HCFC-22 is the world�s most widely used refrigerant. It serves in both residential and commercial applications, from small window units to large water chillers, and everything in between. Its particular combination of efficiency, capacity and pressure has made it a popular choice for equipment designers. Nevertheless, it does have some ODP, so international law set forth in the Montreal Protocol and its Copenhagen and Vienna amendments have put HCFC-22 on a phase out schedule. In developed countries, production of HCFC-22 will end no later than the year 2030. Zeotropic blend HFC-407C has been established as a drop-in alternative for HCFC-22 in the industry due to their zero Ozone Depletion Potential (ODP) and similarities in thermodynamic properties and performance. However, when a system is charged with a zeotropic mixture, it raises concerns about temperature glide at two-phase state, differential oil solubility and internal composition shift. Not enough research has been done to cover all aspects of alternative refrigerants applications in the systems. This research intended to explore behavior of this alternative refrigerants compare to HCFC-22 and challenges facing the industry in design, operation service and maintenance of these equipments. The purpose of this research is to investigate behavior of R407C refrigerant in chiller systems. This includes performance and efficiency variations when it replaces R22 in an existing system as well as challenges involved maintaining the system charged with R407C. It is a common practice in the industry these days to evacuate and completely recharge when part of the new refrigerant blend was leaked from the system. This has proved to be extremely costly exercise with grave environmental ramifications. This research is intended to address challenges faced in the real world and practical terms. Theoretical and experimental approaches used as a methodology in this work. The system mathematically modeled to predict detailed system performance and effect of the leak at various conditions. To make this feasible and accurate enough, two separate approaches made, first system performance for pure R22 and R407C, and second system subjected to range of leak fractions. The earlier model was relatively straight forward when compared to the latter. Modeling a system charged with R407C ternary mixture and subjected to range of leaks posed enormous challenges. A sophisticated experimental test apparatus was also designed and built. Comprehensive and detailed tests at various conditions were conducted with special attention on instrumental accuracy and correct methodology. The first part has been successfully modeled and predicted all the factors and performance with excellent accuracy when compared to the test results. In these approaches pure refrigerants R22 and R407C were used and simulated the system behavior at range of conditions. However, the second part was the most challenging ever. Comprehensive leak process simulations produced trends of R32/R125/R134a composition change as function of rate of leak. Starting from this point, equations have been created to represent the composition change as function of percentage of the leak. The system thermodynamic cycle was also modeled to calculate capacity, power input and COP at the range of the conditions. Despite many affecting parameters and complexity of the model, the mathematical model successfully predicted the test outcome with a very reasonable accuracy, averaging around 3% with some times reaching to 5 to 6%. On the experimental stage the system charged with the new HFC-407C was deliberately subjected to refrigerant leak at various leak stages. The aim was to objectively determine to what extend the gas leak can be still acceptable without going through the expensive complete gas charge. The effect of leak was tested and verified at 10% steps, from 10% up to 50% mass fraction for the total charge. It has been observed that at the leaks beyond 30%, the adverse effect on the capacity becomes more significant, from 8 to about 15% decrease. While the power input decreased at slower pace, from 3% up to about 8% depending on the test conditions. This translated to COP decrease ranging from 4 to about 7%. This capacity loss and efficiency decrease are significant figures which suggests that the system, here chiller, can not be allowed to degrade the performance to that extend and still continue operating.

