Luiz Pereira Ramos

The chemistry involved in the steam treatment of lignocellulosic materials

Pretreatment of lignocellulosic materials is essential for bioconversion because of the various physical and chemical barriers that greatly inhibit their susceptibility to bioprocesses such as hydrolysis and fermentation. The aim of this article is to review some of the most important pretreatment methods developed to date to enhance the conversion of lignocellulosics. Steam explosion, which precludes the treatment of biomass with high-pressure steam under optimal conditions, is presented as the pretreatment method of choice and its mode of action on lignocellulosics is discussed. The optimal pretreatment conditions for a given plant biomass are defined as those in which the best substrate for hydrolysis is obtained with the least amount of soluble sugars lost to side reactions such as dehydration. Therefore, pretreatment optimization results from a compromise between two opposite trends because hemicellulose recovery in acid hydrolysates can only be maximized at lower pretreatment severities, whereas the development of substrate accessibility requires more drastic pretreatment conditions in which sugar losses are inevitable. To account for this heterogeneity, the importance of several process-oriented parameters is discussed in detail, such as the pretreatment temperature, residence time into the steam reactor, use of an acid catalyst, susceptibility of the pretreated biomass to bioconversion, and process design.

Bioethanol from lignocelluloses: Status and perspectives in Brazil.

The National Alcohol Program--PróAlcool, created by the government of Brazil in 1975 resulted less dependency on fossil fuels. The addition of 25% ethanol to gasoline reduced the import of 550 million barrels oil and also reduced the emission CO(2) by 110 million tons. Today, 44% of the Brazilian energy matrix is renewable and 13.5% is derived from sugarcane. Brazil has a land area of 851 million hectares, of which 54% are preserved, including the Amazon forest (350 million hectares). From the land available for agriculture (340 million hectares), only 0.9% is occupied by sugarcane as energy crop, showing a great expansion potential. Studies have shown that in the coming years, ethanol yield per hectare of sugarcane, which presently is 6000 L/ha, could reach 10,000 L/ha, if 50% of the produced bagasse would be converted to ethanol. This article describes the efforts of different Brazilian institutions and research groups on second generation bioethanol production, especially from sugarcane bagasse.

PRODUÇÃO DE BIOCOMBUSTÍVEL ALTERNATIVO AO ÓLEO DIESEL ATRAVÉS DA TRANSESTERIFICAÇÃO DE ÓLEO DE SOJA USADO EM FRITURAS

In this work, the utilization of used frying oil for the production of biodiesel is presented. The performance of biodiesel in diesel engines, as well as the characterization of the emissions derived from this process, are also discussed and compared to the emissions derived from engines running on unused vegetable oils and conventional diesel.

Fractionation of Eucalyptus grandis chips by dilute acid-catalysed steam explosion

Steam explosion of Eucalyptus grandis has been carried out under various pretreatment conditions (200-210 degrees C, 2-5 min) after impregnation of the wood chips with 0.087 and 0.175% (w/w) H2SO4. This study, arranged as a 2(3) factorial design, indicated that pretreatment temperature is the most critical variable affecting the yield of steam-treated fractions. Pretreatment of 0.175% (w/w) H2SO4-impregnated chips at 210 degrees C for 2 min was the best condition for hemicellulose recovery (mostly as xylose) in the water soluble fraction, reaching almost 70% of the corresponding xylose theoretical yield. By contrast, lower pretreatment temperatures of 200 degrees C were enough to yield steam-treated substrates from which a 90% cellulose conversion was obtained in 48 h, using low enzyme loadings of a Celluclast 1.5 1 plus Novozym 188 mixture (Novo Nordisk). Release of water-soluble chromophores was monitored by UV spectroscopy and their concentration increased with pretreatment severity. The yield of alkali-soluble lignin increased at higher levels of acid impregnation and pretreatment temperatures. Thermoanalysis of these lignin fractions indicated a pattern of lignin fragmentation towards greater pretreatment severities but lignin condensation prevailed at the most drastic pretreatment conditions.

Multivariate monitoring of soybean oil ethanolysis by FTIR.

In this work, an analytical procedure was developed to monitor the ethanolysis of degummed soybean oil (DSO) using Fourier-transformed mid-infrared spectroscopy (FTIR) and methods of multivariate analysis such as principal component analysis (PCA) and partial least squares regression (PLS). The triglycerides (reagents) and ethyl esters (products) involved in ethanolysis were shown to have similar FTIR spectra. However, when the FTIR spectra derived from seven standard mixtures of triolein and ethyl oleate were treated by PCA at the region that represents the CO stretching vibration of ester groups (1700-1800cm(-1)), only two principal components (PC) were shown to capture 99.95% of the total spectral variance (92.37% for the former and 7.58% for the latter PC). This observation supported the development of a multivariate calibration model that was based on the PLS regression of the FTIR data. The prevision capability of this model was measured against 40 reaction aliquots whose ester content was previously determined by size exclusion chromatography. Only small discrepancies were observed when the two experimental data sets were treated by linear regression (R(2)=0.9837) and these deviations were attributed to the occurrence of non-modeled transient species in the reaction mixture (reaction intermediates), particularly at short reaction times. Therefore, the FTIR/PLS model was shown to be a fast and accurate method to predict reaction yields and to follow the in situ kinetics of soybean oil ethanolysis.

