43 resultados para Without Buffer Gas


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Euroopan energiamarkkinat ovat olleet viimeisen kymmenen vuoden aikana suurten muutosten alla. Markkinoiden kehitys on ollut huomattavaa myös Iso-Britanniassa, jossa sähkö- ja kaasumarkkinat ovat olleet avoinna kilpailulle jo muutamia vuosia. Ennen markkinoiden avautumista energiyhtiöt pystyivät siirtämään kaikki riskit suoraan asiakkaan kannettaviksi. Markkinoiden avautumisen myötä lisääntynyt kilpailu on kuitenkin pakottanut energiayhtiöitä ajanmukaistamaan näkemyksiään riskeistä. Riskitekijät, joista ei aiemmin tarvinnut välittää, on nyt pystyttävä tunnistamaan ja hallitsemaan. Tämä työ keskittyy hinta- ja volyymiriskien hallintaan. Rahoitusmarkkinoilla pitkään käytettyjä riskienhallintatyökaluja on otettu käyttöön myös energiamarkkinoilla. Energiamarkkinoiden piirteet poikkeavat kuitenkin rahoitusmarkkinoista, eikä näitä työkaluja voida ottaa käyttöön muutoksitta. Silti, jopa muutosten jälkeen rahoitusmarkkinoiden riskienhallitavälineet aliarvioivat energiamarkkinoiden hinta- ja volyymiriskejä. Tässä yhteydessä työssä esitetään Profit at Risk, PaR. PaR on skenaariopohjainen riskienhallinnan työkalu, joka on kehitetty erityisesti energiamarkkinoille ja täten huomioi niiden erikoispiirteet. Työn rungon muodostavat energiamarkkinoiden käyttäytyminen, hinta- ja volyymiriskitekijät sekä pohdinta miten hinta- ja volyymiriskeiltä voidaan suojautua ja miten niitä voidaan hallita. PaR-metodologiaa verrataan perinteisiin riskienhallintamenetelmiin ja työn tavoitteena on tuoda esiin ne tekijät, joiden ansiosta PaR on sopivampi työkalu energiamarkkinoiden riskienhallintaan kuin perinteiset menetelmät. Käytännön esimerkkinä työssä toimii Fortum Energy plus’n PaR –malli. Koska PaR on kehitetty erityisesti energiamarkkinoille, se huomioi täysin markkinoiden aiheuttamat hinta- ja volyymiriskit. Käytännön esimerkki kuitenkin osoittaa, että PaR menetelmästä ei ole riskienhallinnallista hyötyä ellei työkalun käyttäjällä ole täydellistä tietämystä niin energiamarkkinoista kuin markkinoiden muutoksiin vaikuttavien tekijöiden käyttäytymisestä.

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Tässä diplomityössä suunniteltiin ja rakennettiin kaasuturbiinin kaasusuuttimien virtausmittauslaitteisto. Suuttimien epätasainen toiminta kasvattaa kaasuturbiinin poistolämpötilahajontaa. Virtausmittauksien perusteella voidaan määrittää suuttimien efektiivinen virtauspoikkipinta-ala. Suuttimien asennusjärjestys opti-moidaan suuttimien välisten pinta-alaerojen mukaisesti, jolloin polttoainevirtaus polttokammioihin on mahdollisimman tasainen ja poistolämpötilahajonta pienenee. Kaasuturbiinin MS6001 esittelyssä keskityttiin tärkeimpiin komponentteihin sekä polttoainesuuttimien testauksen kannalta oleellisiin osiin ja niiden toimintaan. Teoriaosuudessa tarkasteltiin tilavuusvirran sekä suutinvirtauksen laskennassa käytettäviä yhtälöitä. Mittalaitteiston suunnittelu ja toteutus olivat tämän työn laajin osa-alue. Laitteiston keskeiset osat ovat kuristuselin ja suutintestausosa. Kuristuselintyypiksi valittiin rengaskammiollinen kuristuslaippa, joka suun-niteltiin standardin SFS-EN ISO 5167:2003 mukaisesti. Standardissa annettujen yhtälöiden antamia tuloksia verrattiin numeerisella virtauslaskentamallilla lasket-tuihin tuloksiin. Suutinrunkojen ja -kärkien mittauksien suunnittelussa sovellettiin samaa standardia sekä numeerista virtauslaskentaa optimaalisen sijainnin löytämiseksi paineyhteelle. Mittauksissa syntyvien epävarmuuksien arviointiin kiinnitettiin erityistä huomiota. Kokeellisessa osuudessa mitattiin yhden kunnostetun suuttimen, käytetyn suut-timen ja suutinrungon virtausta. Tuloksien perusteella laskettiin efektiiviset pinta-alat, joita verrattiin turbiinivalmistajan ilmoittamiin pinta-aloihin. Lopuksi arvioitiin mittaustulosten perusteella laitteiston toimivuutta. Virhe-arvioinnin ja mittaustulosten perusteella laadittiin teknisiä parannusehdotuksia suutintestauslaitteiston luotettavan toiminnan varmistamiseksi.

