Novel Esterification of Glycerol Catalysed by Tin Chloride (II): A Recyclable and Less Corrosive Process for Production of Bio-Additives

Abstract  

In this work, a novel process based on use of a SnCl₂·2H₂O catalyst which is less corrosive, inexpensive, and a water tolerant Lewis acid was employed for synthesis of fuel bio-additives from glycerol. High yields and selectivities were achieved for glycerol esterification with acetic acid under mild reaction conditions. The SnCl₂ catalyst showed to be as active as p-toluene sulfonic and sulfuric acid, catalysts commonly used in acid-catalysed esterification reactions. However, its use has significant advantages in comparison to these Br?nsted acid catalysts, including lower reactor corrosion and unnecessary neutralization at the end reaction. The SnCl₂ catalyst can also be recovered and reused without loss of catalytic activity. Additionally, effects of reaction temperature, HOAc:glycerol molar ratio and catalyst concentration on both selectivity and yield of glycerol acetates were also investigated. The lower corrosiveness, facilitated handling, as well as potential for reuse without activity loss after simple recycle protocols are positive aspects of SnCl₂ catalysts.     

Combining Upscaling and Downscaling of Methane Emissions from Rice Fields: Methodologies and Preliminary Results

The uncertainty in the methane (CH₄) source strength of rice fields is among the highest of all sources in the global CH₄ budget. Methods to estimate the source strength of rice fields can be divided into two scaling categories: bottom-up (upscaling) and top-down (downscaling). A brief review of upscaling and downscaling methodologies is presented. The combination of upscaling and downscaling methodologies is proposed as a potential method to reduce the uncertainty in the regional CH₄ source strength of rice fields. Some preliminary results based on upscaling and downscaling are presented and the limitations of the approaches are discussed. The first case study focuses on upscaling by using a field-scale model in combination with spatial databases to calculate CH₄ emissions for the island of Java. The reliability of upscaling results is limited by the uncertainty in model input parameters such as soil properties and organic carbon management. Because controlling variables such as harvested rice area may change on relatively short time scales, a land use change model (CLUE) was used to quantify the potential land use changes on Java in the period 1994–2010. The predicted changes were evaluated using the CH₄ emission model. Temporal scaling by coupling land use change models and emission models is necessary to answer policy-related questions on future greenhouse gas emissions. In a downscaling case study, we investigate if inverse modeling can constrain the emissions from rice fields by testing a standard CH₄ from rice scenario and a low CH₄ from rice scenario (80 and 30 Tg CH₄ yr^–1, respectively). The results of this study are not yet conclusive; to obtain fine-resolution CH₄ emission estimates over the Southeast Asian continent, the monitoring network atmospheric mixturing ratios need to be extended and located closer to the continental sources.     

Detection and identification of mycobacteria in the Lisbon water distribution system.

Mycobacteria have emerged as a major cause of opportunistic infections. Until the present, only a few studies have characterized mycobacteria present in the water distribution system of urban areas. In this study, we characterize these microorganisms in the Lisbon water distribution system. Our results indicate a high rate of positivities (90.5%) with mainly saprophytic mycobacteria. Around 63% of these results belong to strains of Mycobacterium gordonae indicating a generalized proliferation of this species in the Lisbon water distribution system. A total of 21.05% of the isolates are from M. kansasii, M. intracellulare and M. chelonae.     

The elastic moduli and fatigue properties of canine trabecular bone tissue

The elastic modulus and fatigue properties of canine and human trabecular bone tissues (single trabeculae) were experimentally determined on a microstructural level using four-point bending cyclic test, and they were compared based on microstructural characteristics and mineral density. The results showed that canine trabecular bone tissue had significantly lower modulus and lower fatigue strength than human tissue. The observed microstructural differences between the two tissues may be more responsible for the differences, although the lower mineral density in canine tissue might also have contributed to the lower modulus and fatigue strength.     

