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1.
In a previous work (Siqueira et al. 2010b) the preparation of cellulosic nanoparticles from sisal fibers using different processing routes, viz. a combination of mechanical shearing, acid and enzymatic hydrolysis was reported. It was shown that the pre-enzymatic hydrolysis treatment of bleached sisal pulp helps the preparation of well individualized rod-like nanocrystals. An amorphous polymer (natural rubber—NR) was chosen as model matrix to investigate the effect of these nanoparticles on the thermo-mechanical properties of nanocomposites. Both tensile tests and dynamic mechanical analyses showed improved stiffness for all nanocomposites. The enzymatic treatment allowed production of a huge range of cellulosic nanoparticles which provided completely different mechanical properties to NR matrix.  相似文献   

2.
This paper is an initial study of the implementation of two new enzymes, an endoglucanase and a concoction of hemicellulases and pectinases to obtain cellulosic nanoparticles. In this study, curauá and sugarcane bagasse were dewaxed and bleached prior to enzymatic action for 72 h at 50 °C, and then followed by sonication. The concentration between these two enzymes was varied, and for the concentrations and time of enzymatic treatment used, subsequent sonication was necessary for cellulose nanoparticle release. It was easier to extract cellulose nanofibers from sugarcane bagasse which resulted in nanoparticles without damage of cellulose chains. On the other hand, curauá fibers needed a higher concentration of enzymes and the nanofibers obtained displayed a decrease of crystallinity suggesting that the cellulose structure was compromized. For both fibers, cellulose nanocrystals (single crystals) and larger diameter nanofibers were attained after the sonication.  相似文献   

3.
It has been shown that some surfactants affect the hydrolysis of cellulose by cellulase. In this study, the effect of the surfactant Tween 20 on the hydrolysis of different cellulosic fibers was investigated and related to the cellulose fiber structure. It was found that this non-ionic surfactant enhanced the enzymatic saccharification of highly crystalline cellulosics such as Avicel, Tencel and cotton but not of cuprammonium rayon. The enhanced saccha-rification effected by the surfactant is attributed to inhibition of non-productive sorption of the endoglucanase of the cellulose surface which gives greater access to the cellulose chain ends by the exoglucanase. Although all three fibers lost tensile strength as a result of the enzymatic treatment, no further decrease was effected by the presence of the surfactant.  相似文献   

4.
Quartz crystal microbalance with dissipation (QCM-D) monitoring was performed to investigate the impact of steam treatment (ST) on the enzymatic hydrolysis of lignocellulosic nanofibrils (LCNFs). ST at mild temperatures up to 140 °C mainly affected the hemicellulose content of LCNFs. The hemicellulose constituents in the water-soluble fraction and the residual LCNF were quantified. The impact of changes in hemicellulose by ST on enzymatic hydrolysis was monitored by QCM-D using Acremonium cellulase as a source of multicomponent enzymes including hemicellulases. LCNFs without ST showed distinctive initial changes in frequency and energy dissipation, which differed from those of pure cellulose film, whereas these changes shifted toward typical changes of enzymatic hydrolysis of pure cellulosic films with increasing ST temperature. The QCM-D results suggested that hemicellulose located around cellulose microfibrils is rapidly decomposed, thus exposing the cellulose surface shortly after initial enzymatic hydrolysis, and then the main enzymatic hydrolysis of cellulose occurs.  相似文献   

5.
The biodegradation of cellulose involves the enzymatic action of cellulases (endoglucanases), cellobiohydrolases (exoglucanases), and β-glucosidases that act synergistically. The rate and efficiency of enzymatic hydrolysis of crystalline cellulose in vitro decline markedly with time, limiting the large-scale, cost-effective production of cellulosic biofuels. Several factors have been suggested to contribute to this phenomenon, but there is considerable disagreement regarding the relative importance of each. These earlier investigations were hampered by the inability to observe the disruption of crystalline cellulose and its subsequent hydrolysis directly. Here, we show the application of high-resolution atomic force microscopy to observe the swelling of a single crystalline cellulose fiber and its-hydrolysis in real time directly as catalyzed by a single cellulase, the industrially important cellulase 7B from Trichoderma reesei. Volume changes, the root-mean-square roughness, and rates of hydrolysis of the surfaces of single fibers were determined directly from the images acquired over time. Hydrolysis dominated the early stage of the experiment, and swelling dominated the later stage. The high-resolution images revealed that the combined action of initial hydrolysis followed by swelling exposed individual microfibrils and bundles of microfibrils, resulting in the loosening of the fiber structure and the exposure of microfibrils at the fiber surface. Both the hydrolysis and swelling were catalyzed by the native cellulase; under the same conditions, its isolated carbohydrate-binding module did not cause changes to crystalline cellulose. We anticipate that the application of our AFM-based analysis on other cellulolytic enzymes, alone and in combination, will provide significant insight into the process of cellulose biodegradation and greatly facilitate its application for the efficient and economical production of cellulosic ethanol.  相似文献   

