3种能源草高温液态水预处理的比较实验研究

在最优高温液态水预处理条件(180℃,40 min,固液比1:20,饱和蒸汽压)下,比较3种不同能源草作物的表现,其中杂交狼尾草Ⅰ号、Ⅱ号和柳枝稷的木糖收率分别为88.46％、98.09％、83.65％.3种能源草经高温液态水水解后酶解率增大,最高能接近100％,总糖收率约为90％.3种能源草后续酶解表现也有差异,柳枝...     

Fractionating lignocellulose by formic acid: Characterization of major components

Treatment of corn (Zea mays L.) cob under mild reaction conditions (60 °C and atmospheric pressure) in 88% formic acid was an effective method for separating cellulose from hemicellulose and lignin components in lignocellulose. Most of the hemicellulose degradation and lignin removal occurred within the first 90 min. After 6 h treatment, the decomposition of hemicellulose and the recovery of lignin were over 85% and 70%, respectively. Multi-level structures of lignin and solid residues were further characterized by FTIR, XRD, TG/DTG, SEM and SEC. Peaks attributable to lignin or hemicellulose disappeared in FTIR spectra, indicating complete removal of these two components. The remaining solid residues had a higher crystalline index. The major pyrolysis temperature of corncob was increased after formic acid treatment; the molecular weight (MW) of cellulose in solid residues was higher than that in intact cobs, whereas the hemicellulose remaining in the pulp had a lower MW than the original. Lignin was extracted in an esterified form designated as formic acid lignin (FAL). FAL had two thermal decomposition temperatures (T_d) at 277 °C and 385 °C. The MW of lignin increased following formic acid treatment, which may make it a better starting material for chemical syntheses.     

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.     

Conversion study from lignocellulosic biomass and electric energy to H2 and chemicals

The efficient use of lignocellulosic biomass resources is of great significance to solve environmental pollution and energy crisis. Therefore, the understanding of the reactivity of lignin, hemicellulose, and cellulose, which are the major components of lignocellulosic biomass, on chemical and hydrogen conversion is necessary. So combined with proton exchange membrane electrolysis cell, using polyoxometalate (POM) as the oxidizing agent and electron stockpile carrier, the cyclic electrolytic hydrogen production and degradation of lignin, hemicellulose, and cellulose have been researched in detail. Among them, lignin degraded the best (96.81%), and the average Faradaic efficiency of the herein system was also the highest (95.93%). These results exhibit high conversion efficiency from electric energy to hydrogen energy. Simultaneously, without harsh conditions, lignin is mainly degraded to vanillin, hemicellulose is mainly converted to ester compounds, and cellulose is mainly converted to alcohol compounds, which provides an experiment basis for future chemical conversion.     

Anaerobic digestion of corn silage on a commercial scale: Differential utilization of its chemical constituents and characterization of the solid digestate

The utilization of different chemical constituents of corn silage during industrial-scale anaerobic digestion was determined. Corn silage together with the resulting solid digestate generated during biogas production were collected from an industrial plant during a regular operating period. Moisture, water and ethanol extractives, ash, total nitrogen, starch, cellulose, the monomeric composition of hemicellulose, acid soluble and acid insoluble lignin were measured in both corn silage and corn silage solid digestate. The relative consumption of each component of corn silage during its anaerobic digestion was estimated with reference to acid insoluble lignin. It was assumed that lignin was not digested throughout the process. Starch and large fractions of extractives and acid soluble lignin were digested. In contrast, the digestion of cellulose and particularly hemicellulose were limited (40% and 29% respectively). Of the hemicellulose monomers, xylose was the least digested (20%). The present work shows that the digestate produced by commercial corn-silage anaerobic digestion contains a notable quantity of cell wall polymers. These could potentially be used in biorefinery processes, e.g. ethanol and xylo-oligosaccharide production.     

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.     

