Antonio Aprigio da Silva Curvelo

Delignification of sugarcane bagasse using glycerol–water mixtures to produce pulps for saccharification

This paper describes the organosolv delignification of depithed bagasse using glycerol-water mixtures without a catalyst. The experiments were performed using two separate experimental designs. In the first experiment, two temperatures (150 and 190°C), two time periods (60 and 240 min) and two glycerol contents (20% and 80%, v/v) were used. In the second experiment, which was a central composite design, the glycerol content was maintained at 80%, and a range of temperatures (141.7-198.3°C) and time (23-277 min) was used. The best result, obtained with a glycerol content of 80%, a reaction time of 150 min and a temperature of 198.3°C, produced pulps with 54.4% pulp yield, 7.75% residual lignin, 81.4% delignification and 13.7% polyose content. The results showed that high contents of glycerol tend to produce pulps with higher delignification and higher polyoses content in relation to the pulps obtained from low glycerol content reactions. In addition, the proposed method shows potential as a pretreatment for cellulose saccharification.

Preparation and characterization of thermoplastic starch/zein blends

Blends of starch and zein plasticized with glycerol were prepared by melting processing in an intensive batch mixer connected to a torque rheometer at 160 °C. The resulting mixtures were compression molded and then characterized by scanning electron microscopy, differential scanning calorimetry, wide-angle X ray diffraction and water-absorption experiments. The blends were immiscible, showing two distinct phases of starch and zein. The water uptake at equilibrium and its diffusion coefficient were determined. The water uptake at equilibrium decreased with increasing zein content. The diffusion coefficient fell sharply on addition of 20% zein and remained constant as zein content was increased. No appreciable effect of zein on starch crystallization was observed by X ray diffraction. The use of zein in thermoplastic starch compositions causes a decrease in the water sensitivity of these materials and lower its melt viscosity during processing making zein a suitable and very promising component in TPS compositions.

Low liquid–solid ratio (LSR) hot water pretreatment of sugarcane bagasse

Low liquid–solid ratio (LSR) can be used to obtain high-content xylo-oligosaccharide (XOS) spend liquor by hot water pretreatment. Developing a technology based on low LSR results in more efficient water usage in the system and thus in lower capital and operating costs. Xylans from xylan rich agro-industrial waste are abundant hemicellulosic polymers with enormous potential for industrial applications. Currently, freeze-dried xylo-oligosaccharides are used as bio-based polymers and hydrolysates containing high xylose contents are converted to several chemical products. In this study, sugarcane bagasse was treated with water at low LSRs and mild temperatures in order to assess the effects of varying the pretreatment conditions on the xylo-oligosaccharide and xylose concentrations, and use a central composite experimental design to optimize the process parameters. The pretreatments were performed in the ranges temperature: 143.3–176.7 °C, time: 20–70 min and LSR: 1 : 1 to 11 : 1 (g g−1). The maximum concentrations of xylose and xylan were 13.76 and 36.18 g L−1 (equivalent to 48.29 g L−1 of xylan), respectively, which were achieved by treating bagasse at 170 °C for 60 min, with LSR of 3 g g−1. The amount of xylan removed under these conditions was almost 57%. The soluble xylan consisted mainly of xylo-oligosaccharides (74 wt% of the identified compound in the spent liquor).

Estudo comparativo de amidos termoplásticos derivados do milho com diferentes teores de amilose

Corn starches with approximately 72% and 100 % of amylopectin were processed in an intensive mixer connected to a torque rheometer in the presence of glycerol (plasticizer) at 160oC. The thermoplastic starches were conditioned at 53 ± 2% of relative humidity for two weeks and characterized by X-ray diffraction, tensile test and dynamical mechanical analysis (DMA). The starch with lower amylopectin content presented higher viscosity during the processing which was attributed to linear amylose chains. The thermoplastic starches TPS1 (72% of amylopectin) and TPS2 (100% of amylopectin) did not display significant differences in water absorption. After two weeks of aging, TPS1 exhibited semicrystalline structure, whereas TPS2 presented a amorphous structure. After six weeks, the crystallinity of TPS1 increased and some crystalline behavior could be detected in TPS2. The mechanical and dynamical mechanical properties were affected by starch crystallinity, which is a function of amylose/amylopectin ratio.

Physical and chemical studies of tungsten carbide catalysts: effects of Ni promotion and sulphonated carbon

Ni promoted tungsten carbides have been shown to be an effective catalyst for cellulose conversion reaction. With the use of both in situ and ex situ techniques an investigation into the physical and chemical aspects of the Ni-promoted tungsten carbide catalyst supported on activated carbon either in pure form or functionalized with sulfuric acid was conducted. In situ XRD analysis performed during the carburization process showed that non-promoted samples formed a mixture of nanosized W2C, WC1−x and WC carbide phases. In the case of Ni promoted catalysts, in situ XRD, XANES, XPS and TEM analysis revealed that Ni aids in lowering the carburization temperature by 50 °C but also assisted in the deposition of polymeric carbon onto the catalyst surface which reduced cellulose conversion. However, the results indicate beneficial effects caused by the high carbon coverage by stopping the W2C to WC carbide phase transition. Thus, carburization of Ni promoted samples produced only W2C phase, which is stable up to 800 °C. The functionalization of activated-carbon with –SO3H not only increases the hydrolysis of cellulose but also lead to a greater dispersion of Ni over the catalyst. The resulting improvement in the interaction between Ni/W/C increases the cellulose transformation in a one-pot synthesis towards the production of ethylene glycol.

