FCC-yksikön NOx-päästöjen hallinta

Työssä tutkittiin typen oksidien (NOx) päästöjen muodostumista ja NOx-päästöjen poistomenetelmiä leijukatalyyttisessa krakkausyksikössä (FCC). Koeajossa Porvoon öljynjalostamon FCC-yksikössä tutkittiin NOx-päästöjen hallintaa CO-promoottorin (CO:n palamista edistävä lisäaine) annostelun avulla. Kirjallisuusosassa käsiteltiin NOx-päästöjen muodostumista FCC-yksikön regeneraattorissa. Katalyyttisten lisäaineiden vaikutusta NOx-päästöjen muodostumiseen tarkasteltiin laajasti. Katalyyttisten lisäaineiden ohella käsiteltiin muitakin NOx-päästöjen poistomenetelmiä. Koeajojen tarkoituksena oli optimoida FCC-yksikön katalyyttikiertoon annosteltavan CO-promoottorin määrä. CO-promoottorin sisältämä platina lisää NOx-päästöjen muodostumista regeneraattorissa, mutta vähentää jälkipalamista. Jälkipalamisen vuoksi regeneraattorin ylimenolinjan lämpötila nousee. Regeneraattorin ylimenolinjan lämpötila oli CO-promoottorin vähentämistä rajoittava tekijä, NOx-päästöjä pyrittiin vähentämään ilman merkittävää jälkipalamisen kasvua. Tuorekatalyytin platinapitoisuuden pienentäminen vähentää merkittävästi NOx-päästöjä.

Development of an environmentally friendly method of starch oxidation by hydrogen peroxide and a complex water-soluble Iron catalyst

Oxidized starch is a key component in the paper industry, where it is used as both surfacing sizer and filler. Large quantities are annually used for this purpose; however, the methods for the oxidation are not environmentally friendly. In our research, we have studied the possibility to replace the harmful oxidation agents, such as hypochlorite or iodates and transition metal catalysts, with a more environmentally friendly oxidant, hydrogen peroxide (H2O2), and a special metal complex catalyst (FePcS), of which only a small amount is needed. The work comprised batch and semi-batch studies by H2O2, ultrasound studies of starch particles, determination of low-molecular by-products and determination of the decomposition kinetics of H2O2 in the presence of starch and the catalyst. This resulted in a waste-free oxidation method, which only produces water and oxygen as side products. The starch oxidation was studied in both semi-batch and batch modes in respective to the oxidant (H2O2) addition. The semi-batch mode proved to yield a sufficient degree of substitution (COOH groups) for industrial purposes. Treatment of starch granules by ultrasound was found to improve the reactivity of starch. The kinetic results were found out to have a rather complex pattern – several oxidation phases were observed, apparently due to the fact that the oxidation reaction in the beginning only took place on the surface, whereas after a prolonged reaction time, partial degradation of the solid starch granules allowed further reaction in the interior parts. Batch-mode experiments enabled a more detailed study of the mechanisms of starch in the presence of H2O2 and the catalyst, but yielded less oxidized starch due to rapid decomposition of H2O2 due to its high concentrations. The effect of the solid-liquid (S/L) ratio in the reaction system was studied in batch experiments. These studies revealed that the presence of the catalyst and the starch enhance the H2O2 decomposition.

Kinetics of selective oxidation of lactose to lactobionic acid over Pd-active carbon catalyst

