Degradação de espécies nitroaromáticas e remediação de efluentes da indústria de explosivos, utilizando-se processos redutivos-oxidativos fundamentados no uso de ferro metálico

In this work the potentiality of reductive-oxidative processes based on zero-valent iron was studied aiming the degradation of nitroaromatic compounds and the remediation of residues from the explosive industry. The reductive process was applied as a continuous treatment system, using steel-wool as zero-valent iron source. The process permitted an almost total degradation of nitrobenzene, nitrophenol, nitrotoluene, dinitrotoluene and trinitrotoluene, probably with generation of the respective amine-derivative. The yellow-water residue, containing soluble trinitrotoluene, was notably modified by the reductive process, a fact that permitted a substantial enhancement of its biodegradability. Furthermore, the subsequent photo-Fenton process allowed TOC removal of about 80%.

Em busca da sustentabilidade: células solares sensibilizadas por extratos naturais

The present work reports the use of anthocyanins extracted from mulberry (Morus Alba L.), raspberry (Rubus Idaeus L.) and blueberry (Vaccinium myrtillus L.) as sensitizers in dye-sensitized solar cells. The conversion efficiency of these devices is dependent on the extracts employed and can be rationalized in terms of their composition and spectral properties. Solar cells sensitized by the mulberry extract showed the highest efficiency among the fruits investigated. Moreover, a 16 cm² active area solar cell with the mulberry extract has presented fair good efficiency of conversion for natural dye-based solar cells, besides stability over twenty weeks, showing perspectives for developing these low cost devices with a commercial viability.

Synthesis of percarboxylic acids in microreactor

Percarboxylic acids are commonly used as disinfection and bleaching agents in textile, paper, and fine chemical industries. All of these applications are based on the oxidative potential of these compounds. In spite of high interest in these chemicals, they are unstable and explosive chemicals, which increase the risk of synthesis processes and transportation. Therefore, the safety criteria in the production process should be considered. Microreactors represent a technology that efficiently utilizes safety advantages resulting from small scale. Therefore, microreactor technology was used in the synthesis of peracetic acid and performic acid. These percarboxylic acids were produced at different temperatures, residence times and catalyst i.e. sulfuric acid concentrations. Both synthesis reactions seemed to be rather fast because with performic acid equilibrium was reached in 4 min at 313 K and with peracetic acid in 10 min at 343 K. In addition, the experimental results were used to study the kinetics of the formation of performic acid and peracetic acid. The advantages of the microreactors in this study were the efficient temperature control even in very exothermic reaction and good mixing due to the short diffusion distances. Therefore, reaction rates were determined with high accuracy. Three different models were considered in order to estimate the kinetic parameters such as reaction rate constants and activation energies. From these three models, the laminar flow model with radial velocity distribution gave most precise parameters. However, sulfuric acid creates many drawbacks in this synthesis process. Therefore, a ´´greener´´ way to use heterogeneous catalyst in the synthesis of performic acid in microreactor was studied. The cation exchange resin, Dowex 50 Wx8, presented very high activity and a long life time in this reaction. In the presence of this catalyst, the equilibrium was reached in 120 second at 313 K which indicates a rather fast reaction. In addition, the safety advantages of microreactors were investigated in this study. Four different conventional methods were used. Production of peracetic acid was used as a test case, and the safety of one conventional batch process was compared with an on-site continuous microprocess. It was found that the conventional methods for the analysis of process safety might not be reliable and adequate for radically novel technology, such as microreactors. This is understandable because the conventional methods are partly based on experience, which is very limited in connection with totally novel technology. Therefore, one checklist-based method was developed to study the safety of intensified and novel processes at the early stage of process development. The checklist was formulated using the concept of layers of protection for a chemical process. The traditional and three intensified processes of hydrogen peroxide synthesis were selected as test cases. With these real cases, it was shown that several positive and negative effects on safety can be detected in process intensification. The general claim that safety is always improved by process intensification was questioned.

