Solution thermodynamics of methocarbamol in some ethanol + water mixtures

Apparent thermodynamic functions, Gibbs energy, enthalpy and entropy of solution and mixing, for methocarbamol in ethanol + water mixtures, were evaluated from solubility data determined at temperatures from 293.15 K to 313.15 K and from calorimetric values of drug fusion. The drug solubility was greatest in the mixtures with 0.70 or 0.80 mass fraction of ethanol and lowest in neat water across all temperatures studied. Non-linear enthalpy-entropy compensation was found for the dissolution processes. Accordingly, solution enthalpy drives the respective processes in almost all the solvent systems analyzed.

Use of sorghum straw (Sorghum bicolor) for second generation ethanol production: pretreatment and enzymatic hydrolysis

Agronomic biomass yields of forage sorghum BRS 655 presented similar results to other energy crops, producing 9 to 12.6 tons/ha (dry mass) of sorghum straw. The objective of this study was to evaluate the lignocellulosic part of this cultivar in terms of its potential in the different unit processes in the production of cellulosic ethanol, measuring the effects of pretreatment and enzymatic hydrolysis. Three types of pre-treatments for two reaction times were conducted to evaluate the characteristics of the pulp for subsequent saccharification. The pulp pretreated by alkali, and by acid followed by delignification, attained hydrolysis rates of over 90%.

Química Sem Fronteiras: o desafio da energia

Coal, natural gas and petroleum-based liquid fuels are still the most widely used energy sources in modern society. The current scenario contrasts with the foreseen shortage of petroleum that was spread out in the beginning of the XXI century, when the concept of "energy security" emerged as an urgent agenda to ensure a good balance between energy supply and demand. Much beyond protecting refineries and oil ducts from terrorist attacks, these issues soon developed to a portfolio of measures related to process sustainability, involving at least three fundamental dimensions: (a) the need for technological breakthroughs to improve energy production worldwide; (b) the improvement of energy efficiency in all sectors of modern society; and (c) the increase of the social perception that education is a key-word towards a better use of our energy resources. Together with these technological, economic or social issues, "energy security" is also strongly influenced by environmental issues involving greenhouse gas emissions, loss of biodiversity in environmentally sensitive areas, pollution and poor solid waste management. For these and other reasons, the implementation of more sustainable practices in our currently available industrial facilities and the search for alternative energy sources that could partly replace the fossil fuels became a major priority throughout the world. Regarding fossil fuels, the main technological bottlenecks are related to the exploitation of less accessible petroleum resources such as those in the pre-salt layer, ranging from the proper characterization of these deep-water oil reservoirs, the development of lighter and more efficient equipment for both exploration and exploitation, the optimization of the drilling techniques, the achievement of further improvements in production yields and the establishment of specialized training programs for the technical staff. The production of natural gas from shale is also emerging in several countries but its production in large scale has several problems ranging from the unavoidable environmental impact of shale mining as well as to the bad consequences of its large scale exploitation in the past. The large scale use of coal has similar environmental problems, which are aggravated by difficulties in its proper characterization. Also, the mitigation of harmful gases and particulate matter that are released as a result of combustion is still depending on the development of new gas cleaning technologies including more efficient catalysts to improve its emission profile. On the other hand, biofuels are still struggling to fulfill their role in reducing our high dependence on fossil fuels. Fatty acid alkyl esters (biodiesel) from vegetable oils and ethanol from cane sucrose and corn starch are mature technologies whose market share is partially limited by the availability of their raw materials. For this reason, there has been a great effort to develop "second-generation" technologies to produce methanol, ethanol, butanol, biodiesel, biogas (methane), bio-oils, syngas and synthetic fuels from lower grade renewable feedstocks such as lignocellulosic materials whose consumption would not interfere with the rather sensitive issues of food security. Advanced fermentation processes are envisaged as "third generation" technologies and these are primarily linked to the use of algae feedstocks as well as other organisms that could produce biofuels or simply provide microbial biomass for the processes listed above. Due to the complexity and cost of their production chain, "third generation" technologies usually aim at high value added biofuels such as biojet fuel, biohydrogen and hydrocarbons with a fuel performance similar to diesel or gasoline, situations in which the use of genetically modified organisms is usually required. In general, the main challenges in this field could be summarized as follows: (a) the need for prospecting alternative sources of biomass that are not linked to the food chain; (b) the intensive use of green chemistry principles in our current industrial activities; (c) the development of mature technologies for the production of second and third generation biofuels; (d) the development of safe bioprocesses that are based on environmentally benign microorganisms; (e) the scale-up of potential technologies to a suitable demonstration scale; and (f) the full understanding of the technological and environmental implications of the food vs. fuel debate. On the basis of these, the main objective of this article is to stimulate the discussion and help the decision making regarding "energy security" issues and their challenges for modern society, in such a way to encourage the participation of the Brazilian Chemistry community in the design of a road map for a safer, sustainable and prosper future for our nation.