Laktoosi eli maitosokeri on tärkein ainesosa useimpien nisäkkäiden tuottamassa maidossa. Sitä erotetaan herasta, juustosta ja maidosta. Laktoosia käytetään elintarvike- ja lääketeollisuuden raaka-aineena monissaeri tuotteissa. Lääketeollisuudessa laktoosia käytetään esimerkiksi tablettien täyteaineena. Hapettamalla laktoosia voidaan valmistaa laktobionihappoa, 2-keto-laktobionihappoa ja laktuloosia. Laktobionihappoa käytetään biohajoavien pintojen ja kosmetiikkatuotteiden valmistuksessa, sekä sisäelinten säilöntäliuoksissa, joissa laktobionihappo estää happiradikaalien aiheuttamien kudosvaurioiden syntymistä. Tässä työssä laktoosia hapetettiin laktobionihapoksi sekoittimella varustetussa laboratoriomittakaavaisessa panosreaktorissa käyttäenkatalyyttinä palladiumia aktiivihiilellä. Muutamissa kokeissa katalyytin promoottorina käytettiin vismuttia, joka hidastaa katalyytin deaktivoitumista. Työn tarkoituksena oli saada lisää tietoa laktoosin hapettamisen kinetiikasta. Laktoosin hapettumisessa laktobionihapoksi havaittiin selektiivisyyteen vaikuttavan muunmuassa reaktiolämpötila, paine, pH ja käytetyn katalyytin määrä. Katalyyttiä kierrättämällä eri kokeiden välillä saatiin paremmat konversiot, selektiivisyydet ja saannot. Parhaat koetulokset saatiin hapetettaessa synteettisellä ilmalla 60 oC lämpötilassa ja 1 bar paineessa. Tehdyissä kokeissa pH:n säätö tehtiin manuaalisesti, joten pH ei pysynyt koko ajan haluttuna. Laktoosin konversio oli parhaimmillaan 95 %. Laktobionihapon suhteellinen selektiivisyys oli 100% ja suhteellinen saanto 100 %. Kinetiikan matemaattinen mallinnus tehtiin Modest-ohjelmalla käyttäen kokeista saatuja mittaustuloksia.Ohjelman avulla estimoitiin parametreja ja saatiin matemaattinen malli reaktorille. Tässä työssä tehtiin kineettinen mallinnus myös ravistelureaktorissa tehdyille laktoosin hapetuskokeille, missä pH pysyi koko ajan haluttuna 'in-situ' titrauksen avulla. Työn yhteydessä selvitettiin myös mahdollisuutta käyttää monoliittikatalyyttejä laktoosin hapetusreaktiossa.

Challenges in packaging waste management: A case study in the fast food industry

The main research problem of this thesis is to find out the means of promoting the recovery of packaging waste generated in thefast food industry. The recovery of packaging waste generated in the fast food industry is demanded by the packaging waste legislation and expected by the public. The means are revealed by the general factors influencing the recovery of packaging waste, analysed by a multidisciplinary literature review and a case study focusing on the packaging waste managementof McDonald's Oy operating in Finland. The existing solid waste infrastructure does not promote the recovery ofpackaging waste generated in the fast food industry. The theoretical recovery rate of the packaging waste is high, 93 %, while the actual recovery rate is only 29 % consisting of secondary packaging manufactured from cardboard. The total recovery potential of packaging waste is 64 %, resulting in 1 230 tonnes ofrecoverable packaging waste. The achievable recovery potential of 33 %, equalling 647 tonnes of packaging waste could be recovered, but is not recovered mainly because of non-working waste management practises. The theoretical recovery potential of 31 %, equalling 583 tonnes of packaging waste can not be recovered by the existing solid waste infrastructure because of the obscure status of commecial waste, the improper operation ofproducer organisations, and the municipal autonomy. The sorting experiment indicated that it is possible to reach the achievable recovery potential inthe existing solid waste infrastructure. The achievement is promoted by waste producer -oriented waste management practises. The theoretical recovery potential can be reached by increasing the consistency of the solid waste infrastructure through governmental action.

