Extraction and structural characterization of cellulose from milkweed floss

The aim of this study was to investigate the utilization of milkweed fruit floss residues as a source for the isolation of cellulose. Cellulose was extracted by acidified sodium chlorite and sodium hydroxide treatments. Characterization of the pristine milkweed floss and extracted cellulose was performed by chemical composition analysis, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The extracted cellulose had mainly α-cellulose as the other components hemicellulose and lignin were significantly removed during cellulose extraction process. The FTIR spectra also indicated that the chemical treatments extensively removed hemicellulose and lignin from the pristine milkweed floss. SEM technique was used to investigate the surface morphology of the pristine milkweed floss and extracted cellulose. The intensity of the crystalline peak in the X-ray diffractograms of the extracted cellulose was higher than that of pristine milkweed. Further, the XRD results indicated a structural transformation of cellulose I (pristine milkweed) to cellulose II (extracted cellulose) because of the chemical treatments. The extracted cellulose, which is a high biomass, had better thermal stability than the pristine milkweed floss owing to removal of non-cellulosic components.     

Dissolving grade eco-clean cellulose pulps by integrated fractionation of cardoon (Cynara cardunculus L.) stalk biomass

A biorefinery scheme with separate processing of the two main carbohydrate streams (cellulose and hemicellulose-derived) was employed to the energy crop cardoon (Cynara cardunculus L.) to fractionate the whole stalk material. A high quality xylose-enriched substrate was obtained after selective one-step dilute sulfuric acid hydrolysis of hemicelluloses, yielding 18.1 g of xylose per 100 g of dry biomass. The xylan-free solid residue was delignified by sulfur-free organosolv pulping to produce dissolving grade pulps having 93.8% of α-cellulose (33.1 g per 100 g dry initial biomass) and 79.5% degree of crystallinity. About 76% of crop lignin (13.8 g per 100 g dry initial biomass) was recovered from the spent pulping liquor as a high purity reactive precipitated organosolv lignin. Response surface methodology was used for statistical modeling and optimization of the applied separation processes. The central composite rotatable design was applied to assess the effects of the principal technological parameters on the main reaction outputs.     

Innovative and intensified technology for the biological pretreatment of agro waste for ethanol production

Lignocellulosic biomass is an abundant, renewable resource, but the structural and chemical complexity of biomass acts as a hindrance in its effective utilization for cellulosic ethanol production. Hence, effective pretreatment is always necessary to remove the surrounding matrix of lignin prior to the enzymatic hydrolysis. Pretreatment of rice straw by Pleurotus florida was found to be effective and resulted in 49% lignin degradation, whereas fungus along with grape leaves resulted in 99% lignin degradation. This method not only explores a pathway for utilizing the solid agro waste but also results in a value-added product of edible mushrooms that has proved to be the best pretreatment technology for ethanol production. FTIR and SEM analysis confirmed the structural transformation taking place during the pretreatment. The components of grape leaves were also analyzed using GC-MS.     

Structural Variation of Bamboo Lignin before and after Ethanol Organosolv Pretreatment

In order to make better use of lignocellulosic biomass for the production of renewable fuels and chemicals, it is necessary to disrupt its recalcitrant structure through pretreatment. Specifically, organosolv pretreatment is a feasible method. The main advantage of this method compared to other lignocellulosic pretreatment technologies is the extraction of high-quality lignin for the production of value-added products. In this study, bamboo was treated in a batch reactor with 70% ethanol at 180 °C for 2 h. Lignin fractions were isolated from the hydrolysate by centrifugation and then precipitated as ethanol organosolv lignin. Two types of milled wood lignins (MWLs) were isolated from the raw bamboo and the organosolv pretreated residue separately. After the pretreatment, a decrease of lignin (preferentially guaiacyl unit), hemicelluloses and less ordered cellulose was detected in the bamboo material. It was confirmed that the bamboo MWL is of HGS type (p-hydroxyphenyl (H), vanillin (G), syringaldehyde (S)) associated with a considerable amount of p-coumarate and ferulic esters of lignin. The ethanol organosolv treatment was shown to remove significant amounts of lignin and hemicelluloses without strongly affecting lignin primary structure and its lignin functional groups.     

