969 resultados para Pyrolytic reactor


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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.

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This thesis is devoted to understanding and improving technologically important III-V compound semiconductor (e.g. GaAs, InAs, and InSb) surfaces and interfaces for devices. The surfaces and interfaces of crystalline III-V materials have a crucial role in the operation of field-effect-transistors (FET) and highefficiency solar-cells, for instance. However, the surfaces are also the most defective part of the semiconductor material and it is essential to decrease the amount of harmful surface or interface defects for the next-generation III-V semiconductor device applications. Any improvement in the crystal ordering at the semiconductor surface reduces the amount of defects and increases the material homogeneity. This is becoming more and more important when the semiconductor device structures decrease to atomic-scale dimensions. Toward that target, the effects of different adsorbates (i.e., Sn, In, and O) on the III-V surface structures and properties have been investigated in this work. Furthermore, novel thin-films have been synthesized, which show beneficial properties regarding the passivation of the reactive III-V surfaces. The work comprises ultra-high-vacuum (UHV) environment for the controlled fabrication of atomically ordered III-V(100) surfaces. The surface sensitive experimental methods [low energy electron diffraction (LEED), scanning tunneling microscopy/spectroscopy (STM/STS), and synchrotron radiation photoelectron spectroscopy (SRPES)] and computational density-functionaltheory (DFT) calculations are utilized for elucidating the atomic and electronic properties of the crucial III-V surfaces. The basic research results are also transferred to actual device tests by fabricating metal-oxide-semiconductor capacitors and utilizing the interface sensitive measurement techniques [capacitance voltage (CV) profiling, and photoluminescence (PL) spectroscopy] for the characterization. This part of the thesis includes the instrumentation of home-made UHV-compatible atomic-layer-deposition (ALD) reactor for growing good quality insulator layers. The results of this thesis elucidate the atomic structures of technologically promising Sn- and In-stabilized III-V compound semiconductor surfaces. It is shown that the Sn adsorbate induces an atomic structure with (1×2)/(1×4) surface symmetry which is characterized by Sn-group III dimers. Furthermore, the stability of peculiar ζa structure is demonstrated for the GaAs(100)-In surface. The beneficial effects of these surface structures regarding the crucial III-V oxide interface are demonstrated. Namely, it is found that it is possible to passivate the III-V surface by a careful atomic-scale engineering of the III-V surface prior to the gate-dielectric deposition. The thin (1×2)/(1×4)-Sn layer is found to catalyze the removal of harmful amorphous III-V oxides. Also, novel crystalline III-V-oxide structures are synthesized and it is shown that these structures improve the device characteristics. The finding of crystalline oxide structures is exploited by solving the atomic structure of InSb(100)(1×2) and elucidating the electronic structure of oxidized InSb(100) for the first time.

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The fuel element of LMFBR consists of a bundle of rods wrapped with an helical wire as spacer, surrounded by an hexagonal duct. In the present work, a semi-empirical model is developed to calculate bundle average and subchannel based friction factors and flow redistribution. The obtained results were compared to experimental data and they were considered satisfactory for wide range of geometrical parameters.

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Fuel elements of PWR type nuclear reactors consist of rod bundles, arranged in a square array, and held by spacer grids. The coolant flows, mainly, axially along the rods. Although such elements are laterally open, experiments are performed in closed type test sections, originating the appearance of subchannels with different geometries. In the present work, utilizing a test section of two bundles of 4x4 pins each, experiments were performed to determine the friction and the grid drag coefficients for the different subchannels and to observe the effect of the grids in the crossflow, in cases of inlet flow maldistribution.