Kaasutuskaasun puhdistus

Tässä diplomityössä on selvitetty hiilestä, jätteestä tai biopolttoaineesta kaasutetun kaasun märkä- ja kuivapuhdistusta. Kaasutuskaasun puhdistuksella voidaan likainen ja jopa ongelmallinen aines muuttaa tai puhdistaa sellaiseksi ympäristökelpoiseksi polttoaineeksi, että sitä voidaan käyttää nykyisissä kulutuskohteissa ongelmitta. Lisäkannustusta kaasutuskaasun puhdistus saa uusista EU-direktiiveistä, jotka tulevat rajoittamaan jätteiden läjittämistä kaatopaikoille. Loppusijoitukseen meneviä jätevirtoja voidaan energiakäytöllä pienentää huomattavasti.Työ on tehty PVO-Engineering Oy:n voimalaitostekniikan osastolle kevään 2001 aikana. Työn tavoitteena oli kasvattaa yrityksen tietomäärää kaasutuskaasun puhdistuksen osalta. Lisäksi pyrittiin selvittämään uuden keraamisen pussisuodatinmateriaalin käyttöä kaasutuskaasun kuumakuivasuodatuksessa. Työn ensimmäisessä osassa esitetään kaasutuskaasun koostumuksen ja syntymisen lisäksi tämän työn lähtökohdat ja tavoitteet. Toisessa osassa selvitetään kaasulle asetettavia vaatimuksia eri käyttötapojen mukaan. Kolmannessa ja neljännessä osassa selvitetään puhdistettavien komponenttien käyttäytymistä ja sopivia puhdistusmenetelmiä.Kaasutuskaasun puhdistustekniikka vaihtelee paljonkin riippuen kaasun käyttökohteesta. Eroja syntyy käyttökohteen asetettamista vaatimuksista polttoaineelle, kaasutettavan polttoaineen koostumuksesta ja laadun vaihtelusta. Puhdistuksessa keskitytään kloori -, rikki -, typpi - ja metalliyhdisteiden poistamiseen kaasuvirrasta. Erotuskyvyllä arvioituna eri puhdistusmenetelmistä tehokkaimpia ovat pesurisähkösuodatinyhdistelmät. Niiden suuret jätemäärät ovat kuitenkin iso ongelma. Kuumakuivapuhdistuksessa pyritään kehittämään menetelmä, jossa syntyvät jätemäärät ovat pieniä ja puhdistustulos on riittävä. Puhdistuksen apukeinona käytetään usein erilaisia katalyyttejä. Tunnetuimpia ovat erilaiset kalsiumpohjaiset materiaalit ja mineraalit. Katalyyteillä voidaan tehostaa tarpeellisia kemiallisia reaktioita puhdistusprosessissa. Kaikki puhdistukseen liittyvät ongelmat ovat kooltaan niin suuria, että niiden ratkaisemiseksi on tulevaisuudessa tehtävä lujasti töitä. Markkinanäkymät toimivalle puhdistustekniikalle ovat nykymaailmassa hyvät. Niinpä tuotekehitykseen laitetut panokset voivat tulevaisuudessa olla yritykselle kullan arvoisia.

Small scale waste management. Composting project in selected schools in Mwanza, Tanzania

No 2/2008, sivu 8.

Methods for assessing the sustainability of integrated municipal waste management and

