999 resultados para Recirculação química com reforma-RQR. MCM-41.Transportadores de oxigênio. Gás de síntese


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Nickel-containing catalysts are developed to oligomerize light olefins. Two nickel-containing zincosilicates (Ni-CIT-6 and Ni-Zn-MCM-41) and two nickel-containing aluminosilicates (Ni-HiAl-BEA and Ni-USY) are synthesized as catalysts to oligomerize propylene into C3n (C6 and C9) products. All catalysts oligomerize propylene, with the zincosilicates demonstrating higher average selectivities to C3n products, likely due to the reduced acidity of the Zn heteroatom.

To test whether light alkanes can be incorporated into this oligomerization reaction, a supported homogeneous catalyst is combined with Ni-containing zincosilicates. The homogeneous catalyst is included to provide dehydrogenation/hydrogenation functions. When this tandem catalyst system is evaluated using a propylene/n-butane feed, no significant integration of alkanes are observed.

Ni-containing zincosilicates are reacted with 1-butene and an equimolar propylene/1-butene mixture to study other olefinic feeds. Further, other divalent metal cations such as Mn2+, Co2+, Cu2+, and Zn2+ are exchanged onto CIT-6 samples to investigate stability and potential use for other reactions. Co-CIT-6 oligomerizes propylene, albeit less effectively than Ni-CIT-6. The other M-CIT-6 samples, while not able to oligomerize light olefins, may be useful for other reactions, such as deNOx.

Molecular sieves are synthesized, characterized, and used to catalyze the methanol-to-olefins (MTO) reaction. The Al concentration in SSZ-13 samples is varied to investigate the effect of Al number on MTO reactivity when compared to a SAPO-34 sample with only isolated Si Brønsted acid sites. These SSZ-13 samples display reduced transient selectivity behavior and extended reaction lifetimes as Si/Al increases; attributable to fewer paired Al sites. MTO reactivity for the higher Si/Al SSZ-13s resembles the SAPO-34 sample, suggesting that both catalysts owe their stable reaction behavior to isolated Brønsted acid sites.

Zeolites CHA and RHO are prepared without the use of organic structure-directing agents (OSDAs), dealuminated by steam treatments (500°C-800°C), and evaluated as catalysts for the MTO reaction. The effects of temperature and steam partial pressure during steaming are investigated. X-ray diffraction (XRD) and Ar physisorption show that steaming causes partial structural collapse of the zeolite, with degradation increasing with steaming temperature. 27Al MAS NMR spectra of steamed materials reveal the presence of tetrahedral, pentacoordinate, and hexacoordinate aluminum.

Proton forms of as-synthesized CHA (Si/Al=2.4) and RHO (Si/Al=2.8) rapidly deactivate under MTO testing conditions (400°C, atmospheric pressure). CHA samples steamed at 600°C performed best among samples tested, showing increased olefin selectivities and catalyst lifetime. Acid washing these steamed samples further improved activity. Reaction results for RHO were similar to CHA, with the RHO sample steamed at 800°C producing the highest light olefin selectivities. Catalyst lifetime and C2-C3 olefin selectivities increase with increasing reaction temperature for both CHA-type and RHO-type steamed samples.

