of process parameters during hydrothermal gasification of biomass model compounds to generate hydrogen-rich gas products

Hydrothermal gasification in subcritical and supercritical water is gaining attention as an attractive option to produce hydrogen from lignocellulosic biomass. However, for process optimization, it is important to understand the fundamental phenomenon involved in hydrothermal gasification of synthetic biomass or biomass model compounds, namely cellulose, hemicellulose and lignin. In this study, the response surface methodology using the Box-Behnken design was applied for the first time to optimize the process parameters during hydrothermal (subcritical and supercritical water) gasification of cellulose. The process parameters investigated include temperature (300–500 °C), reaction time (30–60 min) and feedstock concentration (10–30 wt%). Temperature was found to be the most significant factor that influenced the yields of hydrogen and total gases. Furthermore, negligible interaction was found between lower temperatures and reaction time while the interaction became dominant at higher temperatures. Hydrogen yield remained at about 0.8 mmol/g with an increase in the reaction time from 30 min to 60 min at the temperature range of 300–400 °C. When the temperature was raised to 500 °C, hydrogen yield started to elevate at longer reaction time. Maximum hydrogen yield of 1.95 mmol/g was obtained from supercritical water gasification of cellulose alone at 500 °C with 12.5 wt% feedstock concentration in 60 min. Using these optimal reaction conditions, a comparative evaluation of the gas yields and product distribution of cellulose, hemicellulose (xylose) and lignin was performed. Among the three model compounds, hydrogen yields increased in the order of lignin (0.73 mmol/g) < cellulose (1.95 mmol/g) < xylose (2.26 mmol/g). Based on the gas yields from these model compounds, a possible reaction pathway of model lignocellulosic biomass decomposition in supercritical water was proposed.     

Supercritical water gasification of biomass for hydrogen production

Hydrogen from waste biomass is considered to be a clean gaseous fuel and efficient for heat and power generation due to its high energy content. Supercritical water gasification is found promising in hydrogen production by avoiding biomass drying and allowing maximum conversion. Waste biomass contains cellulose, hemicellulose and lignin; hence it is essential to understand their degradation mechanisms to engineer hydrogen production in high-pressure systems. Process conditions higher than 374 °C and 22.1 MPa are required for biomass conversion to gases. Reaction temperature, pressure, feed concentration, residence time and catalyst have prominent roles in gasification. This review focuses on the degradation routes of biomass model compounds such as cellulose and lignin at near and supercritical conditions. Some homogenous and heterogeneous catalysts leading to water–gas shift, methanation and other sub-reactions during supercritical water gasification are highlighted. The parametric impacts along with some reactor configurations for maximum hydrogen production and technical challenges encountered during hydrothermal gasification processes are also discussed.     

Effects of biochemical composition on hydrogen production by biomass gasification

Gasification of cellulose, hemicellulose, lignin and three types of real biomass was conducted using an updraft fixed-bed reactor to investigate the effects of temperature (in the range of 920–1220 °C) on the yield and chemical composition of the produced syngas. The experimental results showed that the gasification products of cellulose and hemicellulose were similar to each other, but they were different from those of lignin; it is likely due to the difference in volatile compounds. Cellulose and hemicellulose can be gasified more rapidly producing more CO and CH₄ and less H₂ and CO₂ than lignin, and the real biomass fell in between. Biomass with more lignin produced more hydrogen than others. These differences were resulted from the relative amount of lignin, hemicellulose, and cellulose in the biomass. Linear superposition method was used to simulate the gasification characteristics of real biomass and it showed a certain linear correlation between the simulation and experimental data.     

深度共熔溶剂预处理对木质纤维素生物质作用机制的研究进展

深度共熔溶剂（DES）是一类可再生、对环境友好的新型混合溶剂体系,用于预处理木质纤维素生物质可有效去除半纤维素及木质素组分,并可保留较为完整的纤维素组分。本文综述DES预处理对木质纤维素生物质作用机制的研究进展。通常情况下,大部分DES对纤维素溶解性较差,但可改变纤维素的外貌形态;一些酸性DES对半纤维素具有良好的溶解性能;碱性DES及部分酸性DES对木质素具有优异的溶解性能,在预处理过程中木质素的结构发生解聚或缩合反应;三元DES体系在木质素提取、分离及回收等方面均展现出更多优势。DES对木质素的去除效果及作用机制受DES的构成、摩尔比、生物质类型及预处理条件如温度等多种因素的影响。理解DES在木质纤维素生物质预处理中结构与功能的关系,研究DES在预处理过程中对木质素及半纤维素去除的作用机制,有助于合理设计新的DES体系并为实现生物质三大组分的高效分离及转化奠定理论基础与技术指导。     