The general striving to bring down the number of municipal landfills and to increase the reuse and recycling of waste-derived materials across the EU supports the debates concerning the feasibility and rationality of waste management systems. Substantial decrease in the volume and mass of landfill-disposed waste flows can be achieved by directing suitable waste fractions to energy recovery. Global fossil energy supplies are becoming more and more valuable and expensive energy sources for the mankind, and efforts to save fossil fuels have been made. Waste-derived fuels offer one potential partial solution to two different problems. First, waste that cannot be feasibly re-used or recycled is utilized in the energy conversion process according to EU’s Waste Hierarchy. Second, fossil fuels can be saved for other purposes than energy, mainly as transport fuels. This thesis presents the principles of assessing the most sustainable system solution for an integrated municipal waste management and energy system. The assessment process includes: · formation of a SISMan (Simple Integrated System Management) model of an integrated system including mass, energy and financial flows, and · formation of a MEFLO (Mass, Energy, Financial, Legislational, Other decisionsupport data) decision matrix according to the selected decision criteria, including essential and optional decision criteria. The methods are described and theoretical examples of the utilization of the methods are presented in the thesis. The assessment process involves the selection of different system alternatives (process alternatives for treatment of different waste fractions) and comparison between the alternatives. The first of the two novelty values of the utilization of the presented methods is the perspective selected for the formation of the SISMan model. Normally waste management and energy systems are operated separately according to the targets and principles set for each system. In the thesis the waste management and energy supply systems are considered as one larger integrated system with one primary target of serving the customers, i.e. citizens, as efficiently as possible in the spirit of sustainable development, including the following requirements: · reasonable overall costs, including waste management costs and energy costs; · minimum environmental burdens caused by the integrated waste management and energy system, taking into account the requirement above; and · social acceptance of the selected waste treatment and energy production methods. The integrated waste management and energy system is described by forming a SISMan model including three different flows of the system: energy, mass and financial flows. By defining the three types of flows for an integrated system, the selected factor results needed in the decision-making process of the selection of waste management treatment processes for different waste fractions can be calculated. The model and its results form a transparent description of the integrated system under discussion. The MEFLO decision matrix has been formed from the results of the SISMan model, combined with additional data, including e.g. environmental restrictions and regional aspects. System alternatives which do not meet the requirements set by legislation can be deleted from the comparisons before any closer numerical considerations. The second novelty value of this thesis is the three-level ranking method for combining the factor results of the MEFLO decision matrix. As a result of the MEFLO decision matrix, a transparent ranking of different system alternatives, including selection of treatment processes for different waste fractions, is achieved. SISMan and MEFLO are methods meant to be utilized in municipal decision-making processes concerning waste management and energy supply as simple, transparent and easyto- understand tools. The methods can be utilized in the assessment of existing systems, and particularly in the planning processes of future regional integrated systems. The principles of SISMan and MEFLO can be utilized also in other environments, where synergies of integrating two (or more) systems can be obtained. The SISMan flow model and the MEFLO decision matrix can be formed with or without any applicable commercial or free-of-charge tool/software. SISMan and MEFLO are not bound to any libraries or data-bases including process information, such as different emission data libraries utilized in life cycle assessments.

Sustainable Waste-to-Energy Production: Performance Evaluation of Distributed Generation fuelled by Landfill Gas

The environmental impact of landfill is a growing concern in waste management practices. Thus, assessing the effectiveness of the solutions implemented to alter the issue is of importance. The objectives of the study were to provide an insight of landfill advantages, and to consolidate landfill gas importance among others alternative fuels. Finally, a case study examining the performances of energy production from a land disposal at Ylivieska was carried out to ascertain the viability of waste to energy project. Both qualitative and quantitative methods were applied. The study was conducted in two parts; the first was the review of literatures focused on landfill gas developments. Specific considerations were the conception of mechanism governing the variability of gas production and the investigation of mathematical models often used in landfill gas modeling. Furthermore, the analysis of two main distributed generation technologies used to generate energy from landfill was carried out. The review of literature revealed a high influence of waste segregation and high level of moisture content for waste stabilization process. It was found that the enhancement in accuracy for forecasting gas rate generation can be done with both mathematical modeling and field test measurements. The result of the case study mainly indicated the close dependence of the power output with the landfill gas quality and the fuel inlet pressure.