Advances in ethanol reforming for the production of hydrogen

Catalytic steam reforming of ethanol (SRE) is a promising route for the production of renewable hydrogen (H2). This article reviews the influence of doping supported-catalysts used in SRE on the conversion of ethanol, selectivity for H2, and stability during long reaction periods. In addition, promising new technologies such as membrane reactors and electrochemical reforming for performing SRE are presented.

Amphoteric behavior of di-2-pyridyl ketone benzoylhydrazone in ethanol-water mixtures

The ligand di-2-pyridyl ketone benzoylhydrazone (DPKBH) is widely used for the determination of transition metal ions in environmental samples. Due to its low solubility in water it is used in aqueous-ethanol (1:1) solvent and for higher sensitivity the pH must be properly adjusted. The properties of DPKBH solutions must be known at different ethanol-water percentages in order to achieve higher sensitivity and/or selectivity for metal analysis. The acid-base behavior of this reagent in aqueous-ethanol solvent and the dissociation/ionization constants (pK1 and pK2) of DPKBH have been determined in different aqueous-ethanol solvent mixtures (10, 20, 30 and 50 % V/V of ethanol) from potentiometric titrations at 25.0 ± 0.1° C. As the amount of ethanol increases from 10 to 30% the pK1 and pK2 values increased, but they decreased in 50% of the organic solvent. The results are correlated with the medium composition and its effects.

Effect of alcohol concentration and electrode composition on the ethanol electrochemical oxidation

The electrochemical oxidation on platinum and platinum rhodium bimetallic electrodes was studied by Differential Electrochemical Mass Spectrometry for several ethanol concentrations in solution. It is found that increasing the ethanol concentration the production of the partially oxidized products (acetaldehyde) increases as the concentration increases. On the other hand, addition of 25% at. of rhodium increases the full oxidation to CO2. Another interesting result observed is a correlation between the intensity of the dehydrogenations peak at 0.3 V vs. RHE and the CO2 yield for the different ethanol concentration studied.

Feasibility study for acidic biorefinery concept

The integration a recovery process for spent sulfite liquor from a sulfite cooking process with a kraft pulp mill was studied in this thesis work. The process includes a fermentation process for the production of biofuel. The calculation for three cases was done. The three cases considered were with a spruce sulfite pulp production of 100, 250 and 1000 Adt/day corresponding to 10, 25 and 100% of the total pulp production. A kraft cooking process with prehydrolysis was taken in consideration as reference. Compared to kraft cooking with prehydrolysis a bigger amount of ethanol can be produced by sulfite cooking. In the kraft prehydrolysis case 40 t/day of ethanol and 1000 Adt/day pine pulp is produced and in the sulfite case the production is 113 t/day of ethanol and 1000 Adt/day of spruce pulp. The energy consumption in the sulfite process is assumed to be slightly higher than in the kraft prehydrolysis process. The recovery system for spent liquor mix was studied. The evaporation of the spent cooking liquors should be done separately. The approximately composition of melt was calculated. A comparison of all four cases was done and profitability was estimated.