Benzylated pulps from sugar cane bagasse

An optimized ethanol/water process has been employed for the pulping of fibres from sugar cane bagasse. After pretreatment with aqueous NaOH, unbleached pulps were subjected to benzylation at 110 °C for different periods of time. The resulting purified products were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), gel permeation chromatography (GPC) and infrared spectroscopy (IR). The results showed that benzylation proceeded to various extents depending on the reaction time, as assessed by weight gain. During the first 3 h, a loss of mass was observed due to the occurrence of benzylation of low molecular weight polyoses, which were eliminated in the purification step. After that period of time a drastic weight increase was observed probably because crystalline regions had developed. The samples with low degrees of benzylation were insoluble, whereas the more benzylated counterparts showed limited solubility in THF. Partially soluble samples and a completely soluble one showed very different GPC elution profiles. This may be attributed to the efficiency of the pre treatment which, in the latter case, employed more concentrated alkali. Thermogravimetric analyses showed that all samples were degraded above 310 °C. Glass transition temperatures ranged between 42 °C and 65 °C, increasing as the extent of benzylation increased

An Organic Aqueous Gel as Electrolyte for Application in Electrochromic Devices Based in Bismuth Electrodeposition

The purpose of this work was to study the deposition/dissolution behavior of bismuth in an aqueous electrolytic gel media from the point of view of electrochromic phenomena. The gel was made from a derivative polymer of animal protein. This polymer is extremely consistent, and it becomes a transparent gel from 350 to 850 nm ~visible region!. Moreover, voltammetry and chronoamperometry experiments have shown that the bismuth deposition/dissolution has excellent electrochemical reversibility with a large variation of transmittance values ~around 60%! when Cu

Piassava fibers (Attalea funifera): NMR spectroscopy of their lignin

Lignin of piassava (Attalea funifera) was analyzed by 1H- and 13C-NMR spectroscopy. The HGS-nature of this lignin was confirmed but p-coumarate units are also present in the lignin. Methoxyl and phenolic hydroxyl contents per phenylpropanic unit were determined by 1HNMR spectroscopy to be 0.57 and 0.68, respectively and are in agreement with wet chemistry methods. A small extent of lignin condensation (35%) was explained by the high content of cinnamyl alcohol structures, evidenced by 13CNMR-DEPT. An extended C9formula for the piassava lignin was established to be

Physical Vapor Deposited Thin Films of Lignins Extracted from Sugar Cane Bagasse: Morphology, Electrical Properties, and Sensing Applications

The concern related to the environmental degradation and to the exhaustion of natural resources has induced the research on biodegradable materials obtained from renewable sources, which involves fundamental properties and general application. In this context, we have fabricated thin films of lignins, which were extracted from sugar cane bagasse via modified organosolv process using ethanol as organic solvent. The films were made using the vacuum thermal evaporation technique (PVD, physical vapor deposition) grown up to 120 nm. The main objective was to explore basic properties such as electrical and surface morphology and the sensing performance of these lignins as transducers. The PVD film growth was monitored via ultraviolet-visible (UV-vis) absorption spectroscopy and quartz crystal microbalance, revealing a linear relationship between absorbance and film thickness. The 120 nm lignin PVD film morphology presented small aggregates spread all over the film surface on the nanometer scale (atomic force microscopy, AFM) and homogeneous on the micrometer scale (optical microscopy). The PVD films were deposited onto Au interdigitated electrode (IDE) for both electrical characterization and sensing experiments. In the case of electrical characterization, current versus voltage (I vs V) dc measurements were carried out for the Au IDE coated with 120 nm lignin PVD film, leading to a conductivity of 3.6 × 10(-10) S/m. Using impedance spectroscopy, also for the Au IDE coated with the 120 nm lignin PVD film, dielectric constant of 8.0, tan δ of 3.9 × 10(-3), and conductivity of 1.75 × 10(-9) S/m were calculated at 1 kHz. As a proof-of-principle, the application of these lignins as transducers in sensing devices was monitored by both impedance spectroscopy (capacitance vs frequency) and I versus time dc measurements toward aniline vapor (saturated atmosphere). The electrical responses showed that the sensing units are sensible to aniline vapor with the process being reversible. AFM images conducted directly onto the sensing units (Au IDE coated with 120 nm lignin PVD film) before and after the sensing experiments showed a decrease in the PVD film roughness from 5.8 to 3.2 nm after exposing to aniline.

Monodisperse lignin fractions as standards in size-exclusion analysis Comparison with polystyrene standards

The difficulty of preparing monodisperse lignin fractions on a large scale is a limiting factor in many applications. The present paper addresses this problem by examining the properties and size-exclusion behavior of lignin isolated by the acetosolv pulping process from post-extraction crushed sugarcane bagasse. The isolated lignin was subjected to a solvent pretreatment, followed by preparative gel permeation chromatography fractionation. The fractions were analyzed by high-performance size-exclusion chromatography (HPSEC) and these samples showed a great decrease in polydispersity, compared to the original acetosolv lignin. Several fractions of very low polydispersity, close to unity, were employed as calibration curve standards in HPSEC analysis. This original analytical approach allowed calibration with these lignin fractions to be compared with the polystyrene standards that are universally employed for lignin molecular mass determination. This led to a noteworthy result, namely that the lignin fractions and polystyrene standards showed very similar behavior over a large range of molecular masses in a typical HPSEC analysis of acetosolv lignin.