O objetivo desse trabalho foi o estudo da utilização do carbonato de potássio para a absorção de CO2, tendo como principal foco o uso dessa tecnologia para o beneficiamento de biogás em instalações de pequeno e médio porte. O estudo foi dividido em três partes. Na primeira, realizou-se um projeto fatorial, baseado em resultados obtidos por meio de simulação via ASPEN Plus, com o intuito de quantificar a influência da vazão de líquido, da vazão de gás, da concentração da solução e da temperatura do líquido na quantidade de gás carbônico absorvida. Na segunda, foram realizados ensaios de absorção de CO2 em coluna recheada com anéis de Raschig de vidro, utilizando soluções de carbonato de potássio, com objetivo de comparar os resultados obtidos pelo projeto fatorial e estudar o seu potencial para o processo de beneficiamento de biogás. Na terceira, quatro substâncias foram separadamente utilizadas em mistura com solução de carbonato de potássio, de maneira a verificar seu poder como promotores da reação de gás carbônico com carbonato de potássio. Os resultados do projeto fatorial apresentaram a temperatura, vazão e concentração de líquido como as variáveis independentes de maior influência positiva na absorção de CO2, enquanto que a vazão de gás teve influência negativa de baixa intensidade. A quantidade de gás carbônico absorvida em solução sem promotores e em pressão ambiente foi baixa, como relata a literatura. A utilização de promotores possibilitou um aumento substancial da absorção, principalmente com o uso da piperazina. / The objective of this work is to study the use of potassium carbonate for CO2 absorption, aiming to use this technology for biogas upgrade for small and medium scale plants. The study was divided in three parts. In the first one, a factorial design was done, based in results obtained by simulation via ASPEN Plus, to verify the influence of four process variables, namely: liquid volumetric flow rate, gas volumetric flow rate, solution concentration and liquid temperature. Secondly, CO2 absorption experiments were run in columns packed with glass Raschig rings, using potassium carbonate, in order to compare the results obtained by the factorial design and to study the solution\'s potential for biogas upgrade. Lastly, four substances were separately mixed into potassium carbonate solutions, aiming to verify their potential as CO2 absorption promoters. The results of the factorial design presented the liquid temperature, the liquid volumetric flow rate and the solution concentration as the most positively influential independent variables in carbon dioxide absorption, while the gas volumetric flow rate had a negative influence with low intensity. The amount of CO2 absorbed in solution without promoters and in ambient pressure was low, fact that is mentioned by other researchers. The use of promoters allowed a substantial increase in efficiency of CO2 absorption, mainly with the use of piperazine.

Chemical absorption and desorption processes are two fundamental operations in the process industry. Due to the rate-controlled nature of these processes, classical equilibrium stage models are usually inadequate for describing the behaviour of chemical absorption and desorption processes. A more effective modelling method is the non-equilibrium rate-based approach, which considers the effects of the various driving forces across the vapour-liquid interface. In this thesis, a new non-equilibrium rate-based model for chemical absorption and desorption is developed and applied to the hot potassium carbonate process CO₂ Removal Trains at the Santos Moomba Processing Facility. The rate-based process models incorporate rigorous thermodynamic and mass transfer relations for the system and detailed hydrodynamic calculations for the column internals. The enhancement factor approach was used to represent the effects of the chemical reactions. The non-equilibrium rate-based CO₂ Removal Train process models were implemented in the Aspen Custom Modeler® simulation environment, which enabled rigorous thermodynamic and physical property calculations via the Aspen Properties® software. Literature data were used to determine the parameters for the Aspen Properties® property models and to develop empirical correlations when the default Aspen Properties® models were inadequate. Preliminary simulations indicated the need for adjustments to the absorber column models, and a sensitivity analysis identified the effective interfacial area as a suitable model parameter for adjustment. Following the application of adjustment factors to the absorber column models, the CO₂ Removal Train process models