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Nickel-bases catalysts have been used in several reform reactions, such as in the partial oxidation of methane to obtain H2 or syngas (H2 + CO). High levels of conversion are usually obtained using this family of catalysts, however, their deactivation resulting from carbon deposition still remains a challenge. Different approaches have been tested aiming at minimizing this difficulty, including the production of perovskites and related structures using modern synthesis methods capable of producing low cost materials with controlled microstructural characteristics at industrial scale. To establish grounds for comparison, in the present study LaNixFe1-xO3 (x=0, 0.3 or 0.7) perovskites were prepared following the Pechini method and by microwave assisted self-combustion. All samples were sub sequently calcined at 900 °C to obtain the target phase. The resulting ceramic powders were characterized by thermogravimetric analysis, infrared spectroscopy, X ray diffraction, specific area and temperature programmed reduction tests. Calcined samples were also used in the partial oxidation reaction of methane to evaluate the level of conversion, selectivity and carbon deposition. The results showed that the calcined samples were crystalline and the target phase was formed regardless of the synthesis method. According to results obtained by Rietveld refinement, we observed the formation of 70.0% of LaNi0.3Fe0.7O3 and 30.0% of La2O3 for samples LN3F7-900- P, LN3F7-900-M and 41,6% of LaNi0.7Fe0.3O3, 30.7% of La2NiO4 and 27.7% of La2O3 for samples LN7F3-900-P and LN7F3-900-M.Temperature-programmed profiles of the LaNiO3 sample revealed the presence of a peak around 510 °C, whereas the LaFeO3 sample depicted a peak above 1000°C. The highest l evel of methane conversion was obtained for LaNiO3 synthesized by the Pechini method. Overall, catalysts prepared by the Pechini method depicted better conversion levels compared to those produced by microwave assisted self-combustion

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Terephthalic acid (PTA) is one of the monomers used for the synthesis of the polyester, polyethylene terephthalate (PET), that is used for the large-scale manufacture of synthetic fibers and plastic bottles. PTA is largely produced from the liquid-phase oxidation of petroleum-derived p-xylene (PX). However, there are now ongoing worldwide efforts exploring alternative routes for producing PTA from renewable, biomass resources.

In this thesis, I present a new route to PTA starting from the biomass-derived platform chemical, 5-hydroxymethylfurfural (HMF). This route utilizes new, selective Diels-Alder-dehydration reactions involving ethylene and is advantageous over the previously proposed Diels-Alder-dehydration route to PTA from HMF via 2,5-dimethylfuran (DMF) since the H2 reduction of HMF to DMF is avoided. Specifically, oxidized derivatives of HMF are reacted as is, or after etherification-esterification with methanol, with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids in order to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA) is reacted with high pressure ethylene over a pure-silica molecular sieve catalyst containing framework tin (Sn-Beta) to produce the Diels-Alder-dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with ~30% selectivity at ~20% yield. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) to produce methyl 4-(methoxymethyl)benzenecarboxylate (MMBC) with >70% selectivity at >20% yield. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the Diels-Alder-dehydration product is observed.

An investigation to elucidate the reaction network and side products in the conversion of MMFC to MMBC was performed, and the main side products are found to be methyl 4-formylcyclohexa-1,3-diene-1-carboxylate and the ethylene Diels-Alder adduct of this cyclohexadiene. These products presumably form by a different dehydration pathway of the MMFC/ethylene Diels-Alder adduct and should be included when determining the overall selectivity to PTA or DMT since, like MMBC, these compounds are precursors to PTA or DMT.

Fundamental physical and chemical information on the ethylene Diels-Alder-dehydration reactions catalyzed by the Lewis acid-containing molecular sieves was obtained. Madon-Boudart experiments using Zr-Beta as catalyst show that the reaction rates are limited by chemical kinetics only (physical transport limitations are not present), all the Zr4+ centers are incorporated into the framework of the molecular sieve, and the whole molecular sieve crystal is accessible for catalysis. Apparent activation energies using Zr-Beta are low, suggesting that the overall activation energy of the system may be determined by a collection of terms and is not the true activation energy of a single chemical step.

