Catalyst pore plugging effects on hydrocracking reactions in an Ebullated bed reactor operation

This paper analyzes the deactivation effects of NiMo/Al₂O₃ catalyst during the operation in an Ebullated bed reactor for Heavy residue hydrocracking. The spent catalysts were characterized by chemical analysis, ¹³C NMR, ESM, DRX, and by using thermal programmed oxidation and diffusion studies in a shallow bed micro-reactor. The deactivations were performed in a 5 l continuously stirred tank reactor, while the spent catalysts were tested in a 0.05 l micro-reactor. The study focused on determining the properties of the external layer of the catalyst and on evaluating the internal coke and metal deposition. The results indicated that initial deactivation is mainly due to coke depositions, while its impact on mass transfer reaction control depends on temperature. In long-term deactivation, the metal deposition plays a more important role in blocking the internal micro- and meso-structures and in building up the external layer of the pellets.     

Evaluation of optimisation techniques and control variable formulations for a batch cooling crystallization process

The mathematical optimisation of a batch cooling crystallization process is considered in this work. The objective is to minimize the standard deviation of the final crystal size distribution (CSD), which is an important feature in many industrial processes. The results with the problem written as a nonlinear programming and solved with the successive quadratic programming (SQP) coupled with the discretization of the control variable are compared with those obtained when SQP coupled with the parameterisation of the control variable is applied. Also it is proposed the implementation of the genetic algorithm (GA) coupled with parameterisation of the control variable. Extensive evaluations show that the SQP method is sensitive both to the parameterisation formulation and to the initial estimate. The solution with GA provided the control variable profile that leads to the minimum standard deviation of the final CSD. Nevertheless, it is a very time-consuming technique, which hampers its utilization in real time applications. However, its feature of global searching suggests its suitability in solving offline problems, in order to provide initial setup profiles. Bearing this in mind, it is proposed an algorithm which allows for the implementation of GA solution in a real time fashion, taking advantage of its robustness to find out the optimal solution.     

A comparison of lipids from liver and hepatoma subcellular membranes

Subcellular fractions of nuclei, mitochondria, endoplasmic reticulum, plasma membrane and cytosol were prepared from liver and hepatoma 72288CTC. Marker enzyme activities, biochemical compositions and electron microscopy were used to establish purity. Hepatoma NADH: cytochrome C reductase and 5′-nucleotidase exhibited abnormal subcellular distributions. The lipids from the subcellular fractions were examined in detail. Mitochondria and plasma membranes were characterized by elevated percentages of diphosphatidylglycrerol and sphingomyelin, respectively, in both tissues. All hepatoma subcellular fractions contained dramatically elevated levels of sphingomyelin and cholesterol, two components that form preferential strong complexes in vitro. The fatty acid composition of hepatoma sphingomyelin differed markedlg from liver and, unlike liver, did not exhibit organelle specific compositions. Some hepatoma lipid classes contained reduced percentages of palmitate while others contained higher levels. Hepatoma phosphatidylcholine and phosphatidylethanolamine from organelles contained lower percentages of long chain polyunsaturated fatty acids than liver. Generally, unique fatty acid profiles exhibited by individual phospholipid classes of liver subcellular fractions were absent or much reduced in the hepatoma. The ratios of oleate to vaccenate were near one for most of the phospholipid classes of most liver fractions, but all hepatoma classes, with few exceptions, contained a much higher percentage of oleate in all subcellular fractions. The hypothesis is proposed that the origin of some acyl moieties for the biosynthesis of various hepatome lipid classes differs from liver sources. The possible changes in acyl pools, sources and compartments for complex lipid biosynthesis could result in change in the quantities of molecular species that could contribute to the abnormal properties of the hepatoma membranes.     

Variability for oil and fatty acid composition in castorbean varieties

Thirty-six castorbean varieties were surveyed for oil and fatty acid composition, in order to determine variability of these seed compounds. A large variability of seed oil percentage was observed, ranging from 39.6 to 59.5%. Concerning the fatty acids, little variability was observed for ricinoleic acid, which was the most abundant in the oil, ranging from 83.65 to 90.00%. The other fatty acids appeared in small concentrations and showed a small range: 0.87 to 2.35, 0.68 to 1.84, 2.96 to 5.64, 3.19 to 5.98, and 0.34 to 0.91%, for palmitic, stearic, oleic, linoleic, and linolenic acid, respectively. Non-significant correlations were observed between fatty acids and seed oil percentage. However, significant correlations were observed among fatty acid concentrations: positive and negative ones. These significant correlations could be associated with the biosynthetic pathways of the fatty acids, which are not fully elucidated. They suggest, however, that selection for a particular fatty acid will tend to increase those positively correlated, and decrease those negative ones. Selection and plant breeding techniques could then be applied to modify the oil content of the castorbean seeds, considering the variability observed. For the fatty acid composition, however, the variability was not large enough to make substantial changes in their concentrations by selection procedures. More varieties should be surveyed to find out if such variability is available.     

Off-line optimization and control for real time integration of a three-phase hydrogenation catalytic reactor

In order to develop and test the integration procedure, in this paper a real time process integration involving the optimization and control of the process is presented, in this case, with the two-layer approach. The used optimization algorithms were Levenberg–Marquardt and SQP that solve a non-linear least square problem subject to bounds on the variables. The two-layer approach is a hierarchical control structure where an optimization layer calculates the set points and manipulated variables to the advanced controller, which is based on the dynamic matrix control with constraints (QDMC). The non-isothermal dynamic model of the three-phase slurry catalytic reactor with appropriate solution procedure was utilized in this work (Vasco de Toledo, E. C., Santana, P. L., Maciel, M. R. W., & Maciel Filho, R. (2001). Dynamic modeling of a three-phase catalytic slurry reactor. Chemical Engineering Science, 56, 6055–6061). The model consists on mass and heat balance equations for the catalyst particles as well as for the bulk phases of gas and liquid. The model was used to describe the dynamic behavior of hydrogenation reaction of o-cresol to obtain 2-methil-cyclohexanol, in the presence of a catalyst Ni/SiO₂.     