were successfully validated against steady-state plant data. The success of the Aspen Custom Modeler® process models demonstrated the suitability of the non-equilibrium rate-based approach for modelling the hot potassium carbonate process. Unfortunately, the hot potassium carbonate process could not be modelled as such in HYSYS®, Santos’s preferred simulation environment, due to the absence of electrolyte components and property models and the limitations of the HYSYS® column operations in accommodating chemical reactions and non-equilibrium column behaviour. While importation of the Aspen Custom Modeler® process models into HYSYS® was possible, it was considered impractical due to the significant associated computation time. To overcome this problem, a novel approach involving the HYSYS® column stage efficiencies and hypothetical HYSYS® components was developed. Stage efficiency correlations, relating various operating parameters to the column performance, were derived from parametric studies performed in Aspen Custom Modeler®. Preliminary simulations indicated that the efficiency correlations were only necessary for the absorber columns; the regenerator columns were adequately represented by the default equilibrium stage models. Hypothetical components were created for the hot potassium carbonate system and the standard Peng-Robinson property package model in HYSYS® was modified to include tabular physical property models to accommodate the hot potassium carbonate system. Relevant model parameters were determined from literature data. As for the Aspen Custom Modeler® process models, the HYSYS® CO₂ Removal Train process models were successfully validated against steady-state plant data. To demonstrate a potential application of the HYSYS® process models, dynamic simulations of the two most dissimilarly configured trains, CO₂ Removal Trains #1 and #7, were performed. Simple first-order plus dead time (FOPDT) process transfer function models, relating the key process variables, were derived to develop a diagonal control structure for each CO₂ Removal Train. The FOPDT model is the standard process engineering approximation to higher order systems, and it effectively described most of the process response curves for the two CO₂ Removal Trains. Although a few response curves were distinctly underdamped, the quality of the validating data for the CO₂ Removal Trains did not justify the use of more complex models than the FOPDT model. While diagonal control structures are a well established form of control for multivariable systems, their application to the hot potassium carbonate process has not been documented in literature. Using a number of controllability analysis methods, the two CO₂ Removal Trains were found to share the same optimal diagonal control structure, which suggested that the identified control scheme was independent of the CO₂ Removal Train configurations. The optimal diagonal control structure was tested in dynamic simulations using the MATLAB® numerical computing environment and was found to provide effective control. This finding confirmed the results of the controllability analyses and demonstrated how the HYSYS® process model could be used to facilitate the development of a control strategy for the Moomba CO₂ Removal Trains. In conclusion, this work addressed the development of a new non-equilibrium rate-based model for the hot potassium carbonate process and its application to the Moomba CO₂ Removal Trains. Further work is recommended to extend the model validity over a wider range of operating conditions and to expand the dynamic HYSYS® simulations to incorporate the diagonal control structures and/or more complex control schemes. / http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1350259 / Thesis (Ph.D.) - University of Adelaide, School of Chemical Engineering, 2009

Chemical absorption and desorption processes are two fundamental operations in the process industry. Due to the rate-controlled nature of these processes, classical equilibrium stage models are usually inadequate for describing the behaviour of chemical absorption and desorption processes. A more effective modelling method is the non-equilibrium rate-based approach, which considers the effects of the various driving forces across the vapour-liquid interface. In this thesis, a new non-equilibrium rate-based model for chemical absorption and desorption is developed and applied to the hot potassium carbonate process CO₂ Removal Trains at the Santos Moomba Processing Facility. The rate-based process models incorporate rigorous thermodynamic and mass transfer relations for the system and detailed