Safety study of hydrogen peroxide direct synthesis

Kandidaatintyön johdantokappaleessa esitellään vetyperoksidi ja mihin sitä käytetään teollisuudessa. Työssä vertaillaan antrakinoniprosessia ja suoraa prosessia sekä selvitetään nykyisin enemmän vetyperoksidituotantoon käytetyn antrakinoniprosessin ongelmakohdat ja osoitetaan, miksi suora synteesi vetyperoksidin tuotannossa olisi parempi vaihtoehto. Kandidaatintyön käsittelee suurilta osin turvallisuusongelmia, joita esiintyy suoran synteesin yhteydessä. Kirjallisuudesta on etsitty ratkaisuja näihin ongelmiin, kuten membraaniprosessin käyttöä räjähdysvaaran välttämiseksi. Pienemmän reaktorin eli ns. mikroreaktorin käyttö tuo mukanaan monia etuja vetyperoksidin tuotantoon. Tällöin prosessi on turvallisempi ja sitä on helpompi hallita. Mikroreaktorissa voidaan käyttää korkeampia lämpötiloja ja paineita kuin makroreaktorilla ilman, että räjähdysvaara prosessissa kasvaisi. Mikroreaktorin sisällä olevat mikrokanavat luovat turvallisen ympäristön synteesille. Aspen plus – simulointiohjelmalla mallinnettiin ja simulointiin suoran prosessin kriittisiä virtoja mikroreaktorissa. Tarkoituksena oli löytää virrat, joissa kulkee mahdollisesti räjähtävä kaasuseos. Kaasumaiset prosessivirrat ovat kriittisimmät vetyperoksidin suorassa synteesissä, koska ne aiheuttavat todennäköisemmin räjähdyksen kuin nestemäiset prosessivirrat. Kaikkein eniten prosessiturvallisuutta uhkaavat ainevirrat ennen ja jälkeen mikroreaktoria.

Development of a process for the direct synthesis of hydrogen peroxide in a novel microstructured reactor

Microreactors have proven to be versatile tools for process intensification. Over recent decades, they have increasingly been used for product and process development in chemical industries. Enhanced heat and mass transfer in the reactors due to the extremely high surfacearea- to-volume ratio and interfacial area allow chemical processes to be operated at extreme conditions. Safety is improved by the small holdup volume of the reactors and effective control of pressure and temperature. Hydrogen peroxide is a powerful green oxidant that is used in a wide range of industries. Reduction and auto-oxidation of anthraquinones is currently the main process for hydrogen peroxide production. Direct synthesis is a green alternative and has potential for on-site production. However, there are two limitations: safety concerns because of the explosive gas mixture produced and low selectivity of the process. The aim of this thesis was to develop a process for direct synthesis of hydrogen peroxide utilizing microreactor technology. Experimental and numerical approaches were applied for development of the microreactor. Development of a novel microreactor was commenced by studying the hydrodynamics and mass transfer in prototype microreactor plates. The prototypes were designed and fabricated with the assistance of CFD modeling to optimize the shape and size of the microstructure. Empirical correlations for the mass transfer coefficient were derived. The pressure drop in micro T-mixers was investigated experimentally and numerically. Correlations describing the friction factor for different flow regimes were developed and predicted values were in good agreement with experimental results. Experimental studies were conducted to develop a highly active and selective catalyst with a proper form for the microreactor. Pd catalysts supported on activated carbon cloths were prepared by different treatments during the catalyst preparation. A variety of characterization methods were used for catalyst investigation. The surface chemistry of the support and the oxidation state of the metallic phase in the catalyst play important roles in catalyst activity and selectivity for the direct synthesis. The direct synthesis of hydrogen peroxide was investigated in a bench-scale continuous process using the novel microreactor developed. The microreactor was fabricated based on the hydrodynamic and mass transfer studies and provided a high interfacial area and high mass transfer coefficient. The catalysts were prepared under optimum treatment conditions. The direct synthesis was conducted at various conditions. The thesis represents a step towards a commercially viable direct synthesis. The focus is on the two main challenges: mitigating the safety problem by utilization of microprocess technology and improving the selectivity by catalyst development.

Lakisääteiset hitsaustyöt ja niiden laadunhallinta

Tässä diplomityössä selvitettiin UPM Kaukaan tehtailla esiintyviin lakisääteisiin hitsauskohteisiin liittyvää lainsäädäntöä ja lainsäädännön vaikutusta hitsaukselle. Lakisääteisiä hitsauskohteita ovat räjähdysvaaralliset tilat, painelaitteet, kemikaaliputkistot, kemikaalisäiliöt, maakaasulaitteet sekä kantavat teräsrakenteet. Diplomityössä selvitettiin lisäksi hitsauksen laadunhallintaa huomioiden korjaushitsaustyöt sekä uuden rakentaminen. Lakisääteet tuovat hitsauksen suorittamiselle usein tarkasti määritellyt velvoitteet koskien esimerkiksi dokumentointia, hitsaushenkilöstön pätevyyksiä, materiaaleja ja niin edelleen. Lakisääteet lisääntyvät jatkuvasti ja soveltamisalueet laajenevat, jolloin asioiden ylläpitäminen vaatii jatkuvaa seurantaa. Työssä luotiin ohjeistus koskien yleisesti hitsausta ja lisäksi käyttäjän ja omistajan velvoitteita koskevat ohjeet painelaitteista, maakaasulaitteista ja kemikaalilaitteista. Hitsauksen yleisohje koskee jokaista hitsaustapahtumaa korjaushitsauksesta uuden rakentamiseen. Ohje soveltuu lisäksi sopimusliitteeksi hitsaustyön tilauksissa.