Hydrothermal carbonization of microalgae

Hydrothermal carbonization is a process in which biomass is heated in water under pressure to create a char product. With higher plants, the chemistry of the process derives primarily from lignin, cellulose and hemicellulose components. In contrast, green and blue-green microalgae are not lignocellulosic in composition, and the chemistry is entirely different, involving proteins, lipids and carbohydrates (generally not cellulose). Employing relatively moderate conditions of temperature (ca. 200 °C), time (<1 h) and pressure (<2 MPa), microalgae can be converted in an energy efficient manner into an algal char product that is of bituminous coal quality. Potential uses for the product include creation of synthesis gas and conversion into industrial chemicals and gasoline; application as a soil nutrient amendment; and as a carbon neutral supplement to natural coal for generation of electrical power.     

Utilization of lignin: A sustainable and eco-friendly approach

The use of renewable carbon sources as a substitute for fossil resources is an extensively essential and fascinating research area for addressing the current issues related to climate and future fuel requirements. The utilization of lignocellulosic biomasses as a source for renewable fuel/chemicals/mesoporous biochar derivative is gaining considerable attention due to the neutral carbon cycle. The cellulose and hemicellulose are highly utilized components of biomass, and on the other hand, lignin is a plentiful, under-utilized component of the lignocellulosic biomass in 2G ethanol and paper industry. Significant researchers have contributed towards lignin valorization, with a central goal of the production and upgradation of phenolic, unstable, acidic and oxygen-containing bio-oil to valuable chemicals or fuel grade hydrocarbons. This review is aimed to present the lignin valorization potential from pretreatment of biomass as an initial step to the final process, i.e., lignin bio-oil upgradation with mechanistic pathways. The review offers the source, structure, composition of various lignocellulosic biomasses, followed by a discussion of various pre-treatment techniques for biomass depolymerization. Different thermochemical approaches for bio-oil production from dry and wet biomasses are highlighted with emphasis on pyrolysis and liquefaction. The physical, chemical properties of lignin bio-oil and different upgradation methods for bio-oil as well as its model compounds are thoroughly discussed. It also addresses the related activity, selectivity, stability of numerous catalysts with reaction pathways and kinetics in a broad manner. The challenges and future research opportunities of lignin valorization are discussed in an attempt to place lignin as a feedstock for the generation of valuable chemical and fuel grade hydrocarbons.     

Solvent fractionation of renewable woody feedstocks: Organosolv generation of biorefinery process streams for the production of biobased chemicals

A new organosolv biomass fractionation process (Clean Fractionation, CF) for the separation of lignocellulosic raw material into cellulose, hemicellulose and lignin has been developed. The lignocellulosic material is separated with a ternary mixture of methyl isobutyl ketone, ethanol and water in the presence of an acid promoter, which selectively dissolves lignin and hemicellulose, leaving cellulose as an undissolved solid. The resulting single phase liquor is treated with water giving an organic phase containing lignin and an aqueous phase containing hemicellulose. For woody feedstocks, the yield of the cellulose fraction across all separations averaged 47.7 wt% (±1.1). Representative separations gave cellulose fractions with average Klason lignin contents of 2.0% at acid concentrations of 0.1 M H₂SO₄ or greater. Little or no galactose, mannose or arabinose is observed in the cellulose, and at an acid concentration of 0.2 M, average xylose contents as low as 0.22% were observed. Average glucan contents for representative cellulose samples of 92.7% were observed, and rose as high as 98.2% for separations using 0.2 M H₂SO₄. Glucan contents as high as 97% were also observed if the cellulose was bleached using either a QPD or QPDE sequence. The average yield of the lignin fraction was 18.3 wt%. Representative lignin samples gave an average Klason lignin value of 91% with selected lignin samples exhibiting residual sugar levels of <0.5%. The aqueous hemicellulose fraction contains a higher level of non-sugar components, but can be purified by ion exchange chromatography.     