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Tämän kandidaatintyön tarkoituksena on selvittää maailman tämän hetkinen tilanne ydinvoimalahankkeista, jotka on rakennettu ja olleet käytössä, mutta suljettu ennenaikaisesti. Mukaan otetaan reaktorit, joiden käyttöikää ei ole jatkettu vaikka se teknisesti olisi ollut mahdollista. Tarkasteluun otetaan vain kaupalliseen käyttöön tarkoitetut tehoreaktorit. Koereaktorit, prototyypit ja pienet esittelyreaktorit jätetään tarkastelun ulkopuolelle, koska niiden käyttöikä ja tarkoitus ei välttämättä ole määriteltävissä. Tarkastelun ulkopuolelle jätetään myös reaktorit, jotka ovat tuhoutuneet onnettomuuden takia.

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Advanced oxidation processes (AOPs) have been studied and developed to suffice the effective removal of refractory and toxic compounds in polluted water. The quality and cost of wastewater treatment need improvements, and electric discharge technology has a potential to make a significant difference compared to other established AOPs based on energy efficiency. The generation of active oxidant species such as ozone and hydroxyl radicals by high voltage discharge is a relatively new technology for water treatment. Gas-phase pulsed corona discharge (PCD), where a treated aqueous solution is dispersed between corona-producing electrodes free of the dielectric barriers, was developed as an alternative approach to the problem. The short living radicals and ozone formed in the gas phase and at the gas-liquid interface react with dissolved impurities. PCD equipment has a relatively simple configuration, and with the reactor in an enclosed compartment, it is insensitive towards gas humidity and does not need the gas transport. In this thesis, PCD was used to study and evaluate the energy efficiency for degrading various organic compounds, as well as the chemistry of the oxidation products formed. The experiments investigate the aqueous oxidation of phenol, humic substances, pharmaceutical compounds (paracetamol, ibuprofen, indomethacin, salicylic acids, -estradiol), as well as lignin degradation and transformation to aldehydes. The study aims to establish the influence of initial concentration of the target pollutant, the pulsed discharge parameters, gas phase composition and the pH on the oxidation kinetics and the efficiency. Analytical methods to measure the concentrations of the target compounds and their by-products include HPLC, spectrophotometry, TOC and capillary electrophoresis. The results of the research included in this summary are presented in the attached publications and manuscripts accepted for publication. Pulsed corona discharge proved to be highly effective in oxidizing each of the target compounds, surpassing the closest competitor, conventional ozonation. The increase in oxidation efficiencies for some compounds in oxygen media and at lower pulse repetition frequencies shows a significant role of ozone. The role of the ·OH radicals was established in the surface reactions. The main oxidation products, formation of nitrates, and the lignin transformation were quantified. A compound specific approach is suggested for optimization of the PCD parameters that have the most significant impact on the oxidation energy efficiency because of the different characteristics and responses of the target compound to the oxidants, as well as different admixtures that are present in the wastewater. Further studies in the method’s safety (nitration and nitrosation of organic compounds, nitrite and nitrate formation enhancement) are needed for promoting the method.

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Tämän kandidaatintyön tarkoituksena on tutkia jäähdytteen poistamisen vaikutusta RBMK-koereaktorin kasvukertoimeen ja erityisesti sitä, kuinka hyvin Monte Carlo -menetelmää käyttävä Serpent-laskentakoodi pystyy mallintamaan jäähdytteen poistamisen vaikutuksen. Aluksi tarkastellaan taustatietoina käytettyä raporttia käsiteltävän koereaktorin kriittisyysajoista ja aiemmista simulaatioista, sekä RBMK-reaktorin ominaispiirteitä ja Monte Carlo -simulaation teoriaa. Seuraavaksi esitellään koereaktorista luotu malli, selitetään mallinnettaessa tehdyt yksinkertaistukset ja kuvataan simulaation alkutilanne. Lopuksi käsitellään simulaation tuloksia ja Serpentillä luodun mallin soveltuvuutta verrattuna aiemmin suoritettuihin simulaatioihin.

