Rigorous CO₂ absorption models were developed for aqueous 4.5 m K+/4.5 m PZ, monoethanolamine (7m - 9m), and piperazine (8m) in Aspen Plus® RateSepTM. The 4.5 m K+/4.5 m PZ model uses the Hilliard thermodynamic representation and kinetics based on work by Chen. The MEA (Phoenix) and PZ (5deMayo) models incorporate new data for partial pressure of CO₂ vs. loading and kinetics from wetted wall column data. They use reduced reaction sets based on the more relevant species present at the expected operating loading. Kinetics were regressed to match reported carbon dioxide flux data using a wetted wall column (WWC). Density and viscosity were satisfactorily regressed to match newly obtained experimental data. The activity coefficient of CO₂ was also regressed to include newly obtained CO₂ solvent solubility data. The models were reconciled and validated using pilot plant data obtained from five campaigns conducted at the Pickle Research Center. Performance was matched within 10% of NTU for most runs. Temperature profiles are adequately represented in all campaigns. The calculated temperature profiles showed the effect of the L/G on the location and magnitude of the temperature bulge. As the L/G is increased the temperature bulge moves from near the top of the column towards the bottom and its magnitude decreases. Performance improvement due to intercooling was validated across the campaigns that evaluated this process option. Absorber intercooling was studied using various solvent rates (Lmin, 1.1 Lmin and 1.2 Lmin). It is most effective at the critical L/G where the temperature bulge without intercooling is in the middle of the column. In this case it will allow for higher absorption by reducing the magnitude of the bulge temperature. The volume of packing to get 90% removal with L/Lmin =1.1 at the critical L/G is reduced by 30% for 8m PZ. For MEA and a solvent flow rate of 1.1 Lmin packing volume is increased with intercooling at constant L/G. This increase is compensated by higher solvent loadings that suggest lower stripping energy requirements. The critical L/G is 4.3 for 8m PZ, 6.9 for 9m MEA and 4.1 for K+/PZ. / text

[pt] A indústria da borracha sintética tem grande importância e está presente no cotidiano da sociedade mundial. A borracha de butadieno ou polibutadieno é um dos polímeros mais utilizados neste campo, principalmente na produção de pneus. Portanto, o controle das condições operacionais e das propriedades finais do polímero formado são pontos importantes a serem estudados, pois são um desafio para a indústria. Assim, o presente trabalho tem como foco simular a polimerização em solução de polibutadieno utilizando o software Aspen Plus, onde foram utilizados 1,3-butadieno, tetracloreto de titânio, trietilalumínio e hexano como monômero, catalisador, cocatalisador e solvente, respectivamente. Nesta parte do trabalho, obtiveram-se gráficos de distribuição de massa molar que apresentaram propriedades semelhantes aos polibutadienos comerciais e alguns polibutadienos sintetizados em escala de bancada encontrados na literatura. Além disso, em uma segunda parte do trabalho, estuda-se e explica-se a técnica de distribuição instantânea e como foi gerada uma base de dados para um modelo de aprendizagem de máquina chamado de XGBoost, onde pontos dos gráficos da MMD (molar mass distribution) do polímero serviram como entrada do modelo a fim de prever as constantes cinéticas da polimerização. Ambos os estudos e simulações mostram que três e quatro sítios de catalisadores ativos são capazes de sintetizar polímeros com propriedades semelhantes aos polibutadienos comerciais e em escala de bancada. / [en] The synthetic rubber industry is of great importance and is present in the daily life of world society. Butadiene rubber or polybutadiene is one of the most used polymers in this field, mainly in the production of tires. Therefore, controlling the operating conditions and the final properties of the polymer formed are important points to be studied, as they are a challenge for the industry. Thus, the present work focuses on simulating the polymerization in solution of polybutadiene using the Aspen Plus software, where 1,3-butadiene, titanium tetrachloride, triethylaluminum and hexane were used as monomer, catalyst, cocatalyst and solvent, respectively. From the work, molar mass distribution graphs were obtained that showed properties similar to commercial polybutadienes and some polybutadienes synthesized on a bench scale found in the literature. Furthermore, in a second part of the work, the instant distribution technique is studied and explained and how a database was generated for a machine learning model called XGBoost, where points from the MMD (molar mass distribution) graphs of the polymer served as input to the model in order to predict the kinetic constants of polymerization. Both studies and simulations show that three and four sites of active catalysts are able to synthesize polymers with properties similar to commercial and bench-scale polybutadienes.

