I värme- och kraftvärmeverk förbränns olika typer av bränslen för produktion av el och fjärrvärme. Vid förbränningen bildas rökgaser som innehåller föroreningar, till exempel tungmetaller, från bränslet. Anläggningarna har ofta krav på utsläpp både via rökgaserna och avloppsvatten. Rökgaserna renas därmed genom olika tekniker var av en vanlig teknik är rökgaskondensering. Vid rökgaskondenseringen bildas en vätska, kallad rökgaskondensat, som delvis innehåller tungmetaller från bränslet. Rökgaskondensatet måste renas innan det kan lämna anläggningen och det görs bland annat med tungmetalljonbytare. Jonbytarmassan i tungmetalljonbytarkolonnerna behöver bytas ungefär två gånger per driftsäsong då den inte längre kan binda mer tungmetaller. Detta är en kostnad för värme- och kraftvärmeverken som de vill minimera. I denna studie undersöktes om lokal provtagning och analys på ett kraftvärmeverk av ett antal utvalda tungmetaller i rökgaskondensat är en bra metod för att optimering av reningssteget med tungmetalljonbytare. Samt om detta kan säkerställa att miljökraven för tungmetaller i det renade rökgaskondensatet uppfylls. Med optimering avses att jonbytarmassornas fulla kapacitet utnyttjas, d.v.s. att byten av jonbytarmassor kan reduceras utan att riskera otillåtna halter av tungmetaller i de renade rökgaskondensatet till följd av att jonbytarmassorna använts för länge. Även tiden som behöver avsättas för lokal provtagning och analys dokumenterades. I dagsläget sker analyser hos ackrediterade laboratorium där det tar drygt två veckor att få resultatet och under väntetiden kan mycket på anläggningen förändras. En verifiering av resultaten från studien gjordes mot resultat från ett sådant. I denna studie undersöktes lokal provtagning och analys med mätinstrumentet FREEDD som bygger på tekniken kvartskristall mikrobalans (QCM-teknik). Andra alternativ för lokal analys har inte undersökts här.  Resultatet visade att det i dagsläget är svårt att med lokal provtagning optimera reningssteget med jonbytarmassor samt kontrollera utsläppen av tungmetaller via det renade rökgaskondensatet. Korrigeringar hos mätinstrumentet och provpunkterna behöver göras för att få pålitligt resultat. Tiden som behöver avsättas för provtagning och analys beror på vilken metall som ska analyseras då tiden för preparering av prov varierar. Men om det kan möjliggöra att anläggningarna kan använda jonbytarmassorna längre samt får kontroll på utsläppen via det renade rökgaskondensatet kan det vara lönsamt att avvara den tiden. / In heating and combined heat and power plants, different types of fuels are burned to produce electricity and district heating. During the combustion flue gases containing pollutants, such as heavy metals, are formed from the flue. The plants have requirements for low emissions, both from the flue gases and the wastewater. The flue gases are purified by various techniques and a common technique is flue gas condensation. During the flue gas condensation, a liquid called flue gas condensate, is formed, which partly contains heavy metals from the flue. The flue gas condensate must be cleaned before it can leave the plant. A step in the purification of the flue gas condensate is usually heavy metal ion-exchanger. The ion-exchange mass in the heavy metal ion-exchange columns needs to be changed approximately twice per operating season as it no longer has room to bind more heavy metals. This is an expensive cost for the heating and combined heat and power plants that they want to minimize. This study investigated whether local sampling and analysis at a cogeneration plant of a number selected heavy metals in flue gas condensate is a good method for optimizing the purifications step with heavy metal ion-exchangers. And if this can ensure that the environmental requirements for the heavy metals in the purified flue gas condensate are met. Optimization means that the full capacity of the ion-exchange masses is utilized, i.e. that the exchange of ion-exchange masses can be reduced without risking unauthorized levels of heavy metals in the purified flue gas condensate as a result of the ion exchange masses being used for too long.  The time needed for local sampling and analysis was also documented. At present, analyzes are done at accredited laboratories where it takes over two weeks to get the result and during that time much can be changes at the plant. A verification of the result of the study was also made against the result of an accredited laboratory. In this study, local analysis was made with the measuring instrument FREEDD which is based on quartz crystal microbalance (QCM-technology). Other options for local sampling and analysis have not been investigated. The result showed that, in the present, it is difficult to optimize the purification step with ion-exchange masses and check emissions of heavy metals with the purified flue gas condensate. To obtain reliable result, corrections to the measuring instrument and test points need to be made. The time that needs to be set aside for sampling and analysis depends on the metal, as the time for sample preparation varies.  But if it can enable the plants to use the ion-exchange masses longer and gain control of the emissions of heavy metals with the purified flue gas condensate, it can be profitable to save that time.