生物质三组分的催化气化特性研究

以生物质三组分(纤维素、半纤维素和木质素)作为实验原料,采用常用的白云石作为催化剂,在小型气流床气化炉上进行气化催化实验。重点研究了白云石对生物质三组分的催化气化特性以及焦油析出特性的差异。结果表明:白云石对纤维素、半纤维素、木质素均起到正向催化作用,提高了三者的碳转化率、气化效率以及气体热值;同时,白云石对三组分的催化作用存在明显差异,其中,对半纤维素的促进催化作用最为显著,木质素次之,对纤维素的促进作用不明显。因此,针对不同组分含量和特性的生物质选择适当的催化剂是必要的。     

Biomass characterization of Agave and Opuntia as potential biofuel feedstocks

Sustainable production of lignocellulosic biofuels requires a sufficient supply of biomass feedstocks. Agave and Opuntia represent highly water-use efficient bioenergy crops that are suitable for expanding feedstock production into semi-arid marginal lands. These feedstocks have garnered interest as dedicated biofuel feedstocks because of their high water- and fertilizer-use efficiency and not competing with major food crops or conventional biofuel feedstocks. To better understand the potential of these feedstocks, the biomass composition of Agave tequilana and Opuntia ficus-indica was analyzed. Previous extraction procedures and analytical methods have led to variable estimates of the chemical compositions of the biomass of these species. Therefore, National Renewable Energy Laboratory (NREL) standard methods were used in the present study. A. tequilana showed higher mass fractions of water-soluble constituents, structural carbohydrates, cellulose, hemicellulose, and lignin than O. ficus-indica. In contrast, O. ficus-indica had higher protein, water, and ash mass fractions than A. tequilana. Both species had lower lignin mass fractions, thus yielding lower heating values, but had higher water and ash mass fractions than most woody biomass feedstocks. The high water mass fractions of these species (85–94%) could prove advantageous for biomass deconstruction and aqueous phase catalytic conversion processes as less exogenous water inputs would be needed. Lastly, solid-state NMR analysis revealed that both A. tequilana and O. ficus-indica had high amorphous and para-crystalline cellulose mass fractions (>80%), indicating that these biomass feedstocks would be far less recalcitrant to deconstruction than traditional lignocellulosic biomass feedstocks.     

木质纤维素生物质生产乙醇的预处理技术

木质纤维素生物质经过预处理后，原料的内孔面积增大，纤维素的结晶性降低，并且半纤维素和木质素被去除．预处理后的生物质容易进行酶水解生产燃料乙醇。总结了近些年来的预处理技术，如物理法、化学法和生物法。     

Compositional differences among upland and lowland switchgrass ecotypes grown as a bioenergy feedstock crop

Feedstock quality mainly depends upon the biomass composition and bioenergy conversion system being used. Higher cellulose and hemicellulose concentrations are desirable for biochemical conversion, whereas higher lignin is favored for thermochemical conversion. The efficiency of these conversion systems is influenced by the presence of high nitrogen and ash concentrations. Switchgrass (Panicum virgatum L.) varieties are classified into two ecotypes based on their habitat preferences, i.e., upland and lowland. The objectives of this study were to quantify the chemical composition of switchgrass varieties as influenced by harvest management, and to determine if ecotypic differences exist among them. A field study was conducted near Ames, IA during 2012 and 2013. Upland (‘Cave-in-Rock’, ‘Trailblazer’ and ‘Blackwell’) and lowland switchgrass varieties (‘Kanlow’ and ‘Alamo’) were grown in a randomized block design with six replications. Six biomass harvests were collected at approximately 2-week intervals each year. In both years, delaying harvest increased cellulose, hemicellulose and lignin concentrations while decreasing nitrogen and ash concentrations in all varieties. On average, Kanlow had the highest cellulose and hemicellulose concentration (354 and 321 g kg⁻¹ DM respectively), and Cave-in-Rock had the highest lignin concentration (33 g kg⁻¹ DM). The lowest nitrogen and ash concentrations were observed in Kanlow (14 and 95 g kg⁻¹ DM respectively). In general, our results indicate that delaying harvest until fall improves feedstock quality, and ecotypic differences do exist between varieties for important feedstock quality traits. These findings also demonstrate potential for developing improved switchgrass cultivars as bioenergy feedstock by intermating lowland and upland ecotypes.     