The global fossil reserves are dwindling and there is need to find alternative sources of energy. With global warming in mind, some of the most commonly considered suitable alternatives include solar, wind, nuclear, geothermal and hydro energy. A common challenge with use of most alternative energy sources is ensuring continuity of supply, which necessitates the use of energy storage. Hydrogen has properties that make it attractive as an energy carrier. To efficiently store energy from alternative sources in hydrogen, several methods of hydrogen production are under study. Several literature sources show thermochemical cycles as having high potential but requiring further development. Using literature sources, an initial screening of thermochemical cycles was done to select a candidate thermochemical cycle. The copper–chlorine thermochemical cycle was selected due to its relatively low peak operating temperature, which makes it flexible enough to be connected to different energy sources. Once the copper–chlorine cycle was identified, the three main copper–chlorine cycles were simulated in Aspen Plus to examine which is the best configuration. Using experimental data from literature and calculating optimal conditions, flowsheets were developed and simulated in Aspen Plus. The simulation results were then used to determine the configuration with the most favourable energy requirements, cycle efficiency, capital requirements and product cost. Simulation results show that the overall energy requirements increase as the number of steps decrease from five–steps to three–steps. Efficiencies calculated from simulation results show that the four and five–step cycles perform closely with 39% and 42%, respectively. The three–step cycle has a much lower efficiency, even though the theoretical calculations imply that the efficiency should also be close to that of the four and five–step cycles. The five–step reaction cycle has the highest capital requirements at US$370 million due to more equipment and the three–step cycle has the lowest requirement at US$ 275 million. Payback analysis and net present value analysis indicate that the hydrogen costs are highest for the three–step cycle at between US$3.53 per kg for a 5–10yr payback analysis and the five–step cycle US$2.98 per kg for the same payback period. / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

The global fossil reserves are dwindling and there is need to find alternative sources of energy. With global warming in mind, some of the most commonly considered suitable alternatives include solar, wind, nuclear, geothermal and hydro energy. A common challenge with use of most alternative energy sources is ensuring continuity of supply, which necessitates the use of energy storage. Hydrogen has properties that make it attractive as an energy carrier. To efficiently store energy from alternative sources in hydrogen, several methods of hydrogen production are under study. Several literature sources show thermochemical cycles as having high potential but requiring further development. Using literature sources, an initial screening of thermochemical cycles was done to select a candidate thermochemical cycle. The copper–chlorine thermochemical cycle was selected due to its relatively low peak operating temperature, which makes it flexible enough to be connected to different energy sources. Once the copper–chlorine cycle was identified, the three main copper–chlorine cycles were simulated in Aspen Plus to examine which is the best configuration. Using experimental data from literature and calculating optimal conditions, flowsheets were developed and simulated in Aspen Plus. The simulation results were then used to determine the configuration with the most favourable energy requirements, cycle efficiency, capital requirements and product cost. Simulation results show that the overall energy requirements increase as the number of steps decrease from five–steps to three–steps. Efficiencies calculated from simulation results show that the four and five–step cycles perform closely with 39% and 42%, respectively. The three–step cycle has a much lower efficiency, even though the theoretical calculations imply that the efficiency should also be close to that of the four and five–step cycles. The five–step reaction cycle has the highest capital requirements at US$370 million due to more equipment and the three–step cycle has the lowest requirement at US$ 275 million. Payback analysis and net present value analysis indicate that the hydrogen costs are highest for the three–step cycle at between US$3.53 per kg for a 5–10yr payback analysis and the five–step cycle US$2.98 per kg for the same payback period. / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