6.
Cellulose nanocrystals were prepared from cotton fibers by a two-stage method involving ionic liquid swelling treatment followed by hydrolysis under mild acid conditions. Controlled swelling of cellulosic fibers was achieved in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) at 80 °C, while avoiding extensive dissolution of crystalline regions. Since the accessibility of the substrate was considerably enhanced, the hydrolysis occurred even under mild conditions, using up to 60 times less sulfuric acid than the traditional extraction methods based on concentrated sulfuric acid. The effects of process parameters on nanoparticle morphology, composition and stability were investigated. The individual rod-like nanocrystals, observed under field emission gun scanning electron microscopy, exhibited an average diameter of around 20 nm and a length ranging from 150 to 350 nm. According to X-ray photoelectron spectroscopy and thermogravimetric analysis, the surface of the so-extracted nanoparticles proved to be deprived of contaminating sulfate groups leading to significantly higher thermal stability with respect to cellulose nanocrystals extracted by traditional method in concentrated sulfuric acid.  相似文献   

7.
Quantification of the mechanical properties of cellulose nanomaterials is key to the development of new cellulose nanomaterial based products. Using contact resonance atomic force microscopy we measured and mapped the transverse elastic modulus of three types of cellulosic nanoparticles: tunicate cellulose nanocrystals, wood cellulose nanocrystals, and wood cellulose nanofibrils. These modulus values were calculated with different contact mechanics models exploring the effects of cellulose geometry and thickness on the interpretation of the data. While intra-particle variations in modulus are detected, we did not observe a measureable difference in modulus between the three types of cellulose particles. Improved practices and experimental complications for the characterization of cellulosic nanomaterials with atomic force microscopy are discussed.  相似文献   

8.
This paper investigates the enzymatic hydrolysis of three main allomorphic forms of microcrystalline cellulose using different cellulases, from Trichoderma reesei and from Aspergillus niger, respectively. It was demonstrated that both the morphological and crystalline structures are important parameters that have a great influence on the course of the hydrolysis process. The efficiency of the enzymatic hydrolysis of cellulosic substrates was estimated by the amounts of reducing sugar and by the yield of the reaction. Changes in the average particle sizes of the cellulose allomorphs were determined during enzymatic hydrolysis. The accumulation of soluble sugar within the supernatant was used as a measure of the biodegradation process’s efficiency, and was established by HPLC-SEC analysis. Any modifications in the supramolecular structure of the cellulosic residues resulting from the enzymatic hydrolysis were determined by X-ray diffraction. The action of each cellulase was demonstrated by a reduction in the crystalline index and the crystallite dimensions of the corresponding allomorphic forms. The crystalline structure of allomorphic forms I and II did not suffer significant modifications, while cellulose III recorded a partial return to the crystalline structure of cellulose I. The microstructures of cellulose allomorph residues were presented using optical microscopy and scanning electron microscopy.  相似文献   

9.
Sorghum is a tropical grass grown primarily in semiarid and drier parts of the world, especially areas too dry for corn. Sorghum production also leaves about 58 million tons of by-products composed mainly of cellulose, hemicellulose, and lignin. The low lignin content of some forage sorghums such as brown midrib makes them more digestible for ethanol production. Successful use of biomass for biofuel production depends on not only pretreatment methods and efficient processing conditions but also physical and chemical properties of the biomass. In this study, four varieties of forage sorghum (stems and leaves) were characterized and evaluated as feedstock for fermentable sugar production. Fourier transform infrared spectroscopy and X-ray diffraction were used to determine changes in structure and chemical composition of forage sorghum before and after pretreatment and the enzymatic hydrolysis process. Forage sorghums with a low syringyl/guaiacyl ratio in their lignin structure were easy to hydrolyze after pretreatment despite the initial lignin content. Enzymatic hydrolysis was also more effective for forage sorghums with a low crystallinity index and easily transformed crystalline cellulose to amorphous cellulose, despite initial cellulose content. Up to 72% hexose yield and 94% pentose yield were obtained using modified steam explosion with 2% sulfuric acid at 140 °C for 30 min and enzymatic hydrolysis with cellulase (15 filter per unit (FPU)/g cellulose) and β-glucosidase (50 cellobiose units (CBU)/g cellulose).  相似文献   

