Capturing and utilizing the emissions of CO2 has become a method to reduce the occurring emissions from industrial flue gases. One of the methodologies to capture and use the CO2 is through the CO2 capture and reduction (CCR) process. This process uses a bi-functional catalyst to capture CO2 from diluted gas streams and subsequently reduce it to CO in the presence of H2. The obtained product (syngas) can be further used as feedstock in for example the Fischer-Tropsch process. To implement a novel technology in industry, the technology itself should be economical feasible. To determine the feasibility of the process a technoeconomical analysis is executed. The analysis uses process parameters obtained by evaluating the catalytic activity of the bifunctional catalysts. Two catalytic systems have been evaluated: Cu-K/𝛾-Al2O3 and FeCrCuK/PMG20. Effect on the synthesis conditions of Cu-K/𝛾-Al2O3 were also investigated. Cu-K/𝛾-Al2O3 without additional drying steps during the synthesis shows a higher CO2 capacity and a faster CO production rate compared to the other catalysts. Furthermore, to estimate the H2 requirement in an industrialized process the consumption of H2 during the process has been quantified. To ensure a continuous process operation, a two reactor process has been proposed in the techno-economical analysis. The sizing and subsequent cost of the process equipment has been determined by utilizing the obtained process parameters. Besides the capital costs, the operating costs were also estimated to determine the profitability of the process. After the monetary benefit of selling the syngas was determined, it could be stated that the process is profitable under certain conditions. The process is profitable if the used H2 source has a buying price below $1.8 per kilogram. If sales of allowances is possible, the buying price of H2 needs to be below $2.4 to ensure a profitable process.

Ammonia is essential for global food production as a component of fertiliser, and a potential energy carrier in the energy transition. Electrochemical ammonia synthesis faces numerous challenges as an alternative to the carbon intensive Haber-Bosch process, including competition from hydrogen evolution, and mass transport limitations. An unconventional cell design with a hydrogen permeable electrode could help to address these problems. The reaction mechanism and performance of ammonia synthesis using hydrogen permeable electrodes was investigated at elevated temperatures and pressures of up to 120 °C and 8 bar. Furthermore, a facile method for enhancing the electrochemical surface area of the electrode was developed and tested. Operation at elevated pressure resulted in a moderate increase in cell performance. However, replenishment of the nitrogen vacancies in the nickel nitride catalyst through dinitrogen adsorption is identified as the elementary step that limits activity and stability. The amount of pre-deposited N is found to significantly influence the ammonia production rate and its stability. Dynamics of ammonia desorption could also play a role in nitride regeneration. In future studies, the presence of a decomposition reaction of the nitride should be investigated. Usage of more stable nitride species or a combination of host nitride and dopants is recommended to improve stability and simultaneously promote dinitrogen activation and hydrogenation to ammonia. These findings expand the understanding of the mechanisms underlying the nitrogen reduction reaction, paving the way for the development of a more efficient green ammonia synthesis process.

Since the industrial revolution in the 1760s, the CO2 concentration in the atmosphere has been rising incessantly driving global warming closer to the point of no return. The world requires urgent actions to not only reduce CO2 emissions but also capture the CO2 for utilization to mitigate the future environmental crisis. CO2 hydrogenation to CH3OH offers an alternative to produce a feasible and economic substitute for oil. This technology also resembles the nearly 100 years old CH3OH synthesis processes from syngas containing H2, CO, and CO2. The conventional Cu/ZnO/Al2O3 catalyst has also been applied for more than 50 years, and its high performance stems from synergies between Cu and ZnO. However, the true nature of the interfacial sites is still extensively debated. Moreover, lower temperature and higher pressure are thermodynamically favorable for maximum CO2 conversion and CH3OH selectivity according to Le Châtelier’s principle and beneficial in terms of energy consumption and catalyst stability against sintering. The limitation in the catalytic performance of Cu/ZnO/Al2O3 in such conditions demands the exploration of novel catalysts. Part I of this dissertation is dedicated to gaining a deeper understanding of Cu-ZnO synergistic structure as well as other Cu-based catalysts. In Chapter 2, we proposed a greener synthesis route for Cu/ZnO catalysts via urea hydrolysis of acetate precursors that can achieve comparable activity to commercial Cu/ZnO/Al2O3 catalysts without producing wastewater. Co-precipitated Cu-Zn hydroxycarbonate mineral-like precursors are crucial for a high inter-dispersion between CuO and ZnO after calcination and providing Cu-ZnO interfacial sites for the reaction. In Chapter 3, the effects of key process conditions, namely temperature and pressure, on CO2 hydrogenation over a commercial Cu/ZnO/Al2O3 catalyst were investigated using a space-resolved study. The gradients of reactants/products concentration and catalyst bed temperature within the catalytic reactor can reveal the significant effect of temperature on the dominant reaction pathways. CH3OH is formed through direct CO2 