The modern concept of “biorefinery” is dominantly based on chemical pulp mills to create more value than cellulose pulp fibres, and energy from the dissolved lignins and hemicelluloses. This concept is characterized by the conversion of biomass into various bio-based products. It includes thermochemical processes such as gasification and fast pyrolysis. In thermo-mechanical pulp (TMP) mills, the feedstock available to the gasification-based biorefinery is significant, including logging residues, bark, fibre material rejects, bio-sludges and other available fuels such as peat, recycled wood and paper products. On the other hand, mechanical pulping processes consume a great amount of electricity, which may account for up to 40% of the total pulp production cost. The huge amount of purchased electricity can be compensated for by self-production of electricity from gasification, or the involved cost can be compensated for by extra revenue from bio-transport fuel production. This work is to study co-production of bio-automotive fuels, bio-power, and steam via gasification of the waste biomass streams in the context of the mechanical pulp industry. Ethanol and substitute natural gas (SNG) are chosen to be the bio-transport fuels in the study. The production processes of biomass-to-ethanol, SNG, together with heat and power, are simulated with Aspen Plus. Based on the model, the techno-economic analysis is made to evaluate the profitability of bio-transport fuel production when the process is integrated into a TMP mill.The mathematical modelling starts from biomass gasification. Dual fluidized bed gasifier (DFBG) is chosen for syngas production. From the model, the yield and composition of the syngas and the contents of tar and char can be calculated. The model has been evaluated against the experimental results measured on a 150 KWth Mid Sweden University (MIUN) DFBG. As a reasonable result, the tar content in the syngas decreases with the gasification temperature and the steam to biomass (S/B) ratio. The biomass moisture content is a key parameter for a DFBG to be operated and maintained at a high gasification temperature. The model suggests that it is difficult to keep the gasification temperature above 850 ℃ when the biomass moisture content is higher than 15.0 wt.%. Thus, a certain amount of biomass or product gas needs to be added in the combustor to provide sufficient heat for biomass devolatilization and steam reforming.For ethanol production, a stand-alone thermo-chemical process is designed and simulated. The techno-economic assessment is made in terms of ethanol yield, synthesis selectivity, carbon and CO conversion efficiencies, and ethanol production cost. The calculated results show that major contributions to the production cost are from biomass feedstock and syngas cleaning. A biomass-to-ethanol plant should be built over 200 MW.In TMP mills, wood and biomass residues are commonly utilized for electricity and steam production through an associated CHP plant. This CHP plant is here designed to be replaced by a biomass-integrated gasification combined cycle (BIGCC) plant or a biomass-to-SNG (BtSNG) plant including an associated heat & power centre. Implementing BIGCC/BtSNG in a mechanical pulp production line might improve the profitability of a TMP mill and also help to commercialize the BIGCC/BtSNG technologies by taking into account of some key issues such as, biomass availability, heat utilization etc.. In this work, the mathematical models of TMP+BIGCC and TMP+BtSNG are respectively built up to study three cases: 1) scaling of the TMP+BtSNG mill (or adding more forest biomass logging residues in the gasifier for TMP+BIGCC); 2) adding the reject fibres in the gasifier; 3) decreasing the TMP SEC by up to 50%.The profitability from the TMP+BtSNG mill is analyzed in comparison with the TMP+BIGCC mill. As a major conclusion, the scale of the TMP+BIGCC/BtSNG mill, the prices of electricity and SNG are three strong factors for the implementation of BIGCC/BtSNG in a TMP mill. A BtSNG plant associated to a TMP mill should be built in a scale above 100 MW in biomass thermal input. Comparing to the case of TMP+BIGCC, the NR and IRR of TMP+BtSNG are much lower. Political instruments to support commercialization of bio-transport fuel are necessary. / Gasification-based Biorefinery for Mechanical Pulp Mills