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The use of biofuels remotes to the eighteenth century, when Rudolf Diesel made the first trials using peanut oil as fuel in a compression ignition engine. Based on these trials, there was the need for some chemical change to vegetable oil. Among these chemical transformations, we can mention the cracking and transesterification. This work aims at conducting a study using the thermocatalytic and thermal cracking of sunflower oil, using the Al-MCM-41 catalyst. The material type mesoporous Al-MCM-41 was synthesized and characterized by Hydrothermical methods of X-ray diffraction, scanning electron microscopy, nitrogen adsorption, absorption spectroscopy in the infrared and thermal gravimetric analysis (TG / DTG).The study was conducted on the thermogravimetric behavior of sunflower oil on the mesoporous catalyst cited. Activation energy, conversion, and oil degradation as a function of temperature were estimated based on the integral curves of thermogravimetric analysis and the kinetic method of Vyazovkin. The mesoporous material Al-MCM-41 showed one-dimensional hexagonal formation. The study of the kinetic behavior of sunflower oil with the catalyst showed a lower activation energy against the activation energy of pure sunflower oil. Two liquid fractions of sunflower oil were obtained, both in thermal and thermocatalytic pyrolisis. The first fraction obtained was called bio-oil and the second fraction obtained was called acid fraction. The acid fraction collected, in thermal and thermocatalytic pyrolisis, showed very high level of acidity, which is why it was called acid fraction. The first fraction was collected bio-called because it presented results in the range similar to petroleum diesel

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In this study, was used a very promising technique called of pyrolysis, which can be used for obtaining products with higher added value. From oils and residues, since the contribution of heavier oils and residues has intensified to the world refining industry, due to the growing demand for fuel, for example, liquid hydrocarbons in the range of gasoline and diesel. The catalytic pyrolysis of vacuum residues was performed with the use of a mesoporous material belonging the M41S family, which was discovered in the early 90s by researchers Mobil Oil Corporation, allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal arrangement of mesopores with pore diameters between 2 and 10 nm and a high specific surface area, making it very promising for use as a catalyst in petroleum refining for catalytic cracking, and their mesopores facilitate the access of large hydrocarbon molecules. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more positive for application in the petrochemical industry. The mesoporous material of the type Al-MCM41 (ratio Si / Al = 50) was synthesized by hydrothermal method starting from the silica gel, NaOH and distilled water added to the gel pseudobohemita synthesis. Driver was used as structural CTMABr. Removal of organic driver (CTMABr) was observed by TG / DTG and FTIR, but this material was characterized by XRD, which was observed the formation of the main peaks characteristic of mesoporous materials. The analysis of adsorption / desorption of nitrogen this material textural parameters were determined. The vacuum residues (VR's) that are products of the bottom of the vacuum distillation tower used in this study are different from oil fields (regions of Ceará and Rio de Janeiro). Previously characterized by various techniques such as FTIR, viscosity, density, SARA, elemental analysis and thermogravimetry, which was performed by thermal and catalytic degradation of vacuum residues. The effect of AlMCM-41 was satisfactory, since promoted a decrease in certain ranges of temperature required in the process of conversion of hydrocarbons, but also promoted a decrease in energy required in the process. Thus enabling lower costs related to energy expenditure from degradation during processing of the waste

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The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc

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Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the “hydrogen economy” faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn21 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.

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A new titanium catalyst easily synthesized from ethylmaltol bidentate chelator ligand was studied in homogeneous and heterogeneous ethylene polymerization. The dichlorobis(3-hydroxy-2-ethyl-4-pyrone)titanium(IV) complex was characterized by 1H and 13C NMR (nuclear magnetic resonance), UV-Vis and elemental analysis. Theoretical study by density functional theory (DFT) showed that the complex chlorines exhibit cis configuration, which is important for the activity in olefin polymerization. The complex was supported by two methods, direct impregnation or methylaluminoxane (MAO) pre-treatment, in five mesoporous supports: MCM-41 (micro and nano), SBA-15 and also the corresponding modified Al species. All the catalytic systems were active in ethylene polymerization and the catalytic activity was strongly influenced by the method of immobilization of the catalyst and the type of support.