This master’s thesis elaborates a design of water heating and heating system for a building of a rehabilitation center in Horný Hričov. The theoretical section describes operational efficiency of gas boilers and associated calculation methods. The experimental section covers measurements of condensing gas boiler at various temperatures of heating water conducted in university laboratory. Operational efficiency was then calculated using indirect method based on the measurement results. Subsequently, calculated values and values measured by an operational efficiency analyzer were compared. The comparison revealed minor deviations in operational efficiency values and different values of condensing heat utilization between the calculations and the analyzer results. The analytical section of the thesis consists of complex designs of two versions of the heating system and the water heating. The first design version uses condensing gas boilers as a heat source while the second version uses a water-air heat pump instead. The project section of the thesis is executed in the scope for a building permit and consists of a technical report and a design documentation.

Diploma thesis deals with problematics of offtake of flue gasses. In experimental part there was measured compound of flue gasses by analyzator of flue gates. Aplication is a project of heating of object of The Academy of Sciences of the Czech Republic in Brno. Project solves design of heating system, flue and of source of heat. Heating area is created by floor convectors,towel rails and radiators. Source of heat is designed in two variants : as a cascade of condensation boilers and as a cascade of low-temperature boilers.

Modern societies produce large quantities of municipal solid waste (MSW), which is commonly disposed of by incineration. This has several advantages: it reduces the waste’s volume and sterilizes it while also enabling energy recovery. However, MSW incineration has some notable disadvantages, the most widely debated of which is probably the production and release of persistent organic pollutants (POP) such as polychlorinated dibenzofurans (PCDF), dibenzo-p-dioxins (PCDD), biphenyls (PCB) and naphthalenes (PCN). Of the 210 PCDF and PCDD congeners, 17 are toxic, with hormone-disrupting and carcinogenic properties. Twelve of the 209 PCB congeners and at least 2 of the 75 PCN also exhibit such properties. These POP form in the post-combustion zones of MSW incineration plants and are removed from the flue gas using filtering devices that trap them in the fly ash This thesis concerns the formation and degradation of POP in processes related to MSW incineration. The first paper describes a case study in which PCDD were forming in filters designed to remove them from flue gases, causing emission-related issues in a full-scale MSW incineration plant. It was shown that the PCDD formation was probably due to chlorophenol condensation on the filters’ surfaces. The second paper describes the validation of a cooling probe designed to prevent POP formation during high temperature (>450 °C) flue gas sampling. The results obtained also confirmed that PCDF and PCDD formation takes place at temperatures below 600 °C. In the third paper, three different fly ashes were subjected to thermal treatment under an inert atmosphere in a rotary kiln and in sealed ampoules at 400 °C. The concentrations, degrees of chlorination and congener profiles of the POP in the treated ashes and emitted gases were compared to those for the untreated ashes. The trends observed for PCDF mirrored those for PCN, while the trends for PCDD closely resembled those for PCB. The PCDF congener profiles of the kiln ash were similar regardless of the initial ash composition, suggesting that the mechanisms of PCDF formation were similar in all cases. The fourth paper describes the