hydrodynamic calculations for the column internals. The enhancement factor approach was used to represent the effects of the chemical reactions. The non-equilibrium rate-based CO₂ Removal Train process models were implemented in the Aspen Custom Modeler® simulation environment, which enabled rigorous thermodynamic and physical property calculations via the Aspen Properties® software. Literature data were used to determine the parameters for the Aspen Properties® property models and to develop empirical correlations when the default Aspen Properties® models were inadequate. Preliminary simulations indicated the need for adjustments to the absorber column models, and a sensitivity analysis identified the effective interfacial area as a suitable model parameter for adjustment. Following the application of adjustment factors to the absorber column models, the CO₂ Removal Train process models were successfully validated against steady-state plant data. The success of the Aspen Custom Modeler® process models demonstrated the suitability of the non-equilibrium rate-based approach for modelling the hot potassium carbonate process. Unfortunately, the hot potassium carbonate process could not be modelled as such in HYSYS®, Santos’s preferred simulation environment, due to the absence of electrolyte components and property models and the limitations of the HYSYS® column operations in accommodating chemical reactions and non-equilibrium column behaviour. While importation of the Aspen Custom Modeler® process models into HYSYS® was possible, it was considered impractical due to the significant associated computation time. To overcome this problem, a novel approach involving the HYSYS® column stage efficiencies and hypothetical HYSYS® components was developed. Stage efficiency correlations, relating various operating parameters to the column performance, were derived from parametric studies performed in Aspen Custom Modeler®. Preliminary simulations indicated that the efficiency correlations were only necessary for the absorber columns; the regenerator columns were adequately represented by the default equilibrium stage models. Hypothetical components were created for the hot potassium carbonate system and the standard Peng-Robinson property package model in HYSYS® was modified to include tabular physical property models to accommodate the hot potassium carbonate system. Relevant model parameters were determined from literature data. As for the Aspen Custom Modeler® process models, the HYSYS® CO₂ Removal Train process models were successfully validated against steady-state plant data. To demonstrate a potential application of the HYSYS® process models, dynamic simulations of the two most dissimilarly configured trains, CO₂ Removal Trains #1 and #7, were performed. Simple first-order plus dead time (FOPDT) process transfer function models, relating the key process variables, were derived to develop a diagonal control structure for each CO₂ Removal Train. The FOPDT model is the standard process engineering approximation to higher order systems, and it effectively described most of the process response curves for the two CO₂ Removal Trains. Although a few response curves were distinctly underdamped, the quality of the validating data for the CO₂ Removal Trains did not justify the use of more complex models than the FOPDT model. While diagonal control structures are a well established form of control for multivariable systems, their application to the hot potassium carbonate process has not been documented in literature. Using a number of controllability analysis methods, the two CO₂ Removal Trains were found to share the same optimal diagonal control structure, which suggested that the identified control scheme was independent of the CO₂ Removal Train configurations. The optimal diagonal control structure was tested in dynamic simulations using the MATLAB® numerical computing environment and was found to provide effective control. This finding confirmed the results of the controllability analyses and demonstrated how the HYSYS® process model could be used to facilitate the development of a control strategy for the Moomba CO₂ Removal Trains. In conclusion, this work addressed the development of a new non-equilibrium rate-based model for the hot potassium carbonate process and its application to the Moomba CO₂ Removal Trains. Further work is recommended to extend the model validity over a wider range of operating conditions and to expand the dynamic HYSYS® simulations to incorporate the diagonal control structures and/or more complex control schemes. / http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1350259 / Thesis (Ph.D.) - University of Adelaide, School of Chemical Engineering, 2009