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Substances emitted into the atmosphere by human activities in urban and industrial areas cause environmental problems such as air quality degradation, respiratory diseases, climate change, global warming, and stratospheric ozone depletion. Volatile organic compounds (VOCs) are major air pollutants, emitted largely by industry, transportation and households. Many VOCs are toxic, and some are considered to be carcinogenic, mutagenic, or teratogenic. A wide spectrum of VOCs is readily oxidized photocatalytically. Photocatalytic oxidation (PCO) over titanium dioxide may present a potential alternative to air treatment strategies currently in use, such as adsorption and thermal treatment, due to its advantageous activity under ambient conditions, although higher but still mild temperatures may also be applied. The objective of the present research was to disclose routes of chemical reactions, estimate the kinetics and the sensitivity of gas-phase PCO to reaction conditions in respect of air pollutants containing heteroatoms in their molecules. Deactivation of the photocatalyst and restoration of its activity was also taken under consideration to assess the practical possibility of the application of PCO to the treatment of air polluted with VOCs. UV-irradiated titanium dioxide was selected as a photocatalyst for its chemical inertness, non-toxic character and low cost. In the present work Degussa P25 TiO2 photocatalyst was mostly used. In transient studies platinized TiO2 was also studied. The experimental research into PCO of following VOCs was undertaken: - methyl tert-butyl ether (MTBE) as the basic oxygenated motor fuel additive and, thus, a major non-biodegradable pollutant of groundwater; - tert-butyl alcohol (TBA) as the primary product of MTBE hydrolysis and PCO; - ethyl mercaptan (ethanethiol) as one of the reduced sulphur pungent air pollutants in the pulp-and-paper industry; - methylamine (MA) and dimethylamine (DMA) as the amino compounds often emitted by various industries. The PCO of VOCs was studied using a continuous-flow mode. The PCO of MTBE and TBA was also studied by transient mode, in which carbon dioxide, water, and acetone were identified as the main gas-phase products. The volatile products of thermal catalytic oxidation (TCO) of MTBE included 2-methyl-1-propene (2-MP), carbon monoxide, carbon dioxide and water; TBA decomposed to 2-MP and water. Continuous PCO of 4 TBA proceeded faster in humid air than dry air. MTBE oxidation, however, was less sensitive to humidity. The TiO2 catalyst was stable during continuous PCO of MTBE and TBA above 373 K, but gradually lost activity below 373 K; the catalyst could be regenerated by UV irradiation in the absence of gas-phase VOCs. Sulphur dioxide, carbon monoxide, carbon dioxide and water were identified as ultimate products of PCO of ethanethiol. Acetic acid was identified as a photocatalytic oxidation by-product. The limits of ethanethiol concentration and temperature, at which the reactor performance was stable for indefinite time, were established. The apparent reaction kinetics appeared to be independent of the reaction temperature within the studied limits, 373 to 453 K. The catalyst was completely and irreversibly deactivated with ethanethiol TCO. Volatile PCO products of MA included ammonia, nitrogen dioxide, nitrous oxide, carbon dioxide and water. Formamide was observed among DMA PCO products together with others similar to the ones of MA. TCO for both substances resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide and water. No deactivation of the photocatalyst during the multiple long-run experiments was observed at the concentrations and temperatures used in the study. PCO of MA was also studied in the aqueous phase. Maximum efficiency was achieved in an alkaline media, where MA exhibited high fugitivity. Two mechanisms of aqueous PCO – decomposition to formate and ammonia, and oxidation of organic nitrogen directly to nitrite - lead ultimately to carbon dioxide, water, ammonia and nitrate: formate and nitrite were observed as intermediates. A part of the ammonia formed in the reaction was oxidized to nitrite and nitrate. This finding helped in better understanding of the gasphase PCO pathways. The PCO kinetic data for VOCs fitted well to the monomolecular Langmuir- Hinshelwood (L-H) model, whereas TCO kinetic behaviour matched the first order process for volatile amines and the L-H model for others. It should be noted that both LH and the first order equations were only the data fit, not the real description of the reaction kinetics. The dependence of the kinetic constants on temperature was established in the form of an Arrhenius equation.