10.
This techno-economic study deals with the production of sugars and alcohols from cellulosic materials. It covers such key subjects as: potential raw materials; the state-of-the-art on production technologies; the economics of extant processes; and finally infers implications for developing countries from the foregoing. It is clear that a large number of cellulose-, starch-, and sugarcontaining plants can be processed to produce sugars and alcohols. Sugar-containing plants such as sugarcane, sweet sorghum, and nipa palm are the best candidates for the high-yield production of alcohol fuel. Likewise, the starch-containing crops such as cassava, sweet potatoes, yams, taro, and tannia are good candidates, but require an additional step to break down starch to sugar. However, the emphasis of this report is on the major part of biomass containing cellulose and which, therefore, needs special treatment before it can be used to produce glucose and alcohols. To utilize cellulosic containing raw materials the following steps are necessary:
  1. Growth, harvest, and delivery of raw materials to processing plants; or, alternatively, the collection and delivery of cellulosic “waste” products.
  2. Pretreatment or conversion of the raw material by mechanical, physical, chemical, or enzymatic methods to break down the cellulose to sugars and to modify or remove unwanted side-products, usually lignin and hemicellulose.
  3. Recovery and purification of sugars from reaction mixture.
  4. Fermentation of sugars to alcohol and purification by distillation.
  5. Treatment of process residues to reduce pollution and to recover potentially valuable side-products.
From the considerable research and development work carried out in all areas of pretreatment, it appears acid and enzymatic hydrolysis processes hold the most promise for developing countries. Though acid hydrolysis technology is more advanced, greater ultimate potential is seen in the enzymatic hydrolysis, which is, therefore, recommended for developing countries. The economics of producing alcohol from cellulosic materials is at this time not favorable. Nevertheless, it is recommended that further research and development be undertaken in this area in order to accomplish one or more commercially attractive processes for producing alcohol from fermenting cellulose. If this was accomplished, the developing countries could gain in the following manner:
  • ? Increase self-sufficiency since alcohols can to a great part substitute for petroleum fuels.
  • ? Achieve a better balance of trade.
  • ? Be able to increase employment, especially in rural areas.
  • ? Achieve a higher level of technical competence in biotechnology and related areas.
  • ? Be in a position to expand chemical industries.
  • ? Establish an improved agricultural base by being able to utilize alternative crops and by being able to use what was previously termed agricultural wastes.
  •   相似文献   

    11.
    Various cellulosic substrates were examined for bound water content by differential thermal analysis (DTA) and thermogravimetry (TG). Samples were heated in the range of 30-100 degrees C at a rate of 3 degrees C/min. DTA vaporization curves for different cellulose samples indicated that the bound water (Wf) was vaporized at higher temperature than free water (Wf) at the surface. Weight loss was observed in two stages, corresponding to Wf and Wb in TG curves. The bound water content was dependent on the degree of crystallinity of cellulose. Among different cellulosic substrates, Walseth cellulose showed the highest bound water content, and it also was found to be the least crystalline. The alkaline-active, alkali-stable cellulase was obtained from the alkalotolerant Fusarium sp. The substrate specificity and viscometric characteristics confirmed the enzyme to be an endoglucanase. The Wb content of Walseth cellulose was lowered during the enzymatic hydrolysis. The possible application of bound water analysis in understanding the hydrolysis of cellulosic substrates of different crystallinity is discussed.  相似文献   

    12.
    The Department of Energy’s Office of the Biomass Program has set goals of making ethanol cost competitive by 2012 and replacing 30% of 2004 transportation supply with biofuels by 2030. Both goals require improvements in conversions of cellulosic biomass to sugars as well as improvements in fermentation rates and yields. Current best pretreatment processes are reasonably efficient at making the cellulose/hemicellulose/lignin matrix amenable to enzymatic hydrolysis and fermentation, but they release a number of toxic compounds into the hydrolysate which inhibit the growth and ethanol productivity of fermentation organisms. Conditioning methods designed to reduce the toxicity of hydrolysates are effective, but add to process costs and tend to reduce sugar yields, thus adding significantly to the final cost of production. Reducing the cost of cellulosic ethanol production will likely require enhanced understanding of the source and mode of action of hydrolysate toxic compounds, the means by which some organisms resist the actions of these compounds, and the methodology and mechanisms for conditioning hydrolysate to reduce toxicity. This review will provide an update on the state of knowledge in these areas and can provide insights useful for the crafting of hypotheses for improvements in pretreatment, conditioning, and fermentation organisms.  相似文献   

