Model-based study of a chemical-looping combustion process

Chemical-looping combustion (CLC) is a novel combustion technology with inherent separation of the greenhouse gas CO2. The technique typically employs a dual fluidized bed system where a metal oxide is used as a solid oxygen carrier that transfers the oxygen from combustion air to the fuel. The oxygen carrier is looping between the air reactor, where it is oxidized by the air, and the fuel reactor, where it is reduced by the fuel. Hence, air is not mixed with the fuel, and outgoing CO2 does not become diluted by the nitrogen, which gives a possibility to collect the CO2 from the flue gases after the water vapor is condensed. CLC is being proposed as a promising and energy efficient carbon capture technology, since it can achieve both an increase in power station efficiency simultaneously with low energy penalty from the carbon capture. The outcome of a comprehensive literature study concerning the current status of CLC development is presented in this thesis. Also, a steady state model of the CLC process, based on the conservation equations of mass and energy, was developed. The model was used to determine the process conditions and to calculate the reactor dimensions of a 100 MWth CLC system with bunsenite (NiO) as oxygen carrier and methane (CH4) as fuel. This study has been made in Oxygen Carriers and Their Industrial Applications research project (2008 – 2011), funded by the Tekes – Functional Material program. I would like to acknowledge Tekes and participating companies for funding and all project partners for good and comfortable cooperation.

Evaluation of seasonal changes in chemical composition and antibacterial activity of Elyonurus muticus (sprengel) O. Kuntze (Gramineae)

Aerial parts of Elyonurus muticus were collected in the four seasons of the year in the Brazilian Pantanal and subjected to extractrion with cold ethanol and to hydrodistillation. Sesquiterpenoids (E)-caryophyllene, bicyclogermacrene, spathulenol and caryophyllene oxide were the main components identified in the essential oils and their concentrations varied according to the plant collection period. The essential oils and the ethanolic crude extracts were active against Bacillus cereus MIP 96016, Pseudomonas aeruginosa ATCC 27853 and Staphylococcus aureus ATCC 25923 and were not active against Escherichia coli ATCC 25922. The antibacterial activities varied according to the plant collection period.

Plant sources of amazon rosewood oil

The aim of this study is to reevaluate the plant sources of the Amazon rosewood oil which have been named Aniba rosaeodora Ducke and Aniba duckei Kosterm. There is some disagreement on the exact botanical status of these species. Some Lauraceae specialists analyzing available material from both species concluded that there is no basis for regarding them as different. Based on our results we are confirming that the chemical composition of both species is quite different from that previously reported. So we are suggesting to bring back the previous botanical rosewood status as proposed by Adolph Ducke.

Chemical composition and antimicrobial activity of the essential oil from Aeolanthus suaveolens Mart. ex Spreng

The essential oils from leaves (sample A) and flowers (sample B) of Aeolanthus suaveolens Mart. ex Spreng were obtained by hydrodistillation and analyzed by GC, GC-MS, and chiral phase gas chromatography (CPGC). Six compounds have been identified from the essential oils, representing ca 94.3 and 93% of the oils corresponding to samples A and B, respectively. The major constituents of samples A and B essential oils were respectively, linalool (34.2%/34.9%), (-)-massoialactone (25.9%/17.0%) and (E)-beta-farnesene (25.4%/29.1%). The enantiomeric distribution of the monoterpene linalool was established by analysis on heptakis- (6-O-methyl-2,3-di-O-pentyl)-beta-cyclodextrin capillary column. The antimicrobial activity of the essential oil from leaves and isolated compounds was also evaluated.

A thermogravimetric analysis of the combustion of a Brazilian mineral coal

Knowledge of coal combustion kinetics is crucial for burner design. This work aims to contribute on this issue by determining the kinetics of a particular Brazilian bituminous coal. Non-isothermal thermogravimetry was applied for determining both the pre-exponential factor and the activation energy. Coal samples of 10 mg and 775 mm mean size were used in synthetic air atmospheres (21 % O2). Heating rates from 10 to 50 ºC/min were applied until the temperature reached 850 ºC, which was kept constant until burnout. The activation energy for the primary and the secondary combustion resulted, respectively, in 135.1 kJ/mol and 85.1 kJ/mol.

Thermoanalysis of soybean oil extracted by two methods

The thermal stability of vegetable oils is an important factor that affects their quality. In this study, we investigated the thermal stability of oil and lecithin extracted from soybeans by two distinct processes: mechanical extraction (pressing) and physical extraction (solvent). Thermal analysis was used to obtain information about different methodologies of extraction. The physically extracted products proved more stable than those extracted mechanically. Raman and UV-Vis techniques were applied to underpin the discussion of process differences.

Supercritical CO2 recovery of caffeine from green coffee oil: new experimental solubility data and modeling

The caffeine solubility in supercritical CO2 was studied by assessing the effects of pressure and temperature on the extraction of green coffee oil (GCO). The Peng-Robinson¹ equation of state was used to correlate the solubility of caffeine with a thermodynamic model and two mixing rules were evaluated: the classical mixing rule of van der Waals with two adjustable parameters (PR-VDW) and a density dependent one, proposed by Mohamed and Holder² with two (PR-MH, two parameters adjusted to the attractive term) and three (PR-MH3 two parameters adjusted to the attractive and one to the repulsive term) adjustable parameters. The best results were obtained with the mixing rule of Mohamed and Holder² with three parameters.

Chemical composition and antimicrobial activity of the essential oil of Hyptis pectinata (l.) Poit.