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Waste combustion has gone from being a volume reducing discarding-method to an energy recovery process for unwanted material that cannot be reused or recycled. Different fractions of waste are used as fuel today, such as; municipal solid waste, refuse derived fuel, and solid recovered fuel. Furthermore, industrial waste, normally a mixture between commercial waste and building and demolition waste, is common, either as separate fuels or mixed with, for example, municipal solid waste. Compared to fossil or biomass fuels, waste mixtures are extremely heterogeneous, making it a complicated fuel. Differences in calorific values, ash content, moisture content, and changing levels of elements, such as Cl and alkali metals, are common in waste fuel. Moreover, waste contains much higher levels of troublesome trace elements, such as Zn, which is thought to accelerate a corrosion process. Varying fuel quality can be strenuous on the boiler system and may cause fouling and corrosion of heat exchanger surfaces. This thesis examines waste fuels and waste combustion from different angles, with the objective of giving a better understanding of waste as an important fuel in today’s fuel economy. Several chemical characterisation campaigns of waste fuels over longer time periods (10-12 months) was used to determine the fossil content of Swedish waste fuels, to investigate possible seasonal variations, and to study the presence of Zn in waste. Data from the characterisation campaigns were used for thermodynamic equilibrium calculations to follow trends and determine the effect of changing concentrations of various elements. The thesis also includes a study of the thermal behaviour of Zn and a full—scale study of how the bed temperature affects the volatilisation of alkali metals and Zn from the fuel. As mixed waste fuel contains considerable amounts of fresh biomass, such as wood, food waste, paper etc. it would be wrong to classify it as a fossil fuel. When Sweden introduced waste combustion as a part of the European Union emission trading system in the beginning of 2013 there was a need for combustion plants to find a usable and reliable method to determine the fossil content. Four different methods were studied in full-scale of seven combustion plants; 14Canalysis of solid waste, 14C-analysis of flue gas, sorting analysis followed by calculations, and a patented balance method that is using a software program to calculate the fossil content based on parameters from the plant. The study showed that approximately one third of the coal in Swedish waste mixtures has fossil origins and presented the plants with information about the four different methods and their advantages and disadvantages. Characterisation campaigns also showed that industrial waste contain higher levels of trace elements, such as Zn. The content of Zn in Swedish waste fuels was determined to be approximately 800 mg kg-1 on average, based on 42 samples of solid waste from seven different plants with varying mixtures between municipal solid waste and industrial waste. A review study of the occurrence of Zn in fuels confirmed that the highest amounts of Zn are present in waste fuels rather than in fossil or biomass fuels. In tires, Zn is used as a vulcanizing agent and can reach concentration values of 9600-16800 mg kg-1. Waste Electrical and Electronic Equipment is the second Zn-richest fuel and even though on average Zn content is around 4000 mg kg-1, the values of over 19000 mg kg-1 were also reported. The increased amounts of Zn, 3000-4000 mg kg-1, are also found in municipal solid waste, sludge with over 2000 mg kg-1 on average (some exceptions up to 49000 mg kg-1), and other waste derived fuels (over 1000 mg kg-1). Zn is also found in fossil fuels. In coal, the average level of Zn is 100 mg kg-1, the higher amount of Zn was only reported for oil shale with values between 20-2680 mg kg-1. The content of Zn in biomass is basically determined by its natural occurrence and it is typically 10-100 mg kg-1. The thermal behaviour of Zn is of importance to understand the possible reactions taking place in the boiler. By using thermal analysis three common Zn-compounds were studied (ZnCl2, ZnSO4, and ZnO) and compared to phase diagrams produced with thermodynamic equilibrium calculations. The results of the study suggest that ZnCl2(s/l) cannot exist readily in the boiler due to its volatility at high temperatures and its conversion to ZnO in oxidising conditions. Also, ZnSO4 decomposes around 680°C, while ZnO is relatively stable in the temperature range prevailing in the boiler. Furthermore, by exposing ZnO to HCl in a hot environment (240-330°C) it was shown that chlorination of ZnO with HCl gas is possible. Waste fuel containing high levels of elements known to be corrosive, for example, Na and K in combination with Cl, and also significant amounts of trace elements, such as Zn, are demanding on the whole boiler system. A full-scale study of how the volatilisation of Na, K, and Zn is affected by the bed temperature in a fluidised bed boiler was performed parallel with a lab-scale study with the same conditions. The study showed that the fouling rate on deposit probes were decreased by 20 % when the bed temperature was decreased from 870°C to below 720°C. In addition, the lab-scale experiments clearly indicated that the amount of alkali metals and Zn volatilised depends on the reactor temperature.