    13.
    Common reed (Phragmites australis) is often recognized as a promising source of renewable energy. However, it is among the least characterized crops from the bioethanol perspective. Although one third of reed dry matter is cellulose, without pretreatment, it resists enzymatic hydrolysis like lignocelluloses usually do. In the present study, wet oxidation was investigated as the pretreatment method to enhance the enzymatic digestibility of reed cellulose to soluble sugars and thus improve the convertibility of reed to ethanol. The most effective treatment increased the digestibility of reed cellulose by cellulases more than three times compared to the untreated control. During this wet oxidation, 51.7% of the hemicellulose and 58.3% of the lignin were solubilized, whereas 87.1% of the cellulose remained in the solids. After enzymatic hydrolysis of pretreated fibers from the same treatment, the conversion of cellulose to glucose was 82.4%. Simultaneous saccharification and fermentation of pretreated solids resulted in a final ethanol concentration as high as 8.7 g/L, yielding 73% of the theoretical.  相似文献   

    14.
    Enzymatic saccharification of sisal cellulosic pulp has been investigated. Brazil leads global production of lignocellulosic sisal fiber, which has high cellulose content, an important property for producing glucose via saccharification. Hence, sisal pulp can be a good alternative for use in biorefineries. Prior to enzymatic hydrolysis, the starting pulp [85 ± 2% α-cellulose, 15 ± 2% hemicelluloses, 1.2 ± 2% insoluble lignin, viscometric average molar mass (MMvis) 19,357 ± 590 g mol?1, crystallinity index (CI) 74%] was pretreated with alkaline aqueous solution (mercerization, 20 g of pulp L?1, 20% NaOH, 50 °C). The changes in the properties of the cellulosic pulp during this pretreatment were analyzed [α-cellulose content, MMvis, CI, pulp fiber dimensions, and scanning electron microscopy (SEM)]. The unmercerized and mercerized (97.4 ± 2% α-cellulose, 2.6 ± 2% hemicelluloses, 0.3 ± 0.1% insoluble lignin, MMvis 94,618 ± 300 g mol?1, CI 68%) pulps were subjected to enzymatic hydrolysis (48 h, commercial cellulase enzymes, 0.5 mL g?1 pulp); during the reactions, aliquots consisting of unreacted pulp and liquor were withdrawn from the medium at certain times and characterized (unreacted pulp: MMvis, CI, fiber dimensions, SEM; liquor: high-performance liquid chromatography). The changes in pulp properties observed during mercerization facilitated access of enzymes to cellulose chains, and the yield of the hydrolysis reaction increased from 50.2 (unmercerized pulp) to 89.0% (mercerized pulp). These initial results for enzymatic hydrolysis of sisal pulp indicate that it represents a good alternative biomass for bioethanol production.  相似文献   

    15.
    A combination of Douglas fir heartwood and sapwood chips were steam pretreated under three conditions as measured by the Severity Factor (log Ro), which incorporated the time, temperature/pressure of pretreatment. By adjusting the steam pretreatment conditions, it was hoped to recover the majority of the hemicellulose component as monomers in the water-soluble stream, while providing a cellulosic-rich, water-insoluble fraction that could be readily hydrolyzed by cellulases. These three conditions were chosen to represent either high hemicellulose sugar recovery (low severity [L], log Ro=3.08), high-enzyme hydrolyzability of the cellulosic component (high severity [H], log Ro=4.21), and a compromise between the two conditions (medium severity [M], log Ro=3.45). The medium-severity pretreatment conditions (195°C, 4.5 min, 4.5% SO2 logRo=3.45) gave the best compromise in terms of relatively high hemicellulose recovery after stream pretreatment and the subsequent efficiency of enzymatic hydrolysis of the water-insoluble cellulosic fraction. The percent recovery of the original hemicellulose in the water-soluble fraction dropped significantly when the severity was increased (L-76.8%, M-64.7%, and H-37.5%). However, the ease of enzymatic hydrolysis of the cellulose-rich, water-insoluble fraction increased with increasing severity (L-24%, M-86.6%, and H-97.9%). Although more severe pretreatment conditions provided optimum hydrolysis of the cellulosic component, less severe conditions resulted in better recovery of the combined hemicellulose and cellulosic components.  相似文献   

    16.
    Summary: Three different cellulosic substrata, like microcrystalline cellulose, cotton cellulose and spruce dissolving pulp, were chosen for biodegradation. The kinetics of the enzymatic hydrolysis of these celluloses by Trichoderma reesei, has been investigated. The experiments proved the fact that both the morphological structure and the crystalline one are crucial to the process and the ratio of the reactions. In addition, in order to obtain the most accessible cellulose substratum it was studied the biodegradation of cellulose allomorphs of spruce dissolving pulp. The insoluble cellulose fraction remaining after enzymatic hydrolysis was examined by X-ray diffraction method and it was established the degree of crystallinity and the average crystallite size. The enzymatic degradation is also proved by the decrease in the degree of polymerization of hydrolyzed samples.  相似文献   