Production of biodiesel from babassu oil using methanol-ethanol blends

Maranhão state in Brazil presents a big potential for the cultivation of several oleaginous species, such as babassu, soybean, castor oil plant, etc... These vegetable oils can be transformed into biodiesel by the transesterification reaction in an alkaline medium, using methanol or ethanol. The biodiesel production from a blend of these alcohols is a way of adding the technical and economical advantages of methanol to the environmental advantages of ethanol. The optimized alcohol blend was observed to be a methanol/ethanol volume ratio of 80 % MeOH: 20 % EtOH. The ester content was of 98.70 %, a value higher than the target of the ANP, 96.5 % (m/m), and the biodiesel mass yield was of 95.32 %. This biodiesel fulfills the specifications of moisture, specific gravity, kinematic viscosity and percentages of free alcohols (methanol plus ethanol) and free glycerin.

On the potential utilisation of sawdust and wood chip screenings

This work is based on the utilisation of sawdust and wood chip screenings for different purposes. A substantial amount of these byproducts are readily available in the Finnish forest industry. A black liquor impregnation study showed that sawdust-like wood material behaves differently from normal chips. Furthermore, the fractionation and removal of the smallest size fractions did not have a significant effect on the impregnation of sawdust-like wood material. Sawdust kraft cooking equipped with an impregnation stage increases the cooking yield and decreases the lignin content of the produced pulp. Impregnation also increases viscosity of the pulp and decreases chlorine dioxide consumption in bleaching. In addition, impregnation increases certain pulp properties after refining. Hydrotropic extraction showed that more lignin can be extracted from hardwood than softwood. However, the particle size had a major influence on the lignin extraction. It was possible to extract more lignin from spruce sawdust than spruce chips. Wood chip screenings are usually combusted to generate energy. They can also be used in the production of kraft pulp, ethanol and chemicals. It is not economical to produce ethanol from wood chip screenings because of the expensive wood material. Instead, they should be used for production of steam and energy, kraft pulp and higher value added chemicals. Bleached sawdust kraft pulp can be used to replace softwood kraft pulp in mechanical pulp based papers because it can improve certain physical properties. It is economically more feasible to use bleached sawdust kraft pulp in stead of softwood kraft pulp, especially when the reinforcement power requirement is moderate.

Wood consumption rates of forest species by subterranean termites (Isoptera) under field conditions

Termites are well -known for their capacity to damage and destroy wood and wood products of all kinds in the tropics and subtropics. A field test was undertaken to evaluate variations in wood consumption of Pinus sp. and three species of Eucalyptus by subterranean termites. The test consisted of wooden stakes of each species being initially submitted to water immersion for 0, 24, 48 and 72 h, and buried in the ground to natural infestation by subterranean termites for an exposure period of 30, 45 and 60 days. Three species of subterranean termites were identified: Heterotermes longiceps (Snyder), Coptotermes gestroi (Wasmann) (Isoptera: Rhinotermitidae), and Nasutitermes jaraguae (Holmgren) (Isoptera: Termitidae). This is the first record of occurrence of H. longiceps in the state of Rio de Janeiro. Although the wood-consumption rates were not correlated significantly with their wood densities, there was a tendency of the softwoods (E. robusta and Pinus sp.) to be more consumed by subterranean termites than the woods of intermediate hardness (E. pellita and E. urophylla). Among the eucalyptus, E. robusta showed to be more susceptible to attack by subterranean termites than E. pellita and E. urophylla