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Introdução O envelhecimento da população exige uma resposta global, requerendo intervenção com todos os setores e âmbitos. As atividades de lazer constituem-se como um fator importante na promoção da saúde e bem-estar dos indivíduos, particularmente dos idosos. O contato social e relações com outras pessoas tem influência positiva no seu bem-estar e saúde. A participação em atividades de lazer pode manter o seu sentimento de autoestima, evitando os riscos associados com o isolamento, a perda de confiança ou diminuição da autoestima. Objetivos O presente estudo pretende descrever as atividades de lazer das pessoas com 60 e mais anos, residentes em domicílios particulares na área de abrangência de um Centro de Saúde do município de Coimbra. Metodologia Realizou-se um estudo transversal de tipo descritivo. Entrevista realizada num Centro de Saúde urbano-rural, através de questionário (adaptado de Soares et al., 2010) a pessoas com 60 e mais anos residentes em domicílios particulares. Amostra acidental (n=130). O questionário inclui, para além das questões demográficas, várias escalas e sete questões relativas às atividades de lazer - avaliadas numa escala de likert com 7 opções de resposta, classificadas de nunca até diariamente. Para este estudo as variáveis analisadas foram as demográficas e as atividades de lazer. Resultados Os participantes eram maioritariamente do sexo feminino (57,7%) - Média de idades de 71,45 anos; casados/as ou viviam em união de fato (70%), com o 1º ciclo do ensino básico (50%). Como fonte de rendimentos referiram a reforma por invalidez (41,5%). Cerca de 6,1% vivia de transferências financeiras dos filhos, de outros familiares ou do ex-marido/esposa/companheiro/a. Rendimento mensal - ≤ 500 Euros (67,7%); coabitavam com marido/esposa/companheiro/a (51,5%). Responderam na sua maioria como atividades de lazer diárias, ver televisão (91,5%), costura, tricot, jardinagem ou colecionismo (55,4%) e o estar com a família (58,5%). Responderam maioritariamente nunca relativamente a desenvolverem atividades artísticas (98,5%), frequência de atividades fora de casa (96,9%), viajar (72,2%), ouvir música (66,9%), cuidar dos netos/as (69,2%), fazer exercício físico - ex. andar, nadar (56,2%); 95, 4% responderam não terem outras atividades para além das mencionadas no questionário. Os que mencionaram outras atividades (4,6%), referiram a pesca/caça/jogos tradicionais (1,6%), aeromodelismo, uso de computador e voluntariado, respetivamente com 0,8%. Conclusões Estes resultados revelam que os participantes no estudo ocupam as suas atividades de lazer especialmente em casa (ver televisão, a costura/tricot/jardinagem/colecionismos e estar com a família foram as atividades mais referenciadas diariamente). Quanto ás modalidades centradas fora do domicilio, a sua maioria revelou baixa participação nestas atividades, inclusive em atividades artísticas. Salienta-se que 56,2% referiu não fazer exercício físico, como por ex. andar ou nadar. Sugere-se o envolvimento das equipas de saúde comunitárias na promoção da participação ativa das pessoas com mais idade em iniciativas comunitárias promotoras de atividades artísticas, de atividade física e de trabalho voluntário, entre outras.

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Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica Ramo de Processos Químicos