Current Pretreatment Technologies for the Development of Cellulosic Ethanol and Biorefineries.

Lignocellulosic materials, such as forest, agriculture, and agroindustrial residues, are among the most important resources for biorefineries to provide fuels, chemicals, and materials in such a way to substitute for, at least in part, the role of petrochemistry in modern society. Most of these sustainable biorefinery products can be produced from plant polysaccharides (glucans, hemicelluloses, starch, and pectic materials) and lignin. In this scenario, cellulosic ethanol has been considered for decades as one of the most promising alternatives to mitigate fossil fuel dependence and carbon dioxide accumulation in the atmosphere. However, a pretreatment method is required to overcome the physical and chemical barriers that exist in the lignin-carbohydrate composite and to render most, if not all, of the plant cell wall components easily available for conversion into valuable products, including the fuel ethanol. Hence, pretreatment is a key step for an economically viable biorefinery. Successful pretreatment method must lead to partial or total separation of the lignocellulosic components, increasing the accessibility of holocellulose to enzymatic hydrolysis with the least inhibitory compounds being released for subsequent steps of enzymatic hydrolysis and fermentation. Each pretreatment technology has a different specificity against both carbohydrates and lignin and may or may not be efficient for different types of biomasses. Furthermore, it is also desirable to develop pretreatment methods with chemicals that are greener and effluent streams that have a lower impact on the environment. This paper provides an overview of the most important pretreatment methods available, including those that are based on the use of green solvents (supercritical fluids and ionic liquids).

The influence of BHA, BHT and TBHQ on the oxidation stability of soybean oil ethyl esters (biodiesel)

The effect of synthetic antioxidants such as BHT (butyl-hydroxytoluene), BHA (butyl-hydroxyanisol) and TBHQ (t-butyl-hydroxyquinone) was evaluated on the induction time of soybean oil ethyl esters with low oxidation stability, employing the Rancimat method (EN14112). Interaction effects were also investigated by employing a 23 factorial design, which had as minimum and maximum levels the concentrations of zero and 1500 ppm of each antioxidant. Among the synthetic antioxidants evaluated, BHT displayed the highest effectiveness in the concentration range from 200 to 7000 ppm. TBHQ displayed a greater stabilizing potential when used at higher concentrations (8000 ppm), while BHA was found to provide no noticeable increase in the induction time at concentrations greater than 2000 ppm. The combined use of these antioxidants, at the levels tested in this study, yielded no evidence of any positive synergic effect that would justify their use in binary or ternary mixtures.

Production of fumaric acid by fermentation of enzymatic hydrolysates derived from cassava bagasse

Abstract Cassava bagasse is a starch-rich lignocellulosic residue (50% of starch, by weight, on a dry basis) which is discarded daily into rivers. The enzymatic hydrolysate of cassava bagasse was used as the sole carbon source to produce fumaric acid by submerged fermentation using several Rhizopus strains. This work was developed in several steps. Six different sources of nitrogen and six different compositions of the enzymatic hydrolysate were used. An experimental design was carried out to optimize the media cultivation. The strain Rhizopus formosa MUCL 28422 was selected as the best fumaric acid producer, yielding 21.28 g/l in a media containing cassava bagasse as the sole carbon source, KNO 3 as nitrogen source (C/N ratio of 168), 20 g/l of CaCO 3 , 10 μg/l of biotin, 0.04 g/l of ZnSO 4 .7H 2 O, 0.25 g/l of MgSO 4 .7H 2 O, 0.15 g/l of KH 2 PO 4 and 15 ml/l of methanol.

Brazilian Bioethanol Program

Brazil is the largest producer of bioethanol, and sugarcane is the main raw material. Bioethanol, is produced by both batch and continuous processes, and in some cases, flocculating yeast is use. This article analyzes the Bracilian Ethanol Program. for the 1996–1997 havest, Brazil produced 14.16 billion L of ethanol and 13.8 million metrict of sugar, from 286 million metrict of sugarcane. These products were produced by 328 industries inactivity, with 101 autonomousethanol plants producing only ethanol, and 227 sugar mills producing sugar and ethanol. The sugar-ethanol market reaches about 7.5 billion US

New multifunctional materials obtained by the intercalation of anionic dyes into layered zinc hydroxide nitrate followed by dispersion into poly(vinyl alcohol) (PVA)

/yr, accounting for direct and indirect revenues.