Removal of Ca(II) and Mg(II) from aqueous single metal solutions by mercerized cellulose and mercerized sugarcane bagasse grafted with EDTA dianhydride (EDTAD)

In a previous work, chemically modified cellulose (EMC) and sugarcane bagasse (EMMB) were prepared from mercerized cellulose (MC) and twice-mercerized sugarcane bagasse (MMB) using ethylenediaminetetraacetic dianhydride (EDTAD) as modifying agent. In this work we described in detail the modification of these materials in function of reaction time and EDTAD amount in the reaction media. The resistance of ester bond at pH 1, 2, 11, and 12 was also evaluated by FTIR. The results were used to model the hydrolysis process and a kinetic model was proposed. The modified materials (EMMB and EMC) were used to adsorb Ca²⁺ and Mg²⁺ ions from aqueous single solutions. The adsorption isotherms were developed at two pH values. These materials showed maximum adsorption capacities for Ca²⁺ and Mg²⁺ ions ranging from 15.6 to 54.1 mg/g and 13.5 to 42.6 mg/g, respectively. The modified material from sugarcane bagasse (EMMB) showed larger maximum adsorption capacities than modified material from cellulose (EMC) for both metals.     

Valorization of an industrial organosolv–sugarcane bagasse lignin: Characterization and use as a matrix in biobased composites reinforced with sisal fibers

In the present study, the main focus was the characterization and application of the by‐product lignin isolated through an industrial organosolv acid hydrolysis process from sugarcane bagasse, aiming at the production of bioethanol. The sugarcane lignin was characterized and used to prepare phenolic‐type resins. The analysis confirmed that the industrial sugarcane lignin is of HGS type, with a high proportion of the less substituted aromatic ring p‐hydroxyphenyl units, which favors further reaction with formaldehyde. The lignin–formaldehyde resins were used to produce biobased composites reinforced with different proportions of randomly distributed sisal fibers. The presence of lignin moieties in both the fiber and matrix increases their mutual affinity, as confirmed by SEM images, which showed good adhesion at the biocomposite fiber/matrix interface. This in turn allowed good load transference from the matrix to the fiber, leading to biobased composites with good impact strength (near 500 J m^?1 for a 40 wt% sisal fiber‐reinforced composite). The study demonstrates that sugarcane bagasse lignin obtained from a bioethanol plant can be used without excessive purification in the preparation of lignocellulosic fiber‐reinforced biobased composites displaying high mechanical properties. Biotechnol. Bioeng. 2010;107:612–621. © 2010 Wiley Periodicals, Inc.     

Production of granular activated carbons from select agricultural by-products and evaluation of their physical,chemical and adsorption properties

Representative samples of soft, low density, group 1 (rice straw, rice hulls, sugarcane bagasse) and hard, high density, group 2 agricultural by-products (pecan shells) were converted into granular activated carbons (GACs). GACs were produced from group 1 and 2 materials by physical activation or from group 2 materials by chemical activation. Carbons were evaluated for their physical (hardness, bulk density), chemical (ash, conductivity, pH), surface (total surface area), and adsorption properties (molasses color removal, sugar decolorization) and compared with two commercial reference carbons. The results show that the type of by-product, binder, and activation method determine the properties of GACs. Regardless of the binder, sugarcane bagasse showed a better potential than rice straw or rice hulls as precursor of GACs with the desirable properties of a sugar decolorizing carbon. Pecan shells produced GACs that were closest to the reference carbons in terms of all the properties investigated.     

Homogeneous isolation of nanocellulose from sugarcane bagasse by high pressure homogenization

Nanocellulose from sugarcane bagasse was isolated by high pressure homogenization in a homogeneous media. Pretreatment with an ionic liquid (1-butyl-3-methylimidazolium chloride ([Bmim]Cl)) was initially involved to dissolve the bagasse cellulose. Subsequently, the homogeneous solution was passed through a high pressure homogenizer without any clogging. The nanocellulose was obtained at 80MPa for 30 cycles with recovery of 90% under the optimum refining condition. Nanocellulose had been characterized by Fourier transformed infrared spectra, X-ray diffraction, thermogravimetric analysis, rheological measurements and transmission electron microscopy. The results showed that nanocellulose was 10-20nm in diameter, and presented lower thermal stability and crystallinity than the original cellulose. The developed nanocellulose would be a very versatile renewable material.     