Ozone treatment for improving the solubility of cellulose extracted from palm fiber

We investigated effects of ozone treatment on solubility of cellulose and chemical composition in cellulose extracted from palm fiber. The initial holocellulose, α-cellulose, and lignin contents of the extracted cellulose were 88.0, 81.9, and 8.75%, respectively. The extracted cellulose was treated with ozone and NaOH solution. Ozone treatment for 5 hr at 40°C using 3% citric acid decreased the lignin content from 8.75 to 2.71%. Under these conditions, the degree of polymerization (DP) of the cellulose decreased to 29 from 160 and the carboxyl content increased to 2.05 mmol/g. When the solid phase was treated with NaOH after ozone treatment, the mass of the solid phase decreased as the ozone treatment time increased. The lowest mass was 0.43 g. Additionally, the mass of cellulose regenerated from the liquid phase increased with increasing treatment time. The highest mass of regenerated cellulose was 0.54 g. The masses of the solid phase and regenerated cellulose obtained without ozone treatment under the same conditions were 0.76 and 0.18 g, respectively. These results suggest that ozone treatment improves the solubility of cellulose by converting hydroxyl groups in the cellulose to carboxyl groups and reducing the DP.     

汽爆玉米秸秆羧甲基纤维素的制备

秸秆是自然界中资源丰富的天然木质纤维素原料, 本研究以秸秆为反应原料,采用无污染蒸汽爆破技术活化预处理,然后进行羧甲基化反应,通过反应产物理化性质的不同实现秸秆的组分分离并制备出高附加值的羧甲基纤维素。实验结果表明：制备羧甲基纤维素的最优条件为液固比（ml∶g）18∶1,氢氧化钠∶氯乙酸钠(摩尔比)为4∶3,H₂O/底物（ml∶g）为1∶2,75℃反应2 h。在优化的反应条件下,从羧甲基化产物中可分离得到40.70%的羧甲基纤维素,其取代度可达0.91, 而且具有低黏的性质,并利用红外图谱和¹H NMR进行了分析表征;同时,还可从羧甲基化产物中分离出木质素组分,可进一步拓展其在工业方面的用途。相对于目前工业上普遍采用的α-纤维素含量较高的棉浆和木浆等反应原料,不仅原料和预处理成本大为下降, 工艺流程更为简单,而且还实现了秸秆的组分分离与全利用。     

Simulation of Hesperaloe funifera diethanolamine pulping by polynomial and neural fuzzy models

Some alternative, unconventional plant raw materials can provide large amounts of biomass for producing quality cellulose pulp. One such raw material can be Hesperaloe funifera plants, that grows with little water requirements, and which fibre morphology is especially suitable for making cellulose pulp.It uses a factorial design of experiments applied to pulping with diethanolamine and apply polynomial and neural fuzzy models in order to predict the properties of pulp (contents of holocellulose, α-cellulose and lignin, yield, viscosity, Kappa number and beating grade) and paper sheets (tensile index, stretch, burst index, tear index and brightness) according to the operating variables: temperature (155-185 °C), time (30-90 min) and diethanolamine concentration (50-80%).The polynomial and neural fuzzy models tested reproduce the experimental results with errors less than 8-10% for all dependent variables, with the exception of tear index which only reproduces 50% of results with errors less than 10%.     

Characteristics of hemicellulose,cellulose and lignin pyrolysis

The pyrolysis characteristics of three main components (hemicellulose, cellulose and lignin) of biomass were investigated using, respectively, a thermogravimetric analyzer (TGA) with differential scanning calorimetry (DSC) detector and a pack bed. The releasing of main gas products from biomass pyrolysis in TGA was on-line measured using Fourier transform infrared (FTIR) spectroscopy. In thermal analysis, the pyrolysis of hemicellulose and cellulose occurred quickly, with the weight loss of hemicellulose mainly happened at 220–315 °C and that of cellulose at 315–400 °C. However, lignin was more difficult to decompose, as its weight loss happened in a wide temperature range (from 160 to 900 °C) and the generated solid residue was very high (∼40 wt.%). From the viewpoint of energy consumption in the course of pyrolysis, cellulose behaved differently from hemicellulose and lignin; the pyrolysis of the former was endothermic while that of the latter was exothermic. The main gas products from pyrolyzing the three components were similar, including CO₂, CO, CH₄ and some organics. The releasing behaviors of H₂ and the total gas yield were measured using Micro-GC when pyrolyzing the three components in a packed bed. It was observed that hemicellulose had higher CO₂ yield, cellulose generated higher CO yield, and lignin owned higher H₂ and CH₄ yield. A better understanding to the gas products releasing from biomass pyrolysis could be achieved based on this in-depth investigation on three main biomass components.     

