Brewer’s spent grain components (cellulose, hemicellulose and lignin) were fractionated in a two-step chemical pretreatment
process using dilute sulfuric acid and sodium hydroxide solutions. The cellulose pulp produced was hydrolyzed with a cellulolytic
complex, Celluclast 1.5 L, at 45 °C to convert the cellulose into glucose. Several conditions were examined: agitation speed
(100, 150 and 200 rpm), enzyme loading (5, 25 and 45 FPU/g substrate), and substrate concentration (2, 5 and 8% w/v), according
to a 23 full factorial design aiming to maximize the glucose yield. The obtained results were interpreted by analysis of variance
and response surface methodology. The optimal conditions for enzymatic hydrolysis of brewer’s spent grain were identified
as 100 rpm, 45 FPU/g and 2% w/v substrate. Under these conditions, a glucose yield of 93.1% and a cellulose conversion (into
glucose and cellobiose) of 99.4% was achieved. The easiness of glucose release from BSG makes this substrate a raw material
with great potential to be used in bioconversion processes. 相似文献
Cellulose whiskers were obtained by means of sulfuric acid hydrolysis of curauá fibers. Before hydrolysis, the natural fibers were treated with an alkaline solution to remove the non-cellulosic content. Fiber degradation evolution and cellulose whisker formation were analyzed by structural and morphological analysis. The original fiber structure underwent a fragmentation mechanism after being exposed for 3?min to sulfuric acid. Cellulose whiskers were lixiviated from the fiber surface after 10?min of hydrolysis, developing two scenarios: one where the whiskers became unattached from the original fiber, and the other which remained attached. The cellulose whiskers presented a needle-like geometry with an approximate diameter of 11?nm and average length of 185?nm, after 30?min of acid hydrolysis. Based on microscopic characterization, a schematic representation of the morphological evolution of the cellulose fibers submitted to acid hydrolysis is proposed. 相似文献
Dried and never-dried chemical pulps were subjected to strong sulfuric acid hydrolysis and the dimensions of the resulting
cellulose nanocrystals (CNCs) were characterized by AFM image analysis. Although the average length of CNCs was fairly similar
in all samples (55–65 nm), the length distribution histograms revealed that a higher number of longer crystals and a lower
number of shorter crystals were present in the CNC suspensions prepared from never-dried pulps. The distinction was hypothetically
ascribed to tensions building in individual cellulose microfibrils upon drying, resulting in irreversible supramolecular changes
in the amorphous regions. The amorphous regions shaped by tensions were deemed as more susceptible to acid hydrolysis. 相似文献
Microcrystalline cellulose (MCC) particles are mostly prepared by acid hydrolysis of various agro sources. Acid hydrolysis is usually carried out with high concentration (64 wt%) of sulfuric acid. Here, an attempt has been made to optimize lower acid concentrations which can effectively produce MCC particles. In this work, different concentrations of sulfuric acid (20, 30, 35, 40, 47 and 64 wt%) have been used to prepare MCC particles, which have been characterized by XRD, particle size analysis, scanning electron microscopy, transmission electron microscopy, nanoindentation and thermogravimetric analysis. MCC prepared with 35 and 47% sulfuric acid (MCC 35 and MCC 47) had finest particle size and fibrils were produced in the range of 15–25 nm. MCC 20 showed wide particle size distribution, indicating low breakdown of the cellulose chains. The energy absorption behavior and mechanical properties of the MCC pellets were determined by nanoindentation test for the first time. MCC 35 pellets exhibited lowest modulus and hardness. 相似文献
The aim of this work was to compare the effects of microcrystalline cellulose (MCC) and cellulose nanocrystals (CNC) addition on the properties of PLA matrix. The CNC were obtained by acid hydrolysis of the MCC. Both MCC and CNC were separately incorporated in PLA at ratios of 3, 5 and 7 wt%. In some compositions, organophilic silica (R972) was added to improve the cellulose-matrix compatibility. The properties of the materials were evaluated by FTIR, XRD, NMR and mechanical tests. Functional groups and crystalline structure of MCC and CNC were determined by FTIR and XRD, respectively. NMR T1H values showed that films containing CNC presented better interfacial interaction than those containing MCC, and indicated that R972 acts as compatibilizer. MCC and CNC acted as nucleating agents for PLA crystallization and there was an improvement in the mechanical performance of materials with the addition of CNC. 相似文献
This study aims to extract and characterize cellulose nanocrystals (CNCs) from date pits (DP), an agricultural solid waste. Two methods were used and optimized for the cellulose nanocrystals (CNCs) extraction, namely the mechanical stirrer method (CNCs1) and the Soxhlet apparatus method (CNCs2) in terms of chemical used, cost, and energy consumption. The results showed that scanning electron microscopy revealed the difference in the morphology as they exhibit rough surfaces with irregular morphologies due to the strong chemical treatments during the delignification and bleaching process. Moreover, transmission electron microscopy analysis for CNCs reveals the true modification that was made through sulfuric acid hydrolysis as it presents cellulose microfibrils with a packed structure. Fourier transform infrared proved that the CNCs were successfully extracted using the two methods since most of the lignin and hemicellulose components were removed. The crystallinity index of CNCs1 and CNCs2 was 69.99%, and 67.79%, respectively, and both presented a high yield of CNCs (≥10%). Ultimately, both techniques were successful at extracting CNCs. Based on their cost-effectiveness and time consumption, it was concluded that method 1 was less expensive than method 2 based on the breakdown of the cost of each step for CNCs production. 相似文献
