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

Electrochemical reduction of CO2 using renewable energy sources is one of the promising avenues to pursue towards mitigating the emissions of the notorious CO2. However, the CO2 electrolysis in aqueous systems, due to the low solubility of CO2, are severely limited by mass transfer. State of the art review shows that a significant amount of the research is done to improve mass transfer, where a variety of electrolyser designs were studied. Despite the effort, the challenge to enhance mass transfer remains and is the focus of the present work. To improve mass transfer, an innovative concept is proposed - Taylor flow in an electrochemical flow cell. Taylor flow has been extensively studied in the literature, especially in micro channels and monolith reactors. Therefore the characteristics of the Taylor flow are known to a certain extent. But they were never tested in an electrochemical system. For that reason, a numerical investigation is carried out to assess the performance of Taylor flow on the flow cell. A simplified 2D model was formulated using a unit cell strategy and is verified based on experimental data and theoretical concepts. The effect of dissolving bubbles is also modelled using a quasi-steady-state analysis The results of the 2D model show a significant improvement in the performance, i.e. in the current densities of the electrochemical cell compared to a typical flow cell. The maximum calculated current densities increase by an order of magnitude under certain flow conditions. The dissolution studies showed that the current densities deteriorate with time. Nevertheless, the overall performance is still higher than the typical flow cell. Finally, based on the insights from the 2D model, a 1D model is suggested to estimate the current densities and dissolution rates. The present study showed promising results for using Taylor flow in an electrochemical cell. The proposed 2D model can help in aiding future modelling studies while the 1D model can give simple estimates for the experimental work.