The role of network externalities in value creating process of the commercial web service for two-sided international markets

Network externalities and two-sided markets in the context of web services and value creation is not very well discussed topic in academic literature. The explosive rise of the Internet users has created a strong base for many successful web services and pushed many firms towards e-business and online service based business models. Thus the subject of this thesis, the role of network externalities in value creating process of the commer-cial web service for two-sided international markets is very current and interesting topic to examine. The objective of this Master’s Thesis is to advance the study of network externalities from the viewpoint of two-sided markets and network effects as well as describe the value creation & value co-creation process in commercial web service business models. The main proposition suggests that the larger network of customers and the bigger number of users the web service is able to attract, the more value and stronger positive net-work externalities the service is able to create for each customer group. The empirical research of this study was implemented for commercial web service, targeted to Russian consumers and Finnish business users. The findings suggest that the size of the network is highly related to the experi-enced value of the customers and the whole value creation process of commercial web targeted for two-sided international markets varies from the value creation for one-sided or pure domestic markets.

Features for mobile applications popularity

Mobile applications market shows one of the highest growth rates for the market of intellectual products. The market is attractive to investors, despite the fact that the major companies of this industry already firmly consolidated its position. Experts predict the growth of the market for mobile applications with the development of mobile technologies in general. To demonstrate the explosive growth of the market and the scale of its impact, it is worth recalling the mobile game Angry Birds, which was able to achieve a huge reach and formed a full-fledged media brand, comparable to the film industry brands. The reasons why some games become popular and others not, are important for understanding the driving factors of the games industry. The Master’s Thesis explores the factors for mobile games applications popularity and ranking and propose recommendations for mobile games app store optimization of app representation. It discovers particular features of mobile games applications and releases’ influence on their popularity. Also the study assumes usage of such business models as The Business Model Canvas by Osterwalder and The Lean Startup Methodology by Ries, and describes the best practices of mobile application development process and market positioning. Moreover, the Master’s Thesis gives examples of multiple case studies about successful mobile apps developers.

Catalytic direct synthesis of hydrogen peroxide in a novel microstructured reactor

The direct synthesis from hydrogen and oxygen is a green alternative for production of hydrogen peroxide. However, this process suffers from two challenges. Firstly, mixtures of hydrogen and oxygen are explosive over a wide range of concentrations (4-94% H2 in O2). Secondly, the catalytic reaction of hydrogen and oxygen involves several reaction pathways, many of them resulting in water production and therfore decreasing selectivity. The present work deals with these two challenges. The safety problem was dealed by employing a novel microstructured reactor. Selectivity of the reaction was highly improved by development a set of new catalysts. The final goal was to develop an effective and safe continuous process for direct synthesis of hydrogen peroxide from H2 and O2. Activated carbon cloth and Sibunit were examined as the catalysts’ supports. Palladium and gold monometallic and palladium-gold bimetallic catalysts were thoroughly investigated by numerous kinetic experiments performed in a tailored batch reactor and several catalyst charachterization methods. A complete set of data for direct synthesis of H2O2 and its catalytic decomposition and hydrogenation was obtained. These data were used to assess factors influencing selectivity and activity of the catalysts in direct synthesis of H2O2 as well as its decomposition and hydrogenation. A novel microstructured reactor was developed based on hydrodynamics and mass transfer studies in prototype microstractural plates. The shape and the size of the structural elements in the microreactor plate were optimized in a way to get high gas-liquid interfacial area and gas-liquid mass transfer. Finally, empirical correlations for the volumetric mass transfer coefficient were derived. A bench-scale continuous process was developed by using the novel microstructral plate reactor. A series of kinetic experiments were performed to investigate the effects of the gas and the liquid feed rates and their ratio, the amount of the catalyst, the gas feed composition and pressure on the final rate of H2O2 production and selectivity.