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
In an attempt to prepare stable dispersions of cellulose nanocrystals in dipolar aprotic solvents, dilute aqueous suspensions
of cellulose nanocrystals were prepared by sulfuric acid hydrolysis of cotton. The aqueous suspensions were freeze-dried,
and then sonicated in the solvent of interest. Dispersions of 1 and 3% w/v concentration were prepared in polar organic solvents
DMSO and DMF. The dispersions showed flow birefringence. The redispersion was incomplete, and there was some evidence for
aggregation in the suspensions. A small amount of water appeared to be critical to suspension stability. Birefringent cellulose
films were prepared from the dispersions by drying under vacuum and at ambient conditions. 相似文献
There is a resurgence of interest in composite materials incorporating cellulose as fibrous reinforcement in semicrystalline
melt-processed polymers. Potential natural cellulose sources range from flax and ramie fibres down to whiskers and nanocrystals
isolated from bacteria. It has long been known that the crystallization of matrix polymers such as polypropylene may be preferentially
nucleated by Cellulose I surfaces, leading to a “transcrystalline” layer around the fiber. In this note, a transcrystalline
layer at the edge of films cast from cellulose nanocrystal suspensions is demonstrated, and preferential nucleation of polypropylene
on nanocrystals deposited on a glass surface is also observed. 相似文献
The objective of this study was to investigate the preparation and properties of hybrid materials composed of poly(lactic acid) (PLA) and poly(lactic acid)/poly(lactic-co-glycolic acid) (PLA/PLGA) blends employing cellulose nanocrystals (CNCs) and/or organophilic silica (R972) as nanoparticles. The CNCs were obtained by acid hydrolysis of commercially available microcrystalline cellulose (MCC). The materials were produced in film form by solution casting. Organophilic silica was incorporated at a ratio of 3 wt.%, and CNCs were added at ratios of 3 wt.% and 5 wt.% in relation to the weight of the polymer matrix. Two series of films were obtained. The first was prepared using only PLA as the matrix, and the second was obtained using blends of PLA and PLGA. The properties of the films were evaluated by X-ray diffractometry, nuclear magnetic resonance, Fourier-transform infrared spectroscopy and measurement of mechanical properties. The results revealed that each nanoparticle, whether added individually or combined with the other type of nanoparticle, induced different final material properties. Cellulose nanocrystals can act as nucleating agents for the crystallization of PLA. There was an improvement in the mechanical performance of films with the addition of CNCs. Further, the incorporation of silica combined with CNCs resulted in the generation of films with the strongest mechanical properties. The results of this study indicate that silica decreases the surface tension between PLA-cellulose and PLA/PLGA-cellulose. 相似文献
Summary: In this article we present some interesting properties of rodlike cellulose microcrystals (so‐called “whiskers”). These microcrystals can be obtained from different cellulose sources such as wood, cotton, or animal origin. When submitted to acid hydrolysis, the cellulose fibers yield stable aqueous suspensions because of the presence of negative charges on the surface of the microcrystallites during the hydrolysis process. The obtained microcrystals are rod‐shaped particles, the dimensions of which depend on the cellulose origin. For instance, the cotton whiskers have typical dimensions varying from 100 to 300 nm in length, L, and 8 to 10 nm in diameter, d, while those of the tunicate whiskers range from 100 nm to few micrometers in length and 10 to 20 nm in diameter. At very low concentrations, these whiskers are randomly suspended in water and form an isotropic phase. When the concentration reaches a critical value, the whiskers spontaneously display ordered phases showing interesting liquid crystal properties (nematic and chiral nematic). The chiral nematic orders can be retained after evaporation of the solvent (generally water), leaving iridescent films. The reflected color can be controlled by changing either the ionic strength or by applying an electric field. These colloidal particles have been investigated using several techniques including small‐angle neutron scattering (SANS), small angle X‐ray scattering, rheology, and more recently dynamic and static light scattering techniques (DLS and SLS) to highlight their static and dynamic behavior. Because of their geometry, important axis ratio (L/d), and high crystallinity, these rods have been also extensively used to process nanocomposites based on polymer matrices, to reinforce their mechanical properties. All these properties are discussed in this contribution.