Submitted by Isaac Francisco de Souza Dias (isaac.souzadias@ufpe.br) on 2015-05-18T18:24:59Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE - Thibério - Parte escrita - 81 - FINAL.pdf: 8671428 bytes, checksum: 626d3d6a70a811bf559ef1ba89a7d967 (MD5) / Made available in DSpace on 2015-05-18T18:24:59Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE - Thibério - Parte escrita - 81 - FINAL.pdf: 8671428 bytes, checksum: 626d3d6a70a811bf559ef1ba89a7d967 (MD5) Previous issue date: 2015-04-04 / CAPES / Nos últimos anos o biodiesel se tornou uma alternativa para a demanda crescente de combustível no país e no mundo. O próximo passo é conseguir produzir um biodiesel economicamente competitivo com o diesel fóssil em um processo a nível industrial. Uma tecnologia que vem ganhando espaço ultimamente é a destilação reativa. O objetivo deste trabalho foi estudar do ponto de vista computacional e experimental a produção de biodiesel por destilação reativa. Para isso, foi construída uma coluna piloto com 1,5 m de altura em vidro, dotada de toda parte de controle automático para a aquisição de dados. Foi utilizado o Aspen Plus® para realizar as simulações com base nos resultados obtidos experimentalmente. Também foi realizado neste trabalho uma modelagem cinética da transesterificação do óleo de algodão em rota etílica a fim de se obter parâmetros da reação para serem inseridos no simulador. Em seguida, foi comparada a viabilidade da rota etílica com a metílica via simulação e sugerido um processo de extração com o próprio glicerol. Os resultados mostraram que a destilação reativa apresenta melhor desempenho quando comparado a outros processos como por exemplo reatores PFR também estudados neste trabalho. Por fim, foi sugerido um projeto de uma coluna de destilação reativa, extrativa e absortiva para a produção de biodiesel.

Orientador: Antonio José de Almeida Meirelles / Texto em português e inglês / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-21T10:31:20Z (GMT). No. of bitstreams: 1 Batista_FabioRodolfoMiguel_D.pdf: 2503364 bytes, checksum: 981f60d79f8a7a65e7ab2c5b944ab1d7 (MD5) Previous issue date: 2012 / Resumo: A diminuição gradativa das reservas de combustíveis fósseis e a crescente preocupação com os efeitos do aquecimento global vêm impulsionando cada vez mais as pesquisas por fontes de energia limpa. Dentre essas energias, o etanol de cana-de-açúcar, utilizado no Brasil desde a criação do Programa Nacional do Álcool (PROALCOOL) em 1975, vem se consolidando cada vez mais e sofrendo modificações contínuas no seu processo produtivo. Essas modificações se devem,entre outros aspectos, ao surgimento do conceito de biorrefinaria, que visa um aproveitamento integral da biomassa da cana para produção de energia, e ao rápido e contínuo crescimento da indústria alcoolquímica brasileira, utilizando o etanol como matéria prima para a produção de diversos outros produtos,aumentando a demanda por etanol de melhor qualidade e impulsionando pesquisas no melhoramento do processo produtivo atual. Tendo em conta esse atual cenário, essa tese tem por objetivo estudar o processo de destilação alcoólica industrial, por simulação computacional, analisando a influência dos diversos contaminantes do fermentado de cana no funcionamento das colunas de destilação, investigando a possibilidade do desenvolvimento de uma nova planta industrial para a produção de álcool carburante e álcool neutro, um tipo especial de álcool de alto valor agregado com baixo teor de contaminantes utilizado na indústria de química fina e de bebidas. Para o cumprimento desse objetivo, esta tese está dividida em 6 capítulos: o Capítulo 1 apresenta uma revisão bibliográfica da produção científica associada à produção de álcool combustível, apontando as principais lacunas inerentes a esse tema; o Capítulo 2 discute a produção industrial de cachaça por sistema contínuo apresentando um cuidadoso estudo do equilíbrio de fase dos principais componentes do fermentado de cana de açúcar e analisando a influência dos mesmos no processo produtivo; o Capítulo 3 e o Capítulo 4 apresentam o estudo do processo de produção de álcool hidratado combustível discutindo a influência dos componentes do vinho no funcionamento das colunas, técnicas de otimização de processo aplicadas a um processo industrial real e técnicas de controle de processo aplicadas ao controle de acetaldeído e da graduação alcoólica no bioetanol; o Capítulo 5 apresenta uma nova planta industrial para produção de álcool neutro e álcool hidratado discutindo detalhadamente as vantagens e desvantagens do novo processo frente a plantas industriais tradicionais brasileira e francesa; por fim, o Capítulo 6 apresenta as conclusões gerais do trabalho sugerindo temas para investigações futuras. A análise dos resultados obtidos permitiu conluir que, ainda que consolidado, o processo produtivo de etanol através de cana-de-açúcar apresenta lacunas importantes, principalmente quando se deseja