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Työssä vertaillaan eri sähköntuotantovaihtoehtojen taloudellista kannattavuutta. Kannattavuusvertailu suoritetaan pelkkää sähköä tuottaville voimalaitoksille. Sähkön ja lämmön yhteistuotannon lisärakentaminen tulee kattamaan tietyn osuuden lähitulevaisuuden sähkön hankinnan vajeesta, mutta sen lisäksi tarvitaan myös uutta lauhdetuotantokapasiteettia. Tutkittavat voimalaitostyypit ovat: ydinvoimalaitos, maakaasukombilauhdevoimalaitos, kivihiililauhdevoimalaitos, turvelauhdevoimalaitos, puulauhdevoimalaitos ja tuulivoimala. Kannattavuustarkastelu suoritetaan annuiteettimenetelmällä käyttäen 5 % reaalikorkoa ja tammikuun 2008 hintatasoa. Laskelmien perusteella 8000 tunnin huipunkäyttöajalla ydinsähkön tuotantokustannus olisi 35,0 € /MWh, kaasusähkön 59,2 €/MWh ja hiilisähkön 64,4 €/MWh, kun hiilidioksidipäästöoikeuden hintana käytetään 23 €/t. Ilman päästökauppaa kaasusähkön hinta on 51,2 €/MWh ja hiilisähkön 45,7 €/MWh ydinsähkön hinnan pysyessä ennallaan. Herkkyystarkastelun tulosten perusteella ydinvoiman kilpailukyky korostuu muihin tarkasteltuihin tuotantomuotoihin verrattuna. Ydinpolttoaineen suurellakaan hinnan muutoksella ei ole merkittävää vaikutusta ydinsähkön tuotantokustannukseen, kun taas maakaasusähkö on erittäin riippuvainen polttoaineen hinnasta. Myös päästöoikeuden hinnan kasvu lisää merkittävästi ydinvoiman kilpailukykyä kaasu- ja hiilisähköön verrattuna. Ydinvoimainvestoinnin kannattavuutta ja takaisinmaksua tarkastellaan myös yksinään siten, että investoinnilla saavutettavien tuottojen laskennassa käytetään useita eri sähkön markkinahintoja. Investoinnin kannattavuus on erittäin hyvä, kun sähkön markkinahinta on 50 €/MWh tai suurempi.

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The economical competitiveness of various power plant alternatives is compared. The comparison comprises merely electricity producing power plants. Combined heat and power (CHP) producing power will cover part of the future power deficit in Finland, but also condensing power plants for base load production will be needed. The following types of power plants are studied: nuclear power plant, combined cycle gas turbine plant, coal-fired condensing power plant, peat-fired condensing power plant, wood-fired condensing power plant and wind power plant. The calculations are carried out by using the annuity method with a real interest rate of 5 % per annum and with a fixed price level as of January 2008. With the annual peak load utilization time of 8000 hours (corresponding to a load factor of 91,3 %) the production costs would be for nuclear electricity 35,0 €/MWh, for gas based electricity 59,2 €/MWh and for coal based electricity 64,4 €/MWh, when using a price of 23 €/tonCO2 for the carbon dioxide emission trading. Without emission trading the production cost of gas electricity is 51,2 €/MWh and that of coal electricity 45,7 €/MWh and nuclear remains the same (35,0 €/MWh) In order to study the impact of changes in the input data, a sensitivity analysis has been carried out. It reveals that the advantage of the nuclear power is quite clear. E.g. the nuclear electricity is rather insensitive to the changes of nuclear fuel price, whereas for natural gas alternative the rising trend of gas price causes the greatest risk. Furthermore, increase of emission trading price improves the competitiveness of the nuclear alternative. The competitiveness and payback of the nuclear power investment is studied also as such by using various electricity market prices for determining the revenues generated by the investment. The profitability of the investment is excellent, if the market price of electricity is 50 €/MWh or more.

