Process intensification: From optimised flow patterns to microprocess technology

This thesis is focused on process intensification. Several significant problems and applications of this theme are covered. Process intensification is nowadays one of the most popular trends in chemical engineering and attempts have been made to develop a general, systematic methodology for intensification. This seems, however, to be very difficult, because intensified processes are often based on creativity and novel ideas. Monolith reactors and microreactors are successful examples of process intensification. They are usually multichannel devices in which a proper feed technique is important for creating even fluid distribution into the channels. Two different feed techniques were tested for monoliths. In the first technique a shower method was implemented by means of perforated plates. The second technique was a dispersion method using static mixers. Both techniques offered stable operation and uniform fluid distribution. The dispersion method enabled a wider operational range in terms of liquid superficial velocity. Using dispersion method, a volumetric gas-liquid mass transfer coefficient of 2 s-1 was reached. Flow patterns play a significant role in terms of the mixing performance of micromixers. Although the geometry of a T-mixer is simple, channel configurations and dimensions had a clear effect on mixing efficiency. The flow in the microchannel was laminar, but the formation of vortices promoted mixing in micro T-mixers. The generation of vortices was dependent on the channel dimensions, configurations and flow rate. Microreactors offer a high ratio of surface area to volume. Surface forces and interactions between fluids and surfaces are, therefore, often dominant factors. In certain cases, the interactions can be effectively utilised. Different wetting properties of solid materials (PTFE and stainless steel) were applied in the separation of immiscible liquid phases. A micro-scale plate coalescer with hydrophilic and hydrophobic surfaces was used for the continuous separation of organic and aqueous phases. Complete phase separation occurred in less than 20 seconds, whereas the separation time by settling exceeded 30 min. Fluid flows can be also intensified in suitable conditions. By adding certain additives into turbulent fluid flow, it was possible to reduce friction (drag) by 40 %. Drag reduction decreases frictional pressure drop in pipelines which leads to remarkable energy savings and decreases the size or number of pumping facilities required, e.g., in oil transport pipes. Process intensification enables operation often under more optimal conditions. The consequent cost savings from reduced use of raw materials and reduced waste lead to greater economic benefits in processing.

Hylynkäsittelyn ja annostelun vaikutus kartongin laatuun

Tämän työn tavoitteena oli löytää keinot taivekartongin riittävän z-suuntaisen lujuuden saavuttamiseksi tilanteessa, jossa runkokerrokseen annosteltavan hylyn määrää joudutaan pysyvästi vähentämään. Työn kirjallisuusosassa selvitettiin taivekartongin tärkeimmät ominaisuudet, joista tarkemmin tarkasteltiin palstautumislujuutta ja siihen vaikuttavia tekijöitä. Lisäksi käytiin läpi palstautumislujuuden mittausmenetelmät. Merkittävimpiä teoriaosassa käsiteltyjä palstautumislujuuteen vaikuttavia tekijöitä olivat massojen käsittely ja annostelu, kuivalujalisäaineiden käyttö sekä rainanmuodostus. Hylyn annosteluosuuden pienentäminen vähensi taivekartongin paksuussuuntaista lujuutta ja runkomassan vedenpoistovastusta, mutta samanaikaisesti lisääntyivät kartongin paksuus ja taivutusjäykkyys. Hylyn vähäisemmän käytön seurauksena menetettyä lujuutta ei pystytty palauttamaan hylyn jauhatuksen määrää lisäämällä, eikä kartonkikoneen runkoviiraosan vedenpoistoon vaikuttamalla. Kun hylyn annosteluosuus laskettiin 20 %:in, saavutettiin runkokerroksen riittävä lujuus ainoastaan runkomassan pääkomponenttina käytettävän hiokemassaseoksen jauhatusastetta nostamalla tai korvaamalla pieni osa hiokkeesta hyvin hienoksi jauhetulla mäntysellulla. Hiokkeen freeness oli laskettava tasolta 300 ml CSF tasolle 250 ml CSF. Vastaavasti mäntysellu oli jauhettava hyvin pitkälle (°SR 74) tai annosteluosuuden oli oltava vähintään 2 %, jolloin jauhatusaste °SR 49 oli riittävä. Vähäisemmällä hylyn käytöllä saavutettu etu vedenpoistossa saatettaisiin menettää näiden toimenpiteiden vaikutuksesta.