surface characterization of the three fly ashes studied in paper three by SEM, EDX, XPS and XRD. In addition, the thermal desorption and subsequent degradation of POP from the ashes was studied at temperatures of 300-900 °C. The composition of the gases released as the temperature increased differed between the ashes and depended on their composition. Doping experiments using isotopically labelled PCDF and PCDD suggests that PCDD desorbed at lower temperatures than PCDF. This thesis examines several problems relating to POP formation during MSW incineration, from sampling to the ultimate fate of incineration residues. The results obtained illustrate the wide range of processes that contribute to thermal POP formation and degradation during and after MSW incineration. / Förbränning av hushållssopor är en vanlig metod för att hantera ett växande avfallsproblem. Metoden har flera fördelar, såsom minskning av volym och vikt, sterilisering och energiåtervinning. Sopförbränning har dock vissa nackdelar och det mest debatterade är sannolikt utsläpp av persistenta organiska föroreningar (POPs) som polyklorerad dibensofuran (PCDF), dibenso-p-dioxin (PCDD), bifenyl (PCB) och naftalen (PCN). Det finns totalt 210 PCDF- och PCDD- kongener, med mellan ett till åtta klor på kolskelettet, varav 17 är giftiga med hormonstörande och cancerframkallande egenskaper. Även tolv av totalt 209 PCB-kongener samt minst två av totalt 75 PCN-kongener uppvisar liknande egenskaper. Dessa klorerade organiska föroreningar bildas då rökgaserna kyls ner i sopförbränningsanläggningarna och avlägsnas från rökgaserna med hjälp av filter och hamnar i flygaskan. Denna avhandling handlar om bildning och nedbrytning av POPs i sopförbränningsrelaterade processer.   Den första artikeln är en fallstudie där PCDD bildas i filtren i en fullskalig sopförbränningsanläggning. Bildningen ledde till förhöjda halter organiska föroreningar i rökgaserna, vilket ledde till ökade utsläpp. Den funna bildningsvägen för PCDD i filtren befanns sannolikt bero på kondensation av klorfenoler på filterytorna. Den andra artikeln är en valideringsstudie av en kylprob avsedd att användas vid rökgasprovtagning vid hög temperatur (> 450 °C) för att undvika bildning av POPs under provtagningen. Studien bekräftade att majoriteten av PCDF- och PCDD- bildning i rökgaser från sopförbränning sker vid temperaturer under 600 °C. I den tredje artikeln berättas om behandling av tre olika flygaskor från olika sopförbränningsanläggningar. Askorna behandlades vid 400 °C i inert atmosfär i både en roterugn och i förseglade ampuller. De resulterande koncentrationerna, kloreringsgraderna och kongenprofilerna av de organiska föroreningarna jämfördes. Likheter hittades mellan PCDF och PCN, medan PCDD och PCB betedde sig på ett annat sätt. Studien fann också att PCDF kongenprofiler i aska som behandlats i roterugnen liknade varandra, oberoende av askornas sammansättning, vilket tyder på en liknande bildningsväg. För den fjärde artikeln, genomfördes ytkarakterisering (SEM, EDX, XPS och XRD) på de tre flygaskorna från artikel tre som sedan hettades upp från 30 °C till 900 °C i vacuum. Det som frigjordes på grund av uppvärmningen samt nedbrytningsprodukter från askorna studerades med hjälp av masspektrometri och infraröd spektroskopi. Studien fann att de gaser som frigjordes när temperaturen ökade skilde mellan askorna, beroende på deras sammansättning. Studien fann också att när aska dopad med isotopmärkt PCDF och PCDD utsattes för samma behandling, frigjordes PCDD vid lägre temperatur än PCDF. Denna avhandling berör flera aspekter av problematiken kring klorerade organiska föroreningar som bildas vid sopförbränning, från provtagning till hur man ska hantera flygaskan. Avhandlingen belyser även olika typer av bildning och nedbrytning av POPs i varma processer kopplade till sopförbränning.