Made available in DSpace on 2014-06-12T15:54:00Z (GMT). No. of bitstreams: 2 arquivo5189_1.pdf: 2087717 bytes, checksum: 1718a5a73d49c7021a82fe893f78dbfe (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2006 / A Ressonância Magnética Nuclear (RMN) e a Cromatografia em fase gasosa acoplada à espectrometria de massas (GC/MS) fornecem informações sobre a estrutura química de substâncias, bem como, sobre a constituição qualitativa e quantitativa de amostras sem a necessidade de padrões de análise ou pré-tratamento de amostras. Uma jovem estudante de 19 anos morreu de forma súbita após inalar um aerossol cujo componente principal, o 1-1-dicloro-1-fluoretano (HCFC-141b), foi identificado por meio de RMN e GC/MS. Nas vísceras e no sangue da vítima não foram detectados venenos, álcool ou outras drogas. Os resultados dos exames necroscópico, toxicológico e microscópico não excluem a hipótese de morte por inalação do HCFC-141b e estabelecem dois mecanismos de morte como viáveis: asfixia e arritmia cardíaca. As análises realizadas e os dados do inquérito policial suportam probabilisticamente a hipótese de morte por arritmia cardíaca fatal que pode ter ocorrido de forma associada com asfixia. Algumas técnicas de RMN como ¹H, ¹³C, Distortionless Enhancement by Polarization Transfer (DEPT), Cross-Polarization and Magic Angle Spinning (CP/MAS) and Dipolar Dephasing (DD) foram usadas para caracterizar amostras de cocaína. Os deslocamentos químicos dos espectros obtidos foram atribuídos por meio de Heteronuclear Correlation (HETCOR) e Heteronuclear Multiple Bond Correlation (HMBC). As amostras foram primariamente caracterizadas por espectrometria de massas cujos espectros foram comparados com dados obtidos na literatura. Os resultados obtidos indicam que ¹H, ¹³C e DEPT são técnicas bastante eficientes para caracterização de amostras ilícitas de cocaína no estado líquido e que por meio de CP/MAS e CP/MAS/DD RMN é possível distinguir o crack do cloridrato de cocaína de uma maneira não destrutiva. Portanto, a RMN é uma excelente ferramenta para caracterização de amostras ilícitas de cocaína

Climate change and ozone depletion are topical challenges the world over and are both attributed mainly to human activities, particularly emissions of ozone depleting substances (ODSs). One such substance is chlorodifluoromethane (HCFC-22), a cheap, widely used refrigerant with a high global warming potential of 1780. Botswana is a signatory to the Montreal Protocol (MP), which guides international efforts to phase-out HCFC-22 and requires signatories to develop and implement a country-level Hydrochlorofluorocarbon Phase-out Management Plan (HPMP). This study, which used a mixed methods approach, was conducted to evaluate the phase-out of HCFC-22 management strategies and their environmental and socioeconomic implications in Botswana. A census of nine HCFC-22 importing companies was conducted and probability sampling proportional to size was used to select a sample of 159 respondents from the Department of Meteorological Services, HCFC-22 importers, customs officers from 20 purposively selected Botswana entry ports and HCFC-22 consumers from the importing companies. Category-specific respondent questionnaires and interview guides, site visits and assessment of records were used to gather data. Of particular interest were the annual HCFC-22 importation figures for each company, the Botswana Unified Revenue Services and the National Ozone Unit, as well as the level of compliance of the companies’ HCFC-22 phase-out management practices with relevant national regulations, the Botswana HPMP and the MP resolutions. Botswana’s HCFC-22 importers were found to be moderately to highly compliant to nonregulatory elements rather than regulatory elements. Overall, HCFC-22 consumption decreased from the baseline to 10.5% for the first stage (2013-2015), which was slightly more than the 10% reduction expected. A steady decrease in HCFC-22 consumption was noted towards the 35% target for 2020, largely due to awareness-raising initiatives directed at the surveyed stakeholders. Absolute HCFC-22 consumption dropped by approximately 510400 kgs from 2011-2017 or 28072 ozone depleting potential saved. On the downside, gaps were identified in the industry-wide quota-system, data reporting, prevention of illegal ODS trade, service technician training, user knowledge of alternatives and disposal of ODS equipment. The study recommends the use of a planning, policy formulation and implementation framework that integrates and balances three fundamentals, namely, stakeholder involvement, the process and the plan enablers.