Cellulase On-Site Production from Sugar Cane Bagasse Using Penicillium echinulatum

Penicillium echinulatum was evaluated as a cellulolytic enzyme producer in shaking flasks and bioreactor submerged culture using sugarcane bagasse as carbon source. Sodium hydroxide delignified steam-exploded pretreated bagasse (SDB) and hydrothermal pretreated bagasse had a maximum filter paper activity (FPase) of 2.4 and 2.6 FPU/mL, respectively. Delignified acid pretreated bagasse and Celufloc 200TM (CE) carbon sources displayed maximum FPase of 1.3 and 1.6 FPU/mL while in natura bagasse (INB) provided the lowest enzyme activity, ca. 0.4 FPU/mL. Measurement of surface specific area of lignocellulosic material and scanning electron microscopic images showed a possible correlation between fungal mycelia accessibility to lignocellulosic particles and obtained cellulolytic enzyme activity of fermentation broth. Fed-batch experiments performed in a controlled bioreactor attained the highest value of FPase of 3.7 FPU/mL, enzyme productivity of 25.7 FPU/L h, and enzyme yield from cellulose equal to 134 FPU/g with SDB. Enzyme hydrolysis of steam-pretreated bagasse accomplished with the obtained supernatant of fermentation broth (10 FPU/g of biomass and 5 % w/v) performed better than commercial cellulose complex. The results showed that P. echinulatum has potential to be used as an on-site enzyme platform aiming second bioethanol production from sugarcane lignocellulosic residue.     

Surface modification of natural fibers using bacteria: depositing bacterial cellulose onto natural fibers to create hierarchical fiber reinforced nanocomposites

Triggered biodegradable composites made entirely from renewable resources are urgently sought after to improve material recyclability or be able to divert materials from waste streams. Many biobased polymers and natural fibers usually display poor interfacial adhesion when combined in a composite material. Here we propose a way to modify the surfaces of natural fibers by utilizing bacteria ( Acetobacter xylinum) to deposit nanosized bacterial cellulose around natural fibers, which enhances their adhesion to renewable polymers. This paper describes the process of modifying large quantities of natural fibers with bacterial cellulose through their use as substrates for bacteria during fermentation. The modified fibers were characterized by scanning electron microscopy, single fiber tensile tests, X-ray photoelectron spectroscopy, and inverse gas chromatography to determine their surface and mechanical properties. The practical adhesion between the modified fibers and the renewable polymers cellulose acetate butyrate and poly(L-lactic acid) was quantified using the single fiber pullout test.     

Efficient conversion of sugarcane stalks into ethanol employing low temperature alkali pretreatment method

An alternative route for bio-ethanol production from sugarcane stalks (juice and bagasse) featuring a previously reported low temperature alkali pretreatment method was evaluated. Test-tube scale pretreatment-saccharification experiments were carried out to determine optimal LTA pretreatment conditions for sugarcane bagasse with regard to the efficiency of enzymatic hydrolysis of the cellulose. Free fermentable sugars and bagasse recovered from 2 kg of sugarcane stalks were jointly converted into ethanol via separate enzymatic hydrolysis and fermentation (SHF). Results showed that 98% of the cellulose present in the optimally pretreated bagasse was hydrolyzed into glucose after 72-h enzymatic saccharification using commercially available cellulase and β-glucosidase preparations at relatively low enzyme loading. The fermentable sugars in the mixture of the sugar juice and the bagasse hydrolysate were readily converted into 193.5 mL of ethanol by Saccharomyces cerevisiae within 12h, achieving 88% of the theoretical yield from the sugars and cellulose.     