Rodlike nanocrystals in aqueous suspension (left, Tunicate, 1 wt.‐%) and film (right), observed between cross‐polarizers. 相似文献
Nanocrystalline cellulose (NCC) was prepared by sulfuric acid hydrolysis of microcrystalline cellulose. A differential centrifugation
technique was studied to obtain NCC whiskers with a narrow size distribution. It was shown that the volume of NCC in different
fractions had an inverse relationship with relative centrifugal force (RCF). The length of NCC whiskers was also fractionized
by differential RCF. The aspect ratio of NCC in different fractions had a relatively narrow range. This technique provides
an easy way of producing NCC whiskers with a narrow size distribution. 相似文献
Cellulose gel with < 10% of crystallinity was prepared by treatment of microcrystalline cellulose, Avicel, with zinc chloride
solution at a ratio of zinc chloride to cellulose from 1.5 to 18 (w/w). The presence of zinc ions in the cellulose gels enhanced
the rate of hydrolysis and glucose yield. The evidence obtained from X-ray diffraction, iodine absorption experiments; and
Nuclear Magnetic Resonance spectra analysis suggested the presence of zinc-cellulose complex after Avicel was treated with
zinc chloride. Zinc-cellulose complex was more susceptible to hydrolysis than amorphous cellulose. Under the experimental
condition, cellulose gels with zinc ions were hyrolyzed to glucose with 95% theoretical yield and a concentration of 14% (w/v)
by cellulases within 20 h. The same gel was hydrolyzed by acid to glucose with 91.5% yield and a concentration of 13.4% (w/v). 相似文献
Microcrystalline cellulose (MCC), prepared from natural cellulose through acid hydrolysis, has been widely used in the food, chemical and pharmaceutical industries because of its high degree of crystallinity, small particle size and other characteristics. Being different from conventional mineral acids, phosphotungstic acid (H3PW12O40, HPW) was explored for hydrolyzing cellulose selectively for the preparation of MCC in this study. Various reaction parameters, such as the acid concentration, reaction time, temperature and solid-liquid ratio, were optimized. Rod-like MCC was obtained with a high yield of 93.62 % and also exhibited higher crystallinity and narrower particle diameter distribution (76.37 %, 13.77–26.17 μm) compared with the raw material (56.47 %, 32.41–49.74 μm) at 90 °C for 2 h with 58 % (w/w) HPW catalyst and a solid-liquid radio of 1:40. Furthermore, HPW can easily be extracted and recycled with diethyl ether for four runs without affecting the quality of the MCC products. The technology of protecting the crystalline region while selectively hydrolyzing the amorphous region of cellulose as much as possible by using HPW is of great significance. Due to the strong Brønsted acid sites and highest activity in solid heteropoly acid, the use of effective homogeneous HPW may offer an eco-friendly and sustainable way to selectively convert fiber resources into chemicals in the future. 相似文献
The chemical composition and morphology of Syngonanthus nitens (Capim Dourado) fibers were investigated. An unusual low lignin content and high holocellulose content have been observed.