Characterization of ionic liquid pretreatment and the bioconversion of pretreated mixed softwood biomass

In this study, mixed softwoods were pretreated with an ionic liquid, 1-butyl-3-methylimidazolium chloride ([Bmim]Cl), and the bioconversion efficiencies to fermentable sugars were estimated through the enzymatic hydrolysis. The cellulose crystallinity, surface morphology, structures and compositions of softwood were significantly changed after the ionic liquid pretreatment was carried out under a wide range of temperatures and reaction times. And, biomass digestibility significantly increased with increasing pretreatment temperature and reaction time. The enzymatic degradation of pretreated softwoods was remarkably improved at the pretreatment of high temperatures via the modification of crystalline cellulose I to a mixture of easily digestable cellulose II and amorphous structure, and partial removal of hemicellulose. The conversion of cellulose to glucose reached more than 90% at relevant conditions and the highest glucose yield was measured to about 78%. Through the study, it was clearly shown that ionic liquid pretreatment is one of the effective methods to produce high fermentable sugars without lignin dissolution from lignocellulosic biomass.     

Experimental study on the ignition characteristics of cellulose,hemicellulose, lignin and their mixtures

Ignition behaviour of biomass is an essential knowledge for plant design and process control of biomass combustion. Understanding of ignition characteristics of its main chemical components, i.e. cellulose, hemicellulose, lignin and their mixtures will allow the further investigation of ignition behaviour of a wider range of biomass feedstock. This paper experimentally investigates the influences of interactions among cellulose, hemicellulose and lignin on the ignition behaviour of biomass by thermogravimetric analysis. Thermal properties of an artificial biomass, consisting of a mixture of the three components will be studied and compared to that of natural biomass in atmospheres of air and nitrogen in terms of their ignition behaviour. The results showed that the identified ignition temperatures of cellulose, hemicellulose and lignin are 410 °C, 370 °C and 405 °C, respectively. It has been found that the influence of their interactions on the ignition behaviour of mixtures is insignificant, indicating that the ignition behaviour of various biomass feedstock could be predicted with high accuracy if the mass fractions of cellulose, hemicellulose and lignin are known. While the deficiencies of the determined mutual interactions would be further improved by the analytical results of the activation energies of cellulose, hemicellulose, lignin, their mixtures as well as natural and artificial biomass in air conditions.     

Torrefaction and co-torrefaction characterization of hemicellulose, cellulose and lignin as well as torrefaction of some basic constituents in biomass

Torrefaction is a thermal pretreatment process for biomass where raw biomass is heated in the temperatures of 200-300 °C under an inert or nitrogen atmosphere. The main constituents contained in biomass include hemicellulose, cellulose and lignin; therefore, the thermal decomposition characteristics of these constituents play a crucial role in determining the performance of torrefaction of lignocellulosic materials. To gain a fundamental insight into biomass torrefaction, five basic constituents, including hemicellulose, cellulose, lignin, xylan and dextran, were individually torrefied in a thermogravimetry. Two pure materials, xylose and glucose, were torrefied as well for comparison. Three torrefaction temperatures of 230, 260 and 290 °C, corresponding to light, mild and severe torrefactions, were taken into account. The experiments suggested the weight losses of the tested samples could be classified into three groups; they consisted of a weakly active reaction, a moderately active reaction and a strongly active reaction, depending on the natures of the tested materials. Co-torrefactions of the blend of hemicellulose, cellulose and lignin at the three torrefaction temperatures were also examined. The weight losses of the blend were very close to those from the linear superposition of the individual samples, suggesting that no synergistic effect from the co-torrefactions was exhibited.     

氨化水饱和预处理麦秸厌氧消化产气性能的研究

试验以氨水为预处理试剂,研究在水饱和状态下,氨水添加量及负荷率对麦秸厌氧消化产气性能的影响。对氨化预处理前后麦秸的主要组分进行测定,采用傅立叶变换红外光谱(FTIR)对氨化水饱和预处理秸秆及秸秆中木素、纤维素和半纤维素的结构变化进行研究。结果表明,在3种负荷率下,氨化水饱和预处理后麦秸单位质量VS产气量分别提高了14%~23%,26%~36%和31%~45%。4%氨化预处理后的麦秸在65 g/L负荷率下获得最大377 mL/g的生物气产量。组分分析表明,氨化水饱和预处理可有效脱除39%~42%的半纤维素及11%~20%的纤维素,对木素含量影响较小。结构分析表明,氨化水饱和预处理可脱除细胞壁中的蜡质成分,使木素中部分官能团、纤维素中的氢键和糖苷键、半纤维素的部分氢键和糖单元之间的连接键发生断裂;从而使纤维素从木素的包裹中释放出来并发生溶胀,破坏其晶体结构;使半纤维素亲水性增强且更易于降解。这些秸秆内部结构的变化是提高麦秸厌氧消化产气性能的根本原因。