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Aim of this study was to investigate the means to reduce nutrient flows to water systems. Focus in this study was to examine peatland buffer zones as a solution to protect water bodies as well as to examine methane and nitrous oxide release from buffer zones. The literature survey covers a review of research which has been done till this day concerning the effects of forestry on water bodies. It also contains a review of the significance of forests and mires in hydrological cycle, effects of forestry on nutrient loads to water systems and a review of different solutions to diminish it. The solutions contain ditch shaping, submerged dams, sludge sumps, sedimentation ponds and buffer zones. The literature survey also covers nitrous oxide and methane gas emissions from buffer zones. Methane and nitrous oxide emissions from six different mires were studied during the summer of 2007. Measurements were conducted once a month using the static chamber method. Emissions of methane and nitrous oxide were calculated. Effects of water table level and peat temperature on emissions were also studied. The results showed a tendency to increased methane-emissions from natural peat lands when compared with restored buffer zones. The results showed also a tendency to increased CH4 emissions and decreased NO2 emissions with rising level of water table. Other mechanisms that influence emissions are vegetation composition and peat temperature. Considering the global warming as a result of increased greenhouse gas emissions, the emissions of CH4 and NO2 measured in the present study were not particularly high.

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This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

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One of the primary goals for food packages is to protect food against harmful environment, especially oxygen and moisture. The gas transmission rate is the total gas transport through the package, both by permeation through the package material and by leakage through pinholes and cracks. The shelf life of a product can be extended, if the food is stored in a gas tight package. Thus there is a need to test gas tightness of packages. There are several tightness testing methods, and they can be broadly divided into destructive and nondestructive methods. One of the most sensitive methods to detect leaks is by using a non destructive tracer gas technique. Carbon dioxide, helium and hydrogen are the most commonly used tracer gases. Hydrogen is the lightest and the smallest of all gases, which allows it to escape rapidly from the leak areas. The low background concentration of H2 in air (0.5 ppm) enables sensitive leak detection. With a hydrogen leak detector it is also possible to locate leaks. That is not possible with many other tightness testing methods. The experimental work has been focused on investigating the factors which affect the measurement results with the H2leak detector. Also reasons for false results were searched to avoid them in upcoming measurements. From the results of these experiments, the appropriate measurement practice was created in order to have correct and repeatable results. The most important thing for good measurement results is to keep the probe of the detector tightly against the leak. Because of its high diffusion rate, the HZ concentration decreases quickly if holding the probe further away from the leak area and thus the measured H2 leaks would be incorrect and small leaks could be undetected. In the experimental part hydrogen, oxygen and water vapour transmissions through laser beam reference holes (diameters 1 100 μm) were also measured and compared. With the H2 leak detector it was possible to detect even a leakage through 1 μm (diameter) within a few seconds. Water vapour did not penetrate even the largest reference hole (100 μm), even at tropical conditions (38 °C, 90 % RH), whereas some O2 transmission occurred through the reference holes larger than 5 μm. Thus water vapour transmission does not have a significant effect on food deterioration, if the diameter of the leak is less than 100 μm, but small leaks (5 100 μm) are more harmful for the food products, which are sensitive to oxidation.

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Neste Oil has introduced plant oils and animal fats for the production of NExBTL renewable diesel, and these raw materials differ from the conventional mineral based oils. One subject of new raw materials study is thermal degradation, or in another name pyrolysis, of these organic oils and fats. The aim of this master’s thesis is to increase knowledge on thermal degradation of these new raw materials, and to identify possible gaseous harmful thermal degradation compounds. Another aim is to de-termine the health and environmental hazards of identified compounds. One objective is also to examine the formation possibilities of hazardous compounds in the produc-tion of NExBTL-diesel. Plant oils and animal fats consist mostly of triglycerides. Pyrolysis of triglycerides is a complex phenomenon, and many degradation products can be formed. Based on the literature studies, 13 hazardous degradation products were identified, one of which was acrolein. This compound is very toxic and dangerous to the environment. Own pyrolysis experiments were carried out with rapeseed and palm oils, and with a mix-ture of palm oil and animal fat. At least 12 hazardous compounds, including acrolein, were analysed from the gas phase. According to the experiments, the factors which influence on acrolein formation are the time of the experiment, the sphere (air/hydrogen) in which the experiment is carried out, and the characteristics of the used oil. The production of NExBTL-diesel is not based on pyrolysis. This is why thermal degradation is possible only when abnormal process conditions prevail.

