Hydrolysis of acetic anhydride: Non-adiabatic calorimetric determination of kinetics and heat exchange

A simple calorimetric method to estimate both kinetics and heat transfer coefficients using temperature-versus-time data under non-adiabatic conditions is described for the reaction of hydrolysis of acetic anhydride. The methodology is applied to three simple laboratory-scale reactors in a very simple experimental setup that can be easily implemented. The quality of the experimental results was verified by comparing them with literature values and with predicted values obtained by energy balance. The comparison shows that the experimental kinetic parameters do not agree exactly with those reported in the literature, but provide a good agreement between predicted and experimental data of temperature and conversion. The differences observed between the activation energy obtained and the values reported in the literature can be ascribed to differences in anhydride-to-water ratios (anhydride concentrations). (C) 2010 Elsevier Ltd. All rights reserved.

Degradation of Poly(ethylene glycol) in Aqueous Solution by Photo-Fenton and H(2)O(2)/UV Processes

This article reports experimental results obtained in a laboratory-scale photochemical reactor on the photodegradation of poly(ethylene glycol) (PEG) in aqueous solutions by means of the photo-Fenton and H(2)O(2)/UV processes. Dilute water solutions of PEG were fed to a batch reactor, mixed with pertinent reactants, and allowed to react under different conditions. Reaction progress was evaluated by sampling and analyzing the concentration of the total organic carbon (TOC) in solution as a function of the reaction time. Organic acids formed during oxidation were determined by HPLC analyses. The main acids detected in both processes were acetic and formic. Glycolic acid was detected only in the photo-Fenton process, and malonic acid was detected only in the H(2)O(2)/UV treatment, indicating that different reaction paths occur in these processes. The characteristics of both processes are discussed, based on the evolution of the TOC-time curves and the concentration profiles of the monitored organic acids. The experimental results constitute a contribution to the design of industrial processes for the treatment of wastewaters containing soluble polymers with similar properties.

Batch Liquid-Liquid Extraction of Phenol from Aqueous Solutions

The aim of this work is the study of batch liquid-liquid extraction of phenol from aqueous solutions in a bench-scale well-mixed reactor. The influence of the ratio of phase volumes, temperature, and rotational speed on phenol removal (0.72-1.1% w/w) was investigated using methyl isobutyl ketone as an extracting solvent. For this purpose, the ratio of phase volumes were set at 0.1 and 0.2, the temperature at 10, 20, and 30 degrees C, and the rotational speed at 300, 400, and 500 rpm. A physical model based on the material balance of the phases as well as the equation of mass flux between the phases allowed the estimation of the overall coefficient of mass transfer coupled with the superficial area. Moreover, it proved to fit, satisfactorily well, the experimental data of residual phenol concentration in the organic phase versus time under all the conditions investigated.

Photo-Fenton removal of water-soluble polymers

This paper presents the results of experiments carried out in a laboratory-scale photochemical reactor on the photodegradation of different polymers in aqueous solutions by the photo-Fenton process. Solutions of three polymers, polyethyleneglicol (PEG), polyacrylamide (PAM), and polyvinylpyrrolidone(PVP), were tested under different. conditions. The reaction progress was evaluated by sampling and analyzing the total organic carbon concentration in solution (TOC) along the reaction time. The behavior of the different polymers is discussed, based oil the evolution of the TOC-time curves. Under specific reaction conditions, the formation and coalescence of solid particles was Visually observed. Solids formation occurred simultaneously to a sharp decrease in the TOC of the liquid phase. This may be favorable for the treatment of industrial wastewater containing polymers, since the photodegradation process can be Coupled with solid separation systems. which may reduce the treatment cost. (C) 2008 Elsevier B.V. All rights reserved.