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TVO suunnittelee reaktoritehon 10 %:n korotusta Olkiluoto 1 ja 2 -voimalaitoksille. Reaktoriteho nostetaan 2500 MW:sta 2750 MW:iin polttoaineen rikastusastetta nostamalla ja pääkiertovirtausta kasvattamalla. Samalla syöttövesivirtaus reaktoriin ja tuorehöyryvirtaus turpiineille kasvaa. Lauhteenpuhdistusjärjestelmän kapasiteettia ei voida kuitenkaan kasvattaa, joten massavirran lisäys toteutetaan ottamalla käyttöön korkeapainesivulauhteen eteenpäinpumppaus. Lauhteen esilämmityslinjojen, lauhteenpuhdistuksen ja syöttövesipumppujen massavirta säilyy siten nykyisellään. Muita merkittäviä tehonkorotukseen liittyviä laitosmuutoksia ovat pääkiertopumppujen uusinta ja korkeapaineturpiinin muutokset. Tehonkorotetun prosessin käytettävyyden varmistamiseksi tehdään häiriöanalyysejä Apros-prosessisimulointiohjelmistoa käyttäen. OL1 ja OL2 -laitoksista on olemassa validoitu 2500 MW:n laitosmalli, josta muokatulla 2750 MW:n laitosmallilla simuloinnit tehdään. Häiriöanalyysien avulla selvitetään säätöjärjestelmien kyky pitää prosessin tila hallinnassa ilman suojausautomaation laukeamista. Simuloituihin tapauksiin kuuluu pumppujen ja venttiilien vikaantumistapauksia sekä turpiini- ja reaktoripuolen pikasulku- ja osittaispikasulkutapauksia. Myös meriveden lämpötilan vaikutusta häiriötilanteisiin tarkastellaan. Analyysien perusteella voimalaitosten ohjaus- ja suojausautomaatio toimivat hyvin myös korotetulla teholla. Tehonkorotuksen jälkeiset suuremmat massavirrat aiheuttavat kuitenkin voimakkaampia reaktoripaineen ja -tehon vaihteluita varsinkin venttiilien sulkeutumistapauksissa. Simuloinnit osoittivat, että tehonkorotus 2500 MW:sta 2750 MW:iin on mahdollinen, mutta aiheuttaa pieniä muutoksia laitoksen suojausjärjestelmien laukaisurajoihin.