High aspect ratio cellulose whiskers were prepared from these lignocellulosic fibers by an acid hydrolysis treatment. The
average diameter and length were 4.5 nm and 300 nm, respectively, giving rise to an aspect ratio around 67. Natural Rubber
nanocomposite films reinforced with cellulose whiskers extracted from capim dourado were prepared by film casting. The mechanical
properties of the ensuing nanocomposite films were investigated in both the linear and the non-linear range using dynamical
mechanical analysis and tensile tests, respectively. The reinforcing effect observed above the glass transition temperature
of the matrix was higher than the one observed for other polysaccharide nanocrystals and cellulose whiskers extracted from
other sources. 相似文献
Environmentally-friendly SPI/cellulose whisker composites were successfully prepared using a colloidal suspension of cellulose whiskers, to reinforce soy protein isolate (SPI) plastics. The cellulose whiskers, having an average length of 1.2 microm and diameter of 90 nm, respectively, were prepared from cotton linter pulp by hydrolyzing with sulfuric acid aqueous solution. The effects of the whisker content on the morphology and properties of the glycerol-plasticized SPI composites were investigated by scanning electron microscopy, dynamic mechanical thermal analysis, differential scanning calorimetry, ultraviolet-visible spectroscopy, water-resistivity testing and tensile testing. The results indicated that, with the addition of 0 to 30 wt.-% of cellulose whiskers, strong interactions occurred both between the whiskers and between the filler and the SPI matrix, reinforcing the composites and preserving their biodegradability. Both the tensile strength and Young's modulus of the SPI/cellulose whisker composites increased from 5.8 to 8.1 MPa and from 44.7 to 133.2 MPa, respectively, at a relative humidity of 43%, following an increase of the whisker content from 0 to 30 wt.-%. Furthermore, the incorporation of the cellulose whiskers into the SPI matrix led to an improvement in the water resistance for the SPI-based composites. 相似文献
Cellulose nanocrystals (CNCs) have drawn tremendous attention because of their extraordinary physical and chemical properties as well as renewability and sustainability. In this work, after a range of pretreatments, such as freeze-drying, ball-milling, mercerization, N-methylmorpholine-N-oxide dissolution and ionic liquid dissolution, various CNCs with different crystalline properties and morphologies were obtained by hydrolysis or oxidation. XRD and AFM were used to determine the influences of pretreatments on the crystalline properties and morphologies of CNCs. New methods, i.e., specific pretreatments followed by sulfuric acid hydrolysis or 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) oxidation, were developed to obtain sphere-like CNCs. It was found that sphere-like CNCs were more likely to be obtained from cellulose materials possessing high accessibility. Pretreatments produced cellulose with various crystallinities and polymorphs, and therefore changed the yields of CNCs and influenced their morphology. CNCs prepared by TEMPO oxidation generally had smaller size than the corresponding products obtained by sulfuric acid hydrolysis. In addition, for the dissolved/regenerated cellulose, TEMPO oxidation was a better method to yield sphere-like CNCs than sulfuric acid hydrolysis. 相似文献
There is continuing interest in the growing family of nanocellulosic materials prepared from plant cell wall material. While most of the research on cellulose nanocrystals has focused on the product of sulfuric acid hydrolysis stabilized by surface sulfate half-esters, cellulose nanocrystals with surface carboxyl groups have also been prepared by oxidation of lignocellulosic materials with ammonium persulfate. The major difference is that the persulfate oxidation leads to nanocrystals stabilized by surface carboxyl groups. Some properties of cellulose nanocrystals from cotton and wood, prepared by persulfate oxidation, are compared with those observed for nanocrystals prepared by sulfuric acid hydrolysis. Evidence from polarized light microscopy showed that the nanocrystal suspensions prepared by persulfate oxidation also form chiral nematic ordered phases in water. 相似文献
Cellulose nanocrystals (CNC) isolated from bleached bagasse pulp were modified with a second-generation isocyanate dendron (G2-dendron) to prepare dendronized cellulose nanocrystals (DCN). Transmission electron microscopy (TEM), elemental analysis for nitrogen, Fourier transform infrared (FTIR) and 13C magic angle spinning nuclear magnetic resonance (13C MAS NMR) proved occurrence of the modification of cellulose nanocrystals surfaces. The dendronized cellulose nanocrystals were used as templates for formation of ZnS and CdS quantum dots with uniform diameter at low temperature in water. The prepared DCN/QDs were highly soluble in water. TEM images showed that the size of the prepared quantum dots was about 5 nm in diameter. UV-Visible and fluorescence spectroscopy showed absorption and emission at wavelength values lower than that reported for bulk ZnS and CdS. 相似文献