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Nyky yhteiskunta tulee päivä päivältä riippuvaisemmaksi sähköstä ja sen luotettavasta siirrosta ja jakelusta. Suurhäiriö kantaverkossa on erittäin epätodennäköinen, mutta sen mahdollisuutta ei koskaan voida kokonaan rajata pois. Suurhäiriön seuraukset ovat erittäin vakavat ja yhteiskäytön palautus häiriön jälkeen voi pitkittyä. Diplomityössä käsitellään kantaverkkoyhtiö Fingrid Oyj:n kaasuturpiinivaravoimalaitoksia ja niiden ominaisuuksia kantaverkon suurhäiriössä. Varavoimalaitosten pimeäkäynnistysvalmiudet tarkastettiin ja niissä suoritettiin koeajoja, jotka sisälsivät jatkuvan ja dynaamisen tilan koeajo osuudet. Yhdessä laitosyksikössä tehtiin myös pimeäkäynnistys ja saarekekoeajo. Koeajojen perusteella saatiin arvokasta perustietoa kaasuturpiinilaitosten ominaisuuksista ja mahdollisuuksista toimia pimeäkäynnistystilanteissa. Varavoimalaitosten matemaattista mallintamista yksinkertaisella teollisuuskaasuturpiinilaitoksen mallilla kokeiltiin siinä kuitenkaan onnistumatta. Kokemusten perusteella esitetään keskeisimmät havainnot ja ehdotukset kevyen, moniakselisen kaasuturpiinilaitoksen mallintamiseksi.

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One of the main industries which form the basis of Russian Economical structure is oil and gas. This industry is also playing a significant role for CIS countries. Oil and gas industry is developing intensively attracting foreign investments. This situation is providing sustainable development of machinery production for hazardous areas. Operating in oil and gas areas is always related with occurrence of explosion gas atmospheres. Machines for hazardous areas must be furnished with additional protection of different types. Explosion protection is regulated with standards according to which equipment must be manufactured. In Russia and CIS countries explosion-proof equipment must be constructed in compliance with GOST standards. To confirm that equipment is manufactured according to standards’ requirements and is safe and reliable it must undergo the approval procedure. Certification in Russia is governed by Federal Laws and legislation. Each CIS country has its own approval certificates and permissions for operating in hazardous areas.

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Natriumhypokloriittia voidaan valmistaa kloorista ja lipeästä jatkuvatoimisessa absorberissa. Tässä työssä tutkittiin kokeellisesti, miten kaasun ja nesteen virtausnopeudet vaikuttavat täytekappalekolonnin tulvimiseen ja painehäviöön, kuinka nopeasti kloori absorboituu lipeään ja kuinka suuri hypokloriittiliuoksen kierrätys tarvitaan, ettei hypokloriitti ala hajota. Lisäksi luotiin matemaattinen malli, jolla voidaan mitoittaa jatkuvatoiminen vastavirtaperiaatteella toimiva natriumhypokloriittireaktori. Kloori–lipeäsysteemin havaittiin tulvivan suuremmilla virtausnopeuksilla kuin ilma–vesisysteemin. Tosin osa kloorista absorboituu jo ennen täytekappalekerrosta, minkä vuoksi kaasun todellinen virtausnopeus täytekappalekerroksen alaosassa on pienempi kuin mitattu arvo. Kolonnin painehäviö nousee erittäin jyrkästi tulvimispisteen läheisyydessä. Koska kloori absorboituu lähes täydellisesti ja vain kolonnin alaosa tulvii, voidaan kolonnia painehäviön kannalta operoida lähellä tulvimispistettä. Sekä mallinnuksen että koetulosten perusteella yli 99,99 % kloorista absorboituu koeolosuhteissa kahden metrin täytekappalekerroksessa. Nopea absorptio johtuu erittäin nopeasta, irreversiibelistä kloorin reaktiosta ja prosessille tyypillisestä natriumhydroksidikonversion rajoittamisesta alle 94 %:iin. Jotta varmistetaan, ettei hypokloriitti ala hajota, valmista hypokloriittiliuosta täytyy kierrättää kolonniin vähintään noin 4-kertainen määrä tuoreen lipeän syöttömäärän nähden.