Uma visão das tendências e perspectivas em eletrocromismo: a busca de novos materiais e desenhos mais simples

Some aspects of electrochromism phenomena are presented in this review paper. A deep literature revision about the subject dealing with materials and device configurations developed in the last years, is presented. Great efforts of the scientific community have been done in this field. On the other hand, new electrochomic devices based on reversible deposition of metals are specially emphasized here. These devices present many advantages such as simple operation and construction and they have also shown high cycling rates. These factors make them suitable for application in display industry. In this way, many concepts used in the developement of electrodeposition baths are very useful for the improvement of these new devices; specially, all knowledge about the use of additives for modifying films microstructure and morfology.

Novos materiais à base de nanofibras de carbono como suporte de catalisador na decomposição da hidrazina

Today satellites propulsion is based on the use of monopropellant and/or bipropellant chemical systems. The maneuvering of satellite is based on the hydrazine decomposition micropropulsors catalyzed by metallic iridium supported on g-alumina. This reaction is a surface reaction and is strongly exothermic and implies that the operation of the micropropulsor is controlled by the mass and heat diffusions. For this reason and for the fact that the propulsor operation is frequently in pulsed regime, the catalyst should support high pressure and temperature variations within a short time period. The performance and the durability of the commercial catalyst are jeopardized by the low thermal conductivity of the alumina. The low thermal conductivity of the alumina support restricts the heat diffusion and leads to the formation of hot spots on the catalyst surface causing the metal sintering and/or fractures of the support, resulting in loss of the activity and catalyst destruction. This work presents the synthesis and characterization of new carbon composite support for the active element iridium, in substitution of the commercial catalysts alumina based support. These supports are constituted of carbon nanofibers (30 to 40 nm diameter) supported on a macroscopic carbon felt. These materials present high thermal conductivity and mechanical resistance, as well as the easiness to be shaped with different macroscopic shapes. The mechanical stability and the performance of the iridium supported on the carbon composite support, evaluated in a laboratory scale test in hydrazine decomposition reaction, are superior compared to the commercial catalyst.

Efeito do polietilenoglicol e da albumina na imobilização de lipase microbiana e na catálise em meio orgânico

Poly (ethylene) glycol (PEG) and bovine serum albumin (BSA), as additive agents, were used to enhance the activity of immobilized microbial lipase in organic solvent. Controlled pore silica (CPS) was selected as matrix and different immobilization procedures were evaluated: directly lipase binding on CPS and simultaneous addition of lipase and additive agent on the same support. The highest coupling yield (59.6%) was attained when the immobilization procedure was performed at lipase loading of 150 U/g support in the presence of PEG-1.500. This immobilized system was used in esterification reactions under repeated batch cycles and the biocatalyst half-life was found to increase 2.7 times when compared with the control.

Determinação de corantes artificiais por cromatografia líquida de alta eficiência (CLAE) em pó para gelatina

Synthetic dyes were determined by high performance liquid chromatography in 76 samples of regular jelly and diet jelly powders, of several flavors produced by seven different manufacturers. Three sample of each product, from different batches, were analyzed. The same qualitative composition was observed for products of the same flavor from different manufacturers, but the quantitative composition varied markedly from one manufacturer to the other. There were no or few significant differences between batches from a given manufacturer, demonstrating good quality control in the use of these additives by the food industry. None of the samples exceeded the limit stipulated by Brazilian legislation.