Wet oxidation of recalcitrant lignin waters: Experimental and kinetic studies

The dissertation is based on four articles dealing with recalcitrant lignin water purification. Lignin, a complicated substance and recalcitrant to most treatment technologies, inhibits seriously pulp and paper industry waste management. Therefore, lignin is studied, using WO as a process method for its degradation. A special attention is paid to the improvement in biodegradability and the reduction of lignin content, since they have special importance for any following biological treatment. In most cases wet oxidation is not used as a complete ' mineralization method but as a pre treatment in order to eliminate toxic components and to reduce the high level of organics produced. The combination of wet oxidation with a biological treatment can be a good option due to its effectiveness and its relatively low technology cost. The literature part gives an overview of Advanced Oxidation Processes (AOPs). A hot oxidation process, wet oxidation (WO), is investigated in detail and is the AOP process used in the research. The background and main principles of wet oxidation, its industrial applications, the combination of wet oxidation with other water treatment technologies, principal reactions in WO, and key aspects of modelling and reaction kinetics are presented. There is also given a wood composition and lignin characterization (chemical composition, structure and origin), lignin containing waters, lignin degradation and reuse possibilities, and purification practices for lignin containing waters. The aim of the research was to investigate the effect of the operating conditions of WO, such as temperature, partial pressure of oxygen, pH and initial concentration of wastewater, on the efficiency, and to enhance the process and estimate optimal conditions for WO of recalcitrant lignin waters. Two different waters are studied (a lignin water model solution and debarking water from paper industry) to give as appropriate conditions as possible. Due to the great importance of re using and minimizing the residues of industries, further research is carried out using residual ash of an Estonian power plant as a catalyst in wet oxidation of lignin-containing water. Developing a kinetic model that includes in the prediction such parameters as TOC gives the opportunity to estimate the amount of emerging inorganic substances (degradation rate of waste) and not only the decrease of COD and BOD. The degradation target compound, lignin is included into the model through its COD value (CODligning). Such a kinetic model can be valuable in developing WO treatment processes for lignin containing waters, or other wastewaters containing one or more target compounds. In the first article, wet oxidation of "pure" lignin water was investigated as a model case with the aim of degrading lignin and enhancing water biodegradability. The experiments were performed at various temperatures (110 -190°C), partial oxygen pressures (0.5 -1.5 MPa) and pH (5, 9 and 12). The experiments showed that increasing the temperature notably improved the processes efficiency. 75% lignin reduction was detected at the lowest temperature tested and lignin removal improved to 100% at 190°C. The effect of temperature on the COD removal rate was lower, but clearly detectable. 53% of organics were oxidized at 190°C. The effect of pH occurred mostly on lignin removal. Increasing the pH enhanced the lignin removal efficiency from 60% to nearly 100%. A good biodegradability ratio (over 0.5) was generally achieved. The aim of the second article was to develop a mathematical model for "pure" lignin wet oxidation using lumped characteristics of water (COD, BOD, TOC) and lignin concentration. The model agreed well with the experimental data (R2 = 0.93 at pH 5 and 12) and concentration changes during wet oxidation followed adequately the experimental results. The model also showed correctly the trend of biodegradability (BOD/COD) changes. In the third article, the purpose of the research was to estimate optimal conditions for wet oxidation (WO) of debarking water from the paper industry. The WO experiments were' performed at various temperatures, partial oxygen pressures and pH. The experiments showed that lignin degradation and organics removal are affected remarkably by temperature and pH. 78-97% lignin reduction was detected at different WO conditions. Initial pH 12 caused faster removal of tannins/lignin content; but initial pH 5 was more effective for removal of total organics, represented by COD and TOC. Most of the decrease in organic substances concentrations occurred in the first 60 minutes. The aim of the fourth article was to compare the behaviour of two reaction kinetic models, based on experiments of wet oxidation of industrial debarking water under different conditions. The simpler model took into account only the changes in COD, BOD and TOC; the advanced model was similar to the model used in the second article. Comparing the results of the models, the second model was found to be more suitable for describing the kinetics of wet oxidation of debarking water. The significance of the reactions involved was compared on the basis of the model: for instance, lignin degraded first to other chemically oxidizable compounds rather than directly to biodegradable products. Catalytic wet oxidation of lignin containing waters is briefly presented at the end of the dissertation. Two completely different catalysts were used: a commercial Pt catalyst and waste power plant ash. CWO showed good performance using 1 g/L of residual ash gave lignin removal of 86% and COD removal of 39% at 150°C (a lower temperature and pressure than with WO). It was noted that the ash catalyst caused a remarkable removal rate for lignin degradation already during the pre heating for `zero' time, 58% of lignin was degraded. In general, wet oxidation is not recommended for use as a complete mineralization method, but as a pre treatment phase to eliminate toxic or difficultly biodegradable components and to reduce the high level of organics. Biological treatment is an appropriate post treatment method since easily biodegradable organic matter remains after the WO process. The combination of wet oxidation with subsequent biological treatment can be an effective option for the treatment of lignin containing waters.