produzir etanol de qualidade superior. Nesse sentido, uma nova planta industrial foi proposta com o objetivo de produzir etanol neutro e hidratado em uma única instalação com redução nos custos de instalação (menor numero de colunas) e de consumo de vapor / Abstract: The gradual reduction of fossil fuel reserves and growing concerns about the effects of global warming have encouraged more research on clean energy sources. Among these energies, ethanol from sugar cane, used in Brazil since the creation of the National Alcohol Program (PROALCOOL) in 1975, has undergone continuous changes in their production process. These changes were due to the emergence of the concept of biorefineries, aiming at a full utilization of sugarcane biomass for energy production, and the continuous and quick growth of the Brazilian alcohol-chemical industry, using the ethanol as raw material for the production of several other products, increasing the demand for ethanol with better quality and boosting the research to improving the current production process.Taking into account this present scenario, this thesis aims to study an industrial process for ethanol production, by computational simulation, analyzing the influence of the contaminants of the fermented sugar cane in the operation of distillation columns, investigating the possibility of developing a new plant for the industrial production of fuel alcohol and neutral alcohol, a particular type of hydrated alcohol of high economic value and low content of contaminants used in the manufacture of fine chemicals and beverages. To fulfill this objective, this thesis is divided into six chapters: Chapter 1 presents a literature review of scientific literature related to the production of fuel alcohol, pointing out the main shortcomings inherent in this theme; Chapter 2 discusses an industrial process for cachaça production by continuous distillation featuring a careful study of the phase equilibrium of the main components of the fermented sugar cane and analyzing their influence in the production process; Chapter 3 and Chapter 4 presents the study of an industrial plant for hydrated fuel ethanol production discussing the influence of the main components of the wine in the columns operation, techniques of process optimization applied to a real industrial process and techniques of control process applied to the control of acetaldehyde and alcoholic graduation in bioethanol; Chapter 5 presents a new plant for neutral and hydrated alcohol productions, discussing in detail the advantages and disadvantages of the new process compared to traditional Brazilian and French industrial plants; finally, the Chapter 6 presents the overall findings of the study and suggesting topics for future investigations. Taking into account the results of this thesis, was possible to concluded that, although consolidated, the ethanol production process using sugar cane as raw material presents important gaps especially when related with high quality ethanol. Some of these shortcomings were solved by proposing a new industrial configuration in order to produce neutral and hydrated ethanol in a single installation with lower installation costs (less number of columns) and steam consumption / Doutorado / Engenharia de Alimentos / Doutor em Engenharia de Alimentos

A research report submitted in partial fulfilment requiremenrs of degree Master of Science tothe School of Chemical and Metallurgical Engineering, Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, South Africa, January 2018 / South Africa’s energy sector is vital to the development of its economy. Instability in the form of disruption in supply affects production costs, investments, and social and economic growth. Domestic sources are no longer able to meet the country’s demands. South Africa must find a local alternative fuel source in order to reclaim stability and encourage social and economic development. Biomass is one of the most abundant renewable energy sources, and has great potential as a fuel source. Currently biomass contributes 12% of the world’s energy supply, while in some developing countries it is responsible for up to 50% of the energy supply. South Africa is the highest maize producer on the African continent. Many studies carried out indicated that maize, and its residue contain valuable materials, and has the highest lower heating value in comparison to other agricultural crops. This indicates that maize can be a potential biomass for renewable energy generation in South Africa. A means for energy conversion for biomass, is the process of gasification. Gasification results in gaseous products H2, CO and CO2. Since the process of biomass gasification