Master of Science / Department of Biological and Agricultural Engineering / Stacy L. Hutchinson / Coal-fired generation accounts for 45% of the United States electricity and generates harmful emissions, such as sulfur dioxide. With the implementation of Flue Gas Desulfurization (FGD) systems, sulfur dioxide is removed as an air pollutant and becomes a water pollutant. Basic physical/chemical wastewater treatment can be used to treat FGD wastewater, but increased regulations of effluent water quality have created a need for better, more economical wastewater treatment systems, such as constructed wetlands. At Jeffrey Energy Center, north of St. Mary’s, KS, a pilot-scale constructed wetland treatment system (CWTS) was implemented to treat FGD wastewater before releasing the effluent into the Kansas River. The objectives of this study were to 1.) determine if a portable water quality meter could be used to assess water quality and track pollutant concentrations, 2.) develop a water balance of the CTWS, 3.) generate a water use coefficient for the CWTS, and 4.) create a mass balance on the pollutants of concern. Water quality measurements were taken with a HORIBA U-50 Series Multi Water Quality Checker and compared to analytical water tests provided by Continental Analytic Services, Inc. (CAS) (Salina, KS). The water balance was created by comparing inflows and outflows of data determined through flow meters and a Vantage Pro2™ weather station. Information from the on-site weather station was also used to compute the system water use coefficient. Water sampling was conducted from date to date at 10 locations within the CWTS. In general, there was little to no relationship between the HORIBA water quality measurements and the analytical water tests. Therefore, it was recommended that JEC continue to send water samples on a regular basis to an analytical testing laboratory to assess the CWTS function and track pollutants of concern. Because the water balance was conducted during system initiation, there was a great deal of fluctuation due to problems with the pumping system, issues with the upstream FGD treatment system, extreme weather events, and immature vegetation. This fluctuation resulted in the system having a non-steady state operation, which weakened the ability to calculate a system water use coefficient. However, during periods of strong system function, the water use coefficient was similar to previous studies with maximum water use being approximately equal to the reference evapotranspiration. The results of the mass balance indicated high removals mercury, selenium, and fluoride, but low removals of boron, manganese, chloride, and sulfate were exported from the CWTS.

D. Tech. Mechanical Engineering. / Investigates and/or rank the performance of locally available materials (i.e. limestone, dolomite, or calcrete) as sorbents in the capture of SO2 emissions from coal-fired power plants. Two experimental procedures were adopted in this work: the pH-stat method was used to simulate conditions encountered in wet flue gas desulphurisation (WFGD); and the fixed-bed reactor was used to simulate conditions encountered in the dry in-duct flue gas desulphurisation (DFGD) process. It is important to note that most studies of using calcium-based materials as sorbents for SO2 removal have been carried out in overseas countries. These studies were carried out using materials and research conditions prevailing in the particular countries. Furthermore, all South African coal-fired power stations burn low grade coal allowing the high grade coal to be exported. As a result, coal-fired power stations in South Africa emit higher emissions than the overseas power stations which are operated on high grade coals. Thus the results achieved internationally may not be directly translated to the South African conditions.

One of the new approaches for capturing carbon dioxide from treated flue gas (post-combustion capture) and fuel gas (pre-combustion capture) is based on gas hydrate crystallization. The presence of small amount of tetrahydrofuran (THF) substantially reduces the hydrate formation pressure from a flue (CO2/N2) gas mixture and offers the possibility to capture CO2 at medium pressures [1]. A conceptual flow sheet for a medium pressure hydrate process for pre-combustion capture from a fuel gas (CO2/H2) was also developed and presented. In order to test the hydrate-based separation processes for pre and post combustion capture of CO2 at a larger scale a new apparatus that can operate with different gas/water contact modes is set up and presented.