基于离子液体的生物质组分分离研究进展

生物质资源的开发利用是解决资源危机和能源危机的重要途径,但传统的生物质组分分离工艺效率较低且污染严重,极大地制约了生物质资源的高值化利用。作为一类新型溶剂,离子液体可以溶解纤维素、木质素和天然生物质材料,为生物质的组分分离及加工转化提供了有力的工具。本文简述了离子液体在生物质组分分离中的应用,包括离子液体作为溶剂直接从木质纤维素类生物质中提取分离纤维素和木质素,以及在离子液体介质中通过化学反应降解生物质来分离主要组分的方法。从离子液体优选、反应路径设计、生物质预处理、溶解条件和再生剂等方面分析了生物质组分分离工艺。成本高、效率低且容易引起二次污染是阻碍离子液体用于生物质组分分离的主要因素。为了提高生物质组分分离的经济性和绿色性,今后应着力设计低成本、低黏度、热稳定性强和低毒的离子液体,研发绿色高效的生物质组分分离工艺和离子液体再生方法。     

木质纤维原料组分分离的研究

从木质纤维原料预处理对微生物转化的必要性和回收利用半纤维素、木质素意义两个方面分析了木质纤维原料组分分离的必要性。木质纤维原料组分分离意味着木质纤维原料的精制,不是把木质纤维原料仅作为纤维素单一资源看待,而是把它视为一种多组分物料,将木质纤维原料精制成为具有一定纯度的各种组分,并分别加工成有价值的产品,这也是生物量全利用对于木质纤维原料预处理提出的新要求,赋予新的哲理思想。根据生物量全利用的要求,提出了木质纤维原料组分分离技术的新定性评价标准。根据利用汽爆和乙醇萃取法联合对麦草组分分离的研究结果,可提出一条经济可行的麦草组分分离的工艺过程,半纤维素和木质素回收率分别达到了80%和75%,纤维素酶解率达90%以上。     

Chemicals Generated During Oxygen-Organosolv Pulping of Wood

In this paper, we have characterized the black liquors from oxygen-organosolv pulping of Eucalyptus globulus wood in ethanol/water solutions (50:50, V/V) and acetic acid/water solutions (80:20, V/V).

After pulp separation, the organic solvent has been distilled and recycled; the precipitated lignin has been recovered by filtration. The degradation products in solution have been easily separated by simple extraction techniques. Five main groups of compounds have been isolated: solid lignin (11–12% o.d.w.), sugars (10–17% o.d.w.), aliphatic acids (12,5%), aromatic acids (2% o.d.w.) and low molecular weight phenols (1% o.d.w.). Most of these compounds were identified by HPLC and GC. Solid lignins have been analyzed by FTIR and ¹³C NMR spectroscopy.

It has been çoncluded that oxygen-organosolv pulping process can be a new and interesting way for pulp preparation with little pollution and possibility of total biomass recovery; alternatively, it can be used for the fractionation and valorization of the components of lignocellulosics, including agriculture residues.     

Utilization of lignocellulosic waste for ethanol production : Enzymatic digestibility and fermentation of pretreated shea tree sawdust

Enzymatic hydrolysis and fermentation methods were evaluated on alkaline peroxide pretreated shea tree sawdust conversion to ethanol. Optimum pretreatment conditions of 120 °C reaction temperature, 30 min reaction time, and 20 mL L^?1 of water hydrogen peroxide concentration (1%(v/v)H₂O₂) solubilized 679 g kg^?1 of hemicellulose and 172 g kg^?1 of lignin. 617 g kg^?1 cellulose was retained in the solid fraction. The maximum yield of reducing sugar with optimized enzyme loadings by two enzyme preparations (cellulase and β-glucosidase) was 165 g kg^?1 of dry biomass. The ethanol yield was 7.35 g L^?1 after 72 h incubation period under the following conditions: 2% cellulose loading, enzyme concentration was 25 FPU (g cellulose)^?1 loading, yeast inoculums was 10% (v/v), 32 oC, and pH 4.8. The pretreatments gave information about the hindrances caused by lignin presence in lignocellulosic materials and that hemicelluloses are better hydrolyzed than lignin, thereby enhancing enzymatic digestibility of the sawdust material.     