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O experimento foi conduzido com o objetivo de avaliar diferentes pressões parciais de O2 e CO2 durante o armazenamento em atmosfera controlada (AC) sobre a qualidade físico-química de pêssegos, cv. Chiripá. As pressões parciais de gases avaliadas foram: 0,8kPaO2/3kPaCO2; 1kPaO2/3kPaCO2; 1kPaO2/4kPaCO2; 1kPaO2/5kPaCO2; 2kPaO2/6kPaCO2; 2kPaO2/7kPaCO2, 2kPaO2/8kPaCO2, ar/10kPaCO2 e tratamento-controle, mantido sob armazenamento refrigerado (AR). O delineamento experimental utilizado foi o inteiramente casualizado, com quatro repetições de 20 frutos. As avaliações foram realizadas após 4 e 8 semanas de armazenamento a -0,5ºC ± 0,2ºC, mais 2 dias a 20ºC. Os resultados evidenciaram que o controle de atmosfera reduz a degradação da clorofila da epiderme e a perda de peso, porém tem pouco efeito sobre a firmeza, teor de só lidos solúveis totais (SST) e acidez titulável dos frutos. A pressão parcial de 1kPa de O2, associada a 3kPa de CO2, reduz a manifestação dos sintomas de lanosidade durante 8 semanas de armazenamento. A incidência de podridões dos frutos é reduzida quando armazenados sob a condição de 2kPa de O2, associada a 8kPa de CO2. Tanto o armazenamento refrigerado quanto o armazenamento sob atmosfera controlada mantêm boa qualidade dos frutos por quatro semanas a -0,5ºC, mais 2 dias a 20ºC. Oito semanas de armazenamento em AC é um período muito prolongado para uma satisfatória manutenção da qualidade de pêssegos da cultivar Chiripá. A elevada incidência de podridões e de lanosidade são as causas que mais contribuem para a redução da qualidade de pêssegos, cv. Chiripá, durante períodos prolongados de armazenamento.

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In this contribution a few new gold(I)phosphine complexes, [2-(PPh2)C6H4CO 2H]AuX (where X = Cl, SCN, Br3) and a similar gold(III) derivative [{2-(PPh2)C6H4CO 2H}AuIII Cl (C6H4CH2NMe2 )]Cl have been synthesised and characterised. The phosphine, 2-(diphenylphosphino)benzoic acid, has been employed for the first time in gold chemistry. This ligand is potentially bidentate through bonding of the phosphine and carboxylate groups. The X-ray structure of the complex chloro[2-(diphenylphosphino) benzoic acid]gold(I) has been elucidated and the bond lengths encountered show great similarity to those of chloro(triphenylphosphine)gold(I). [2-(PPh2)C6H4CO 2H]AuCl crystallises in the space group P2(1)/c with a = 9.113(2) Å, b = 10.925(2) Å, c = 23.069(4) Å, beta = 99.95º(3), V = 2299 ų, Z = 4 and R = 0.091. Biological tests for anti-fungal and anti-bacterial activity demostrate that [2-(PPh2)C6H4CO 2H]AuCl exhibits broad spectrum activity against a range of organisms.

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The binuclear [Fe(CNBu t)(CO)4(HgSO4 )] adduct was obtained in the reaction of HgSO4 with [Fe(CNBu t)(CO)4] in methanol. This adduct, without a similar in the homoleptic pentacarbonyliron, was characterized by analytical and spectroscopic data. Further Mössbauer and molar conductivity studies have confirmed it's adduct nature.

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Macroscopic samples of fullerene nanostructures are obtained in a modified arc furnace using the electric arc method with a Helium atmosphere at low pressures. High purity graphite rods are used as electrodes but, when drilled and the orifices filled with powders of transition metals (Fe, Co, Ni) acting as catalysts, the resulting particles are carbon nanostructures of the fullerene family, known as Single Wall Nanotubes (SWNTs). They have typical diameters of 1.4 nm, lengths up to tenths of microns and they are arranged together in bundles containing several SWNTs. Those samples are observed and analyzed using Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) techniques.

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Derivatives of N-tryptophyl-5-benzylidene-2,4-thiazolidinedione (7a-c) and N-tryptophyl-5-benzylidene-rhodanine (7d-f) were prepared by condensation of the intermediates 5 and 6 with different benzaldehydes, respectively. Their structural elucidation was carried through by IR, ¹H NMR and MS. The acute toxicity and antiedematogenic activity of the compounds 7b,c and 7e,f were evaluated. The data did not reveal any sign of toxicity, and no mortality was registered. As indomethacin (10 mg/kg; v.o.), the antiedematogenic activity of the compounds 7b (50 mg/kg; v.o.) and 7e, 7f (50 or 100 mg/kg; v.o.) against carrageenan-induced paw edema was verified at time intervals of 180 min.