Essential oil was extracted from leaves of Hyptis pectinata using hydrodistillation, and its composition determined using GC-FID and GC-MS. Chemical analysis showed that there was a predominance of sesquiterpenes, of which β-caryophyllene (18.34%), caryophyllene oxide (18.00%) and calamusenone (24.68%) were measured for the first time in the genus Hyptis. Twenty-one compounds were identified, and calamusenone was isolated using preparative thin layer chromatography with a silica gel plate (60 PF254). The minimal inhibitory concentration (MIC) and minimal microbicidal concentration (MMC) were determined for various pathogenic microorganisms. H. pectinata oil was most effective against Gram (+) bacteria and yeasts.

Antimicrobial and antileishmanial activity of essential oil from the leaves of Annona foetida (Annonaceae)

bicyclogermacrene (35.12%), (E)-caryophyllene (14.19%) and α-copaene (8.19%). The antimicrobial and antileishmanial activities were investigated. The oil showed potent antimicrobial activity against Candida albicans and Rhodococcus equi. The oil also showed significant antileishmanial activity, giving the best results against Leishmania guyanensis. A preliminary cytotoxicity assay for this oil was carried out on hamster and mice (Balb/c) peritoneal macrophages. The results obtained were similar to pentamidine and considered not to be cytotoxic to macrophages.

In vitro antimicrobial and antioxidant activities of a crude extract and fractions from Buddleja thyrsoides Lam. Leaves

Crude extract and fractions of Buddleja thyrsoides were investigated regarding antioxidant activities by DPPH, total phenolic contents by Folin-Ciocalteau and antimicrobial activity by the broth microdilution method. Total phenolics varied from 214.07 ± 3.6 to 438.4 ± 0.3 mg g-1. Crude extract, ethyl acetate, dichloromethane and butanolic fractions exhibited a weak scavenging activity (SC50=186.04 ± 10.8, 137.70 ± 8.5, 146.89 ± 9.0 and 165.71 ± 3.2 µg mL-1, respectively). A correlation between the antioxidant activities and total phenolic contents could be shown (r=0.857, p<0.01). The lowest value of MIC was observed with butanolic fraction against Saccharomyces cerevisiae (MIC and MFC at 62.5 µg mL-1). Dichloromethane and ethyl acetate fractions were effective against Staphylococcus aureus with MIC value at 250 and 500 µg mL-1 respectively.

Avaliação de biocombustível derivado do bio-óleo obtido por pirólise rápida de biomassa lignocelulósica como aditivo para gasolina

A biofuel was prepared from acid aqueous fraction (pH = 2) of bio-oil produced by fast pyrolysis (Bioware Technology) of lignocellulosic biomass (sugar cane residue) and tested in blends (2, 5, 10 e 20% v/v) with gasoline type C (common) marketed in Brazil. The specification tests made in the Refinery President Getúlio Vargas (PETROBRAS) showed increasing in the octane number (MON) and antiknock index (AKI) with reduction in the residue generation during the combustion. The physicochemical characteristics of the biofuel were similar that combustible alcohol allowing its use as gasoline additive.

Synthesis of liquid menthol by hydrogenation of dementholized peppermint oil over Ni catalysts

Hydrogenation of (-)-menthone and (+)-isomenthone was studied at 2.7 MPa and 100 ºC. The objective was to produce a liquid menthol mixture rich in (-)-menthol from dementholized peppermint oil. Ni-based catalysts were tested and compared for this reaction: a) 6 and 12% Ni dispersed into a nonstoichiometric magnesium aluminate (Ni-Mg-Al) with spinel structure; b) Ni-Raney catalyst. Both types of catalysts were active for (-)-menthone and (+)-isomenthone hydrogenation. Lower conversion but higher selectivity to (-)-menthol was obtained with Ni-Mg-Al catalysts. However, they rapidly lost their activity. Instead Ni-Raney catalysts kept its original activity even after several hydrogenation runs.

Avaliação das incertezas associadas à determinação do parâmetro de solubilidade de Hildebrand de petróleos

Asphaltenes are fractions of crude oils that can precipitate and one of the parameters used in the prediction of the conditions in which this phenomenon occurs is the Hildebrand solubility parameter. In this work, it was evaluated the uncertainty propagation in the experimental determination of the solubility parameter of different crude oils, calculated from data of the asphaltenes precipitation by the addition of n-heptane, identified by optical microscopy. It was verified that the solubility parameter of an oil and the associated uncertainty are specific, being recommended that, whenever viable, it is determined parallel both, conferring higher credibility to the results.

Diesel/biodiesel soot oxidation with ceo2 and ceo2-zro2-modified cordierites: a facile way of accounting for their catalytic ability in fuel combustion processes

CeO2 and mixed CeO2-ZrO2 nanopowders were synthesized and efficiently deposited onto cordierite substrates, with the evaluation of their morphologic and structural properties through XRD, SEM, and FTIR. The modified substrates were employed as outer heterogeneous catalysts for reducing the soot originated from the diesel and diesel/biodiesel blends incomplete combustion. Their activity was evaluated in a diesel stationary motor, and a comparative analysis of the soot emission was carried out through diffuse reflectance spectroscopy. The analyses have shown that the catalyst-impregnated cordierite samples are very efficient for soot oxidation, being capable of reducing the soot emission in more than 60%.

Nanostructured systems containing an essential oil: protection against volatilization

The goal of this study was to evaluate the feasibility of preparing nanocapsules and nanoemulsions using tea tree oil as oily phase aiming to protect its volatilization. The nanostructures presented nanometric mean size (160-220 nm) with a polydispersity index below 0.25 and negative zeta potential. The pH values were 6.43 ± 0.37 and 5.98 ± 0.00 for nanoemulsions and nanocapsules, respectively. The oil content after preparation was 96%. The inclusion of tea tree oil in nanocapsules showed higher protection against volatilization. The analysis of mean size and polydispersity index of formulations presented no significant alteration during the storage time.