Estudo eletroquímico de um novo banho galvânico de zinco alcalino livre de cianetos

A systematic electrochemical study of a novel cyanide free galvanic plating solution of alkaline zinc is presented. Cell Hull tests and potentiodynamic linear polarization measurements were carried out to evaluate the influence of operational parameters, such as concentration, current efficiency and degradation of additives. The stability of the bath was assessed by a long term test during 40 h at 200 A m-2. The morphology of the coatings was characterized by scanning electron microscopy. The results showed good performance of the plating solution. The cost is similar to that of the commercial cyanide bath and lower than that of the commercial cyanide free bath.

Ação de colorantes na degradação e estabilização de polímeros

Dyes and pigments are additives used in polymers to improve mainly the aesthetic properties of the material. However, the incorporation of these additives can directly affect polymer stability. The colorants can drastically decrease the lifetime and the performance of the material or can act as a stabilizer, improving significantly the stability of the polymer against degradation. Interaction between colorants and polymers is the cause of the stability changes. Some mechanisms are proposed to explain the action of colorants on polymers. However it is difficult to foresee this action without experiments. This work reviews the main mechanisms involved in the degradation and stabilization of polymers containing colorants.

Estudo do efeito do tratamento superficial por moagem sobre as propriedades das partículas de uma liga de hidreto metálico

This work reports results of studies on the electrochemical and structural properties of a Ti/Zr-based metal hydride alloy covered by Ni and LaNi4,7Sn0,3 powder additives by ball milling. The effect of this treatment is investigated for the activation time, hydrogen storage capacity and equilibrium pressure, cycling stability and the hydration/dehydration kinetics. Charge and discharge cycles show a significant decrease of the activation time due to an increase of the active area caused by the milling treatment, independent of the additive. However, other results have evidenced little effect of the milling surface treatment on the charge storage capacity, hydrogen equilibrium pressure, and hydration/dehydration kinetics, for both the Ni and LaNi4,7Sn0,3 covered materials.

The effect of microfibrillated cellulose addition on drying shrinkage and dimensional stability of wood-free paper

Microfibrillated cellulose (MFC) is known to enhance strength properties of paper. Improved strength usually means increased bonding which is strongly connected to dimensional instability of paper. Dimensional instability is due to changes in moisture content of paper; when paper is moistened it expands and when dried, it shrinks. Hygroexpansion is linked to end-use problems and excessive drying shrinkage consumes strength potential. Effective use of materials requires controlling of these phenomena. There isn’t yet data concerning dimensional stability of papers containing MFC which restricts wider use of MFC. Main objective of the work was to evaluate dimensional stability of wood-free paper containing different amounts of MFC. Sheets were dried with different methods to see how drying strains effected on drying shrinkage and hygroexpansion. Also tensile strength was measured to find out the effect of MFC. Results were compared to sheets containing kraft fines and in some test points cationic starch was used alongside with MFC. MFC increased the dimensional instability of freely dried sheets. As the amounts of MFC increased the effects on dimensional stability became more severe. However the fineness of MFC didn’t play any important role. Both hygroexpansion and drying shrinkage were decreased with cationic starch addition. Prevention of drying shrinkage over powered the effects of additives on hygroexpansion. Tensile strength improved up till 7 % addition amount which could be set as the upper limit of MFC addition when paper preparation and tensile strength are concerned.