involves a series of complex chemical reactions involving a number of parameters, which include flow, heat transfer and mass transfer, it is very difficult to study the process of gasification by relying on experimentation only. Numerical simulation was used to provide further insight on this process, and accelerate development and application of maize gasification in a cost effective and efficient manner. The objective of this study was therefore, to verify and evaluate the feasibility of maize gasification and liquid fuels production in South Africa from an economic and energy perspective. The simulation model was developed in Aspen Plus® based on two thermodynamic models specified as Soave – Redlich – Kwong and the Peng Robinson equation of state. All binary parameters required for this simulation were available in Aspen Plus®. The gasification unit was modelled based on a modified Gibbs free energy minimization model. Gasification of maize and downstream processing in the form of Fischer-Tropsch (FT) synthesis and gas to liquids (GTL) processing for liquid fuels production was modelled in Aspen Plus®. Sensitivity analyses were carried out on the process variables: equivalence ratio (ER), steam to biomass ratio (SBR), temperature and pressure, to obtain the optimum gasification conditions. The optimum reactor conditions, which maximized syngas volume and quality was found to be an ER of 0.22 and SBR of 0.2 at a temperature of 611ºC. An increase in pressure was found to have a negative effect; therefore atmospheric conditions of 101.325 kPa were chosen, in order to maximize CO and H2 molar volumes. Based on these conditions the produced syngas consisted of 35% H2, 16% CO, 24% CO2 and 3%CH4. The results obtained from gasification, based on a modified Gibbs free energy model, show a closer agreement with experimental data, than other simulations based on the assumption that equilibrium is reached and no tar is formed. However, these results were still idealistic as it under predicted the formation of CO and CH4. Although tar was accounted for as 5.5% of the total product from the gasifier (Barman et al., 2012), it may have been an insufficient estimation resulting in the discrepancy in CO and CH4. The feasibility of maize as a feed for gasification was examined based on quality of syngas produced in relation to the requirements for FT synthesis. A H2/CO ratio of 2.20 was found, which is within range of 2.1 – 2.56 found to support greater conversions of CO with deactivation of the FT catalyst (Lillebo et al., 2017). The syngas produced from maize was found to have a higher H2/CO ratio than conventional fossil fuel feeds; implying that maize can result in a syngas feed which is both renewable and richer in CO and H2 molar volumes. Liquid fuels generation was modelled based on experimental production distributions obtained from literature for FT synthesis and hydrocracking. The liquid fuel production for 1000 kg/hr maize feed, was found to be 152 kg/hr LPG, 517 kg/hr petrol and 155 kg/hr diesel. The simulation of liquid fuels production via the Fischer-Tropsch synthesis and hydrocracking process showed fair agreement with literature. Where significant deviations were found, they could be reasonably explained and supported. This simulation was found to be a suitable means to predict liquid fuels production from maize gasification and downstream processing. The feasibility of liquid fuels production from maize in South Africa was examined based on the country’s resource capacity to support additional maize generation. It was found that based on 450 000 hectares of underutilized land found in the Homelands, an additional 1.216 billion litre/annum of synthetic fuels in the form of diesel and petrol could be produced. This has the potential to supplement South African liquid fuels demand by 6% using a renewable fuel source. This fuel generation from maize will not impact food security due to the use of underutilized arable land for maize cultivation, or impact water supply as maize does not require irrigation. In addition, fuel generation in this manner supports the Biofuels Industry Strategy (2007) by targeting the use of underutilized land, ensuring minimal impact on food security, and exceeds its primary objective of achieving a 2% blending rate from renewable sources. The economic feasibility of liquid fuels derived from maize was determined based on current economic conditions in 2016. Based on these conditions of 49 $/bbl Brent Crude, 40 $/MT coal and 6.5 $/mmBTU of natural gas at a R/$ exchange rate of R14.06 per U.S. dollar, it was found that coal, natural gas and oil processing are more economically viable feeds for fuel