Adsorption of heavy metal ion from aqueous single metal solution by chemically modified sugarcane bagasse

This work describes the preparation of new chelating materials derived from sugarcane bagasse for adsorption of heavy metal ions in aqueous solution. The first part of this report deals with the chemical modification of sugarcane bagasse with succinic anhydride. The carboxylic acid functions introduced into the material were used to anchor polyamines, which resulted in two yet unpublished modified sugarcane bagasse materials. The obtained materials were characterized by elemental analysis and infrared spectroscopy (IR). The second part of this reports features the comparative evaluation of the adsorption capacity of the modified sugarcane bagasse materials for Cu(2+), Cd(2+), and Pb(2+) ions in aqueous single metal solution by classical titration. Adsorption isotherms were studied by the Freundlich and Langmuir models.     

Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels

Toward exploiting the attractive mechanical properties of cellulose I nanoelements, a novel route is demonstrated, which combines enzymatic hydrolysis and mechanical shearing. Previously, an aggressive acid hydrolysis and sonication of cellulose I containing fibers was shown to lead to a network of weakly hydrogen-bonded rodlike cellulose elements typically with a low aspect ratio. On the other hand, high mechanical shearing resulted in longer and entangled nanoscale cellulose elements leading to stronger networks and gels. Nevertheless, a widespread use of the latter concept has been hindered because of lack of feasible methods of preparation, suggesting a combination of mild hydrolysis and shearing to disintegrate cellulose I containing fibers into high aspect ratio cellulose I nanoscale elements. In this work, mild enzymatic hydrolysis has been introduced and combined with mechanical shearing and a high-pressure homogenization, leading to a controlled fibrillation down to nanoscale and a network of long and highly entangled cellulose I elements. The resulting strong aqueous gels exhibit more than 5 orders of magnitude tunable storage modulus G' upon changing the concentration. Cryotransmission electron microscopy, atomic force microscopy, and cross-polarization/magic-angle spinning (CP/MAS) 13C NMR suggest that the cellulose I structural elements obtained are dominated by two fractions, one with lateral dimension of 5-6 nm and one with lateral dimensions of about 10-20 nm. The thicker diameter regions may act as the junction zones for the networks. The resulting material will herein be referred to as MFC (microfibrillated cellulose). Dynamical rheology showed that the aqueous suspensions behaved as gels in the whole investigated concentration range 0.125-5.9% w/w, G' ranging from 1.5 Pa to 105 Pa. The maximum G' was high, about 2 orders of magnitude larger than typically observed for the corresponding nonentangled low aspect ratio cellulose I gels, and G' scales with concentration with the power of approximately three. The described preparation method of MFC allows control over the final properties that opens novel applications in materials science, for example, as reinforcement in composites and as templates for surface modification.     

Physical and chemical properties of selected agricultural byproduct-based activated carbons and their ability to adsorb geosmin

The objectives of this study were to evaluate selected physical and chemical properties of agricultural byproduct-based activated carbons made from pecan shells and sugarcane bagasse, and compare those properties to a commercial coal-based activated carbon as well as to compare the adsorption efficiency of these carbons for geosmin. Comparison of the physical and chemical properties of pecan shell- and bagasse-based carbons to the commercial carbon, Calgon Filtrasorb 400, showed that pecan shell carbon, but not the bagasse carbon, compared favorably to Filtrasorb 400, especially in terms of surface area, bulk density, ash and attrition. A carbon dosage study done in a model system showed the amount of geosmin adsorbed to be greater for Filtrasorb 400 and the bagasse-based carbon at low carbon concentrations than for the pecan shell carbons, but geosmin adsorption was similar in all carbons at higher carbon dosages. Application of the Freundlich isotherm model to the adsorption data showed that carbons made by steam activation of pecan shells or sugarcane bagasse had geosmin adsorption characteristics most like those of the commercial carbon. In terms of physical, chemical and adsorptive properties, steam-activated pecan shell carbon most resembled the commercial carbon and has the potential to replace Filtrasorb 400 in applications involving removal of geosmin from aqueous environments.     