Membrane emulsification in preparation of single site catalyst

In the theory part the membrane emulsification was studied. Emulsions are used in many industrial areas. Traditionally emulsions are prepared by using high shear in rotor-stator systems or in high pressure homogenizer systems. In membrane emulsification two immiscible liquids are mixed by pressuring one liquid through the membrane into the other liquid. With this technique energy could be saved, more homogeneous droplets could be formed and the amount of surfactant could be decreased. Ziegler-Natta and single-site catalysts are used in olefin polymerization processes. Nowadays, these catalysts are prepared according to traditional mixing emulsification. More homogeneous catalyst particles that have narrower particle size distribution might be prepared with membrane emulsification. The aim of the experimental part was to examine the possibility to prepare single site polypropylene catalyst using membrane emulsification technique. Different membrane materials and solidification techniques of the emulsion were examined. Also the toluene-PFC phase diagram was successfully measured during this thesis work. This phase diagram was used for process optimization. The polytetrafluoroethylene membranes had the largest contact angles with toluene and also the biggest difference between the contact angles measured with PFC and toluene. Despite of the contact angle measurement results no significant difference was noticed between particles prepared using PTFE membrane or metal sinter. The particle size distributions of catalyst prepared in these tests were quite wide. This would probably be fixed by using a membrane with a more homogeneous pore size distribution. It is also possible that the solidification rate has an effect on the particle sizes and particle morphology. When polymeric membranes are compared PTFE is probably still the best material for the process as it had the best chemical durability.

Integration of the Food Waste Disposer Unit to the Existing Sewage System

Among the numerous approaches to food waste treatment, the food waste disposers method (FWDs), as a newcomer, has become slowly accepted by the general public owing to the worries about its impact on the existing sewage system. This paper aims to justify the role of FWDs in the process of urbanization in order to better prepare a city to take good care of the construction of its infrastructure and the solid waste treatment. Both the literatures and the case study help to confirm that FWDs has no negative effects on the wastewater treatment plant and it is also environmental friendly by reducing the greenhouse gas emissions. In the case study, the Lappeenranta waste water treatment plant has been selected in order to figure out the possible changes to a WWTP following the integration of FWDs: the observation shows only minor changes take place in a WWTP, in case of 25% application, like BOD up 7%, TSS up 6% and wastewater flowrate up 6%, an additional sludge production of 200 tons per year and the extra yield of methane up to 10000m3 per year; however, when the utilization rate of FWD is over 75%, BOD, TSS, and wastewater flowrate will experience more significant changes, thus exerting much pressure on the existing WWTP. FWDs can only be used in residential areas or cities equipped with consummate drainage network within the service sphere of WWTP, therefore, the relevant authority or government department should regulate the installation frequency of FWDs, while promoting the accessory application of FWDs. In the meanwhile, WWTP should improve their treatment process in order to expand their capacity for sludge treatment so as to stay in line with the future development of urban waste management.

Quasi-objects and actors in the web of belief. Formation of a national nuclear waste management system: the case of Finland

Paper presented in ISA RC23 meeting, Gothenburg July 16th 2010

Waste Stream Investigation from Perspective of Changing Waste Legislation at Green Sand Foundries

The update of the Finnish legislation concerning waste was unavoidable, to comply with the European Union (EU) requirements defined in the EU-Directive on Waste. The new waste law updates were enacted into the Finnish legislation on the 11.03.2011 and targeted for applicability by the 11.03.2012. This thesis investigates the implications of the new amendments to the waste legislation from the perspective of green sand foundries. The investigations are conducted by comparing two of Componenta’s green sand foundries and evaluating their waste streams. Additionally, the impacts of legislation amendments are critiqued on their environmental and economic aspects. The study’s comparison of waste fractions at the two foundries reveals that sand is dominant in absolute tonnage and costs. The increments of waste taxes forces foundries to focus on waste management, recycling and disposing. The new legislation’s promotion of material efficiency, also guides foundries towards the prevention of waste. A potential preventive measure is to regenerate waste sand resulting to cost savings on both raw-materials and waste management. However, the lack of absolute targets for waste prevention or recycling rates discourages the interests towards creating or adopting new technologies and methods for the waste handling.