Este trabalho apresenta os resultados da pesquisa "Análise do Escoamento de Fluidos Refrigerantes Alternativos ao HCFC 22 em Tubos Capilares Adiabáticos", desenvolvida para obtenção do título de Doutor em Engenharia no Departamento de Engenharia Mecânica da EPUSP. Essa pesquisa foi motivada pelas resoluções do Protocolo de Montreal, que prevêem a eliminação gradativa do HCFC 22 e, conseqüentemente, impõem a necessidade da realização de estudos sobre o comportamento de fluidos alternativos ecologicamente aceitáveis nos sistemas de refrigeração e seus componentes. Até o momento, as pesquisas e as referências bibliográficas indicam a utilização de misturas zeotrópicas e quase-azeotrópicas como a melhor alternativa para substituição do HCFC 22. Desta forma, foi realizado um extenso levantamento experimental do escoamento do R-407C (uma mistura zeotrópica) e do R-410A (uma mistura quase-azeotrópica) através de tubos capilares, em uma unidade laboratorial construída para essa finalidade. Esse levantamento, realizado para condições de entrada subresfriada e saturada, caracterizou a influência destes fluidos refrigerantes e dos diversos parâmetros operacionais e geométricos no comportamento do tubo capilar em sistemas de refrigeração. Foram desenvolvidos dois modelos (fases separadas e homogêneo) para a modelagem matemática do escoamento de fluidos refrigerantes através de tubos capilares, a fim de verificar o efeito do tipo de escoamento adotado nessa modelagem. A validação dos programas de simulação desenvolvidos, tanto para os dados experimentais obtidos no presente trabalho quanto para dados de literatura, mostra que os dois modelos podem ser utilizados para essa modelagem, apresentando desvios semelhantes em relação aos dados experimentais. A fim de aprimorar os modelos, é necessária a realização de estudos mais aprofundados sobre o atraso de vaporização e a ocorrência de blocagem na saída do tubo capilar. Por fim, foi realizado um estudo numérico comparativo do desempenho do HCFC 22 e dos alternativos R-407C e R-410A, que indicou que o primeiro é adequado tanto para o "retrofit" de equipamentos existentes quanto para utilização em novos equipamentos, enquanto que o segundo deve ser utilizado apenas em novos equipamentos. / This work presents the results of the research activities on the "Analysis of HCFC 22 Alternatives Flow Through Adiabatic Capillary Tubes", developed at the Mechanical Engineering Department of Escola Politécnica da Universidade de São Paulo. Such research was motivated by the resolutions of Montreal Protocol, which imposes gradational elimination of several refrigerants, among them HCFC 22. This leads to the necessity of carrying out studies on the behaviour of ecologically acceptable refrigerants in refrigeration systems and components. So far, researches and literature indicate the usage of zeotropic and near azeotropic refrigerant mixtures as the best alternative to HCFC 22. Therefore, it was performed an extensive experimental survey on R-407C (a zeotropic mixture) and R-410A (a near azeotropic mixture) flow through capillary tubes. Such survey, which was carried out for both subcooled and two-phase inlet conditions, characterised the influence of these refrigerants, as well as the several operating and geometric parameters on the behaviour of capillary tubes used in refrigeration systems. In order to analyse the effect of different approaches for two-phase flow, it was developed two models (separated flow model and homogeneous model) for mathematical simulation of refrigerant flow through adiabatic capillary tubes. Models validation using both experimental and literature data shows that the two models are suitable for such simulation, with the same error level in relation to experimental data. It was also noticed that it is necessary to perform more comprehensive studies on the delay of vaporisation and capillary tube outlet shocking flow phenomena. Finally, it was performed a comparative study on the performance of HCFC 22, R-407C and R-410A, which indicates that R-407C is suitable both for retrofitting actual equipment and for new ones, while R-410A is suitable only for new equipment.