The major goals of this thesis were to: (1) create a site-isolated aminosilica material with higher amine loadings than previously reported isolation methods, (2) use spectroscopic, reactivity, and catalytic (olefin polymerization precatalysts) probes to determine isolation of amine groups on these organic/inorganic hybrid materials, (3) synthesize an organic/inorganic hybrid material capable of activating Group 4 olefin polymerization precatalysts, and (4) synthesize a high amine loaded organic/inorganic hybrid material capable of reversibly capturing CO2 in a simulated flue gas stream. The underlying motivation of this research involved the synthesis and design of novel amine and sulfonic acid materials. Traditional routes to synthesize aminosilicas have led to the formation of a high loading of multiple types of amine sites on the silica surface. Part of this research involved the creation of a new aminosilica material via a protection/deprotection method designed to prevent multiple sites, while maintaining a relatively high loading. As a characterization technique, fluorescence spectroscopy of pyrene-based fluorophores loaded on traditional aminosilicas and site-isolated aminosilicas was used to probe the degree of site-isolation obtained with these methods. Also, this protection/deprotection method was compared to other reported isolation techniques with heterogeneous Group 4 constrained-geometry inspired catalysts (CGCs). It was determined that the degree of separation of the amine sites could be controlled with protection/deprotection methods. Furthermore, an increase in the reactivity of the amines and the catalytic activity of CGCs built off of the amines was determined for aminosilicas synthesized by a protection/deprotection method. The second part of this work involved developing organic/inorganic hybrid materials as heterogeneous Brønsted acidic cocatalysts for activation of olefin polymerization precatalysts. This was the first reported organic/inorganic hybrid sulfonic acid functionalized silica material capable of activating metallocenes for the polymerization of ethylene when small amounts of an alkylaluminum was added. Lastly, an organic/inorganic hybrid hyperbranched aminosilica material capable of capturing carbon dioxide from flue gas streams was synthesized. This material was determined to capture CO2 with capacities higher than currently reported aminosilica adsorbents.

This study incorporates the potential use of Variable Frequency Drives on various motors as well as areas of improved heat transfer in an older, mid-sized coal fired power plant. In power plants, fluid flow rates are often controlled using dampers or valves while the motors that power the pumps stay at full speed resulting in a significant amount of wasted electrical power; energy is also lost due to poor heat recovery prior to gases leaving the system. By examining pump usage as well as additional heat available for recovery, potential energy savings will be determined. Preliminary results of five motors suggested for variable frequency drive application show annual savings that total 31.1 GWh, resulting in a 1.66% increase in overall plant efficiency. Total project costs are near $2 million resulting in a simple payback period of less than two years assuming 0.04 $/kWh. For every degree reduction of the flue gas temperature by means of heat recovery that is reused elsewhere in the cycle, 2 Billion BTU of coal would be saved annually. One realistic scenario suggested heat recovery resulting in a 120°F degree reduction of flue gas temperature amounting to a 2.54% increase in cycle efficiency.

The function of a flue-gas quench is to remove additional contaminants from flue-gas and to reduce the wastewater from a waste incineration plant. The aim of this degree project is to find how the system is affected by using a quench and what factors limits the performance. This is done by modelling and simulating a waste incineration plant in Aspen Plus. Data and plant schematics were obtained by a study visit to Mälarenergi Plant 6 situated in Västerås, Sweden, which were used as model input and for model validation. The results have shown that the amount of wastewater can be reduced by more than half compared to a plant without a quench. The heat produced in the condenser, when discharging water to the boiler, would be lowered by up to 20%. For systems with a quench present when more water was discharged to the boiler both the heat production and the pollutant capturing became better. However, the system has limits regarding the amount that could be recirculated, in the form of temperature limits in different parts of the system. In addition, if the heat load is low there is an insufficient amount of wastewater generated in the condenser to run the quench. In that situation, clean (fresh) water needs to be used instead. Using clean water is unwanted since the plant will then consume more resources while still producing less heat than a plant without a quench would.