Kalkin sammutus kalsiumkarbonaatin saostuksessa

Tässä työssä tutkittiin sammutetun kalkin vaikutusta kalsiumkarbonaatin saostamiseen ja saostetun kalsiumkarbonaatin ominaisuuksiin. Työn kirjallisuusosa käsittelee mm. kalkin sammutusta yleisesti, sammutuslaitteita, sammutetun kalkin ominaisuuksiin ja agglomeroitumiseen vaikuttavia tekijöitä sekä partikkelikoon analyysimenetelmiä. Kirjallisuusosan mukaan sammutusolosuhteilla sekä sammutuslaitteilla on vaikutusta sammutetun kalkin ominaisuuksiin. Työn kokeellisessa osassa tutkittiin kalkin sammutuksen vaikutusta kalsiumkarbonaatin saostamiseen sekä saostetun kalsiumkarbonaatin ominaisuuksiin. Sammutuskokeet tehtiin neljällä eri sammutuslaitteella ja sammutettavina kalkkeina käytettiin neljää ominaisuuksiltaan erilaista poltettua kalkkia. Karbonoinnit suoritettiin sekä laboratorio- että pilot-laitteilla. Lisäksi tutkittiin neljän lisäaineen; natriumdodekyylisulfaatin, trietanoliamiinin, lignosulfonaatin sekä sakkaroosin vaikutusta kalkin sammuttamiseen sekä miten lisäaineen käyttäminen sammutuksessa vaikuttaa kalsiumkarbonaatin saostamiseen. Tulosten perusteella kalkin sammutuksella on vaikutusta kalsiumkarbonaatin saostamiseen ja saostetun kalsiumkarbonaatin ominaisuuksiin. Eri sammutusmenetelmillä sammutetuilla kalkeilla on mm. erilainen vaikutus karbonointiaikaan. Myös lisäaineet vaikuttavat mm. sammutetun kalkin ominaispinta-alaan ja partikkelin muotoon. Lisäaineet lisäksi pidentävät karbonointiaikaa ja vaikuttavat saostettujen kalsiumkarbonaattipartikkeleiden agglomeroitumiseen.

Teores de corantes artificiais em alimentos determinados por cromatografia líquida de alta eficiência

Synthetic dyes are much used in processed foods. HPLC was applied to different types of snacks, such as colored cereals, chocolate confetti, chewing gums and candies for the determination of those additives. In the case of artificially colored breakfast cereals, 71% of the samples exceeded the allowed limits. Regarding the portions recommended for consumption by the makers of two of the samples, the amounts exceeded those allowed by the Brazilian legislation. In the case of chocolate confetti and candies none of the samples showed higher amounts than those allowed. However 37% of the chewing gum samples presented larger contents than the authorized ones, and one sample contained five times more synthetic dyes than allowed.

Obtenção de titânio metálico com porosidade controlada por metalurgia do pó

Titanium is an attractive material for structural and biomedical applications because of its excellent corrosion resistance, biocompatibility and high strength-to-weight ratio. The high reactivity of titanium in the liquid phase makes it difficult to produce it by fusion. Powder metallurgy has been shown to be an adequate technique to obtain titanium samples at low temperatures and solid-phase consolidation. The production of compacts with different porosities obtained by uniaxial pressing and vacuum sintering is briefly reviewed. Powder particle size control has been shown to be very important for porosity control. Sample characterization was made using scanning electron microscopy (SEM) images.

Decomposição térmica de espumas de poliuretano para fabricação de vitrocerâmica celular de Li2O-ZrO2-SiO2-Al2O3 (LZSA)

Characterization of the thermal decomposition of polyurethane (PUR) foams was performed by Fourier-transformed infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). Three main weight loss paths were observed by TGA, the residue being lower than 3 wt.% for 3 different PUR foams analyzed. FT-IR spectra indicated CO2, CO, NH3 and isocyanides as main decomposition products. PUR foams of different cell sizes were immersed in a slurry of the parent glass ceramic of composition Li2O-ZrO2-SiO2-Al 2O3 (LZSA) and submitted to heat treatment. The LZSA cellular glass ceramics obtained after sintering and crystallization resembled the original morphology of the PUR foams.

Redução de vitamina C em suco de caju (Anacardium occidentale L.) industrializado e cajuína

Vitamin C degradation was evaluated in industrialized cashew juice of high pulp content and in cajuina by the method of Tillmans during eleven days of storage after the opening of the flask. For recently opened juices, vitamin C was found in the concentration range of 112 to 170 mg for 100 g of juice. The degradation of vitamin C in industrialized cashew juices changes when different additives are used. All of the cajuinas presented a vitamin C content below that specified on the label.