    17.
    In this study, ultrasound-assisted alkaline pretreatment is developed to evaluate the morphological and structural changes that occur during pretreatment of cellulose, and its effect on glucose production via enzymatic hydrolysis. The pretreated samples were characterized using scanning electron microscopy, infrared spectroscopy, and X-ray diffraction to understand the change in surface morphology, crystallinity and the fraction of cellulose Iβ and cellulose II. The combined pretreatment led to a great disruption of cellulose particles along with the formation of large pores and partial fibrillation. The effects of ultrasound irradiation time (2, 4 h), NaOH concentration (1–10 wt%), initial particle size (20–180 μm) and initial degree of polymerization (DP) of cellulose on structural changes and glucose yields were evaluated. The alkaline ultrasonic pretreatment resulted in a significant decrease in particle size of cellulose, besides significantly reducing the treatment time and NaOH concentration required to achieve a low crystallinity of cellulose. More than 2.5 times improvement in glucose yield was observed with 10 wt% NaOH and 4 h of sonication, compared to untreated samples. The glucose yields increased with increase in initial particle size of cellulose, while DP had no effect on glucose yields. The glucose yields exhibited an increasing tendency with increase in cellulose II fraction as a result of combined pretreatment.  相似文献   

    18.
    This study investigates the potential of wood wastes, specifically post-consumer fiberboards, as a new source for cellulose nanocrystals (CNC). This underused resource has currently no commercially viable way to recycle it and so the volumes of fiberboard waste are growing rapidly. A sequential chemical fractionation was used to separate the three main constituents of wood, namely cellulose, hemicelluloses and lignin, and the non-wood components present in fiberboards, such as resins and finishes (e.g. varnishes, paints, plastics, laminates, etc.). Most of the non-cellulosic components and non-wood elements were removed by an alkali treatment followed by bleaching, resulting in a cellulosic fraction which is suitable for the further isolation of CNC by an acid hydrolysis step. The intermediate and final products were characterized by chemical composition, microscopic, spectroscopic and X-ray diffraction methods. The CNC obtained from wood waste are totally devoid of traces of contaminants and possess comparable characteristics and quality to those extracted from virgin wood fibers. The results indicate that fiberboard wastes can be used as promising alternative source for nanocelluloses production.  相似文献   

    19.
    The microstructure and chemical composition of alfa (Stipa tenacissima) were investigated. The polysaccharide and lignin contents were around 70 and 20 wt%, respectively. From the bleached and delignified fibers, two types of nanosized cellulosic particles were extracted, namely cellulose nanocrystals and microfibrillated cellulose (MFC). The former correspond typically to the elementary crystallite units of the cellulose fibers, with a rod-like morphology and an aspect ratio of about 20. The latter, mechanically disintegrated from oxidized bleached fibres, presents an entangled fibrillar structure with widths in the range 5-20 nm. The reinforcing potential of the ensuing nanoparticles was investigated by casting a mixture of acrylic latex and aqueous dispersion of cellulose nanoparticles. Thermo-mechanical analysis revealed a huge enhancement of the stiffness above the glass transition of the matrix. Significant differences in the mechanical reinforcing capability of the nanoparticles were reported.  相似文献   

    20.
    A process for converting lignocellulosic biomass to ethanol hydrolyzes the hemicellulosic fraction to soluble sugars (i.e., pretreatment), followed by acid- or enzyme-catalyzed hydrolysis of the cellulosic fraction. Enzymatic hydrolysis may be improved by using an alkali to extract a fraction of the lignin from the pretreated material. The removal of the lignin may increase the accessibility of the cellulose to enzymatic attack, and thus improve overall economics of the process, if the alkali-treated material can still be effectively converted to ethanol. Pretreated Douglas fir produced by a sulfuric-acid-catalyzed steam explosion was treated with NaOH, NH4OH, and lime to extract some of the lignin. The treated material, along with an untreated control sample, was tested by an enzymatic-digestion procedure, and converted to ethanol by simultaneous saccharification and fermentation using a glucose-fermenting yeast. NaOH was most effective at removing lignin (removed 29%), followed by NH4OH and lime. However, the susceptibility of the treated material to enzymatic digestion was lower than the control and decreased with increasing lignin removal. Ethanol production was similar for the control and NaOH-treated material, and lower for NH4OH- and lime-treated material.  相似文献   

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