This work presents multi-scale approaches to investigate 3D printed structured Mn–Na–W/SiO₂ catalysts used for the oxidative coupling of methane (OCM) reaction. The performance of the 3D printed catalysts has been compared to their conventional analogues, packed beds of pellets and powder. The physicochemical properties of the 3D printed catalysts were investigated using scanning electron microscopy, nitrogen adsorption and X-ray diffraction (XRD). Performance and durability tests of the 3D printed catalysts were conducted in the laboratory and in a miniplant under real reaction conditions. In addition, synchrotron-based X-ray diffraction computed tomography technique (XRD-CT) was employed to obtain cross sectional maps at three different positions selected within the 3D printed catalyst body during the OCM reaction. The maps revealed the evolution of catalyst active phases and silica support on spatial and temporal scales within the interiors of the 3D printed catalyst under operating conditions. These results were accompanied with SEM-EDS analysis that indicated a homogeneous distribution of the active catalyst particles across the silica support.

Brazil’s large biofuels industry generates significant amounts of effluents, e.g., vinasse from bioethanol, that can effectively be used as substrate for production of biogas via Anaerobic Digestion (AD). The Oxidative Coupling of Methane (OCM) is the heterogeneous catalytic oxidation of methane into ethylene, which is a main building block for the chemical industry. This work investigates the potential and competitiveness of bio-ethylene production via OCM using biogas produced by biological anaerobiosis of vinasse as a feedstock. The proposed process can add incentive to treat of vinasse via AD and replace fossil ethylene, thus potentially reducing emissions of Greenhouse Gases (GHG). A process model is developed in Aspen Plus v10 software and used to design an economic Biogas-based Oxidative Coupling of Methane (Bio-OCM) process that consumes biogas and oxygen as educts and produces ethylene, ethane, and light off-gases as products. Operating conditions in the reaction section are optimized and a reaction product yield of 16.12% is reached by applying two adiabatic Packed Bed Reactors (PBRs) in series. For the downstream CO₂ removal section, a standalone amine-absorption process is simulated and compared to a hybrid membrane-absorption process on an economic basis. For the distillation section, two different configurations with and without Recycle Split Vapor (RSV) are simulated and compared. The bio-ethylene production cost for a Bio-OCM plant to be installed in Brazil is estimated considering a wide range of prices for educts, utility, side products, and equipment within a Monte Carlo simulation. The resulting average production cost of bio-ethylene is 0.53 ±$0.73$ USD ${\mathrm{kg}}_{{\mathrm{C}}_2{\mathrm{H}}_4}^{-1}$. The production cost is highly sensitive to the sales price assigned to a light off-gas side-product stream containing mostly the un-reacted methane. A sales price close to that of Brazilian pipeline natural gas has been assumed based on the characteristics of this stream. The Monte Carlo simulation shows that a bio-ethylene production cost below or equal to $0.70$ USD ${\mathrm{kg}}_{{\mathrm{C}}_2{\mathrm{H}}_4}^{-1}$ is achieved with a 55.2% confidence, whereas market values for fossil ethylene typically lie between 0.70USD ${\mathrm{kg}}_{{\mathrm{C}}_2{\mathrm{H}}_4}^{-1}$–1.50USD ${\mathrm{kg}}_{{\mathrm{C}}_2{\mathrm{H}}_4}^{-1}$. Technical and economic challenges for the industrial implementation of the proposed Bio-OCM process are identified and relevant opportunities for further research and improvement are discussed.

In the second part of this paper (Part II), the potentials and characteristics of an industrial-scale Oxidative Coupling of Methane (OCM) process integrated with CO₂-hydrogenation, ethane dehydrogenation, and methane reforming processes are highlighted. This novel process concept comprises a direct conversion of methane to ethane and ethylene and further conversion of the resulted carbon dioxide and remaining unreacted methane, respectively, to methanol and syngas. In this context, the selected experimental results of the catalytic CO₂-hydrogenation to methanol reported in the first part of this paper (Part I), were utilized to represent its industrial-scale performance. The experimental results of the mini plant-scale operation of an OCM reactor and CO₂ removal units along with the experimental and industrial data available for representing the operation and performance of all process-units in the integrated process structures were utilized to perform a comparative techno-economic environmental analysis using Aspen-Plus simulation and an Aspen Economic Process Analyzer. The experimental procedure and the results of testing the sequence of OCM and CO₂-hydrogenation reactors are particularly discussed in this context. It was observed that in the sequential operation of these reactors, ethylene will be also hydrogenated to ethane over the investigated catalysts. Therefore, the parallel-operation of these reactors was found to be a promising alternative in such an integrated process. The main assumptions and the conceptual conclusions made in this analysis are reviewed and discussed in this paper in the light of the practical limitations encountered in the experimentations. In the context of a multi-scale analysis, the contributions of the design and operating parameters in the scale of catalyst and reactor as well as in the process-scale represented by analyzing the type and operating conditions of the downstream-units and the process-flowsheets on the economic and environmental performance of the integrated process structures were studied. Moreover, the economic impacts of extra ethylene and methanol produced respectively via the integrated ethane dehydrogenation and CO₂-hydrogenation sections were analyzed in detail. The required capital investment was found to be even smaller than the yearly operating cost of the plant. The environmental impacts and sustainability of the integrated OCM process were found to be enhanced by securing a minimum direct CO₂-emission and energy-efficient conversion of CO₂ and the unreacted CH₄, respectively, to methanol and syngas. Besides producing such value-added by-products, efficient operation of downstream process-units was secured by minimizing the energy usage and ethylene losses. Under the considered conditions in this analysis, the specifications of the finally selected integrated OCM process structure, providing the fastest return of investments (less than 8 years), are highlighted.