Effect of ZnO contents at the surface of brass-plated steel cord on the adhesion property to rubber compound

An effect of ZnO concentration at the surface of brass-plated steel cord on the adhesion property between a rubber compound and a brass-plated steel cord was investigated. Cord composition was determined by an Auger microscope with Ar ion sputtering. Two different steel cords were prepared; one (cord A) had higher ZnO concentration at the cord surface compared to the other (cord B). Pull-out force of unaged adhesion sample of cord A was lower than that of cord B. But the adhesion durability of the humidity-aged adhesion sample of cord A was better than the latter. Rubber coverage of the pull out cord for the unaged adhesion samples of cord A was poor, indicating insufficient formation of an adhesion layer. Pull-out force of the thermal-aged adhesion samples decreased with increasing aging time and that of cord A was lower than that of cord B. The enhancement of rubber coverage during initial aging period could be explained by an additional formation of copper sulfide at the adhesion interphase and an increase of modulus of rubber compound adjacent to the adhesion layer. With further increases of aging time, adhesion interphase grew excessively and the physical property of rubber compound deteriorated significantly, such that rubber coverage of adhesion samples decreased markedly with increasing aging time.     

Nucleation and growth of aluminium oxide on silicon in the CVD process

Films of aluminium oxide have been formed on single crystal silicon substrates using AlCl₃-CO₂-H₂ gas mixtures in a cold-walled chemical vapour deposition (CVD) reactor. The nucleation and subsequent growth of the deposit have been observed under the varying process parameters. It is found that the nucleation and growth of the Al₂O₃ are dependent on the H₂O flux and H₂O supersaturation. An activation energy of 34.8 Kcal mol^–1 is obtained for the growth rate indicating that the CVD of Al₂O₃ on silicon is a thermally activated process and limited by surface reaction. Scanning electron micrographs (SEM) show that the deposited films are amorphous at low temperature, 850° C, but change to fine grained polycrystalline structure at high temperature, 1000° C.     

The effects of soluble gas stabilisation on the quality of packed sardine fillets (Sardina pilchardus) stored in air,VP and MAP

Sardine (Sardina pilchardus) is a species that for its abundance assumes great importance in the Portuguese fishing sector. In order to contribute for a better utilisation of this species, the aim of this study was to investigate the effect of the pre‐treatment with soluble gas stabilisation (SGS) (100% CO₂ at 2 bar, during 15 and 30 min) on the quality and shelf‐life of sardine fillets, packed in air (AP), vacuum (VP) and modified atmosphere (MAP: 5% O₂/35% CO₂/60% N₂). During the chilled storage, the quality changes were evaluated by sensory evaluation, chemical and microbiological analysis. The total volatile basic nitrogen content remained almost constant, between 16 and 19 mg N/100 g muscle, during the storage period, for all samples. The TBARs values increased with storage time, for all batches and storage conditions. The application of SGS treatment to sardine fillets, resulted in a bacteriostatic effect, contributing to the improvement of the microbiological quality of fillets. Considering a sensory criteria, the shelf‐life of SGS pre‐treated sardine fillets was found to be 5 days in AP and MAP while in VP‐treated fillets a shelf‐life of 8 days was reported. At sensory rejection, sardine fillets presented a K‐value of 30% in AP and MAP batches and 40% in VP batch.     

Density and viscosity of tetralin and trans-decalin

New measurements are reported for the density and viscosity of tetralin and trans-decalin. The density was determined from room temperature to 60°C for tetralin and to 95°C for trans-decalin. The kinematic viscosity was measured up to temperatures slightly above 100°C. Our results improve upon the values recommended by the American Petroleum Institute for these liquids.     

Design and optimization of an extrusion die for the production of wood–plastic composite profiles

In this work, the optimization of an extrusion die designed for the production of a wood–plastic composite (WPC) decking profile is investigated. The optimization was performed with the help of numerical tools, more precisely, by solving the continuity and momentum conservation equations that govern such flow, and aiming to balance properly the flow distribution at the extrusion die flow channel outlet. To capture the rheological behavior of the material, we used a Bird‐Carreau model with parameters obtained from a fit to the (shear viscosity versus shear‐rate) experimental data, collected from rheological tests. To yield a balanced output flow, several numerical runs were performed by adjusting the flow restriction at different regions of the flow‐channel parallel zone cross‐section. The simulations were compared with the experimental results and an excellent qualitative agreement was obtained, allowing, in this way, to attain a good balancing of the output flow and emphasizing the advantages of using numerical tools to aid the design of profile extrusion dies. POLYM. ENG. SCI., 55:1849?1855, 2015. © 2014 Society of Plastics Engineers