USE OF SOLAR ENERGY IN THE TREATMENT OF WATER CONTAMINATED WITH PHENOL BY PHOTOCHEMICAL PROCESSES

The solar driven photo-Fenton process for treating water containing phenol as a contaminant has been evaluated by means of pilot-scale experiments with a parabolic trough solar reactor (PTR). The effects of Fe(II) (0.04-1.0 mmol L(-1)), H(2)O(2) (7-270 mmol L(-1)), initial phenol concentration (100 and 500 mg C L(-1)), solar radiation, and operation mode (batch and fed-batch) on the process efficiency were investigated. More than 90% of the dissolved organic carbon (DOC) was removed within 3 hours of irradiation or less, a performance equivalent to that of artificially-irradiated reactors, indicating that solar light can be used either as an effective complementary or as an alternative source of photons for the photo-Fenton degradation process. A non-linear multivariable model based on a neural network was fit to the experimental results of batch-mode experiments in order to evaluate the relative importance of the process variables considered on the DOC removal over the reaction time. This included solar radiation, which is not a controlled variable. The observed behavior of the system in batch-mode was compared with fed-batch experiments carried out under similar conditions. The main contribution of the study consists of the results from experiments under different conditions and the discussion of the system behavior. Both constitute important information for the design and scale-up of solar radiation-based photodegradation processes.

Optimal synthesis of Fenton reactor networks for phenol degradation

There is an increasing need to treat effluents contaminated with phenol with advanced oxidation processes (AOPs) to minimize their impact on the environment as well as on bacteriological populations of other wastewater treatment systems. One of the most promising AOPs is the Fenton process that relies on the Fenton reaction. Nevertheless, there are no systematic studies on Fenton reactor networks. The objective of this paper is to develop a strategy for the optimal synthesis of Fenton reactor networks. The strategy is based on a superstructure optimization approach that is represented as a mixed integer non-linear programming (MINLP) model. Network superstructures with multiple Fenton reactors are optimized with the objective of minimizing the sum of capital, operation and depreciation costs of the effluent treatment system. The optimal solutions obtained provide the reactor volumes and network configuration, as well as the quantities of the reactants used in the Fenton process. Examples based on a case study show that multi-reactor networks yield decrease of up to 45% in overall costs for the treatment plant. (C) 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Model for facilities or vendors location in a global scale considering several echelons in the Chain

The facilities location problem for companies with global operations is very complex and not well explored in the literature. This work proposes a MILP model that solves the problem through minimization of the total logistic cost. Main contributions of the model are the pioneer carrying cost calculation, the treatment given to the take-or-pay costs and to the international tax benefits such as drawback and added value taxes in Brazil. The model was successfully applied to a real case of a chemical industry with industrial plants and sales all over the world. The model application recommended a totally new sourcing model for the company.

Emerging Threats and Opportunities for Large-Scale Ecological Restoration in the Atlantic Forest of Brazil

Over the past 150 years, Brazil has played a pioneering role in developing environmental policies and pursuing forest conservation and ecological restoration of degraded ecosystems. In particular, the Brazilian Forest Act, first drafted in 1934, has been fundamental in reducing deforestation and engaging private land owners in forest restoration initiatives. At the time of writing (December 2010), however, a proposal for major revision of the Brazilian Forest Act is under intense debate in the National Assembly, and we are deeply concerned about the outcome. On the basis of the analysis of detailed vegetation and hydrographic maps, we estimate that the proposed changes may reduce the total amount of potential areas for restoration in the Atlantic Forest by approximately 6 million hectares. As a radically different policy model, we present the Atlantic Forest Restoration Pact (AFRP), which is a group of more than 160 members that represents one of the most important and ambitious ecological restoration programs in the world. The AFRP aims to restore 15 million hectares of degraded lands in the Brazilian Atlantic Forest biome by 2050 and increase the current forest cover of the biome from 17% to at least 30%. We argue that not only should Brazilian lawmakers refrain from revising the existing Forest Law, but also greatly step up investments in the science, business, and practice of ecological restoration throughout the country, including the Atlantic Forest. The AFRP provides a template that could be adapted to other forest biomes in Brazil and to other megadiversity countries around the world.