hydrogenation at low temperatures, while CH3OH formation is mediated via CO which is formed by a reverse water–gas shift reaction at a high temperature. Although pressure did not influence the reaction pathway, higher pressure helped suppress CH3OH decomposition to CO. In Chapter 4, the decisive roles of peripheral promoters to Cu nanoparticles in promoting CH3OH selectivity were elucidated. The model Cu-based catalysts (Cu-M/SiO2, M = Zn, Ga, and In) were prepared via surface organometallic chemistry (SOMC). The M+ sites played important roles in stabilizing formate species spillovered from Cu and determining the reactivity of formate hydrogenation. Improving the spillover and tuning the reactivity of formate help suppress formate decomposition to CO over Cu and ultimately boost CH3OH selectivity. Part II is dedicated to exploring the novel catalysts for low-temperature CO¬2 hydrogenation, as well as, gaining a deeper understanding of the state-of-the-art Re/TiO2 catalyst. In Chapter 5, the bifunctionality of Re supported on TiO2 was deciphered, where metallic Re functions as the H2 activator and cationic Re as the CO2 activator. Re/TiO2 suffers from additional CH4 formation, and the active intermediates and reaction pathways for CH3OH and CH4 were identified. Understanding the nature of active sites and reaction mechanisms over Re/TiO2 led to approaches for CH4 selectivity mitigation in Chapter 6. Exploring various transition metals under low-temperature conditions provided insights into the formate stabilization of the coinage metals (Cu, Ag, and Au). Since the balance between metallic and cationic Re limited the CH3OH selectivity of Re/TiO2, the addition of Ag complemented the role of cationic Re. A synergistic interplay between Ag and Re did not only improve CH3OH selectivity significantly by suppressing intermediates in the reaction pathways toward CH4 but also exhibited superior stability. Finally, the dissertation conveys a message that obtaining the definitive synthesis of well-defined active sites, expansive structure-activity relationships, and comprehensive reaction mechanisms are the major prerequisites for the rational design of novel catalysts. @en

Steelmaking process is a highly carbon-intensive process. This is mainly due to the use of coke as a reducing agent in the blast furnaces to produce carbon-rich pig iron, which in turn, is used for the production of low-carbon steel in the basic oxygen furnaces. The exhaust gases from the blast and basic oxygen furnaces, which mainly contain CO and CO2, are utilised for electricity generation, and thus, these pollutants are released to the atmosphere. One of the possible ways to treat these work’s arising gases (WAGs) is to convert them into syngas, which can then be further converted into syncrude via Fischer-Tropsch synthesis (FTS). The FTS syncrude can then be further refined and processed to produce liquid fuels such as gasoline, kerosene, diesel, etc. These synthetic fuels are sulphur-lean and are essentially capable of replacing the existing fossil-derived liquid fuels, thus contributing to curbing the carbon emissions. The main objective of this thesis was to develop a detailed model of a multi-tubular fixed-bed reactor (MTFBR) to produce synthetic crude from syngas via Fischer-Tropsch synthesis (FTS). The model was then used to simulate a reactor that utilises the syngas obtained from the processing of work’s arising gases of an integrated steel mill to produce synthetic crude. The FTS product distribution was modelled using the kinetic model based on CO-insertion mechanism, developed by Todic et al. A basic MTFBR model was initially developed using the equations and assumptions from the fixed-bed reactor model of Todic, and the basic MTFBR model was able to produce similar results as that of the Todic’s model, with slight deviations in the temperature and pressures profiles. The basic MTFBR model was then further improved to render it comparable with the commercial FT reactors. The main improvements in the model include the dynamic extraction of thermodynamic and transport properties of the system components using Aspen Properties; calculation of dynamic vapour-liquid equilibrium, liquid holdup and catalyst effectiveness factor; and the use of improved heat transfer and pressure drop equations. A sensitivity analysis was performed to determine the effect of design and process parameters on the performance of the MTFBR model. The most crucial design parameter was observed to be the tube diameter as it had a considerable effect on the heat management and the pressure drop in the reactor bed. The most important process parameters for the reactor were observed to be the inlet temperature and the feed flow rate. A simplified FTS gas loop process was also modelled in Aspen Plus in order to introduce a recycle stream into the MTFBR. The effect of tail gas recycle for the recovery of unreacted H2 and CO was also studied, and it was observed that higher recycle ratios resulted in lower conversions per pass; however, overall CO conversions were observed to increase until a maximum, and then decrease thereafter. The optimum conditions for the simplified gas loop process were estimated to be with an inlet temperature of 484.5K and a total recycle of tail gas to the recovery section, for a inlet pressure of 30 bar. Optimised process conditions resulted in a CO conversion per pass of 46%, an overall CO conversion of 89%, a C5+ selectivity of 86.6%, a CH4 selectivity of 6.2%, and a C5+ productivity of 252,540 tonnes/y. The optimised model results, in terms of C5+ selectivity and overall CO conversion, were also pretty much inline with the available data from the Shell SMDS plant in Bintulu.