generation relative to maize. However, based on projected market conditions for South Africa, the R/$ exchange rate is expected to weaken further, the coal supply is expected to diminish and supply of natural gas is expected to be a continued issue for South Africa. Based on this, maize should be considered as a feed for fuel generation to reduce the dependency on non-renewable fossil fuel sources. The energy feasibility of liquid fuels produced from maize was only evaluated from a thermal energy perspective. It was found that maize gasification and FT processing requires 0.91 kg steam/kg feed. This 0.91kg of steam accounts for the raw material feed, distillation and heating required for every 1kg of maize processed. It was found that 2.56 kg steam/kg feed was generated from the reactor units. This was assumed to be in the form of 10 bar steam, as in this form it can be sent to steam turbines for electricity generation to assist with overall energy efficiency for this process. In addition, the amount of CO2 (kg/kg feed) produced, was examined for maize processing in comparison to fossil fuel feeds: natural gas and coal. The CO2 production from liquid fuels processing based on a maize feed, was found to be the highest at 0.66 kg/kg feed. However, a coal feed has higher ash and fix carbon content indicating greater solid waste generation in the gasifer. While dry reforming of natural gas is a net consumer of CO2, but had significantly higher steam requirements in order to achieve the same H2/CO ratio as maize. This indicates that although maize results in more CO2/kg feed, it is 88% more energy efficient than dry methane reforming. Additional experimental work on FT processing using syngas derived from maize is recommended. This will assist in further verification of liquid fuels quantity, quality and process energy requirements. / XL2018

With the Paris agreement calling to limit global warming to 2°C below pre-industrial levels, with further efforts to ensure it stays below 1.5°C, the Finnish government passed the Lakihiilen energiakäytön kieltämisestä (416/2019), i.e., Act of Prohibition of Coal Energy,which stipulates that the use of coal as a fuel for heat/electricity production to be bannedfrom 1 May 2029. This affects Helsinki’s energy industry and a key concern to this work is the Salmisaari Combined Heat and Power plant, which is set to be decommissioned. This plant currently generates heat and electricity by using wood pellets and coal to cater toaround 25-45% of the District Heating consumption of the city of Helsinki. To compensate for this decommissioning, there arises a need for more heat production,around 300-500MW of capacity. One alternative is the heat recovery of seawater by utilising the phase change heat of freezing. The present project investigates a technical feasibility study of a system to generate ice slurry, which is then used to extract heat fromseawater at ~0°C via a heat pump. The competitiveness of an ice-slurry based system to state-of-the-art water or ice-based storage is analysed as well. The proposed system is then modelled in Aspen Plus, and the pressure drop characteristics of the generated ice slurry are studied. Finally, a sensitivity analysis of the pressure ratio of the compressor on the performance of the system is studied. Based on prior works, level of commercialisation and technical feasibility, it was found that a vacuum ice generation method, in combination with heat pumps, is a viable solution to cater to the district heating demand of the city. Further, it is concluded that the pressure drop occurring during transport of the ice slurry is quite minimal – less than 0.5% of the total power consumed whilst producing 300MW of district heat. The COP of the system varies between 2.6-2.8 depending on the pressure ratio of the compressor and thus is energy efficient. Overall, the proposed solution seems to be promising and with further socio-techno-economic analysis, this could be the potential alternative to bridge the deficit. / Med Parisavtalet som kräver att den globala uppvärmningen ska begränsas till 2 °C under förindustriella nivåer, med ytterligare ansträngningar för att säkerställa att den håller sigunder 1,5 °C, antog den finska regeringen Laki hiilen energiakäytön kieltämisestä (416/2019), dvs. Förbud mot kolenergi, som föreskriver att användningen av kol som bränsle för värme-/elproduktion ska förbjudas från och med den 1 maj 2029. Detta påverkar Helsingfors energiindustri och en central fråga för detta arbete är Salmisaarikraftvärmeverk, som är planlagt på att avvecklas. Denna anläggning genererar för närvarande värme och elektricitet genom att använda träpellets och kol för