O objetivo desse trabalho foi o estudo da utilização do carbonato de potássio para a absorção de CO2, tendo como principal foco o uso dessa tecnologia para o beneficiamento de biogás em instalações de pequeno e médio porte. O estudo foi dividido em três partes. Na primeira, realizou-se um projeto fatorial, baseado em resultados obtidos por meio de simulação via ASPEN Plus, com o intuito de quantificar a influência da vazão de líquido, da vazão de gás, da concentração da solução e da temperatura do líquido na quantidade de gás carbônico absorvida. Na segunda, foram realizados ensaios de absorção de CO2 em coluna recheada com anéis de Raschig de vidro, utilizando soluções de carbonato de potássio, com objetivo de comparar os resultados obtidos pelo projeto fatorial e estudar o seu potencial para o processo de beneficiamento de biogás. Na terceira, quatro substâncias foram separadamente utilizadas em mistura com solução de carbonato de potássio, de maneira a verificar seu poder como promotores da reação de gás carbônico com carbonato de potássio. Os resultados do projeto fatorial apresentaram a temperatura, vazão e concentração de líquido como as variáveis independentes de maior influência positiva na absorção de CO2, enquanto que a vazão de gás teve influência negativa de baixa intensidade. A quantidade de gás carbônico absorvida em solução sem promotores e em pressão ambiente foi baixa, como relata a literatura. A utilização de promotores possibilitou um aumento substancial da absorção, principalmente com o uso da piperazina. / The objective of this work is to study the use of potassium carbonate for CO2 absorption, aiming to use this technology for biogas upgrade for small and medium scale plants. The study was divided in three parts. In the first one, a factorial design was done, based in results obtained by simulation via ASPEN Plus, to verify the influence of four process variables, namely: liquid volumetric flow rate, gas volumetric flow rate, solution concentration and liquid temperature. Secondly, CO2 absorption experiments were run in columns packed with glass Raschig rings, using potassium carbonate, in order to compare the results obtained by the factorial design and to study the solution\'s potential for biogas upgrade. Lastly, four substances were separately mixed into potassium carbonate solutions, aiming to verify their potential as CO2 absorption promoters. The results of the factorial design presented the liquid temperature, the liquid volumetric flow rate and the solution concentration as the most positively influential independent variables in carbon dioxide absorption, while the gas volumetric flow rate had a negative influence with low intensity. The amount of CO2 absorbed in solution without promoters and in ambient pressure was low, fact that is mentioned by other researchers. The use of promoters allowed a substantial increase in efficiency of CO2 absorption, mainly with the use of piperazine.

Biomass combustion can be seen as CO2 neutral, thereby biomass combustion plants can have negative CO2 emissions if retrofitted with post combustion capture (PCC) technology using liquid absorbents. Monoethanolamine (MEA) has been used for carbon capture in coal combustion plants but are not suitable for use in biomass combustion plants due to corrosion and high solvent regeneration cost. Instead, the hot potassium carbonate (HPC) process using potassium carbonate (K2CO3) as absorbent show better attributes in these aspects. Although, K2CO3 has slow reaction kinetics with CO2 which need to be improved using promoters. Piperazine is the most tested promoter but are hazardous to humans. Recent research has revealed promising alternatives, among these different amino acid salts such as glycine, proline, and isonipecotic acid which are chemically benign. Biomass flue gas composition vary depending on the biomass fuel characteristics. How this affects the degradation and potential formation of hazardous substances need to be studied further. Biomass combustion plants are generally equipped with flue gas condensation systems, making retrofitting more feasible due to increased system flexibility and energy recovery options. The operation costs of carbon capture and sequestration (CCS) in biomass combustion plants need to be monitored to optimize the plant revenue. To make implementation of HPC in biomass combustion plants a reality, piperazine should be used as promoter. Meanwhile, research should focus on improving the absorption rate in HPC process with more chemically safe promoters.