The rise of CO2 concentration in the atmosphere is a leading cause of global warming. Utilizing CO2 ob- tained from point sources, such as chemical industries, as a feedstock to produce high energy density fuels and chemicals could mitigate the emission of CO2 as well as provide various economic bene- fits. One promising technology is the electrochemical reduction of CO2, however, the presence of contaminants in the industry-supplied feedstock and the separation of products downstream would be challenging in a continuously operated large-scale plant. To address these challenges and indentify the bottlenecks involved, it is important to study which pre-treatment and post-treatment steps are required and how to integrate these in a large-scale electrochemical CO2 reduction process. The gas and liquid feed streams to the CO2 electrolyzers are first cleaned to the desired levels. The liquid feed stream is water from the river Rhine that is purified so the specifications of the water meet the requirements for type 1 water (ultrapure water). The gas feed stream is the flue gas stream of an average steel-producing plant in Europe and is cleaned to remove sulfur and nitrogen compounds. A two-step electrolysis process is used where CO2 is first reduced to CO, followed by the reduction of CO to C2+ products. The electrolyzer for the first step is a membrane electrode assembly-based flow cell with a current density of 300 𝑚𝐴 𝑐𝑚2− and a faradaic efficiency (FE) of 96% to CO. In the second step, a gas diffusion electrode-based flow cell with a current density of 300 𝑚𝐴 𝑐𝑚2− and a faradaic efficiency of 9.35%, 15.49%, 45.57%, and 16.38% towards acetic acid, ethanol, ethylene, and propanol, respectively, is used. The anolyte and catholyte in the reactors are recycled 3,500 and 2,000 times, respectively, to reduce the size of purification of the liquid feed stream section and increase the liquid product concentration. In both steps, unreacted CO2 and CO are recycled. The gaseous and liquid products are separated and purified to meet the industry standards using established separation techniques. The total capital investment for a process with an industrial gas feed of 381.678 tons per hour is 4,053.5 million dollars with a daily operating cost of 7.403 million dollars. The daily income from selling the products is 2.363 million dollars, but this could increase if the FE towards acetic acid is increased since this product has the highest income per electron consumed. The net present value (NPV) for the base case, assuming current technological and market conditions, is -19.4 billion dollars after 15 years. To analyze which parameters have the most influence on the NPV, a sensitivity analysis is also per- formed with a better and optimistic scenario. It was found that the economic feasibility of the currently designed process is not limited by the technological progress, but mainly by the market conditions. The target of this process is to reduce the emission of CO2, however, the operation of the plant itself contributes to some CO2 emissions. Therefore the process should consume more CO2 than it emits. The units that consume most energy and emit the most CO2 are the CO to C2+ products electrolyzer and the first distillation column in the liquid product separation section to remove acetic acid. It was found that the process is only carbon negative when the consumed energy is generated by nuclear, wind, or solar energy. The net CO2 emission is the lowest when nuclear or wind is used as an energy source. Generating all the required energy from these sustainable sources brings another challenge since the total installed capacity of these sources are currently not sufficient to cater to the needs of such a large-scale continuously operating CO2 electrolysis plant. Keywords: Electrochemical CO2 reduction, large-scale, pre-treatment, post-treatment, technoeconomical analysis, energy analysis