Sustainable Production of Levulinic Acid from the Cellulosic Fraction of Pinus Pinaster Wood: Operation in Aqueous Media Under Microwave Irradiation

The fractionation of the structural components of lignocellulosic biomass (cellulose, hemicelluloses, and lignin) and the separate utilization of the resulting fractions for specific purposes, according to the philosophy of biorefineries, enables the development of sustainable processes for biomass utilization. In this work, Pinus pinaster wood was subjected to aqueous processing to remove water-soluble extractives and hemicelluloses, and the resulting solid was subjected to pulping with HCl-catalyzed acetic acid solutions (Acetosolv method). The pulp was employed as a substrate for levulinic acid manufacture by reaction in acidic media under microwave irradiation. The effects of the major operational variables (temperature, reaction time, and acid concentration) on the levulinic acid yield were established by statistical modeling of experimental data. Operating under the best reaction conditions (at 191.2°C for 18.9 min in aqueous media containing 1.10% HCl), the levulinic acid yield accounted for 56.4% of the stoichiometric value.     

Application of optical microscopy as a screening technique for cellulose and lignin solvent systems

Rapid and facile screening techniques to determine the effectiveness of solvents for cellulose or biomass dissolution can advance biomass processing research. Here, we report the use of a simple optical microscopy method to screen potential cellulose and lignin solvents. The described methodology was used to screen the dissolution of cellulose and lignin in two imidazolium‐based ionic liquids (ILs), two phosphonium‐based ILs, as well as a N,N‐dimethylacetamide/lithium chloride (DMAc/LiCl) solution in less time than other techniques. The imidazolium‐based ILs and the DMAc/LiCl were found to dissolve both cellulose and lignin. Also, it was observed that one of the phosphonium‐based ILs dissolved lignin and not cellulose, demonstrating a potential for biomass fractionation applications. © 2011 Canadian Society for Chemical Engineering     

Comparative studies of oil compositions produced from sawdust,rice husk,lignin and cellulose by hydrothermal treatment

The objective of this study is to investigate the distribution of products, i.e. liquid, gas and solid from wood (sawdust) and non-wood biomass (rice husk), and major biomass components, i.e. lignin, cellulose produced by hydrothermal treatment (280 °C for 15 min) and analysis of liquid hydrocarbons (oils) for the differences in the hydrocarbon composition with respect to feed material. Cellulose showed the highest conversion among the four samples investigated in the present study. Sawdust and rice husk has almost similar conversions. Liquid products were recovered with various solvents (ether, acetone, and ethyl acetate) and analyzed by GC–MS. The oil (ether extract) from the hydrothermal treatment of cellulose consisted of furan derivatives whereas lignin-derived oil contained phenolic compounds. The compositions of oils (ether extract) from sawdust and rice husk contained both phenolic compounds and furans, however phenolic compounds were dominant. Rice husk derived oil consists of more benzenediols than sawdust derived oil. The volatility distribution of oxygenated hydrocarbons were carried out by C-NP gram and it showed that the majority of oxygenated hydrocarbons from sawdust, rice husk and lignin were distributed at n-C₁₁, whereas they were distributed at n-C₈ and n-C₁₀ in cellulose-derived oil. The gaseous products were carbon dioxide, carbon monoxide, methane in sawdust, rice husk, lignin and cellulose. In addition to this, ethylene, ethane and propane were observed for sawdust, rice husk and lignin. The major gas product was carbon dioxide for all samples.     

Elemental chlorine-free bleaching halfa pulp

Halfa, also known as Stipa tenacissima, is grown in North Africa and south Spain. Due to its short fiber length, paper of halfa remains bulk and takes the block letters well. In this study halfa was evaluated for bleached pulp production. Two cellulose pulps with different chemical compositions were pulped by conventional Kraft process: one from the original halfa material and the other from halfa pretreated by diluted acid. The pulp produced from halfa pretreated by diluted acid was bleached by elemental chlorine-free sequences, DEPD and DEDP. Yield, Kappa number, brightness and α-cellulose contents of bleached and unbleached pulps were evaluated. The results show that during the chemical pulping process, treated halfa was easily cooked than that original halfa. Treated halfa pulp also showed very good bleaching, showing brightness level of 94.8% ISO, yield 93.6% and α-cellulose content 96.8% with DEDP bleaching sequence compared to 83.2% ISO brightness level, 92.8% yield and 95.1% α-cellulose content for bleached pulp with DEPD bleaching sequence. On the other hand, the physicomechanical properties of pulp were not notably reduced by the bleaching process. Breaking length, tear and burst index of paper sheets were acceptable. Therefore, this halfa material could be a worthwhile choice for cellulosic fiber supply.     