Reduction of specific energy consumption of a thermomechanical pulping plant

Kuumahiertoprosessi on erittäin energiaintensiivinen prosessi, jonka energianominaiskulutus (EOK) on yleisesti 2–3.5 MWh/bdt. Noin 93 % energiasta kuluu jauhatuksessa jakautuen niin, että kaksi kolmasosaa kuluu päälinjan ja yksi kolmasosa rejektijauhatuksessa. Siksi myös tämän työn tavoite asetettiin vähentämään energian kulutusta juuri pää- ja rejektijauhatuksessa. Päälinjan jauhatuksessa tutkimuskohteiksi valittiin terityksen, tehojaon ja tuotantotason vaikutus EOK:een. Rejektijauhatuksen tehostamiseen pyrittiin yrittämällä vähentää rejektivirtaamaa painelajittelun keinoin. Koska TMP3 laitoksen jauhatuskapasiteettia on nostettu 25 %, tavoite oli nostaa päälinjan lajittelun kapasiteettia saman verran. Toisena tavoitteena oli pienentää rejektisuhdetta pää- ja rejektilajittelussa ja siten vähentää energiankulutusta rejektijauhatuksessa. Näitä tavoitteita lähestyttiin vaihtamalla päälinjan lajittimiin TamScreen-roottorit ja rejektilajittimiin Metso ProFoil-roottorit ja optimoimalla kuitufraktiot sihtirumpu- ja prosessiparametrimuutoksin. Syöttävällä terätyypillä pystyttiin vähentämään EOK:ta 100 kWh/bdt, mutta korkeampi jauhatusintensiteetti johti myös alempiin lujuusominaisuuksiin, korkeampaan ilmanläpäisyyn ja korkeampaan opasiteettiin. Myös tehojaolla voitiin vaikuttaa EOK:een. Kun ensimmäisen vaiheen jauhinta kuormitettiin enemmän, saavutettiin korkeimmillaan 70 kWh/bdt EOK-vähennys. Tuotantotason mittaamisongelmat heikensivät tuotantotasokoeajojen tuloksia siinä määrin, että näiden tulosten perusteella ei voida päätellä, onko EOK tuotantotasoriippuvainen vai ei. Päälinjan lajittelun kapasiteettia pystyttiin nostamaan TS-roottorilla vain 18 % jääden hieman tavoitetasosta. Rejektilajittelussa pystyttiin vähentämään rejektimäärää huomattavasti Metso ProFoil-roottorilla sekä sihtirumpu- ja prosessiparametrimuutoksin. Lajittamokehityksellä saavutettu EOK-vähennys arvioitiin massarejektisuhteen pienentymisen ja rejektijauhatuksessa käytetyn EOK:n avulla olevan noin 130 kWh/bdt. Yhteenvetona voidaan todeta, että tavoite 300 kWh/bdt EOK-vähennyksestä voidaan saavuttaa työssä käytetyillä tavoilla, mikäli niiden täysi potentiaali hyödynnetään tuotannossa.

Water consumption when exposed to sun and shade for native goats in the semiarid of the State of Paraiba, Brazil

This work aimed to evaluate the preference and water consumption of native goats in the semiarid of Brazil. The water was freely supplied, in individual buckets, one exposed to the sun and the other in the shade. The experiment was realized using 18 animals of Moxotó, Graúna and Azul breeds, with average weight of 16,6 ± 2,4 kg, kept in confinement in individual stalls equipped with feeders and drinkers, during the period from January to February of 2009. The water temperature was measured by sensors (thermocouples type T - copper/constantan), which were coupled to a system of data acquisition. It was observed that the average water temperature exposed to the sun was 29.02 ºC, and 23.85 ºC in the shade. For all breeds there was a preference for the water exposed to the sun, corresponding to an average consumption of 64.71% of the total. Among the breeds, the greatest preference for water exposed to the sun was the Azul (71.18%), followed by the Moxotó (65.95%) and the Graúna (57.00%). The animals consumed more water during the day, and the average water consumption was 1.15 grams day-1, corresponding to 6.9 % of body weight of the animals.