Teollinen internet uuden liiketoiminnan katalysaattorina

TIIVISTELMÄ Lappeenrannan teknillinen yliopisto Teknistaloudellinen tiedekunta Tuotantotalouden koulutusohjelma Seppo Kuittinen Teollinen Internet uuden liiketoiminnan katalysaattorina Case CGI Diplomityö 2015 78 sivua, 33 kuvaa, 1 taulukko, 1 liite Työn tarkastajat: Professori Timo Pihkala Tutkijatohtori Marita Rautiainen Hakusanat: teollinen internet, IoT, kehittynyt analytiikka, sensorit Keywords: Industrial internet, IoT, advanced analytics, sencors Tämän työn tarkoituksena on tutkia asiakaskyselyn avulla luoko teollinen internet case yritykselle uutta ohjelmisto- tai palveluliiketoimintaa. Case yritys valitsi omasta asiakaskunnastaan 15 kohdeasiakasta, joille kysely lähetettiin. Vastauksista käy ilmi, että asiakaskunnassa on näkemys siitä, mitä teollinen internet on. Nykyisten ratkaisujen ei nähdä ratkaisevan kaikkia teollisen internetin mukanaan tuomia ongelmia. Ongelmaksi koetaan sensoridatan analysointi, jonka ei vielä katsota olevan riittävän kehittynyttä ja luotettavaa. Kyselystä voidaan päätellä, ettei mitään räjähtävää kasvua ole odotettavissa lähiaikoina. Teollinen internet tulee olemaan osa yritysten liiketoimintaa, mutta sen käyttö laajenee pikkuhiljaa.

Preclinical evaluation of the antidiabetic effect of Eugenia jambolana seed powder in streptozotocin-diabetic rats

The world is facing an explosive increase in the incidence of diabetes mellitus and cost-effective complementary therapies are needed. The effects of Eugenia jambolana, a household remedy for diabetes, were studied. Streptozotocin diabetic female albino Wistar rats weighing 150-200 g (N = 6) were fed E. jambolana seed powder (250, 500 or 1000 mg/kg) for 15 days. Diabetic rats fed 500 and 1000 mg/kg seed powder showed an increase in body weight on day 20 in relation to day 5 (6 ± 4.7, 9 ± 7.8 vs diabetic control -16 ± 7.1 g, P < 0.001), a decrease in fasting blood glucose (75 ± 11.9, 123 ± 14.4 vs diabetic control -34 ± 12.1 mg/dl, P < 0.001), a difference in post-treatment fasting and peak blood glucose (38 ± 11.9, 36 ± 14.2 vs diabetic control 78 ± 11.9 mg/dl, P < 0.001), and a difference in liver glycogen (50 ± 6.8, 52 ± 7.5 vs normal control 90 ± 6.6 µg/g of liver tissue, P < 0.001). Tri-terpenoids, tannins, gallic acid, and oxalic acid were the chemical constituents detected in E. jambolana seed. The best results were obtained with an oral dose of 500 mg/kg. Subacute toxicity studies with a single administration of 2.5 and 5.0 g/kg seed powder showed no mortality or abnormality. These data on the antidiabetic effect of E. jambolana seed are adequate for approval of phase 2 clinical trials to evaluate this seed powder as complementary therapy in type 2 and type 1 diabetes.

Matemática agradável

This paper suggests a reconsideration of the principle that public deficits should be financed by public debt. Two main reasons are offered. First, it is admitted that public debt is an economic variable whose time behaviour is better described by a first difference equation instead of an accounting identity. The convergence condition thus obtained requires either a nominal negative interest rate or that government bonds are used to raise tax income, hypotheses not theoretically granted. As a consequence, if primary surplus is not sufficient to match interests' payment, it will be observed an explosive trend in the public debt, the due interests and the money issuing. Therefore, it lacks support to the idea that public debt prevents inflation. Second, it is shown that financing public deficit through money issuing leads to a stable equilibrium money stock. The general conclusion is that, in order to simultaneously promote economic growth and inflation control, money issuing is preferable to public debt.

Endividamento público, crescimento, moeda e inflação: comentário a "Matemática agradável", de Gerson Lima

The paper aims at analyzing the article by Gerson Lima on the manner by which fiscal deficit should be covered. It presents a more general dynamic model, where the principle of effective demand is explicitly used. By doing that, it is possible to treat as endogenous variables the national income and the government entries, what brings the result that the public debt must not follow an explosive path unless the very restrictive conditions of Lima's paper prevail. It also evaluates Lima's implicit inflation theory, and argues against his approximation to Friedman's framework.

Endividamento público, crescimento, moeda e inflação: comentário a "matemática agradável", de Gerson Lima - a réplica

This paper aims at replying critical commentaries made by Leite, F. P., Aggio, G. O. e Angeli, E. (this Review, 2009) on two Author's theses. The first one states that, if public deficit is to be financed, then either interest rate applied is negative or government invests as if it where a profit-making business enterprise. Otherwise, public debt will mathematically follow an explosive trend. The second one says that if there is no debt and public deficit is paid with money issuing, then the monetary stock will tend to an equilibrium level.