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The evolution of our society is impossible without a constant progress in life-important areas such as chemical engineering and technology. Innovation, creativity and technology are three main components driving the progress of chemistry further towards a sustainable society. Biomass, being an attractive renewable feedstock for production of fine chemicals, energy-rich materials and even transportation fuels, captures progressively new positions in the area of chemical technology. Knowledge of heterogeneous catalysis and chemical technology applied to transformation of biomass-derived substances will open doors for a sustainable economy and facilitates the discovery of novel environmentally-benign processes which probably will replace existing technologies in the era of biorefinary. Aqueous-phase reforming (APR) is regarded as a promising technology for production of hydrogen and liquids fuels from biomass-derived substances such as C3-C6 polyols. In the present work, aqueous-phase reforming of glycerol, xylitol and sorbitol was investigated in the presence of supported Pt catalysts. The catalysts were deposited on different support materials, including Al2O3, TiO2 and carbons. Catalytic measurements were performed in a laboratory-scale continuous fixedbed reactor. An advanced analytical approach was developed in order to identify reaction products and reaction intermediates in the APR of polyols. The influence of the substrate structure on the product formation and selectivity in the APR reaction was also investigated, showing that the yields of the desired products varied depending on the substrate chain length. Additionally, the influence of bioethanol additive in the APR of glycerol and sorbitol was studied. A reaction network was advanced explaining the formation of products and key intermediates. The structure sensitivity in the aqueous-phase reforming reaction was demonstrated using a series of platinum catalysts supported on carbon with different Pt cluster sizes in the continuous fixed-bed reactor. Furthermore, a correlation between texture physico-chemical properties of the catalysts and catalytic data was established. The effect of the second metal (Re, Cu) addition to Pt catalysts was investigated in the APR of xylitol showing a superior hydrocarbon formation on PtRe bimetallic catalysts compared to monometallic Pt. On the basis of the experimental data obtained, mathematical modeling of the reaction kinetics was performed. The developed model was proven to successfully describe experimental data on APR of sorbitol with good accuracy.

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Torrefaction is one of the pretreatment technologies to enhance the fuel characteristics of biomass. The efficient and continuous operation of a torrefaction reactor, in the commercial scale, demands a secure biomass supply, in addition to adequate source of heat. Biorefinery plants or biomass-fuelled steam power plants have the potential to integrate with the torrefaction reactor to exchange heat and mass, using available infrastructure and energy sources. The technical feasibility of this integration is examined in this study. A new model for the torrefaction process is introduced and verified by the available experimental data. The torrefaction model is then integrated in different steam power plants to simulate possible mass and energy exchange between the reactor and the plants. The performance of the integrated plant is investigated for different configurations and the results are compared.

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Tässä työssä on tutkittu OL1/OL2-suojarakennuksen käyttäytymistä jäähdytteenmenetysonnettomuuden eli LOCA:n aikana. Onnettomuuden simulointiin on kehitetty suojarakennusmalli suomalaiseen APROS 5.09 - ohjelmistoon sisältyvällä LP-koodilla (Lumped Parameter Code). Työssä on keskitytty suojarakennuksen kannalta oleellisimpien suureiden: kaasutilavuuksien paineen sekä lämpötilan ja lauhdutusaltaan lämpötilan ja pinnankorkeuden ajalliseen käyttäytymiseen. Mallinnetut LOCA:t ovat päähöyrylinjan ja sammutetun reaktorin jäähdytysjärjestelmän putkikatkoksia. Simulointeja on tehty laitoksen täyden tehon ja kuumavalmiuden lähtötiloissa ja tarkasteltavien suureiden käyttäytymistä on tutkittu erikseen valituilla konservatiivisilla oletuksilla. Laskentatapaukset rajoittuvat lyhyeen aikaväliin 27.78 tuntia kuvitellusta putkirikosta eteenpäin. Tuloksia on verrattu OL1/OL2- laitostoimittajan, Westinghouse Electric Sweden AB:n, tekemiin lisensiointianalyyseihin. Työssä on myös kuvattu APROS-laskennan epävarmuustekijöitä. Suojarakennuksen on todettu käyttäytyvän fysikaalisesti yhtenevästi lisensiointianalyyseissä ja APROS:lla tehdyissä vertailulaskuissa.