Watershed scale temporal stability of soil water content

The recognition of temporally stable locations with respect to soil water content is of importance for soil water management decisions, especially in sloping land of watersheds. Neutron probe soil water content (0 to 0.8 m), evaluated at 20 dates during a year in the Loess Plateau of China, in a 20 ha watershed dominated by Ust-Sandiic Entisols and Aeolian sandy soils, were used to define their temporal stability through two indices: the standard deviation of relative difference (SDRD) and the mean absolute bias error (MABE). Specific concerns were (a) the relationship of temporal stability with soil depth, (b) the effects of soil texture and land use on temporal stability, and (c) the spatial pattern of the temporal stability. Results showed that temporal stability of soil water content at 0.2 m was significantly weaker than those at the soil depths of 0.6 and 0.8 m. Soil texture can significantly (P<0.05) affect the stability of soil water content except for the existence of an insignificant difference between sandy loam and silt loam textures, while temporal stability of areas covered by bunge needlegrass land was not significantly different from those covered by korshinsk peashrub. Geostatistical analysis showed that the temporal stability was spatially variable in an organized way as inferred by the degree of spatial dependence index. With increasing soil depth, the range of both temporal stability indices showed an increasing trend, being 65.8-120.5 m for SDRD and 148.8-214.1 m for MABE, respectively. This study provides a valuable support for soil water content measurements for soil water management and hydrological applications on sloping land areas. (C) 2010 Elsevier B.V. All rights reserved.

Large-scale ecological restoration of high-diversity tropical forests in SE Brazil

The complex interactions among endangered ecosystems, landowners` interests, and different models of land tenure and use, constitute an important series of challenges for those seeking to maintain and restore biodiversity and augment the flow of ecosystem services. Over the past 10 years, we have developed a data-based approach to address these challenges and to achieve medium and large-scale ecological restoration of riparian areas on private lands in the state of Sao Paulo, southeastern Brazil. Given varying motivations for ecological restoration, the location of riparian areas within landholdings, environmental zoning of different riparian areas, and best-practice restoration methods were developed for each situation. A total of 32 ongoing projects, covering 527,982 ha, were evaluated in large sugarcane farms and small mixed farms, and six different restoration techniques have been developed to help upscale the effort. Small mixed farms had higher portions of land requiring protection as riparian areas (13.3%), and lower forest cover of riparian areas (18.3%), than large sugarcane farms (10.0% and 36.9%, respectively for riparian areas and forest cover values). In both types of farms, forest fragments required some degree of restoration. Historical anthropogenic degradation has compromised forest ecosystem structure and functioning, despite their high-diversity of native tree and shrub species. Notably, land use patterns in riparian areas differed markedly. Large sugarcane farms had higher portions of riparian areas occupied by highly mechanized agriculture, abandoned fields, and anthropogenic wet fields created by siltation in water courses. In contrast, in small mixed crop farms, low or non-mechanized agriculture and pasturelands were predominant. Despite these differences, plantations of native tree species covering the entire area was by far the main restoration method needed both by large sugarcane farms (76.0%) and small mixed farms (92.4%), in view of the low resilience of target sites, reduced forest cover, and high fragmentation, all of which limit the potential for autogenic restoration. We propose that plantations should be carried out with a high-diversity of native species in order to create biologically viable restored forests, and to assist long-term biodiversity persistence at the landscape scale. Finally, we propose strategies to integrate the political, socio-economic and methodological aspects needed to upscale restoration efforts in tropical forest regions throughout Latin America and elsewhere. (C) 2010 Elsevier BA/. All rights reserved.

Ultrasound Irradiation Promoted Large-Scale Preparation in Aqueous Media and Antioxidant Activity of Azoles

The scaled-up preparation of 1H-pyrazole, 1-phenylpyrazole and isoxazole via sonocatalysis is reported. The products were isolated in good yields in short time reaction. These compounds had been assayed for antioxidant activity by ORAC and DPPH methodologies. The results showed that only 1-phenylpyrazole presented good antioxidant activity compared with Trolox(R).