Este trabalho apresenta os resultados da pesquisa "Análise do Escoamento de Fluidos Refrigerantes Alternativos ao HCFC 22 em Tubos Capilares Adiabáticos", desenvolvida para obtenção do título de Doutor em Engenharia no Departamento de Engenharia Mecânica da EPUSP. Essa pesquisa foi motivada pelas resoluções do Protocolo de Montreal, que prevêem a eliminação gradativa do HCFC 22 e, conseqüentemente, impõem a necessidade da realização de estudos sobre o comportamento de fluidos alternativos ecologicamente aceitáveis nos sistemas de refrigeração e seus componentes. Até o momento, as pesquisas e as referências bibliográficas indicam a utilização de misturas zeotrópicas e quase-azeotrópicas como a melhor alternativa para substituição do HCFC 22. Desta forma, foi realizado um extenso levantamento experimental do escoamento do R-407C (uma mistura zeotrópica) e do R-410A (uma mistura quase-azeotrópica) através de tubos capilares, em uma unidade laboratorial construída para essa finalidade. Esse levantamento, realizado para condições de entrada subresfriada e saturada, caracterizou a influência destes fluidos refrigerantes e dos diversos parâmetros operacionais e geométricos no comportamento do tubo capilar em sistemas de refrigeração. Foram desenvolvidos dois modelos (fases separadas e homogêneo) para a modelagem matemática do escoamento de fluidos refrigerantes através de tubos capilares, a fim de verificar o efeito do tipo de escoamento adotado nessa modelagem. A validação dos programas de simulação desenvolvidos, tanto para os dados experimentais obtidos no presente trabalho quanto para dados de literatura, mostra que os dois modelos podem ser utilizados para essa modelagem, apresentando desvios semelhantes em relação aos dados experimentais. A fim de aprimorar os modelos, é necessária a realização de estudos mais aprofundados sobre o atraso de vaporização e a ocorrência de blocagem na saída do tubo capilar. Por fim, foi realizado um estudo numérico comparativo do desempenho do HCFC 22 e dos alternativos R-407C e R-410A, que indicou que o primeiro é adequado tanto para o "retrofit" de equipamentos existentes quanto para utilização em novos equipamentos, enquanto que o segundo deve ser utilizado apenas em novos equipamentos. / This work presents the results of the research activities on the "Analysis of HCFC 22 Alternatives Flow Through Adiabatic Capillary Tubes", developed at the Mechanical Engineering Department of Escola Politécnica da Universidade de São Paulo. Such research was motivated by the resolutions of Montreal Protocol, which imposes gradational elimination of several refrigerants, among them HCFC 22. This leads to the necessity of carrying out studies on the behaviour of ecologically acceptable refrigerants in refrigeration systems and components. So far, researches and literature indicate the usage of zeotropic and near azeotropic refrigerant mixtures as the best alternative to HCFC 22. Therefore, it was performed an extensive experimental survey on R-407C (a zeotropic mixture) and R-410A (a near azeotropic mixture) flow through capillary tubes. Such survey, which was carried out for both subcooled and two-phase inlet conditions, characterised the influence of these refrigerants, as well as the several operating and geometric parameters on the behaviour of capillary tubes used in refrigeration systems. In order to analyse the effect of different approaches for two-phase flow, it was developed two models (separated flow model and homogeneous model) for mathematical simulation of refrigerant flow through adiabatic capillary tubes. Models validation using both experimental and literature data shows that the two models are suitable for such simulation, with the same error level in relation to experimental data. It was also noticed that it is necessary to perform more comprehensive studies on the delay of vaporisation and capillary tube outlet shocking flow phenomena. Finally, it was performed a comparative study on the performance of HCFC 22, R-407C and R-410A, which indicates that R-407C is suitable both for retrofitting actual equipment and for new ones, while R-410A is suitable only for new equipment.