att tillgodosecirka 25–45 % av Helsingfors stads fjärrvärmeförbrukning. För att kompensera för denna avveckling uppstår ett behov av mer värmeproduktion, cirka 300-500MW kapacitet. Ett alternativ är värmeåtervinning från havsvatten genom att utnyttja fasförändringsvärmen från frysning. Detta projekt skall undersöka genom en teknisk förstudie olika system för att generera isslurry (en blandning av is och vatten), som sedan används för att utvinna värme från havsvatten vid ~0°C med hjälp av en värmepump. Konkurrenskraften hos ett isslurrybaserat system jämfört mot toppmoderna vatten- eller isbaserad lagrings system analyseras också. Det föreslagna systemet modelleras sedan i Aspen Plus, och tryckfallsegenskaperna hos den genererade isslurryn studeras. Slutligengörs en känslighetsanalys av kompressorns tryckförhållande och dess påverkan på systemets prestanda. Baserat på tidigare arbeten, kommersialiseringsnivå och teknisk genomförbarhet fann denna rapport att genom en metod för att generera vakuumis, i kombination med värmepumpar att en hållbar lösning för att tillgodose stadens fjärrvärmebehov finns. Vidare dras slutsatsen att tryckfallet som inträffar under transport av isslurryn är minimalt- mindre än 0,5 % av den totala energiförbrukningen samtidigt som den producerar 300MW fjärrvärme. Systemets COP varierar mellan 2,6–2,8 beroende på kompressorns tryckförhållande och är därmed energieffektivt. Sammantaget verkar den föreslagna lösningen vara lovande och med ytterligare socio-teknoekonomisk analys kan detta vara ett potentiellt alternati för att brygga underskottet av fjärrvärme.

Hard carbon is an important material for future fossil-free transport systems, as it is a popular choice for the production of anodes for sodium-ion batteries. Biomass is a popular carbonaceous raw material for making hard carbon. It was only noticed at first because it is a renewable energy source, but with the wide application of carbon materials in several fields, industrial manufacturing using biomass as raw material has also been studied a lot. Process simulation of biomass pyrolysis and carbonization to produce hard carbon, pyrolysis gas, and bio-oil are investigated in this thesis work. The model simulation is assumed based on the current operating data and previous literature review, where the first two models use heat exchangers, and the last case uses by-products to generate heat. Economic analysis based on operating expenses and total capital investment is given based on simulated results. The results show that the yield of hard carbon is about 17% under 1000kg/h biomass feedstock, and the economic performance of using heat exchangers is better than that of pyrolysis gas combustion to supply energy. The economic results and break-even point are used to calculate the minimum selling price, payback period, and sensitivity analysis. The calculated minimum selling price for hard carbon is about SEK 20/kg, which is within the range of the current market price, and the payback period is about 16 years. From the sensitivity analysis results, if electricity prices continue to rise, the economics of using cracked gas may become more significant. / Hårt kol är ett viktigt material för framtida fossilfria transportsystem, eftersom det är ett populärt val för tillverkning av anoder till natriumjonbatterier. Biomassa är en populär kolhaltig råvara för att tillverka hårt kol. Det märktes först bara för att det är en förnybar energikälla, men med den breda användningen av kolmaterial inom flera områden har även industriell tillverkning med biomassa som råvara studerats mycket. Processimulering av biomassa pyrolys och karbonisering för att producera hårt kol, pyrolysgas och bioolja undersöks i detta examensarbete. Modellsimuleringen antas baserat på nuvarande driftdata och tidigare litteraturgenomgång, där de två första modellerna använder värmeväxlare och det sista fallet använder biprodukter för att generera värme. Ekonomisk analys baserad på driftskostnader och totala kapitalinvesteringar ges utifrån simulerade resultat. Resultaten visar att utbytet av hårt kol är cirka 17 % under 1000 kg/h biomassaråvara, och den ekonomiska prestandan för att använda värmeväxlare är bättre än för pyrolysgas förbränning för att leverera energi. De ekonomiska resultaten och brytpunkten används för att beräkna lägsta försäljningspris, återbetalningstid och känslighetsanalys. Det beräknade lägsta försäljningspriset för hårt kol är cirka 20 kr/kg, vilket ligger inom intervallet för gällande marknadspris, och återbetalningstiden är cirka 16 år. Om elpriserna fortsätter att stiga från resultaten av känslighetsanalysen kan ekonomin med att använda krackad gas bli mer betydande.