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。     

Impact of low lignin containing brown midrib sorghum mutants to harness biohydrogen production using mixed anaerobic consortia

Three low lignin containing bmr 3 derivatives, namely DRT 07K1, DRT 07K6 and DRT 07K15 developed through backcrossing were used along with the parent, bmr 3 source mutant (IS 21888) for evaluation of biohydrogen production. Results demonstrated that biohydrogen production varied amongst bmr derivatives under similar fermentation conditions. Significant negative correlation was observed between lignin content and fermentative biohydrogen production. All bmr derivatives with lower lignin content produced higher levels of biohydrogen compared to source bmr 3 (IS 21888) which has more lignin content. The maximum and a minimum biohydrogen production observed was 72 and 50 ml/g Total Volatile Solids (TVS) for the DRT 07K6 bmr3 derivative and bmr 3 (IS 21888) respectively. Acetate and butyrate were accounted >85% of volatile fatty acids, indicating acid type fermentations. Statistical analysis revealed that all bmr mutant derivatives with respect to source differ significantly in cumulative biohydrogen production, plant height, grain yield and lignin content. Biohydrogen production from biomass associated at least two different levels, one at lignin entanglement another at the polymeric nature of cellulose and hemicellulose. Further studies are necessary to determine the effect of biomass structure associated with different bmr traits on the microbial growth and biohydrogen production rate.     

基于原料组分的能源草厌氧发酵产气预测模型

基于原料的组分,运用线性回归的方法建立能源草厌氧发酵产气预测模型。以巴西象草、华南象草、矮象草、台牧B和七种不同月份收割的杂交狼尾草为样本,以组分C含量、N含量、C/N、纤维素含量、半纤维素含量以及木质素含量为自变量,以该能源草的累计产气率为因变量。一元线性分析结果显示,C元素含量、半纤维素含量和累积产气率之间的显著相关性较弱（R2 = 0.02,R2 = 0.03）;C/N、纤维素含量与产气率之间有一定的显著相关性（R2 = 0.37,R2 = 0.313）;N元素含量、木质纤维素含量和产气率之间的显著相关性较好（R2 = 0.461,R2 = 0.51）。通过多元线性回归分析,得出了两个置信度较高、相关性显著和误差较小的模型（R2 = 0.779,R2 = 0.783）,并通过曲线拟合和标准误差计算,分析了模型的准确性,证实模型可靠。     

The effect of temperature and hemicellulose-lignin,cellulose-lignin,and cellulose-hemicellulose on char yield from the slow pyrolysis of rice husk

In this work, the effect of temperature on the char yield of untreated rice husk, cellulose removed (hemicellulose + lignin), hemicellulose removed (cellulose + lignin), and lignin removed (cellulose + hemicellulose) is investigated. The work compares the performance of acid and alkaline hydrolysis in the context of lignin removal as well. The effect of hemicellulose-lignin, cellulose-lignin, and cellulose-hemicellulose on char yield during slow pyrolysis of rice husk is also studied. The study reveals that only low temperatures favor char yield. Alkaline hydrolysis effects better lignin removal than acid hydrolysis. The effect of hemicellulose-lignin on char yield is more than cellulose-lignin and cellulose-lignin.     

Comparative studies on the pyrolysis of cellulose,hemicellulose, and lignin based on combined kinetics

The thermal degradation behavior and pyrolytic mechanism of cellulose, hemicellulose, and lignin are investigated at different heating rates from 10 Kmin^?1 to 100 Kmin^?1 with a step-size of 10 Kmin^?1 using thermogravimetric analysis (TGA) equipment. It is observed that there are one, two, and three stages of pyrolytic reactions takes place in cellulose, hemicellulose, and lignin respectively. Isoconversional method is not suitable to analyse pyrolysis of hemicellulose and lignin as it involves multi-step reactions. The activation energies of the main decomposition stage for cellulose, hemicellulose, and lignin are 199.66, 95.39, and 174.40 kJ mol^?1 respectively. It is deduced that the pyrolysis reaction of cellulose corresponds to random scission mechanism while the pyrolysis reaction of hemicellulose and lignin follows the order based reaction mechanisms.     