Adsorption of Cu(II), Cd(II), and Pb(II) from aqueous single metal solutions by mercerized cellulose and mercerized sugarcane bagasse chemically modified with EDTA dianhydride (EDTAD)

This work describes the preparation of new chelating materials derived from cellulose and sugarcane bagasse for adsorption of Cu²⁺, Cd²⁺, and Pb²⁺ ions from aqueous solutions. The first part involved the mercerization treatment of cellulose and sugarcane bagasse with NaOH 5 mol/L. Non- and mercerized cellulose and sugarcane bagasse were then reacted with ethylenediaminetetraacetic dianhydride (EDTAD) in order to prepare different chelating materials. These materials were characterized by mass percent gain, X-ray diffraction, FTIR, and elemental analysis. The second part consisted of evaluating the adsorption capacity of these modified materials for Cu²⁺, Cd²⁺, and Pb²⁺ ions from aqueous single metal solutions, whose concentration was determined by atomic absorption spectroscopy. These materials showed maximum adsorption capacities for Cu²⁺, Cd²⁺, and Pb²⁺ ions ranging from 38.8 to 92.6 mg/g, 87.7 to 149.0 mg/g, and 192.0 to 333.0 mg/g, respectively. The modified mercerized materials showed larger maximum adsorption capacities than modified non-mercerized materials.     

Major improvement in the rate and yield of enzymatic saccharification of sugarcane bagasse via pretreatment with the ionic liquid 1-ethyl-3-methylimidazolium acetate ([Emim] [Ac])

In this study, sugarcane bagasse was pretreated by six ionic liquids (ILs) using a bagasse/IL ratio of 1:20 (wt%). The solubilization of bagasse in the ILs was followed by water precipitation. On using 1-ethyl-3-methylimidazolium acetate [Emim] [Ac] at 120 °C for 120 min, 20.7% of the bagasse components remained dissolved and enzymatic saccharification experiments resulted on 80% glucose yield within 6h, which evolved to over 90% within 24 h. Moreover, FE-SEM analysis of the precipitated material indicated a drastic lignin extraction and the exposure of nanoscopic cellulose microfibrils with widths of less than 100 nm. The specific surface area (SSA) of the pretreated bagasse (131.84 m2/g) was found to be 100 times that of untreated bagasse. The ability of [Emim] [Ac] to simultaneously increase the SSA and to decrease the biomass crystallinity is responsible for the improved bagasse enzymatic saccharification rates and yields obtained in this work.     

Extraction and characterization of wax from sugarcane bagasse and the enzymatic hydrolysis of dewaxed sugarcane bagasse

Extraction of high-value products from agricultural wastes is an important component for sustainable bioeconomy development. In this study, wax extraction from sugarcane bagasse was performed and the beneficial effect of dewaxing pretreatment on the enzymatic hydrolysis was investigated. About 1.2% (w/w) of crude sugarcane wax was obtained from the sugarcane bagasse using the mixture of petroleum ether and ethanol (mass ratio of 1:1) as the extraction agent. Results of Fourier-transform infrared characterization and gas chromatography–mass spectrometry qualitative analysis showed that the crude sugarcane wax consisted of fatty fractions (fatty acids, fatty aldehydes, hydrocarbons, and esters) and small amount of lignin derivatives. In addition, the effect of dewaxing pretreatment on the enzymatic hydrolysis of sugarcane bagasse was also investigated. The digestibilities of cellulose and xylan in dewaxed sugarcane bagasse were 18.7 and 10.3%, respectively, compared with those of 13.1 and 8.9% obtained from native sugarcane bagasse. The dewaxed sugarcane bagasse became more accessible to enzyme due to the disruption of the outermost layer of the waxy materials.     

Do wood-based panels made with agro-industrial residues provide environmentally benign alternatives? An LCA case study of sugarcane bagasse addition to particle board manufacturing

Purpose

Sugarcane bagasse is one of the main agro-industrial residues which can be used to produce wood-based panels. However, more investigations related to its environmental performance assessment are needed, focusing on questions such as: Does it provide environmental benefits? What are its main environmental impacts? Could it substitute wood as raw material? Accordingly, this paper presents a life cycle assessment (LCA) study of particle board manufactured with sugarcane bagasse residues.