An Accessible Platform for People With Disabilities

This article discusses a modular, accessible platform that provides a computing environment for people with disabilities accessible through adapted control devices and the television set at users’ homes. Relying on a standard television set as the presentation device allows dependent individuals, especially people with disabilities, to introduce new technological advances in communication and information management in their everyday lives. As a proof-of-concept, the solution presented offers a collection of educational and training services related to teleworking and the search of employment targeted to people with disabilities. A smart job advisor included among these services, which was designed to help our target users to locate job offers that best suit the abilities and disabilities of a particular individual, is also discussed to illustrate how semantic technologies can be applied to increase the perceived accessibility and inclusion by reducing the dependence from other persons. The platform developed, the introduction of semantic technologies, and the way adapted interfacing and presentation devices were integrated may also serve as inspiration to provide services to people with disabilities.     

Relationship between mouse liver Δ9 desaturase activity and plasma lipids

This study was undertaken to investigate the total plasma fatty acid composition and the relationship between plasma triacylglycerol (TG) levels and liver Δ9 desaturase activity in mice fed n−3 and/or n−6 fatty acid or hydrogenated coconut oil (HCO) (maximum 25 mg/g) supplemented diets. Generally, plasma TG levels and Δ9 desaturase activity were inversely correlated with the ratio of the sum of long chain n−3 fatty acids to 18∶2n−6 and to the ratio of the sum of long chain n−3 fatty acids to 18∶n−3, but they were positively correlated with the ratio of products and substrates (18∶1/18∶0) of the enzyme in plasma total lipids. The n−3 fatty acid (mainly 20∶5n−3) enriched diet, when compared to the HCO diet at 21 d, caused a significant reduction in plasma TG levels but not in Δ9 desaturase activity. However, a marked reduction in plasma TG content (50–60%) and Δ9 desaturase activity (55–70%) was observed when both 20∶5n−3 and 18∶3n−6 were supplemented in the diet. The plasma TG levels and Δ9 desaturase activity rose again when the animals were fed the HCO diet or chow. The results suggest that low dose supplementation of a mixture of n−3 (mainly 20∶5n−3) and n−6 (18∶3n−6) fatty acids modified both plasma TG content and liver Δ9 desaturase activity, in parallel.     

Sintering-driven effects on the band gap of (Pb,La)(Ti,Ni)O3 photovoltaic ceramics

In this work, the influence of the sintering temperature on the physical properties of (Pb_0.8La_0.2)(Ti_0.9Ni_0.1)O₃ (PLT-Ni) ceramics is reported. The experimental data revealed that the energy band gap of PLT-Ni ceramics could be tailored from approximately 2.7 to 2.0 eV by changing the sintering temperature from 1100°C to 1250°C. It is demonstrated that the simple substitution of Ti⁴⁺ by Ni²⁺ cations is effective to decrease the intrinsic band gap while increasing the tetragonality factor and the spontaneous polarization. However, the additional red-shift observed in the absorption edge of the PLT-Ni with increasing the sintering temperature was associated with a continuous increase in the oxygen vacancies () amount. It is believed that the impact of the creation of these thermally induced is manifold. The presence of and Ni²⁺ ions generate the Ni²⁺- defect-pairs that promoted both a decrease in the intrinsic band gap and an additional increase of the tetragonality factor, consequently, increasing the spontaneous polarization. The creation of Ni²⁺- defects also changed the local symmetry of Ni²⁺ ions from octahedral to a square pyramid, thus lifting the degeneracy of the Ni²⁺ 3d orbitals. With the increase in the sintering temperature, lower-energy absorbing intraband states were also formed due to an excess of , being responsible for an add-on shoulder in the absorption edge, extending the light absorption curve to longer wavelengths and leading to an additional absorption in “all investigated” spectrum as well.     

Organo-zincate molten salts as immobilising agents for organometallic catalysis

The combination of 1-n-butyl-3-methylimidazolium chloride with ZnCl₂ affords ionic mixtures with different melting point temperatures depending on the zinc molar fraction. RuCl₂(PPh₃)₃ immobilised in the low melting mixture (60°C) promotes the 1-hexene hydrogenation (turnover frequencies up to 44 min^–1) and the recovered solid catalyst phase can be reused several times.     

Evaluation of the removal of n-butanol vapor by the poly(lactic acid)-zeolite-TiO2 composite and formation of by-products

The use of polymeric films incorporated with zeolite-TiO₂ composites associated with UV radiation can be an alternative in the removal of volatile organic compounds (VOCs) through the adsorption and photodegradation processes. This study produced poly(lactic acid) (PLA) films incorporated with 13× zeolite, TiO₂, and 13×-TiO₂ zeolite composite to remove n-butanol and evaluate the by-products generated in the process. The results showed that 13× zeolite and TiO₂ added individually or as a composite to PLA, gave the polymer matrix a significant increase in the removal capacity of n-butanol. The best performance was presented by the zeolite-TiO₂, composite, confirming a synergistic effect. However, the formation of CO and CO₂ exceeded the expected values, with the verification that the polymeric matrix underwent photodegradation action by TiO₂. The polymeric film only containing zeolite is the most suitable for the removal of VOCs, as it did not present degradation of the PLA, generating a lower concentration of by-products.