A comprehensive field investigation was conducted at Potrero Hills Landfill (PHL) located in Suisun City, California to quantify emissions of twelve (hydro)chlorofluorocarbons (i.e. F-gases). The specific target constituents for this study included CFC-11, CFC-12, CFC-113, CFC-114, HCFC-21, HCFC-22, HCFC-141b, HCFC-142b, HCFC-151a, HFC-134a, HFC-152a, and HFC-245fa. The majority of the F-gas emission studies have been conducted outside of the United States and very limited field landfill emission data are available in the United States. Because of historical usage of blowing agents in insulation foams including CFC-11, HCFC-142b, HFC-134a, and HFC-245fa, models reported in literature predicted high F-gas emissions from a landfill environment, but very limited field data are available to verify such predictions. In this investigation, the surface flux of the twelve F-gases, methane, and carbon dioxide was quantified from various landfill cover systems and in areas with different waste ages, waste heights, and cover thicknesses at Potrero Hills Landfill. In addition, destruction efficiencies for the twelve F-gases were determined based on inlet and outlet concentrations of the onsite flare system. Lastly, the surface flux values were scaled up to a facility-wide emission value to estimate the total fugitive emissions from the landfill. The F-gas flux values for the daily covers were in the 10 -8 to 10-1 g m-2 day -1 range and 10-7 to 10-2 g m-2 day-1 range for the wet and dry season, respectively. The F-gas flux values for the intermediate covers in the -10-6 to 10-4 g m-2 day-1 range and -10-6 to 10-4 g m-2 day-1 range for the wet and dry season, respectively. The F-gas flux values for the final covers were in the 10-7 to 10-5 g m-2 day-1 range and -10-7 to 10-6 g m-2 day-1 range for the wet and dry season, respectively. F-gas fluxes for the final covers had the highest number of below detection limit cases as well as lower than R2 threshold cases. Thest F-gas fluxes were measured from daily cover system constructed with auto shredder residue (i.e. auto fluff) for the both the wet and dry seasons. The highest fluxes were measured for CFC-11, HCFC-21, and HCFC-141b in the wet season and for CFC-11, HCFC-141b, and HFC-134a in the dry season across the seven cover locations. Lower level of variation was observed for methane and carbon dioxide with flux values ranging over five orders of magnitude for the seven tested locations. The methane flux values for the daily covers were in the 10-2 to 10+1 g m-2 d-1 range and 1 to 10+1 g m-2 day-1 range for the wet and dry season, respectively. The carbon dioxide flux values for the daily covers were in the -10+1 to 10+2 g m-2 day-1 range and -10+1 to 10+1 g m-2 day-1 range for the wet and dry season, respectively. The methane flux values for the intermediate covers were in the -10-2 to 10+1 g m-2 d-1 range and -10-3 to 10+1 g m-2 day-1 range for the wet and dry season, respectively. The carbon dioxide flux values for the intermediate covers were in the 1 to 10+2 g m-2 day-1 range for both seasons. The methane fluxes for the final cover were -10 -3 g m-2 day-1 and 10-4 g m-2 day-1 for the wet and dry season, respectively. The carbon dioxide flux values for the final cover were in the 10+1 g m-2 d-1 range and 1 to 10+1 g m-2 day-1 range for the wet and dry season, respectively. Negative flux values were typically observed during the wet season and at the intermediate and final covers. The destruction efficiencies for the twelve F-gases were above 99.5% for the onsite flare. Highest F-gas raw gas concentrations were measured for HFC-134a while the lowest F-gas concentration was measured for CFC-113. The F-gas concentrations in the raw gas ranged from 103 to 106 pptv. Similar to what has been reported in the literature, the landfill gas flare system was an efficient abatement device in controlling F-gas emissions. The surface emission measurement values from the field investigation were scaled up to estimate facility-wide fugitive emission values using the relative surface areas of the daily, intermediate, and final cover distributions in the landfill. The total fugitive emissions from the landfill including twelve F-gases, methane, and carbon dioxide ranged from 6,900 to 94,000 CO2E tonnes per year during the wet season, from 21,000 to 47,000 CO2E tonnes per year during the dry season, and from 13,000 to 75,000 CO2E tonnes per year during the year, prorated by the season (representing weighted average of 58% wet season emission rate and 42% dry season emission rate in a 12-month calendar year). The total fugitive F-gas emissions ranged from 1,600 to 4,800 CO2E tonnes per year during the wet season, from 140 to 600 CO2E tonnes per year during the dry season, and from 1,000 to 3,000 CO2E tonnes per year, prorated by the season. The total fugitive methane emissions ranged from 530 to 75,000 CO2E tonnes per year during the wet season, 17,000 to 35,000 CO2E tonnes per year during the dry season, and from 7,500 to 58,000 CO2E tonnes per year, prorated by the season. The total fugitive carbon dioxide emissions ranged from 5,000 to 14,000 CO2E tonnes per year during the wet season, 4,200 to 12,000 CO2E tonnes per year during the dry season, and from 4,500 to 13,000 CO2E tonnes per year, prorated by the season. In comparison to the total fugitive emission value derived from the first-order decay (FOD) model reported by USEPA and the total fugitive emission values calculated using waste-in-place (WIP) – landfill gas correlation equation presented in Spokas et al. (2015), the field-derived methane emission values were one to three orders of magnitude lower.