Methods

The cradle-to-gate assessment of 1 m³ of particle board made with sugarcane bagasse (PSB) considered three main subsystems: bagasse generation, bagasse distribution, and PSB production. For the inventory of PSB, dataset from two previous LCA studies related to the conventional particle board production and the ethanol life cycle for the Brazilian context were used. The allocation criterion for the bagasse generation subsystem was 9.08 % (economic base). The potential environmental impact phase was assessed by applying the CML and USEtox methods. PSB was compared with the conventional particle board manufactured in Brazil by the categories of the CML and USETox, and including land use indicators. Finally, two scenarios were analyzed to evaluate the influence of the allocation criteria and the consumption of sugarcane bagasse.

Results and discussion

All hotspots identified by CML and USETox methods are mainly related to the PSB production subsystem (24–100 % of impacts) due to heavy fuel oil, electricity, and urea-formaldehyde resin supply chain. The bagasse generation subsystem was more relevant to the eutrophication category (75 % of impacts). The bagasse distribution subsystem was not relevant because the impacts on all categories were lower than 1 %. PSB can substitute the conventional particle board mainly because of its lower contribution to abiotic depletion and ecotoxicity. Regarding land use impacts, PSB showed lower values according to all indicators (38–40 % of all impacts), which is explained by the lower demand for land occupation in comparison to that of the traditional particle board.

Conclusions

PSB can replace the traditional particle board due to its better environmental performance. The analysis of the economic allocation criterion was relevant only for the EP category, being important to reduce diesel and N-based fertilizers use during sugarcane cultivation. Regarding the influence of the sugarcane bagasse consumption, it is suggested that the sugarcane bagasse be mixed up to 75 % during particle board manufacturing so that good quality properties and environmental performance of panels can be provided.     

Mechanical properties of primary plant cell wall analogues

Mechanical effects of turgor pressure on cell walls were simulated by deforming cell wall analogues based on Acetobacter xylinus cellulose under equi-biaxial tension. This experimental set-up, with associated modelling, allowed quantitative information to be obtained on cellulose alone and in composites with pectin and/or xyloglucan. Cellulose was the main load-bearing component, pectin and xyloglucan leading to a decrease in modulus when incorporated. The cellulose-only system could be regarded as an essentially linear elastic material with a modulus ranging from 200 to 500 MPa. Pectin incorporation modified extensibility properties of the system by topology/architecture changes of cellulose fibril assemblies, but the cellulose/pectin composites could still be described as a linear elastic material with a modulus ranging from 120 to 250 MPa. The xyloglucan/cellulose composite could not be modelled as a linear elastic material. Introducing xyloglucan into a cellulose network or a cellulose/pectin composite led to very compliant materials characterised by time-dependent creep behaviour. Modulus values obtained for the composite materials were compared with mechanical data found for plant-derived systems. After comparing bi-axial and uni-axial behaviour of the different composites, structural models were proposed to explain the role of each polysaccharide in determining the mechanical properties of these plant primary cell wall analogues.     

Surface properties of granular activated carbons from agricultural by-products and their effects on raw sugar decolorization

Granular activated carbons (GACs) were produced from sugarcane bagasse combined with one of two binders (corn syrup, coal tar) by physical activation and from pecan shells by physical and chemical activation. GACs were evaluated for their physical (hardness, bulk density), chemical (ash, pH), surface (surface area, pore size distribution, surface chemistry), and adsorption properties (molasses color removal, sugar decolorization) and compared with two commercial reference carbons. Results showed that larger surface area, a well-developed macro- and mesoporosity, and a minimal surface charge were desirable in GACs designed for sugar decolorization. Steam activation of pecan shells carbon was the only by-product-activation combination that produced GAC with all the above three desirable characteristics of a good sugar decolorizer. Chemical activation of pecan shells yielded GACs with high surface area and adequate pore size distribution but with large surface charge. In contrast, sugarcane bagasse-based GACs exhibited low surface areas and unsatisfactory physical/chemical properties.     