This project aims to evaluate the technical feasibility of an absorption process for carbon capture and storage (CCS). Currently, the CCS process commonly used in the industry is energy and cost-intensive, making its large-scale development a difficult task. The process under evaluation in this project is labeled as an intensified CCS process as it is more energy-efficient, theoretically, compared to the current standard process. The intensified process is based on absorption with aqueous K2CO3/KHCO3 followed by cristallization of KHCO3. The project aims to show the technical feasibility of two parts of the intensified process, the cooling crystallization in the reactor and the regeneration of carbon dioxide through calcination. The cooling crystallization was conducted at different cooling rates for two different solution compositions, while the calcination was conducted the same for all tests. Microscopic images were utilized to examine the relationship between cooling rates, solution composition, crystal size, and clustering. Thermogravimetric analysis was used to simulate the calcination and to analyze the crystals' decomposition and purity. The report concludes that none clustered selective crystallization of potassium bicarbonate and the total regeneration of carbon dioxide through calcination were achieved. A conclusive correlation between cooling rates and crystal yields could not be proven. And the relationship between crystal size and cooling rates substantially deviated from what was expected. Based on the results the intensified process is deemed technically feasible. / Syftet med detta projekt är att utvärdera den tekniska genomförbarheten av en “carbon capture and storage” (CCS) absorptionsprocess. CCS-processen som nuvarande förekommer i industrin är både energi- och kostnadskrävande, detta förhindrar möjligheten till vidare uppskalning. Processen som utvärderas i detta projekt kallas för en intensifierad CCS-process vilket innebär att den är teoretiskt mer energieffektiv jämfört med nuvarande standardprocess. Den intensifierade processen är baserad på absorption med en K2CO3/KHCO3 vattenlösning följt av en kristallisation av KHCO3. Projektet ämnar att visa den tekniska genomförbarheten av specifikt två delar av den intensifierade processen, kylningskristalliseringen i reaktorn samt regenereringen av koldioxid genom kalcinering. Kylningskristalliseringen genomfördes med olika kylningshastigheter för två olika lösningskompositioner medan kalcineringen utfördes likadant för samtliga tester. Mikroskopiska bilder nyttjades för att undersöka förhållandet mellan kylningshastigheten, lösningens sammansättning, kristallstorlek och kristallkluster. Termogravimetrisk analys användes för att efterlikna kalcineringen samt analysera kristallernas sönderdelning och renhet. Rapporten fastställer att selektiv kristallisering av kaliumbikarbonat uppnåddes utan signifikant kluster. En definitiv korrelation mellan kylningshastighet och kristallutbyte kunde ej påvisas. Förhållandet mellan kristallstorlek och kylningshastighet avvek betydande från vad som förväntades. Baserat på resultaten bedömdes den intensifierade processen vara tekniskt genomförbar.

I takt med att behovet av att minska utsläppen av växthusgasen ökar, ökar även intresset för negativa utsläpp. En lovande teknik för att uppnå negativa utsläpp är koldioxidlagring från biomassa, även kallad BECCS (Bio-Energy Carbon Capture and Storage). Trots teknologins mognad är de stora energibehoven vid lösningsmedelsregenerering ett hinder för storskalig implementering. I den här studien utforskas den relativt okända kinetiken för lösningsmedelsregenerering av kaliumkarbonat i ett steg för att optimera processen. Dessutom undersöks möjligheten att använda vanadin(V)oxid som katalysator för att förbättra desorptionshastigheten. Experimentella analyser utfördes i en sats-reaktor och gick ut på att undersöka förändringen av lösningsmedlets loading över tid genom regelbundna titreringar. Utöver detta undersöks den påverkan som temperatur och omrörning har på desorptionshastigheten. Experimenten utförs vid atmosfärstryck och temperaturer från 80°C till 100°C. Resultaten visade på god repeterbarhet trots svårigheter med temperaturöverskridningar. Desorptionshastigheten var lägre vid 80°C och 90°C än vid 100°C, men de logaritmiska hastighetskonstanterna följde inte en linjär relation mot temperaturinverserna vilket antyder att reaktionen är begränsad av massöverföring. Vidare påverkade inte användandet av en katalysator desorptionskinetiken märkbart, vilket än en gång antyder ett massöverföringsberoende. Slutligen visades ingen märkbar skillnad i desorptionshastighet trots olika omrörningshastigheter. Detta beror troligen på den redan höga massöverföringen som sker vid kokpunkten. Sammanfattningsvis bidrar denna studie med insikter för att förbättra effektiviteten hos regenereringen av lösningsmedel vid BECCS, vilket är avgörande för att motverka utsläppen och möta utmaningarna med klimatförändringarna.