麦草碱木素分级和结构特性的研究

用酸沉淀法对山东兖州市造纸厂麦草碱木素按分子量进行沉淀分级．共分为3个级分。探讨了影响分级效果的因素，确定了分级的优化条件。各级分经纯化后分析其结构特性。发现，随着体系PH值的降低，沉淀出的各级分的分子量逐渐降低。碱木素中碳水化合物含量降低，且主要分布于小分子级分中．分级后，碱木素分子量的分布有不同程度的变窄，但各级分的分子量均有相当程度的重叠．硝基苯氧化结果表明，在高分子量级分中，木素的缩会程度较为严重。该方法用于碱木素的简易分级是可行的．     

Purification of Biorefinery Lignin with Alcohols

After hydrothermal pretreatment and enzymatic hydrolysis of wheat straw, a slurry rich in lignin but with a high content of inorganic substances, especially silica, and residual carbohydrates is produced. This slurry was used to develop an ethanol organosolv separation method to produce silica-free lignin fractions. The addition of para toluene sulphonic acid (PTSA) and the use of two alternative long-chain alcohols, oleyl alcohol or nonylphenol, were tested. In every reaction, two lignin fractions were produced and their molecular size and elemental composition were characterized. The yield of each fraction and the change in MWD were studied as a function of temperature and solid to liquid ratio. At 100, 150, and 200°C and with the use of PTSA, high-purity lignin fractions were obtained. After lignin fractionation with nonylphenol, a liquid silica-free product with high lignin content was obtained in yields between 17 and 72%.     

Extraction of cellulose nanocrystals and fabrication of high alumina refractory bricks using pencil chips as a waste biomass source

Extraction of “green” cellulose nanocrystals (CNCs) from waste biomass is a sustainable strategy for high valued valorization in the view of socio-economic and environmental issues. Herein, for the first time, waste pencil chips (PC) as a potential source of cellulose, were used for the extraction of CNCs. CNCs were successfully extracted from PC wastes using alkali and bleaching chemical treatments to remove hemicellulose and lignin followed by acid hydrolysis using concentrated sulfuric acid. The products after each step were characterized in terms of crystallinity, chemical structures, thermal properties, and morphologies. The XRD results showed that the crystalline index increased about 16% from PC (75%) to CNCs (91%). The FTIR analysis confirmed the removal of the hemicellulose and lignin from PC after alkali and bleaching treatments. The TGA analysis showed that the thermal stability of the CNCs is affected mainly by the dehydration reaction caused by sulfate groups. The SEM and FE-SEM images showed that after chemical treatments, defibrillation of fibers occurs and CNCs have a needle/rod like structure. Also, the specific surface aera was greatly increased from 0.495 for PC to 486.430 m²/g for CNCs. Herein, for the first time, lignin-containing cellulose extracted from PC was replaced with sawdust (SRB) in the production of alumina refractory bricks (RBs), as a pore former/binder. Interestingly, the prepared RBs (PC–NaOH/RB) had a greater amount of alumina (83%) and a lower density (0.75 g/cm³) than SRB. The classification temperature increased from 1650 for SRB to 1717 °C for PC-NaOH/RB.     

Pretreatment of <Emphasis Type="Italic">Helianthus tuberosus</Emphasis> residue by flow-through process for production of fermentable sugar

The pretreatment of Helianthus tuberosus residue was studied for fermentable sugar production. The pretreatment was performed by varying the temperature, type of chemical solution, and concentration. Two different catalytic pretreatments using sulfuric acid and aqueous ammonia were operated and compared in a flow-through column reactor system. The flow-through process was required to increase the sugar production yield of biomass. To selectively remove the lignin of biomass and achieve fractionation of hemicellulose in the liquid phase to produce pentose, the flow-through process could be controlled by the pretreatment conditions. Furthermore, the remaining solid underwent enzymatic hydrolysis for hexose production. The mass balances of biomass pretreated with aqueous ammonia and sulfuric acid solution were compared in terms of production of fermentable sugars. The glucose recovery compared to the initial biomass was 71.2% in the pretreatment using aqueous ammonia at 170 °C, and pretreatment using sulfuric acid solution at 150 °C was 52.3%.