Influence of silicone oil modification on properties of ramie fiber reinforced polypropylene composites

This paper focused on the analyses of the composition, microstructure, thermal stability and mechanical behavior of modified ramie fiber and its reinforced polypropylene composites. Ramie fiber (RF) was treated with epoxy-silicone oil (ESO) at 160 °C in argon gas. The FTIR and XRD analyses indicated that some silicone molecular chains were bonded on the surface of modified RF, which decreased the crystallinity of the fiber without changing the crystalline type of cellulose. The SEM results of fracture surface showed that the modified RF/PP composite had better interfacial bonding between RF and PP. The mechanical tests showed that the impact strength and the elongation at break of RF/PP were increased by 17.0% and 196% after modification, respectively. The tensile strength of 30RF/PP was improved from 18.95 MPa to 25.96 MPa compared to pure PP. The results of TGA showed that fiber treatment could improve the degradation temperature of RF/PP composites.     

Feasibility of Manufacturing Cellulose Nanocrystals from the Solid Residues of Second-Generation Ethanol Production from Sugarcane Bagasse

The reuse of the solid residues generated in the production of second-generation (2G) ethanol to obtain high-value products is a potential strategy for improving the economic and environmental viability of the overall process. This study evaluated the feasibility of using the residual solids remaining after the enzymatic hydrolysis of sugarcane bagasse for the production of cellulose nanocrystals (CNC), a valuable bionanomaterial. To this end, sugarcane bagasse subjected to steam explosion (SEB) or liquid hot water (LHWB) pretreatment was hydrolysed using different loadings of a commercial cellulase cocktail. Samples of SEB and LHWB were hydrolysed enzymatically, resulting in glucose releases close to 40 g/L, which would be suitable for producing 2G ethanol by microbial fermentation. The solid residues after the enzymatic hydrolysis step presented cellulose contents of up to 54 %, indicating that a significant amount of recalcitrant crystalline cellulose remained available for subsequent use. These solid residues were purified and submitted to acid hydrolysis, resulting in the successful formation of CNC with crystallinity close to 80 %, lengths of 193–246 nm and diameters of 14–18 nm. The CNC produced presented morphology, dimensions, physical-chemical characteristics, thermal stability and crystallinity within the ranges reported for this type of material. Moreover, the enzyme loading or the type of hydrothermal pretreatment process employed here showed no significant effects on the CNC obtained, indicating that these variables could be flexibly adjusted according to specific interests.     

Investigation on the surface properties of chemically modified natural fibers using inverse gas chromatography

This paper presents the application of inverse gas chromatography (IGC) technique for characterization and comparison of the surface properties of the natural fibers as reinforcement fillers in wood plastic composites. The effects of chemical modification using 1% NaOH were also studied. The fibers used for this work were Iranian cultivated eucalyptus, spruce, bagasse, and wheat straw. Chemical composition of fibers was found to be modified after treatment as characterized by Fourier transform infrared spectroscopy (FTIR). The crystallinity of fibers and the specific interaction was improved by the alkaline treatment, with more relevance to the agro-fibers. The IGC shows also a general increase in the wettability of the modified fiber when compared with the raw (unmodified) samples. Alkaline treatment achieves the best overall improvement in the properties evaluated of the agro-fibers when compared to the wood fibers.     

Image analysis of modified cellulose fibers from sugarcane bagasse by zirconium oxychloride

Surface modification of natural fibers has been made using different methods. In this paper, cellulose fibers from sugarcane bagasse were bleached and modified by zirconium oxychloride in situ. The chemically modified cellulose fibers were compared to those of bleached ones. Cellulose fibers were modified with ZrO₂·nH₂O nanoparticles through the use of zirconium oxychloride in acidic medium in the presence of cellulose fibers using urea as the precipitating agent. The spatial distribution characterization of hydrous zirconium oxide on cellulose fibers was carried out by combining both processing and image analyses obtained by SEM and statistical methodologies. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and thermogravimetric analysis (TG) were also used to characterize the nanocomposite. Results indicated that ZrO₂·nH₂O nanoparticles of about 30-80 nm diameter deposited on cellulose fibers were heterogeneously dispersed.