Den stora oron för de ökade växthusutsläppen och klimatförändringas effekter har uppmuntrat utvecklingen av åtgärder för att motverka de negativa konsekvenserna. En av de tekniker som har uppmärksammats under de senaste decennierna är kolavskiljningstekniken. Men nuförtiden är kolavskiljning en teknik som är relaterad till höga kostnader där både kapital- och driftskostnaderna är höga. Därför utfördes i detta projekt ett försök att minska kostnaden genom att ersätta den absorptionspackade kolonnen med ett nytt kompakt system. I detta fall atomiserade det kompakta systemet lösningsmedlet till droppar för att öka massöverföringen av koldioxidabsorptionen. Syftet med detta projekt var att utföra en jämförande teknisk-ekonomisk utvärdering av den konventionella kemiska absorptionsprocessen med packade kolonner mot en process med ett kompakt system. En processmodell för den konventionella processen etablerades i Aspen Plus. Dessutom manipulerades den berikade lösningen i samma processmodell för att simulera den förbättrade absorptionen på grund av atomatiseringen av lösningsmedlet. Det resulterade i att implementeringen av det kompakta systemet kunde generera tekniska förbättringar som ett minskat användande av lösningsmedel och en lägre återkokningsbelastning i regenereringskolonnen. Det var dock ingen betydande minskning av den totala fångstkostnaden. I det här fallet var de främsta bidragande faktorerna till fångstkostnaden var kompressorkostnaden och det höga elpriset. Känslighetsanalysen visade dock i huvudsak att fångstkostnaden skulle kunna sänkas när elpriset är lägre. Man kan dra slutsatsen att kompakta system är en lovande teknik som skulle kunna bidra till utvecklingen av kolavskiljningstekniken. Framtida undersökningar av processdesignen krävs dock för att sänka fångstkostnaden ännu mer. / The great concern regarding the increased greenhouse emissions and the effects of the climate change has encouraged the development of solution in order to counteract the negative consequences. One of the technologies that has gained attention during the last decades has been the carbon capture technology. However, nowadays the carbon capture has been a technology that has been related to high capture costs where both capital and operational costs usually has been high. Therefore, in this project, an attempt was realized to reduce the capture cost by replacing the absorption packed column with a novel compact system. In this case, the compact system atomized the solvent into droplets in order to enhance the mass transfer of the carbon dioxide absorption. The aim of this project was to perform a comparative techno-economical evaluation of the conventional chemical absorption process with packed columns to a process with a compact system. A process model for the conventional process was established in Aspen Plus. Furthermore, the rich loading was varied in the same process model in order to simulate the enhanced absorption due to the atomization of the solvent. It resulted that the implementation of the compact system could generate technical benefits such as a reduced solvent utilization and a lower reboiler duty in the stripper column. However, there was no significant reduction regarding the total capture cost. In this case, the main contributors to the capture cost were the compressor cost and the high electricity price. Nevertheless, the sensitivity analysis showed principally that the capture cost could be reduced if the power required in the flue gas compressor can be reduced. It could be concluded that the compact system is a promising technology that could contribute to a further development of the carbon capture technology. However, future investigations regarding the process design are required in order reduce the capture cost even more.

Utveckling av en innovativ teknologi för koldioxidavskiljning med användning av aerosoldroppar av en kaliumkarbonatlösning. Laboratorieexperiment för att studera koldioxidabsorptionsprocessen under olika driftsförhållanden (temperatur, K2CO3- och CO2-koncentration, mängd genererad aerosol) / Development of an innovative technology for carbon capture using aerosol droplets of a potassium carbonate solution. Laboratory experiments to study CO2 absorption process with various operating conditions (temperature, K2CO3 and CO2 concentration, amount of aerosol generated)

No description available.