Emulsified systems based on glyceryl monostearate and potassium cetyl phosphate: Scale-up and characterization of physical properties

introducing a pharmaceutical product on the market involves several stages of research. The scale-up stage comprises the integration of previous phases of development and their integration. This phase is extremely important since many process limitations which do not appear on the small scale become significant on the transposition to a large one. Since scientific literature presents only a few reports about the characterization of emulsified systems involving their scaling-up, this research work aimed at evaluating physical properties of non-ionic and anionic emulsions during their manufacturing phases: laboratory stage and scale-up. Prototype non-ionic (glyceryl monostearate) and anionic (potassium cetyl phosphate) emulsified systems had the physical properties by the determination of the droplet size (D[4,3 1, mu m) and rheology profile. Transposition occurred from a batch of 500-50,000 g. Semi-industrial manufacturing involved distinct conditions: intensity of agitation and homogenization. Comparing the non-ionic and anionic systems, it was observed that anionic emulsifiers generated systems with smaller droplet size and higher viscosity in laboratory scale. Besides that, for the concentrations tested, augmentation of the glyceryl monostearate emulsifier content provided formulations with better physical characteristics. For systems with potassium cetyl phosphate, droplet size increased with the elevation of the emulsifier concentration, suggesting inadequate stability. The scale-up provoked more significant alterations on the rheological profile and droplet size on the anionic systems than the non-ionic. (C) 2008 Elsevier B.V. All rights reserved.

Measurement of functional ability following traumatic brain injury using the Clinical Outcomes Variable Scale: A reliability study

This study determined the inter-tester and intra-tester reliability of physiotherapists measuring functional motor ability of traumatic brain injury clients using the Clinical Outcomes Variable Scale (COVS). To test inter-tester reliability, 14 physiotherapists scored the ability of 16 videotaped patients to execute the items that comprise the COVS. Intra-tester reliability was determined by four physiotherapists repeating their assessments after one week, and three months later. The intra-class correlation coefficients (ICC) were very high for both inter-tester reliability (ICC > 0.97 for total COVS scores, ICC > 0.93 for individual COVS items) and intra-tester reliability (ICC > 0.97). This study demonstrates that physiotherapists are reliable in the administration of the COVS.

Air Entrainment Processes in a Full-Scale Rectangular Dropshaft at Large Flows

Rectangular dropshafts, commonly used in sewers and storm water systems, are characterised by significant flow aeration. New detailed air-water flow measurements were conducted in a near-full-scale dropshaft at large discharges. In the shaft pool and outflow channel, the results demonstrated the complexity of different competitive air entrainment mechanisms. Bubble size measurements showed a broad range of entrained bubble sizes. Analysis of streamwise distributions of bubbles suggested further some clustering process in the bubbly flow although, in the outflow channel, bubble chords were in average smaller than in the shaft pool. A robust hydrophone was tested to measure bubble acoustic spectra and to assess its field application potential. The acoustic results characterised accurately the order of magnitude of entrained bubble sizes, but the transformation from acoustic frequencies to bubble radii did not predict correctly the probability distribution functions of bubble sizes.

Turbulent Time and Length Scale Measurements in High-Velocity Open Channel Flows

In high-velocity open channel flows, the measurements of air-water flow properties are complicated by the strong interactions between the flow turbulence and the entrained air. In the present study, an advanced signal processing of traditional single- and dual-tip conductivity probe signals is developed to provide further details on the air-water turbulent level, time and length scales. The technique is applied to turbulent open channel flows on a stepped chute conducted in a large-size facility with flow Reynolds numbers ranging from 3.8 E+5 to 7.1 E+5. The air water flow properties presented some basic characteristics that were qualitatively and quantitatively similar to previous skimming flow studies. Some self-similar relationships were observed systematically at both macroscopic and microscopic levels. These included the distributions of void fraction, bubble count rate, interfacial velocity and turbulence level at a macroscopic scale, and the auto- and cross-correlation functions at the microscopic level. New correlation analyses yielded a characterisation of the large eddies advecting the bubbles. Basic results included the integral turbulent length and time scales. The turbulent length scales characterised some measure of the size of large vortical structures advecting air bubbles in the skimming flows, and the data were closely related to the characteristic air-water depth Y90. In the spray region, present results highlighted the existence of an upper spray region for C > 0.95 to 0.97 in which the distributions of droplet chord sizes and integral advection scales presented some marked differences with the rest of the flow.