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This study combines several projects related to the flows in vessels with complex shapes representing different chemical apparata. Three major cases were studied. The first one is a two-phase plate reactor with a complex structure of intersecting micro channels engraved on one plate which is covered by another plain plate. The second case is a tubular microreactor, consisting of two subcases. The first subcase is a multi-channel two-component commercial micromixer (slit interdigital) used to mix two liquid reagents before they enter the reactor. The second subcase is a micro-tube, where the distribution of the heat generated by the reaction was studied. The third case is a conventionally packed column. However, flow, reactions or mass transfer were not modeled. Instead, the research focused on how to describe mathematically the realistic geometry of the column packing, which is rather random and can not be created using conventional computeraided design or engineering (CAD/CAE) methods. Several modeling approaches were used to describe the performance of the processes in the considered vessels. Computational fluid dynamics (CFD) was used to describe the details of the flow in the plate microreactor and micromixer. A space-averaged mass transfer model based on Fick’s law was used to describe the exchange of the species through the gas-liquid interface in the microreactor. This model utilized data, namely the values of the interfacial area, obtained by the corresponding CFD model. A common heat transfer model was used to find the heat distribution in the micro-tube. To generate the column packing, an additional multibody dynamic model was implemented. Auxiliary simulation was carried out to determine the position and orientation of every packing element in the column. This data was then exported into a CAD system to generate desirable geometry, which could further be used for CFD simulations. The results demonstrated that the CFD model of the microreactor could predict the flow pattern well enough and agreed with experiments. The mass transfer model allowed to estimate the mass transfer coefficient. Modeling for the second case showed that the flow in the micromixer and the heat transfer in the tube could be excluded from the larger model which describes the chemical kinetics in the reactor. Results of the third case demonstrated that the auxiliary simulation could successfully generate complex random packing not only for the column but also for other similar cases.

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Hydrogen stratification and atmosphere mixing is a very important phenomenon in nuclear reactor containments when severe accidents are studied and simulated. Hydrogen generation, distribution and accumulation in certain parts of containment may pose a great risk to pressure increase induced by hydrogen combustion, and thus, challenge the integrity of NPP containment. The accurate prediction of hydrogen distribution is important with respect to the safety design of a NPP. Modelling methods typically used for containment analyses include both lumped parameter and field codes. The lumped parameter method is universally used in the containment codes, because its versatility, flexibility and simplicity. The lumped parameter method allows fast, full-scale simulations, where different containment geometries with relevant engineering safety features can be modelled. Lumped parameter gas stratification and mixing modelling methods are presented and discussed in this master’s thesis. Experimental research is widely used in containment analyses. The HM-2 experiment related to hydrogen stratification and mixing conducted at the THAI facility in Germany is calculated with the APROS lump parameter containment package and the APROS 6-equation thermal hydraulic model. The main purpose was to study, whether the convection term included in the momentum conservation equation of the 6-equation modelling gives some remarkable advantages compared to the simplified lumped parameter approach. Finally, a simple containment test case (high steam release to a narrow steam generator room inside a large dry containment) was calculated with both APROS models. In this case, the aim was to determine the extreme containment conditions, where the effect of convection term was supposed to be possibly high. Calculation results showed that both the APROS containment and the 6-equation model could model the hydrogen stratification in the THAI test well, if the vertical nodalisation was dense enough. However, in more complicated cases, the numerical diffusion may distort the results. Calculation of light gas stratification could be probably improved by applying the second order discretisation scheme for the modelling of gas flows. If the gas flows are relatively high, the convection term of the momentum equation is necessary to model the pressure differences between the adjacent nodes reasonably.

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Kandidaatintyössä esitellään sulasuolareaktorien historian lisäksi lyhyesti reaktorityypin toimintaperiaate ja sulasuolareaktoritutkimuksen nykytilanne. Kandidaatintyöstä käy ilmi, että Oak Ridgen kansallinen laboratorio ORNL oli merkittävä tekijä sulasuolareaktoritutkimuksessa 1940-luvun lopulta aina 1980-luvun alkuun. Ainoat rakennetut sulasuolatekniikkaa käyttävät reaktorit olivat ORNL:n kehittämiä. Oak Ridgen kansallisen laboratorion lopetettua sulasuolatekniikan tutkimusohjelmansa, laantui sulasuolareaktoritutkimus pitkäksi aikaa. 2000-luvun alussa kiinnostus tekniikkaa kohtaan virkosi ja kirjoitushetkellä sulasuolareaktoreita kehitetään useissa tutkimusohjelmissa.