榨糖收贮模式玉米秸秆蒸汽爆破预处理条件优化

使用蒸汽爆破法处理榨糖收贮玉米秸秆榨渣,观察不同蒸汽爆破压力和维压时间下纤维素、半纤维素、木质素（三大素）及纤维素酶水解得率的变化。榨渣三大素含量不同程度下降,半纤维素下降最多,其次是木质素,而纤维素下降最少。处理后进行的水解实验显示压力与维压时间的增加会导致纤维素水解酶得率有所提高,但压力增加对纤维素水解酶影响较小,维压时间对纤维素水解酶的影响较为突出。考虑经济成本的前提下选择1.2 MPa,10 min维压时间为最佳条件,其中纤维素含量为34.42%、半纤维素4.01%、木质素17.09%及纤维素酶水解得率为68.3%。     

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。     

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。     

Evaluation of wet air oxidation as a pretreatment strategy for bioethanol production from rice husk and process optimization

The pretreatment of rice husk by the wet air oxidation (WAO) technique was investigated by means of a statistically designed set of experiments. Reaction temperature, air pressure, and reaction time were the process parameters considered. WAO pretreatment of rice husk increased the cellulose content of the solid fraction by virtue of lignin removal and hemicellulose solubilization. The cellulose recovery was around 92%, while lignin recovery was in the tune of 8–20%, indicating oxidation of a bulk quantity of lignin. The liquid fraction was found to be rich in hexose and pentose sugars, which could be directly utilized as substrate for ethanol fermentation. The WAO process was optimized by multi-objective numerical optimization with the help of MINITAB 14 suite of statistical software, and an optimum WAO condition of 185 °C, 0.5 MPa, and 15 min was predicted and experimentally validated to give 67% (w/w) cellulose content in the solid fraction, along with 89% lignin removal, and 70% hemicellulose solubilization; 13.1 gl^?1 glucose and 3.4 gl^?1 xylose were detected in the liquid fraction. The high cellulose content and negligible residual lignin in the solid fraction would greatly facilitate subsequent enzymatic hydrolysis, and result in improved ethanol yields from rice husk.     

Towards optimal selective fractionation for Nordic woody biomass using novel amine–organic superbase derived switchable ionic liquids (SILs)

Improved fractionation process conditions for wood dissolution with switchable ionic liquids (SILs) were determined. The short time, high temperature (STHT) system was introduced as a selective and efficient way to extract components from lignocellulosic material. A SIL based on monoethanol amine (MEA) and 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) formed via coupling with SO₂, was applied as a solvent in a 1:3 weight ratio with water. In essence, selective dissolution of mainly lignin was achieved by means of the aqueous SIL at 160 °C (∼6.1 bar corresponding to the vapor pressure of water) in 2 h and in a pressure vessel, for both hard- and soft-wood. About 95 wt-% of wood lignin was extracted. The dissolved components in the spent SIL were recovered by the addition of an anti-solvent whereupon over 70% of the dissolved components were recovered; the recovered fraction contained 19 wt-% hemicellulose while the rest of the material was in essence lignin. The non-dissolved, fluffy material contained ∼70 wt-% cellulose and ∼20 wt-% hemicellulose – a consistency resembling that of Kraft pulp.     

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.     

Transformation characteristics of Na and K in high alkali residual carbon during circulating fluidized bed combustion

In this study, the transformation characteristics of sodium (Na) and potassium (K) during combustion of Zhundong coal gasification fly ash in circulating fluidized bed (CFB) reactors were investigated by examining gasification fly ash (TCf) from a 0.1-MW CFB test system. Experimental results indicated that TCf was rich in Na and K, with water-soluble and insoluble Na the main Na forms. Insoluble K was the major K form in TCf, accounting for 70.6% of total K. Reactor bed temperature exerted important effects on Na release during combustion such that, as bed temperature increased, the proportions of Na in bottom and circulating ash decreased while the Na in fly ash increased. Hydrochloric acid-soluble and insoluble Na in ash accounted for a large fraction of total Na. However, insoluble K was the principle K form in ash and bed temperature showed little influence on K release and distribution in ash during combustion. With decreased flue gas temperature, the Na content in deposition ash initially increased, then decreased, and eventually stabilized, while the K content in deposition ash was basically unchanged. Agglomeration of ash particles occurred during combustion, being more apparent at higher gas temperatures, and the agglomerates were rich in Na, K, sulfur (S), chlorine (Cl), and calcium (Ca). Deposition ash Na was mainly contained NaCl and Ca/Na sulfates. The enrichment of these salts as well as of Ca sulfate in ash was the main cause of ash agglomeration and deposition.     

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.     

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.